Graphene composite material and preparation method thereof
11149129 · 2021-10-19
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Inventors
Cpc classification
C08L77/02
CHEMISTRY; METALLURGY
C08L77/00
CHEMISTRY; METALLURGY
C08G63/85
CHEMISTRY; METALLURGY
C08J2367/02
CHEMISTRY; METALLURGY
C08G83/00
CHEMISTRY; METALLURGY
C08L67/02
CHEMISTRY; METALLURGY
C08J5/005
CHEMISTRY; METALLURGY
C08L77/00
CHEMISTRY; METALLURGY
D01F1/106
TEXTILES; PAPER
C08L67/02
CHEMISTRY; METALLURGY
C08K3/042
CHEMISTRY; METALLURGY
C08J2377/02
CHEMISTRY; METALLURGY
D01F1/09
TEXTILES; PAPER
C08K3/042
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention discloses a graphene composite material and a preparation method thereof. By adding pleated graphene oxide microspheres and a catalyst to a precursor, the pleated graphene oxide microspheres are allowed to be highly dispersed and gradually disassociated into single-layer graphene oxide sheets during the process of polycondensation, the partially esterified molecules react with the hydroxyl and carboxyl group on the surface of graphene oxide sheets to form a chemical bond, and the graphene oxide is thermally reduced, to finally obtain a composite material comprising PET and graphene sheets having PET grated to the surface.
Claims
1. A method for preparing a graphene-polyester nanocomposite material, comprising the following steps: (1) drying a dispersion of single-layer graphene oxide with a size of 1-50 μm by atomization drying to obtain pleated graphene oxide microspheres having a carbon/oxygen ratio of 2.5-5; (2) fully mixing 100 parts by weight of terephthalic acid, 50-150 parts by weight of a diol, and 0.01-0.5 part by weight of a catalyst by stirring, and subjecting the mixture to an esterification reaction at 200-260° C. until no water is produced; and (3) adding 0.02-10 parts by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.01-1 part by weight of a catalyst to the esterification product obtained in Step (2), incubating with stirring for 1-3 hrs, heating to 240-310° C. and evacuating to allow the reaction to proceed until no heat is released from the system, and then granulating with water cooling to obtain a graphene-polyester nanocomposite material.
2. The method of claim 1, wherein the diol in Step (2) is butanediol in an amount of 60-76.8 parts by weight, propylene glycol in an amount of 50-70 parts by weight; or 1,4-cyclohexanedimethanol in an amount of 121.4-147.5 parts by weight.
3. The method of claim 1, wherein the catalyst in Step (2) is one or more of an oxide, an inorganic salt and an organic compound of sodium, titanium, lead, and tin.
4. The method of claim 1, wherein the catalyst in Step (3) is one or more of an oxide, an inorganic salt and an organic compound of antimony, titanium, lead, and tin.
5. A method for preparing a graphene-nylon 6 nanocomposite material, comprising the following steps: (1) drying a dispersion of single-layer graphene oxide with a size of 1-50 μm by atomization drying to obtain pleated graphene oxide microspheres having a carbon/oxygen ratio of 2.5-5; (2) adding 0.01-3.5 parts by weight of pleated graphene oxide microspheres and 1-3 parts by weight of deionized water to 100 parts by weight of caprolactam melt, and fully stirring at 80° C. at a high speed (300-500 rpm) to form a dispersion; and (3) preparing a graphene-nylon 6 nanocomposite material in a batch reactor or in a VK tube, where in the batch reactor: under a nitrogen atmosphere, the dispersion is added to the polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 2-4 hrs and then under vacuum for 4-6 hrs to obtain a polymer melt; and finally, the polymer melt is granulated with water cooling to obtain a graphene-nylon 6 nanocomposite material; and in the VK tube: the dispersion is continuously polymerized in the VK tube, where the polymerization temperature is 260° C., and the polymerization time is 20 hrs; and the polymer melt is granulated with water cooling to obtain a graphene-nylon 6 nanocomposite material.
6. The preparation method of claim 5, wherein the atomization drying temperature in Step (1) is 130-160° C.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF THE EMBODIMENTS
(8) The present invention will be specifically described by the following examples, which are only used to further illustrate the present invention, and are not to be construed as limiting the scope of the present invention. Some non-essential changes and adjustments made by those skilled in the art according to the disclosure the present invention are encompassed in the scope of protection of the present invention.
Example 1-1
(9) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 1-3 μm, and the carbon/oxygen ratio is 2.5.
(10) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(11) (3) 1.17 g of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 g of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(12) After the above steps, a graphene/PET nanocomposite material is obtained, as shown in
Example 1-2
(13) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(14) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(15) (3) 1.17 g of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 g of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(16) After the above steps, a graphene/PET nanocomposite material is obtained. Specific properties are shown in Table 1.
Example 1-3
(17) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-45 μm, and the carbon/oxygen ratio is 2.5.
(18) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(19) (3) 1.17 parts by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 g of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(20) After the above steps, a graphene/PET nanocomposite material is obtained. Specific properties are shown in Table 1.
Example 1-4
(21) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 160° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 5.
(22) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(23) (3) 1.17 g of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 g of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(24) After the above steps, a graphene/PET nanocomposite material is obtained. Specific properties are shown in Table 1.
Example 1-5
(25) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(26) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(27) (3) 11.7 g of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 g of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(28) After the above steps, a graphene/PET nanocomposite material is obtained. Specific properties are shown in Table 1.
Example 1-6
(29) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(30) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(31) (3) 58.5 g of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 g of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(32) After the above steps, a graphene/PET nanocomposite material is obtained. Specific properties are shown in Table 1.
Comparative Example 1-1
(33) PET was prepared following the method as described in Example 1, except that no pleated graphene oxide microspheres were added during the preparation process. The performances are shown in Table 1.
Comparative Example 1-2
(34) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 0.3-0.7 μm, and the carbon/oxygen ratio is 2.5.
(35) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(36) (3) 1.17 g of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 g of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(37) After the above steps, a graphene/PET nanocomposite material is obtained. Specific properties are shown in Table 1.
Comparative Example 1-3
(38) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 70-80 μm, and the carbon/oxygen ratio is 2.5.
(39) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(40) (3) 1.17 g of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 g of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(41) After the above steps, a graphene/PET nanocomposite material is obtained. Specific properties are shown in Table 1.
Comparative Example 1-4
(42) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 220° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 10.
(43) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(44) (3) 1.17 parts by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(45) After the above steps, a graphene/PET nanocomposite material is obtained. Specific properties are shown in Table 1.
Comparative Example 1-5
(46) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(47) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(48) (3) 93.6 g of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 g of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(49) After the above steps, a graphene/PET nanocomposite material is obtained. Specific properties are shown in Table 1.
(50) TABLE-US-00001 TABLE 1 Specific parameters and properties of the example Carbon/oxygen Size of Amount of Yield Tensile Elongation Electrical ratio in graphene oxide graphene oxide strength modulus at break conductivity graphene oxide (μm) (wt %) (MPa) (GPa) (%) (S/m) Example 1-1 2.5 1-3 0.1 52 2.38 91 10.sup.−16 Example 1-2 2.5 10-15 0.1 56 2.44 90 10.sup.−16 Example 1-3 2.5 40-45 0.1 58 2.58 88 10.sup.−16 Example 1-4 5 10-15 0.1 59 2.61 83 10.sup.−16 Example 1-5 2.5 10-15 1 64 2.67 78 10.sup.−13 Example 1-6 2.5 10-15 5 60 2.74 77 10.sup.−3 Comparative — — — 42 2.1 85 10.sup.−16 Example 1-1 Comparative 2.5 0.3-0.7 0.1 44 2.15 86 10.sup.−16 Example 1-2 Comparative 2.5 70-80 0.1 45 2.3 67 10.sup.−16 Example 1-3 Comparative 10 10-15 0.1 47 2.14 62 10.sup.−16 Example 1-4 Comparative 2.5 10-15 8 51 2.36 44 10.sup.−2 Example 1-5
(51) It can be found through analysis of Comparative Example 1-1, Comparative Example 1-2, Example 1-1, Example 1-2, Example 1-3, and Comparative Example 1-3 that while the carbon/oxygen ratio in graphene oxide and the amount of graphene oxide added are kept unchanged, the selection of graphene oxide with a size in a suitable range results in a composite material with the optimum performances. In Comparative Example 1-2, the size of graphene oxide is too small, so the graphene oxide cannot be an effective reinforcing material itself; and in Comparative Example 1-3, the size of graphene oxide is too large, it cannot be effectively unfolded into a flake-like graphene oxide after being added to a polymerization system, and can only be used as a pleated spherical filler to reinforce the composite material, resulting in a small increase in the tensile strength and modulus and a slightly decrease in the elongation at break. When the size is in the range of 1-50 μm, as the size increases, graphene oxide can exert a more potent reinforcing effect.
(52) It can be found through analysis of Comparative Example 1-1, Example 1-2, Example 1-4, and Comparative Example 1-4 that as the carbon/oxygen ratio increases, the performance of the composite material becomes better. This is because as the carbon/oxygen ratio increases, the graphene has fewer defects and better performances, which make the composite perform better. However, the carbon/oxygen ratio cannot be too high; otherwise the bonding between graphene oxide sheets is too strong, and the graphene oxide cannot be unfolded during polymerization, so it cannot be effectively enhance, or even greatly reduce the elongation at break (Comparative Example 4).
(53) It can be found through analysis of Comparative Example 1-1, Example 1-2, Example 1-5, Example 1-6, and Comparative Example 1-5 that the increase in the amount of graphene oxide increases the mechanical properties and greatly improves the electrical conductivity of the material. After too much graphene oxide is added, although the electrical conductivity is further improved, the mechanical properties of the material are reduced. This is due to the stacking of excessive graphene, which reduces the reinforcing effect (Comparative Example 1-5)
Example 1-7
(54) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 200° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-50 μm, and the carbon/oxygen ratio is 5.
(55) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(56) (3) 58.5 g of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 g of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs at a stirring speed of 140 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material. The graphene/PET nanocomposite material is tested to have good mechanical and electrical properties.
Example 1-8
(57) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 200° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-50 μm, and the carbon/oxygen ratio is 5.
(58) (2) 1000 g of terephthalic acid, 530 g of ethylene glycol, and 0.2 g of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C., until no water was produced.
(59) (3) 0.117 g of the pleated graphene oxide microspheres obtained in Step (1) and 0.18 g of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 1 hrs at a stirring speed of 200 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material. The graphene/PET nanocomposite material is tested to have good mechanical and electrical properties.
Example 2-1
(60) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 1-3 μm, and the carbon/oxygen ratio is 2.5.
(61) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(62) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(63) (4) The composite material obtained in Step (3) was dried, pre-crystallized, solid-phase polycondensed, cooled, and subjected to high-speed melt spinning. The drying temperature was 175° C., the pre-crystallization temperature was 180° C., the solid-phase polycondensation temperature was 215° C., the intrinsic viscosity after the solid-phase polycondensation was 1.1, the cooling temperature was 70° C., the spinning temperature was 290° C., the winding speed was 4000 m/min, and the draw ratio was 3.
(64) After the above steps, a graphene/polyester composite fiber for a cord is obtained, as shown in
Example 2-2
(65) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 6-10 μm, and the carbon/oxygen ratio is 2.5.
(66) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(67) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(68) (4) The composite material obtained in Step (3) was dried, pre-crystallized, solid-phase polycondensed, cooled, and subjected to high-speed melt spinning. The drying temperature was 175° C., the pre-crystallization temperature was 180° C., the solid-phase polycondensation temperature was 215° C., the intrinsic viscosity after the solid-phase polycondensation was 1.1, the cooling temperature was 70° C., the spinning temperature was 290° C., the winding speed was 4000 m/min, and the draw ratio was 3.
(69) After the above steps, a graphene/polyester composite fiber for a cord is obtained. Specific properties are shown in Table 2.
Example 2-3
(70) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 160° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 6-10 μm, and the carbon/oxygen ratio is 5.
(71) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(72) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(73) (4) The composite material obtained in Step (3) was dried, pre-crystallized, solid-phase polycondensed, cooled, and subjected to high-speed melt spinning. The drying temperature was 175° C., the pre-crystallization temperature was 180° C., the solid-phase polycondensation temperature was 215° C., the intrinsic viscosity after the solid-phase polycondensation was 1.1, the cooling temperature was 70° C., the spinning temperature was 290° C., the winding speed was 4000 m/min, and the draw ratio was 3.
(74) After the above steps, a graphene/polyester composite fiber for a cord is obtained. Specific properties are shown in Table 2.
Example 2-4
(75) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 6-10 μm, and the carbon/oxygen ratio is 2.5.
(76) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(77) (3) 0.585 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(78) (4) The composite material obtained in Step (3) was dried, pre-crystallized, solid-phase polycondensed, cooled, and subjected to high-speed melt spinning. The drying temperature was 175° C., the pre-crystallization temperature was 180° C., the solid-phase polycondensation temperature was 215° C., the intrinsic viscosity after the solid-phase polycondensation was 1.12, the cooling temperature was 70° C., the spinning temperature was 290° C., the winding speed was 4000 m/min, and the draw ratio was 3.
(79) After the above steps, a graphene/polyester composite fiber for a cord is obtained. Specific properties are shown in Table 2.
Example 2-5
(80) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 6-10 μm, and the carbon/oxygen ratio is 2.5.
(81) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(82) (3) 1.17 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite material.
(83) (4) The composite material obtained in Step (3) was dried, pre-crystallized, solid-phase polycondensed, cooled, and subjected to high-speed melt spinning. The drying temperature was 175° C., the pre-crystallization temperature was 180° C., the solid-phase polycondensation temperature was 215° C., the intrinsic viscosity after the solid-phase polycondensation was 1.14, the cooling temperature was 70° C., the spinning temperature was 290° C., the winding speed was 4000 m/min, and the draw ratio was 3.
(84) After the above steps, a graphene/polyester composite fiber for a cord is obtained. Specific properties are shown in Table 2.
Comparative Example 2-1
(85) PET was prepared following the method as described in Example 1, except that no pleated graphene oxide microspheres were added during the preparation process. The performances are shown in Table 2.
Comparative Example 2-2
(86) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 0.3-0.7 μm, and the carbon/oxygen ratio is 2.5.
(87) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(88) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(89) (4) The composite material obtained in Step (3) was dried, pre-crystallized, solid-phase polycondensed, cooled, and subjected to high-speed melt spinning. The drying temperature was 175° C., the pre-crystallization temperature was 180° C., the solid-phase polycondensation temperature was 215° C., the intrinsic viscosity after the solid-phase polycondensation was 1.1, the cooling temperature was 70° C., the spinning temperature was 290° C., the winding speed was 4000 m/min, and the draw ratio was 3.
(90) After the above steps, a graphene/polyester composite fiber for a cord is obtained. Specific properties are shown in Table 2.
Comparative Example 2-3
(91) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-45 μm, and the carbon/oxygen ratio is 2.5.
(92) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(93) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(94) (4) The composite material obtained in Step (3) was dried, pre-crystallized, solid-phase polycondensed, cooled, and subjected to high-speed melt spinning. The drying temperature was 175° C., the pre-crystallization temperature was 180° C., the solid-phase polycondensation temperature was 215° C., the intrinsic viscosity after the solid-phase polycondensation was 1.31, the cooling temperature was 70° C., the spinning temperature was 290° C., the winding speed was 4000 m/min, and the draw ratio was 3.
(95) After the above steps, the obtained melt has a too large viscosity, and has difficulty in continuous spinning.
Comparative Example 2-4
(96) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 220° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 6-10 μm, and the carbon/oxygen ratio is 10.
(97) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(98) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(99) (4) The composite material obtained in Step (3) was dried, pre-crystallized, solid-phase polycondensed, cooled, and subjected to high-speed melt spinning. The drying temperature was 175° C., the pre-crystallization temperature was 180° C., the solid-phase polycondensation temperature was 215° C., the intrinsic viscosity after the solid-phase polycondensation was 1.1, the cooling temperature was 70° C., the spinning temperature was 290° C., the winding speed was 4000 m/min, and the draw ratio was 3.
(100) After the above steps, it is found that the spinneret is clogged, the continuity of the spun yarn is less good, and the frequency of yarn breakage is high.
Comparative Example 2-5
(101) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 6-10 μm, and the carbon/oxygen ratio is 2.5.
(102) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(103) (3) 5.85 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite material.
(104) (4) The composite material obtained in Step (3) was dried, pre-crystallized, solid-phase polycondensed, cooled, and subjected to high-speed melt spinning. The drying temperature was 175° C., the pre-crystallization temperature was 180° C., the solid-phase polycondensation temperature was 215° C., the intrinsic viscosity after the solid-phase polycondensation was 1.37, the cooling temperature was 70° C., the spinning temperature was 290° C., the winding speed was 4000 m/min, and the draw ratio was 3.
(105) After the above steps, it is found that the melt viscosity is too high, the spinning is difficult, and the continuity is poor.
(106) TABLE-US-00002 TABLE 2 Specific parameters and properties of the example Carbon/oxygen Size of Amount of Breaking Elongation ratio in graphene oxide graphene oxide strength at break graphene oxide (μm) (wt %) (cN/dtex) (%) Example 2-1 2.5 1-3 0.1 9.35 17.5 Example 2-2 2.5 6-10 0.1 9.42 17.3 Example 2-3 5 6-10 0.1 9.48 17.3 Example 2-4 2.5 6-10 0.5 9.67 16.5 Example 2-5 2.5 6-10 1 9.92 15.2 Comparative — — — 9.13 17.2 Example 2-1 Comparative 2.5 0.3-0.7 0.1 8.83 17.4 Example 2-2 Comparative 2.5 40-45 0.1 — — Example 2-3 Comparative 10 6-10 0.1 — — Example 2-4 Comparative 2.5 6-10 5 — — Example 2-5
(107) It can be found through analysis of Comparative Example 2-1, Comparative Example 2-2, Example 2-1, Example 2-2, and Comparative Example 2-3 that while the carbon/oxygen ratio in graphene oxide and the amount of graphene oxide added are kept unchanged, increasing the graphene size within a suitable range can effectively increase the breaking strength of the fiber. In Comparative Example 2-2, the size of graphene oxide is too small, so the graphene oxide cannot be an effective reinforcing material itself. In Comparative Example 2-3, the size of graphene oxide is too large, the viscosity increasing effect is obvious after being added to a polymerization system; the melt is tackified in the solid-phase polycondensation stage, so the viscosity is further increased, making the spinning difficult, which is not conducive to continuous production. Therefore, the size is defined in the range of 1-10 μm, and graphene oxide can exert a more potent reinforcing effect.
(108) It can be found through analysis of Comparative Example 2-1, Example 2-2, Example 2-3, and Comparative Example 2-4 that as the carbon/oxygen ratio increases, the performance of the composite fiber becomes better. This is because as the carbon/oxygen ratio increases, the graphene has fewer defects and better performances, which make the composite perform better. However, the carbon/oxygen ratio cannot be too high; otherwise the bonding between graphene oxide sheets is too strong, and the graphene oxide is still maintained stacked during polymerization, and clogs the spinneret, causing difficulty in continuous production (Comparative Example 2-4).
(109) It can be found through analysis of Comparative Example 2-1, Example 2-2, Example 2-4, Example 2-5, and Comparative Example 2-5 that the increase in the amount of graphene oxide allows the breaking strength of the composite fiber to increase greatly, which can be attributed to the reinforcing effect of graphene. After too much graphene oxide is added, the viscosity of the system is too large, and the melt spinnability is greatly reduced after tackification, causing difficulty in continuous production (Comparative Example 2-5).
Example 2-6
(110) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 3-5 μm, and the carbon/oxygen ratio is 2.5.
(111) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(112) (3) 0.95 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs at a stirring speed of 140 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite material.
(113) (4) The composite material obtained in Step (3) was dried, pre-crystallized, solid-phase polycondensed, cooled, and subjected to high-speed melt spinning. The drying temperature was 170° C., the pre-crystallization temperature was 175° C., the solid-phase polycondensation temperature was 210° C., the intrinsic viscosity after the solid-phase polycondensation was 0.9, the cooling temperature was 60° C., the spinning temperature was 290° C., the winding speed was 5000 m/min, and the draw ratio was 4.
(114) The obtained graphene/polyester composite fiber for a cord is tested to have perfect mechanical and electrical properties.
Example 2-7
(115) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 200° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 3-5 μma, and the carbon/oxygen ratio is 5.
(116) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(117) (3) 0.95 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 1 hrs at a stirring speed of 200 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite material.
(118) (4) The composite material obtained in Step (3) was dried, pre-crystallized, solid-phase polycondensed, cooled, and subjected to high-speed melt spinning. The drying temperature was 180° C., the pre-crystallization temperature was 185° C., the solid-phase polycondensation temperature was 220° C., the intrinsic viscosity after the solid-phase polycondensation was 1.2, the cooling temperature was 80° C., the spinning temperature was 270° C., the winding speed was 3000 m/min, and the draw ratio was 1.5.
(119) The obtained graphene/polyester composite fiber for a cord is tested to have perfect mechanical and electrical properties.
Example 3-1
(120) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 1-3 μm, and the carbon/oxygen ratio is 2.5.
(121) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(122) (3) 0.585 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(123) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D. A shuttle loom was used for weaving.
(124) After the above steps, a multi-functional graphene/polyester composite fabric is obtained. A photo of the graphene/polyester composite fabric is shown in
Example 3-2
(125) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(126) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(127) (3) 0.585 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(128) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D. A shuttle loom was used for weaving.
(129) After the above steps, a multi-functional graphene/polyester composite fabric is obtained. Specific properties are shown in Tables 3 and 4.
Example 3-3
(130) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-45 μm, and the carbon/oxygen ratio is 2.5.
(131) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(132) (3) 0.585 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(133) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D. A shuttle loom was used for weaving.
(134) After the above steps, a multi-functional graphene/polyester composite fabric is obtained. Specific properties are shown in Tables 3 and 4.
Example 3-4
(135) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 160° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 5.
(136) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(137) (3) 0.585 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(138) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.4 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D. A shuttle loom was used for weaving.
(139) After the above steps, a multi-functional graphene/polyester composite fabric is obtained. Specific properties are shown in Tables 3 and 4.
Example 3-5
(140) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(141) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(142) (3) 1.17 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(143) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.3 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature was 280° C., the spinning speed was 3600 in/min, the draw ratio was 1.5, and the denier number was 100D. A shuttle loom was used for weaving.
(144) After the above steps, a multi-functional graphene/polyester composite fabric is obtained. Specific properties are shown in Tables 3 and 4.
Example 3-6
(145) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(146) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(147) (3) 5.85 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(148) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.5 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D. A shuttle loom was used for weaving.
(149) After the above steps, a multi-functional graphene/polyester composite fabric is obtained. Specific properties are shown in Tables 3 and 4.
Comparative Example 3-1
(150) PET was prepared following the method as described in Example 1, except that no pleated graphene oxide microspheres were added during the preparation process. The performances are shown in Tables 3 and 4.
Comparative Example 3-2
(151) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 0.3-0.7 μm, and the carbon/oxygen ratio is 2.5.
(152) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(153) (3) 0.585 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(154) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.3 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D. A shuttle loom was used for weaving.
(155) After the above steps, a graphene/polyester composite fabric is obtained. Specific properties are shown in Tables 3 and 4.
Comparative Example 3-3
(156) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 70-80 μm, and the carbon/oxygen ratio is 2.5.
(157) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(158) (3) 0.585 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(159) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D. A shuttle loom was used for weaving.
(160) After the above steps, it is found that the spinneret is clogged, the continuity of the spun yarn is less good, and the frequency of yarn breakage is high.
Comparative Example 3-4
(161) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 220° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 10.
(162) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(163) (3) 0.585 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(164) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D. A shuttle loom was used for weaving.
(165) After the above steps, it is found that the spinneret is clogged, the continuity of the spun yarn is less good, and the frequency of yarn breakage is high.
Comparative Example 3-5
(166) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(167) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(168) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(169) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D. A shuttle loom was used for weaving.
(170) A graphene/polyester composite fabric is obtained. Specific properties are shown in Tables 3 and 4.
Comparative Example 3-6
(171) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(172) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(173) (3) 9.36 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(174) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D. A shuttle loom was used for weaving.
(175) After the above steps, it is found that the spinneret is clogged, the continuity of the spun yarn is less good, and the frequency of yarn breakage is high.
(176) TABLE-US-00003 TABLE 3 Specific parameters of the examples Carbon/oxygen Size of Amount of ratio in graphene oxide graphene oxide graphene oxide (μm) (wt %) Example 3-1 2.5 1-3 0.5 Example 3-2 2.5 10-15 0.5 Example 3-3 2.5 40-45 0.5 Example 3-4 5 10-15 0.5 Example 3-5 2.5 10-15 1 Example 3-6 2.5 10-15 5 Comparative — — — Example 3-1 Comparative 2.5 0.3-0.7 0.5 Example 3-2 Comparative 2.5 70-80 0.5 Example 3-3 Comparative 10 10-15 0.5 Example 3-4 Comparative 2.5 10-15 0.1 Example 3-5 Comparative 2.5 10-15 8 Example 3-6
(177) TABLE-US-00004 TABLE 4 Specific properties of the examples Flame spread upon burning in 45° Electrical UV protection direction/length of conductivity factor (UPF) damage (cm) (S/m) of fabric Example 3-1 N/5.1 10.sup.−9 76.1 Example 3-2 N/4.6 10.sup.−9 82.6 Example 3-3 N/4.2 10.sup.−9 85.4 Example 3-4 N/3.1 10.sup.−9 86.2 Example 3-5 N/2.5 10.sup.−7 108.3 Example 3-6 N/1.8 10.sup.−3 146.8 Comparative Y/10.2 .sup. 10.sup.−16 5.1 Example 3-1 Comparative N/6.4 .sup. 10.sup.−12 20.8 Example 3-2 Comparative — — — Example 3-3 Comparative — — — Example 3-4 Comparative N/6.3 .sup. 10.sup.−16 35.6 Example 3-5 Comparative — — — Example 3-6
(178) It can be found through analysis of Comparative Example 3-1, Comparative Example 3-2, Example 3-1, Example 3-2, Example 3-3, and Comparative Example 3-3 that while the carbon/oxygen ratio in graphene oxide and the amount of graphene oxide added are kept unchanged, the selection of graphene oxide with a size in a suitable range results in a functional fabric with the optimum performances. In Comparative Example 3-2, the graphene oxide has a too small the size, and contributes few to the improvement of electrical conductivity, UV resistance and flame retardancy; and in Comparative Example 3, the size of graphene oxide is too large, it cannot be effectively unfolded into a flake-like graphene oxide after being added to a polymerization system, and can only be used as a pleated spherical filler to reinforce the composite material, causing the spinnability and continuity of the material to decrease significantly. When the size is in the range of 1-50 μm, as the size increases, graphene oxide can exert a more potent reinforcing effect.
(179) It can be found through analysis of Comparative Example 3-1, Example 3-2, Example 3-4, and Comparative Example 3-4 that as the carbon/oxygen ratio increases, the performance of the fabric becomes better. This is because as the carbon/oxygen ratio increases, the graphene has fewer defects and better performances, which make the composite perform better. However, the carbon/oxygen ratio cannot be too high; otherwise the bonding between graphene oxide sheets is too strong, and the graphene oxide is still maintained stacked during polymerization, and clogs the spinneret, causing difficulty in continuous production (Comparative Example 3-4).
(180) It can be found through analysis of Comparative Example 3-1, Comparative Example 3-5, Example 3-2, Example 3-5, Example 3-6, and Comparative Example 3-6 that the increase in the amount of graphene oxide increases the flame retardancy, and greatly improves the electrical conductivity and UV resistance of the fabric. At a dosage, the graphene cannot effectively form an electrically conductive network, making the performance of the fabric unable to meet the requirements of flame retardancy and antistatic performance (Comparative Example 3-5). After too much graphene oxide is added, graphene undergoes intense stacking during the reduction process to form an aggregate, which reduces the spinnability (Comparative Example 3-6). Therefore, the amount of graphene oxide needs to be controlled within a reasonable range.
Example 3-7
(181) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 200° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 20-30 μm, and the carbon/oxygen ratio is 5.
(182) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(183) (3) 3.25 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs at a stirring speed of 140 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(184) (4) 100 parts by weight of the graphene/PET nanocomposite material was spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature is 270° C., the spinning speed is 5000 m/min, and the draw ratio is 4. The obtained fiber has a Denier number of 30D. The weaving method is to weave using a loom without a shuttle.
(185) After the above steps, a multi-functional graphene/polyester composite fabric having good performances is obtained.
Example 3-8
(186) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 20-30 μm, and the carbon/oxygen ratio is 5.
(187) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(188) (3) 3.25 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 1 hrs at a stirring speed of 200 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(189) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 10 parts by weight of an anti-oxidant, spun, cooled, oiled, drawn, textured, woven, dyed, and finished to obtain a multi-functional graphene/polyester composite fabric. The spinning temperature is 290° C., the spinning speed is 3000 m/min, and the draw ratio is 1.5. The obtained fiber has a Denier number of 600D. The weaving method is to weave using a loom without a shuttle.
(190) After the above steps, a multi-functional graphene/polyester composite fabric having good performances is obtained.
Example 4-1
(191) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 1-3 μm, and the carbon/oxygen ratio is 2.5.
(192) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(193) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(194) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and casted into a film, to obtain a graphene/PET composite film. The temperature for extruding is 260° C., the rotational speed of the screw is 100 rpm, and the drawing velocity is 8 m/min.
(195) After the above steps, a graphene/PET composite film is obtained, as shown in
Example 4-2
(196) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(197) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(198) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(199) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite film. The temperature for extruding is 260° C., the rotational speed of the screw is 100 rpm, and the drawing velocity is 8 m/min.
(200) After the above steps, a graphene/PET composite film is obtained. Specific properties are shown in Tables 5 and 6.
Example 4-3
(201) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-45 μm, and the carbon/oxygen ratio is 2.5.
(202) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(203) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(204) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite film. The temperature for extruding is 260° C., the rotational speed of the screw is 100 rpm, and the drawing velocity is 8 m/min.
(205) After the above steps, a graphene/PET composite film is obtained. Specific properties are shown in Tables 5 and 6.
Example 4-4
(206) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 160° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 5.
(207) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(208) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(209) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.4 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite film. The temperature for extruding is 260° C., the rotational speed of the screw is 100 rpm, and the drawing velocity is 8 m/min.
(210) After the above steps, a graphene/PET composite film is obtained. Specific properties are shown in Tables 5 and 6.
Example 4-5
(211) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(212) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(213) (3) 1.17 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(214) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.3 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite film. The temperature for extruding is 260° C., the rotational speed of the screw is 100 rpm, and the drawing velocity is 8 m/min.
(215) After the above steps, a graphene/PET composite film is obtained. Specific properties are shown in Tables 5 and 6.
Example 4-6
(216) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(217) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(218) (3) 5.85 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite material.
(219) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.5 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite film. The temperature for extruding is 260° C., the rotational speed of the screw is 100 rpm, and the drawing velocity is 8 m/min.
(220) After the above steps, a graphene/PET composite film is obtained. Specific properties are shown in Tables 5 and 6.
Comparative Example 4-1
(221) PET was prepared following the method as described in Example 1, except that no pleated graphene oxide microspheres were added during the preparation process. The performances are shown in Tables 5 and 6.
Comparative Example 4-2
(222) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 0.3-0.7 μm, and the carbon/oxygen ratio is 2.5.
(223) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(224) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(225) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite film. The temperature for extruding is 260° C., the rotational speed of the screw is 100 rpm, and the drawing velocity is 8 m/min.
(226) After the above steps, a graphene/PET composite film is obtained. Specific properties are shown in Tables 5 and 6.
Comparative Example 4-3
(227) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 70-80 μm, and the carbon/oxygen ratio is 2.5.
(228) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(229) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(230) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite film. The temperature for extruding is 260° C., the rotational speed of the screw is 100 rpm, and the drawing velocity is 8 m/min.
(231) After the above steps, a graphene/PET composite film is obtained. Specific properties are shown in Tables 5 and 6.
Comparative Example 4-4
(232) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 220° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 10.
(233) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(234) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(235) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite film. The temperature for extruding is 260° C., the rotational speed of the screw is 100 rpm, and the drawing velocity is 8 m/min.
(236) After the above steps, a graphene/PET composite film is obtained. Specific properties are shown in Tables 5 and 6.
Comparative Example 4-5
(237) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(238) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(239) (3) 9.36 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite material.
(240) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite film. The temperature for extruding is 260° C., the rotational speed of the screw is 100 rpm, and the drawing velocity is 8 m/min.
(241) After the above steps, a graphene/PET composite film is obtained. Rupture tends to occur during the film formation, the uniformity of the film is poor, and small holes appear on the surface of the film. Specific properties are shown in Tables 5 and 6. The oxygen and water permeability are determined according to GB/T 19789-2005. The UV protection performance is measured according to GB/T 18830-2009. The conductivity is measured with a high-resistance meter.
(242) TABLE-US-00005 TABLE 5 Specific parameters of the examples Carbon/oxygen Size of Amount of ratio in graphene oxide graphene oxide graphene oxide (μm) (wt %) Example 4-1 2.5 1-3 0.1 Example 4-2 2.5 10-15 0.1 Example 4-3 2.5 40-45 0.1 Example 4-4 5 10-15 0.1 Example 4-5 2.5 10-15 1 Example 4-6 2.5 10-15 5 Comparative — — — Example 4-1 Comparative 2.5 0.3-0.7 0.1 Example 4-2 Comparative 2.5 70-80 0.1 Example 4-3 Comparative 10 10-15 0.1 Example 4-4 Comparative 2.5 10-15 8 Example 4-5
(243) TABLE-US-00006 TABLE 6 Specific properties of the examples Oxygen Vapor Film UV permeability permeability Electrical thickness protection (cm.sup.3 m.sup.2 day, (g m.sup.2 day, conductivity (μm) factor (UPF) 0.1 MPa) 0.1 MPa) (S/m) Example 4-1 45 30.2 0.169 0.142 10.sup.−16 Example 4-2 45 32.6 0.157 0.133 10.sup.−16 Example 4-3 45 35.7 0.138 0.114 10.sup.−16 Example 4-4 45 41.9 0.126 0.097 Example 4-5 45 65.6 0.087 0.065 10.sup.−7 Example 4-6 45 97.3 0.045 0.026 10.sup.−3 Comparative 45 7.5 3.054 2.351 10.sup.−16 Example 4-1 Comparative 45 18.1 2.986 2.274 10.sup.−16 Example 4-2 Comparative 45 31.1 2.69 2.113 Example 4-3 Comparative 45 36.4 2.378 2.041 10.sup.−16 Example 4-4 Comparative 45 174.6 — — 10.sup.−2 Example 4-5
(244) It can be found through analysis of Comparative Example 4-1, Comparative Example 4-2, Example 4-1, Example 4-2, Example 4-3, and Comparative Example 4-3 that while the carbon/oxygen ratio in graphene oxide and the amount of graphene oxide added are kept unchanged, the selection of graphene oxide with a size in a suitable range results in a composite material with the optimum performances. In Comparative Example 4-2, the size of graphene oxide is too small, and the reinforcing effect is not obvious; and in Comparative Example 4-3, the size of graphene oxide is too large, it cannot be effectively unfolded into a flake-like graphene oxide after being added to a polymerization system, can only be used as a pleated spherical filler to reinforce the composite material, and contributes few to the UV protection and barrier performance. When the size is in the range of 1-50 μm, as the size increases, graphene oxide can exert a more potent reinforcing effect.
(245) It can be found through analysis of Comparative Example 4-1, Example 4-2, Example 4-4, and Comparative Example 4-4 that as the carbon/oxygen ratio increases, the performance of the composite material becomes better. This is because as the carbon/oxygen ratio increases, the graphene has fewer defects and better performances, which makes the barrier performance of the composite material better. However, the carbon/oxygen ratio cannot be too high; otherwise the bonding between graphene oxide sheets is too strong, and the graphene oxide cannot be unfolded during polymerization to exist in the composite film as flake-like graphene, so it has no the effects of blocking water and oxygen and protecting against UV, and even seriously affects the continuity of film formation (Comparative Example 4-4).
(246) It can be found through analysis of Comparative Example 4-1, Example 4-2, Example 4-5, Example 4-6, and Comparative Example 4-5 that the increase in the amount of graphene oxide increases the barrier performance and greatly improves the UV resistance and electrical conductivity of the composite film. After too much graphene oxide is added, although the electrical conductivity can be further improved, due to the stacking of graphene, the film solvent is broken during the casting process, and the uniformity of the film is greatly reduced, resulting in some micropores, making it difficult to achieve a barrier effect (Comparative Example 4-5).
Example 4-7
(247) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 200° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 20-30 μm, and the carbon/oxygen ratio is 5.
(248) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(249) (3) 0.0117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 1 hrs at a stirring speed of 200 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite material.
(250) (4) 100 parts by weight of the graphene/PET nanocomposite material was melted and extruded, to obtain a graphene/PET composite film. The temperature for extruding is 250° C., the rotational speed of the screw is 40 rpm, and the drawing velocity is 1 m/min.
(251) After the above steps, a graphene/PET composite film having good performances is obtained.
Example 4-8
(252) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 200° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 20-30 μm, and the carbon/oxygen ratio is 5.
(253) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(254) (3) 0.0117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs at a stirring speed of 140 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite material.
(255) (4) 100 parts by weight of the graphene/PET nanocomposite material was melted and extruded, to obtain a graphene/PET composite film. The temperature for extruding is 280° C., the rotational speed of the screw is 300 rpm, and the drawing velocity is 50 m/min.
(256) After the above steps, a graphene/PET composite film having good performances is obtained.
Example 5-1
(257) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 1-3 μm, and the carbon/oxygen ratio is 2.5.
(258) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(259) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(260) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 240° C., the rotational speed of the screw is 70 rpm, and the drawing velocity is 4 m/min.
(261) After the above steps, a graphene/PET composite board is obtained. Specific properties of the composite board are shown in Tables 7 and 8.
Example 5-2
(262) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(263) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(264) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(265) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 240° C., the rotational speed of the screw is 70 rpm, and the drawing velocity is 4 m/min.
(266) After the above steps, a graphene/PET composite board is obtained. Specific properties are shown in Tables 7 and 8.
Example 5-3
(267) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-45 μm, and the carbon/oxygen ratio is 2.5.
(268) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(269) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(270) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 240° C., the rotational speed of the screw is 70 rpm, and the drawing velocity is 4 m/min.
(271) After the above steps, a graphene/PET composite board is obtained. Specific properties are shown in Tables 7 and 8.
Example 5-4
(272) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 160° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 5.
(273) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(274) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(275) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.4 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 240° C., the rotational speed of the screw is 70 rpm, and the drawing velocity is 4 m/min.
(276) After the above steps, a graphene/PET composite board is obtained. Specific properties are shown in Tables 7 and 8.
Example 5-5
(277) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(278) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(279) (3) 1.17 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(280) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.3 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 240° C., the rotational speed of the screw is 70 rpm, and the drawing velocity is 4 m/min.
(281) After the above steps, a graphene/PET composite board is obtained. Specific properties are shown in Tables 7 and 8.
Example 5-6
(282) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(283) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(284) (3) 5.85 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite board.
(285) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.5 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 240° C., the rotational speed of the screw is 70 rpm, and the drawing velocity is 4 m/min.
(286) After the above steps, a graphene/PET composite board is obtained. Specific properties are shown in Tables 7 and 8.
Comparative Example 5-1
(287) PET was prepared following the method as described in Example 1, except that no pleated graphene oxide microspheres were added during the preparation process. The performances are shown in Tables 7 and 8.
Comparative Example 5-2
(288) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 0.3-0.7 μm, and the carbon/oxygen ratio is 2.5.
(289) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(290) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(291) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 240° C., the rotational speed of the screw is 70 rpm, and the drawing velocity is 4 m/min.
(292) After the above steps, a graphene/PET composite board is obtained. Specific properties are shown in Tables 7 and 8.
Comparative Example 5-3
(293) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 70-80 μm, and the carbon/oxygen ratio is 2.5.
(294) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(295) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(296) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 240° C., the rotational speed of the screw is 70 rpm, and the drawing velocity is 4 m/min.
(297) After the above steps, a graphene/PET composite board is obtained. Specific properties are shown in Tables 7 and 8.
Comparative Example 5-4
(298) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 220° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 10.
(299) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(300) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(301) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 240° C., the rotational speed of the screw is 70 rpm, and the drawing velocity is 4 m/min.
(302) After the above steps, a graphene/PET composite board is obtained. Specific properties are shown in Tables 7 and 8.
Comparative Example 5-5
(303) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(304) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(305) (3) 9.36 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite board.
(306) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 240° C., the rotational speed of the screw is 70 rpm, and the drawing velocity is 4 m/min.
(307) After the above steps, a graphene/PET composite board is obtained. Specific properties are shown in Tables 7 and 8. The heat distortion temperature is measured according to GB/T 1634.1-2004. The tensile yield strength and modulus are measured according to GB/T 1040.1-2006. The flame retardancy is tested according to UL94 horizontal and vertical burning test method.
(308) TABLE-US-00007 TABLE 7 Specific parameters of the examples Carbon/oxygen Size of Amount of ratio in graphene oxide graphene oxide graphene oxide (μm) (wt %) Example 5-1 2.5 1-3 0.1 Example 5-2 2.5 10-15 0.1 Example 5-3 2.5 40-45 0.1 Example 5-4 5 10-15 0.1 Example 5-5 2.5 10-15 1 Example 5-6 2.5 10-15 5 Comparative — — — Example 5-1 Comparative 2.5 0.3-0.7 0.1 Example 5-2 Comparative 2.5 70-80 0.1 Example 5-3 Comparative 10 10-15 0.1 Example 5-4 Comparative 2.5 10-15 8 Example 5-5
(309) TABLE-US-00008 TABLE 8 Specific properties of the examples Yield Tensile Elongation Yield strength Dripping Electrical strength modulus at break at 80° C. rate conductivity (MPa) (GPa) (%) (MPa) (s/drop) (S/m) Example 5-1 63.1 2.61 82 32.2 6.89 10.sup.−16 Example 5-2 65.8 2.66 81 33.6 7.04 10.sup.−16 Example 5-3 69.6 2.8 80 35.8 10.39 10.sup.−16 Example 5-4 70.3 2.84 77 36.4 11.87 10.sup.−16 Example 5-5 75.6 2.91 70 39.6 17.95 10.sup.−7 Example 5-6 74.4 2.98 65 39.3 22.68 10.sup.−3 Comparative 52.3 2.3.1 75 27.4 3.68 10.sup.−16 Example 5-1 Comparative 54.7 2.37 79 27.9 4.98 10.sup.−16 Example 5-2 Comparative 55.2 2.53 70 28.3 5.62 10.sup.−16 Example 5-3 Comparative 57.8 2.38 55 29.1 5.83 10.sup.−16 Example 5-4 Comparative 61.1 2.59 36 30.1 8.46 10.sup.−2 Example 5-5
(310) It can be found through analysis of Comparative Example 5-1, Comparative Example 5-2, Example 5-1, Example 5-2, Example 5-3, and Comparative Example 5-3 that while the carbon/oxygen ratio in graphene oxide and the amount of graphene oxide added are kept unchanged, the selection of graphene oxide with a size in a suitable range results in a composite material with the optimum performances. In Comparative Example 5-2, the size of graphene oxide is too small, so the graphene oxide cannot be an effective reinforcing material itself; and in Comparative Example 5-3, the size of graphene oxide is too large, it cannot be effectively unfolded into a flake-like graphene oxide after being added to a polymerization system, and can only be used as a pleated spherical filler to reinforce the composite material, resulting in a small increase in the tensile strength and modulus and a slightly decrease in the elongation at break. When the size is in the range of 1-50 μm, as the size increases, graphene oxide can exert a more potent reinforcing effect.
(311) It can be found through analysis of Comparative Example 5-1, Example 5-2, Example 5-4, and Comparative Example 5-4 that as the carbon/oxygen ratio increases, the performance of the composite material becomes better. This is because as the carbon/oxygen ratio increases, the graphene has fewer defects and better performances, which make the composite perform better. However, the carbon/oxygen ratio cannot be too high; otherwise the bonding between graphene oxide sheets is too strong, and the graphene oxide cannot be unfolded during polymerization, so it cannot be effectively enhance, or even greatly reduce the elongation at break (Comparative Example 5-4).
(312) It can be found through analysis of Comparative Example 5-1, Example 5-2, Example 5-5, Example 5-6, and Comparative Example 5-5 that the increase in the amount of graphene oxide increases the mechanical properties, significantly reduces the dripping rate and greatly improves the electrical conductivity of the material. After too much graphene oxide is added, although the flame retardancy and electrical conductivity is further improved, the mechanical properties of the material are reduced. This is due to the stacking of excessive graphene, which reduces the reinforcing effect and makes the material brittle (Comparative Example 5-5).
Example 5-7
(313) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 200° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 20-30 μm, and the carbon/oxygen ratio is 5.
(314) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(315) (3) 0.0117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 1 hrs at a stirring speed of 200 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite film.
(316) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 10 parts by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 230° C., the rotational speed of the screw is 30 rpm, and the drawing velocity is 0.15 m/min.
(317) After the above steps, a graphene/PET composite board having good performances is obtained.
Example 5-8
(318) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 20-30 μm, and the carbon/oxygen ratio is 5.
(319) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(320) (3) 0.0117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs at a stirring speed of 140 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite film.
(321) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 10 parts by weight of an anti-oxidant, melted and extruded, to obtain a graphene/PET composite board. The temperature for extruding is 260° C., the rotational speed of the screw is 90 rpm, and the drawing velocity is 6 m/min.
(322) After the above steps, a graphene/PET composite board having good performances is obtained.
Example 6-4
(323) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 1-3 μm, and the carbon/oxygen ratio is 2.5.
(324) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(325) (3) 0.234 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(326) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D.
(327) (5) 55 parts of cotton fibers, 40 parts of graphene/PET composite fibers and 15 parts of spandex fiber were blended to obtain a graphene-modified polyester blended fabric.
(328) After the above steps, a graphene-modified polyester blended fabric is obtained, as shown in
Example 6-2
(329) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(330) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(331) (3) 0.234 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(332) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.4 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D.
(333) (5) 55 parts of cotton fibers, 40 parts of graphene/PET composite fibers and 15 parts of spandex fiber were blended to obtain a graphene-modified polyester blended fabric.
(334) After the above steps, a graphene-modified polyester blended fabric is obtained. Specific properties are shown in Table 9.
Example 6-3
(335) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-45 μm, and the carbon/oxygen ratio is 2.5.
(336) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(337) (3) 0.234 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(338) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.3 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D.
(339) (5) 55 parts of cotton fibers, 40 parts of graphene/PET composite fibers and 15 parts of spandex fiber were blended to obtain a graphene-modified polyester blended fabric.
(340) After the above steps, a graphene-modified polyester blended fabric is obtained. Specific properties are shown in Table 9.
Example 6-4
(341) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 160° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 5.
(342) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(343) (3) 0.234 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C., and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(344) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.6 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D.
(345) (5) 55 parts of cotton fibers, 40 parts of graphene/PET composite fibers and 15 parts of spandex fiber were blended to obtain a graphene-modified polyester blended fabric.
(346) After the above steps, a graphene-modified polyester blended fabric is obtained, Specific properties are shown in Table 9.
Example 6-5
(347) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(348) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(349) (3) 1.17 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(350) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.8 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D.
(351) (5) 55 parts of cotton fibers, 40 parts of graphene/PET composite fibers and 15 parts of spandex fiber were blended to obtain a graphene-modified polyester blended fabric.
(352) After the above steps, a graphene-modified polyester blended fabric is obtained. Specific properties are shown in Table 9.
Example 6-6
(353) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(354) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(355) (3) 5.85 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(356) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.5 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D.
(357) (5) 55 parts of cotton fibers, 40 parts of graphene/PET composite fibers and 15 parts of spandex fiber were blended to obtain a graphene-modified polyester blended fabric.
(358) After the above steps, a graphene-modified polyester blended fabric is obtained. Specific properties are shown in Table 9.
Comparative Example 6-1
(359) PET was prepared following the method as described in Example 1, except that no pleated graphene oxide microspheres were added during the preparation process. The performances are shown in Table 9.
Comparative Example 6-2
(360) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 0.3-0.7 μm, and the carbon/oxygen ratio is 2.5.
(361) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(362) (3) 0.234 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(363) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D.
(364) (5) 55 parts of cotton fibers, 40 parts of graphene/PET composite fibers and 15 parts of spandex fiber were blended to obtain a graphene-modified polyester blended fabric.
(365) After the above steps, a graphene/polyester composite fabric is obtained. Specific properties are shown in Table 9.
Comparative Example 6-3
(366) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 70-80 μm, and the carbon/oxygen ratio is 2.5.
(367) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(368) (3) 0.234 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(369) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D.
(370) After the above steps, it is found that the spinneret is clogged, the continuity of the spun yarn is less good, and the frequency of yarn breakage is high.
Comparative Example 6-4
(371) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 220° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 10.
(372) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(373) (3) 0.234 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(374) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D.
(375) After the above steps, it is found that the spinneret is clogged, the continuity of the spun yarn is less good, and the frequency of yarn breakage is high.
Comparative Example 6-5
(376) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(377) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(378) (3) 0.0585 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(379) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.5 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D.
(380) (5) 55 parts of cotton fibers, 40 parts of graphene/PET composite fibers and 15 parts of spandex fiber were blended to obtain a graphene-modified polyester blended fabric.
(381) After the above steps, a graphene/polyester composite fabric is obtained. Specific properties are shown in Table 9.
Comparative Example 6-6
(382) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(383) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(384) (3) 9.36 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(385) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.5 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 280° C., the spinning speed was 3600 m/min, the draw ratio was 1.5, and the denier number was 100D.
(386) After the above steps, it is found that the spinneret is clogged, the continuity of the spun yarn is less good, and the frequency of yarn breakage is high.
(387) TABLE-US-00009 TABLE 9 Specific parameters and properties of the example Flame spread upon Carbon/oxygen Size of Amount of burning in 45° UV protection ratio in graphene oxide graphene oxide direction/length of factor (UPF) graphene oxide (μm) (wt %) damage (cm) of fabric Example 6-1 2.5 1-3 0.2 N/6.9 63.2 Example 6-2 2.5 10-15 0.2 N/6.4 66.2 Example 6-3 2.5 40-45 0.2 N/5.8 70.6 Example 6-4 5 10-15 0.2 N/5.5 72.1 Example 6-5 2.5 10-15 1 N/3.6 89.3 Example 6-6 2.5 10-15 5 N/2.2 114.6 Comparative — — — Y/12.7 2.8 Example 6-1 Comparative 2.5 0.3-0.7 0.2 N/8.5 19.2 Example 6-2 Comparative 2.5 70-80 0.2 — — Example 6-3 Comparative 10 10-15 0.2 — — Example 6-4 Comparative 2.5 10-15 0.05 N/10.2 10.1 Example 6-5 Comparative 2.5 10-15 8 — — Example 6-6
(388) The flame retardancy is tested by the burning rate in a 45° direction. The UV protection factor (UPF) is obtained by measuring with a UV spectrophotometer and calculating.
(389) It can be found through analysis of Comparative Example 6-1, Comparative Example 6-2, Example 6-1 Example 6-2, Example 6-3, and Comparative Example 3 that while the carbon/oxygen ratio in graphene oxide and the amount of graphene oxide added are kept unchanged, the selection of graphene oxide with a size in a suitable range results in a blended fabric with the optimum performances. In Comparative Example 6-2, the graphene oxide has a too small the size, and contributes few to the improvement of electrical conductivity, UV resistance and flame retardancy; and in Comparative Example 6-3, the size of graphene oxide is too large, it cannot be effectively unfolded into a flake-like graphene oxide after being added to a polymerization system, and can only be used as a pleated spherical filler to reinforce the composite material, causing the spinnability and continuity of the material to decrease significantly. When the size is in the range of 1-50 μm, as the size increases, graphene oxide can exert a more potent reinforcing effect.
(390) It can be found through analysis of Comparative Example 6-1, Example 6-2, Example 6-4, and Comparative Example 6-4 that as the carbon/oxygen ratio increases, the performance of the fabric becomes better. This is because as the carbon/oxygen ratio increases, the graphene has fewer defects and better performances, which make the composite perform better. However, the carbon/oxygen ratio cannot be too high; otherwise the bonding between graphene oxide sheets is too strong, and the graphene oxide is still maintained stacked during polymerization, and clogs the spinneret, causing difficulty in continuous production (Comparative Example 6-4).
(391) It can be found through analysis of Comparative Example 6-1, Comparative Example 6-5, Example 6-2, Example 6-5, Example 6-6, and Comparative Example 6-6 that the increase in the amount of graphene oxide increases the flame retardancy, and greatly improves the UV resistance of the fabric. At a low dosage, graphene does not work effectively graphene (Comparative Example 6-5). However, where the dosage is too high, graphene is reduced and undergoes intense stacking during polymerization to form an aggregate, which reduces the spinnability (Comparative Example 6-6). Therefore, the amount of graphene oxide needs to be controlled within a reasonable range.
(392) In summary, by controlling the amount of the pleated graphene oxide microspheres, the carbon/oxygen ratio, and the size of graphene oxide within a reasonable range, a blended fabric with excellent UV resistance and flame retardancy can be obtained.
Example 6-7
(393) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 200° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 20-30 μm, and the carbon/oxygen ratio is 5.
(394) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(395) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs at a stirring speed of 140 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(396) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 10 parts by weight of an anti-oxidant, spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 270° C., the spinning speed was 3000 m/min, the draw ratio was 1.5, and the denier number was 400D.
(397) (5) 40 parts of cotton fibers, 30 parts of graphene/PET composite fibers and 10 parts of spandex fiber were blended to obtain a graphene-modified polyester blended fabric.
(398) After the above steps, a graphene-modified polyester blended fabric with good performance is obtained.
Example 6-8
(399) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 20-30 μm, and the carbon/oxygen ratio is 5.
(400) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(401) (3) 5.85 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 1 hrs at a stirring speed of 200 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(402) (4) 100 parts by weight of the graphene/PET nanocomposite material was spun, cooled, oiled, drawn, and textured, to obtain a graphene/PET composite fiber. The spinning temperature was 285° C., the spinning speed was 3600 m/min, the draw ratio was 4, and the denier number was 30D.
(403) (5) 60 parts of cotton fibers, 50 parts of graphene/PET composite fibers and 20 parts of spandex fiber were blended to obtain a graphene-modified polyester blended fabric.
(404) After the above steps, a graphene-modified polyester blended fabric with good performance is obtained.
Example 7-1
(405) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 1-3 μm, and the carbon/oxygen ratio is 2.5.
(406) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(407) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(408) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 280° C., and the winding speed is 3600 m/min.
(409) After the above steps, a graphene-modified flame-retardant UV-resistant polyester fiber is obtained. Specific properties are shown in Tables 10 and 11.
Example 7-2
(410) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(411) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(412) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(413) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 280° C., and the winding speed is 3600 m/min.
(414) After the above steps, a graphene-modified flame-retardant UV-resistant polyester fiber is obtained. Specific properties are shown in Tables 10 and 11.
Example 7-3
(415) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-45 μm, and the carbon/oxygen ratio is 2.5.
(416) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(417) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(418) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 280° C., and the winding speed is 3600 m/min.
(419) After the above steps, a graphene-modified flame-retardant UV-resistant polyester fiber is obtained. Specific properties are shown in Tables 10 and 11.
Example 7-4
(420) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 160° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 5.
(421) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(422) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(423) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.4 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 280° C., and the winding speed is 3600 m/min.
(424) After the above steps, a graphene-modified flame-retardant UV-resistant polyester fiber is obtained. Specific properties are shown in Tables 10 and 11.
Example 7-5
(425) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(426) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(427) (3) 1.17 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(428) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.3 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 280° C., and the winding speed is 3600 m/min.
(429) After the above steps, a graphene-modified flame-retardant UV-resistant polyester fiber is obtained. Specific properties are shown in Tables 10 and 11.
Example 7-6
(430) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(431) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(432) (3) 5.85 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite board.
(433) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.5 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 280° C., and the winding speed is 3600 m/min.
(434) After the above steps, a graphene-modified flame-retardant UV-resistant polyester fiber is obtained. Specific properties are shown in Tables 10 and 11.
Comparative Example 7-1
(435) PET was prepared following the method as described in Example 1, except that no pleated graphene oxide microspheres were added during the preparation process. The performances are shown in Tables 10 and 11.
Comparative Example 7-2
(436) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 0.3-0.7 μm, and the carbon/oxygen ratio is 2.5.
(437) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(438) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(439) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.3 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 280° C., and the winding speed is 3600 m/min.
(440) After the above steps, a graphene-modified flame-retardant UV resistant polyester fiber is obtained. Specific properties are shown in Tables 10 and 11.
Comparative Example 7-3
(441) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 70-80 μm, and the carbon/oxygen ratio is 2.5.
(442) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(443) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(444) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 280° C., and the winding speed is 3600 m/min.
(445) After the above steps, it is found that the spinneret is clogged, the continuity of the spun yarn is less good, and the frequency of yarn breakage is high.
Comparative Example 7-4
(446) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 220° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 10.
(447) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(448) (3) 0.117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(449) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 280° C., and the winding speed is 3600 m/min.
(450) After the above steps, it is found that the spinneret is clogged, the continuity of the spun yarn is less good, and the frequency of yarn breakage is high.
Comparative Example 7-5
(451) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 10-15 μm, and the carbon/oxygen ratio is 2.5.
(452) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(453) (3) 9.36 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 2 hrs at a stirring speed of 160 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET composite board.
(454) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 0.2 part by weight of an anti-oxidant, spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 280° C., and the winding speed is 3600 m/min.
(455) After the above steps, it is found that the spinneret is clogged, the continuity of the spun yarn is less good, and the frequency of yarn breakage is high.
(456) TABLE-US-00010 TABLE 10 Specific parameters of the examples Carbon/oxygen Size of Amount of ratio in graphene oxide graphene oxide graphene oxide (μm) (wt %) Example 7-1 2.5 1-3 0.1 Example 7-2 2.5 10-15 0.1 Example 7-3 2.5 40-45 0.1 Example 7-4 5 10-15 0.1 Example 7-5 2.5 10-15 1 Example 7-6 2.5 10-15 5 Comparative — — — Example 7-1 Comparative 2.5 0.3-0.7 0.1 Example 7-2 Comparative 2.5 70-80 0.1 Example 7-3 Comparative 10 10-15 0.1 Example 7-4 Comparative 2.5 10-15 8 Example 7-5
(457) TABLE-US-00011 TABLE 11 Specific properties of the examples Flame spread upon burning in 45° Breaking UV protection direction/length of strength factor (UPF) damage (cm) (cN/dtex) of fabric Example 7-1 N/5.7 3.61 34.4 Example 7-2 N/5.2 3.89 38.6 Example 7-3 N/4.8 4.08 45.2 Example 7-4 N/4.5 4.34 47.4 Example 7-5 N/3.9 4.67 143.4 Example 7-6 N/3.3 4.98 162.8 Comparative Y/10.2 3.12 6.3 Example 7-1 Comparative N/7.2 3.38 21.3 Example 7-2 Comparative — — — Example 7-3 Comparative — — — Example 7-4 Comparative — — — Example 7-5
(458) It can be found through analysis of Comparative Example 7-1, Comparative Example 7-2, Example 7-1, Example 7-2, Example 7-3, and Comparative Example 7-3 that while the carbon/oxygen ratio in graphene oxide and the amount of graphene oxide added are kept unchanged, the selection of graphene oxide with a size in a suitable range results in a composite fiber with the optimum performances. In Comparative Example 7-2, the size of graphene oxide is too small, so the graphene oxide cannot be an effective reinforcing material itself; and in Comparative Example 3, the size of graphene oxide is too large, it cannot be effectively unfolded into a flake-like graphene oxide after being added to a polymerization system, and can only be used as a pleated spherical filler to reinforce the composite material, causing the spinnability and continuity of the material to decrease significantly. When the size is in the range of 1-50 μm, as the size increases, graphene oxide can exert a more potent reinforcing effect.
(459) It can be found through analysis of Comparative Example 7-1, Example 7-2, Example 7-4, and Comparative Example 7-4 that as the carbon/oxygen ratio increases, the performance of the composite fiber becomes better. This is because as the carbon/oxygen ratio increases, the graphene has fewer defects and better performances, which makes the composite perform better. However, the carbon/oxygen ratio cannot be too high; otherwise the bonding between graphene oxide sheets is too strong, and the graphene oxide is still maintained stacked during polymerization, and clogs the spinneret, causing difficulty in continuous production (Comparative Example 7-4).
(460) It can be found through analysis of Comparative Example 7-1, Example 7-2, Example 7-5, Example 7-6, and Comparative Example 7-5 that the increase in the amount of graphene oxide allows the mechanical properties, UV resistance and flame retardancy of the composite fiber to increase significantly. After too much graphene oxide is added, graphene undergoes intense stacking during the reduction process to form an aggregate, which reduces the spinnability (Comparative Example 7-5).
Example 7-7
(461) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 200° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 20-30 μm, and the carbon/oxygen ratio is 5.
(462) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(463) (3) 0.0117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 1 hrs at a stirring speed of 200 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(464) (4) 100 parts by weight of the graphene/PET nanocomposite material was uniformly mixed with 10 parts by weight of an anti-oxidant, spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 280° C., and the winding speed is 3000 m/min.
(465) After the above steps, a graphene-modified flame-retardant UV-resistant polyester fiber with good performance is obtained.
Example 7-8
(466) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 200° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 20-30 μm, and the carbon/oxygen ratio is 5.
(467) (2) 100 parts by weight of terephthalic acid, 53 parts by weight of ethylene glycol, and 0.02 part by weight of sodium acetate were fully mixed by stirring, and subjected to an esterification reaction at 250° C. until no water was produced.
(468) (3) 0.0117 part by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.018 part by weight of antimony ethylene glycol were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs at a stirring speed of 140 rpm, heated to 285° C. and evacuated to allow the reaction to proceed until no heat was released from the system, and then granulated with water cooling to obtain a graphene/PET nanocomposite material.
(469) (4) 100 parts by weight of the graphene/PET nanocomposite material was spun, cooled, oiled, drawn, and wound, to obtain a graphene-modified flame-retardant UV-resistant polyester fiber. The temperature for extruding is 285° C., and the winding speed is 4800 m/min.
(470) After the above steps, a graphene-modified flame-retardant UV-resistant polyester fiber with good performance is obtained.
Example 8-1
(471) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 180° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-50 μm, and the carbon/oxygen ratio is 5.
(472) (2) 100 parts by weight of terephthalic acid, 72 parts by weight of butanediol, and 0.02 part by weight of tetrabutyl titanate were fully mixed by stirring, and subjected to an esterification reaction at 235° C. until no water is produced.
(473) (3) 8 parts by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.02 part by weight of tetrabutyl titanate were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs, heated to 255° C. and evacuated to allow the reaction to proceed until no heat is released from the system, and then granulated with water cooling to obtain a graphene/PBT nanocomposite material.
(474) After the above steps, a graphene/PBT nanocomposite material is obtained, as shown in
(475) In addition, through a large number of comparative tests, it is found that the size of graphene oxide (1-50 μm), carbon/oxygen ratio (2.5-5), atomization drying temperature (130-200° C.), and proportion of graphene oxide in the whole system are all requisite conditions for obtaining a graphene/PBT composite material with uniform dispersion and excellent performance. Compared with neat PBT, the tensile strength is increased by more than 5%, and the modulus is increased by more than 10%, the resistivity is 10.sup.7-10.sup.3Ω m, and the UV protection factor (UPF) is greater than 40 after being spun and woven into a fabric. This example shows only a further preferred result. The tensile strength and modulus are 25% and 45% higher than those of neat PBT, the resistivity is 10.sup.3Ω m, and the UV protection factor (UPF) is greater than 130 after being spun and woven into a fabric.
Example 8-2
(476) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 140° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-50 μm, and the carbon/oxygen ratio is 3.
(477) (2) 100 parts by weight of terephthalic acid, 63 parts by weight of propanediol, and 0.02 part by weight of tetrabutyl titanate were fully mixed by stirring, and subjected to an esterification reaction at 240° C. until no water is produced.
(478) (3) 8 parts by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.02 part by weight of tetraisobutyl titanate were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs, heated to 260° C. and evacuated to allow the reaction to proceed until no heat is released from the system, and then granulated with water cooling to obtain a graphene/PBT nanocomposite material.
(479) After the above steps, a graphene/PTT nanocomposite material is obtained.
(480) In addition, through a large number of comparative tests, it is found that the size of graphene oxide (1-50 μm), carbon/oxygen ratio (2.5-5), atomization drying temperature (130-200° C.), and proportion of graphene oxide in the whole system are all requisite conditions for obtaining a graphene/PTT composite material with uniform dispersion and excellent performance. Compared with neat PTT, the tensile strength is increased by more than 5%, and the modulus is increased by more than 8%, the resistivity is 10′-10.sup.3Ω m, and the UV protection factor (UPF) is greater than 40 after being spun and woven into a fabric. This example shows only a further preferred result. The tensile strength and modulus are 20% and 50% higher than those of neat PET, the resistivity is 10.sup.3Ω m, and the UV protection factor (UPF) is greater than 140 after being spun and woven into a fabric.
Example 8-3
(481) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 180° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-50 μm, and the carbon/oxygen ratio is 5.
(482) (2) 100 parts by weight of terephthalic acid, 132 parts by weight of 1,4-cyclohexanedimethanol, and 0.01 part by weight of tetrabutyl titanate were fully mixed by stirring, and subjected to an esterification reaction at 220° C. until no water is produced.
(483) (3) 7 parts by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.03 part by weight of tetrabutyl titanate were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs, heated to 290° C. and evacuated to allow the reaction to proceed until no heat is released from the system, and then granulated with water cooling to obtain a graphene/PCT nanocomposite material.
(484) After the above steps, a graphene/PCT nanocomposite material is obtained.
(485) In addition, through a large number of comparative tests, it is found that the size of graphene oxide (1-50 μm), carbon/oxygen ratio (2.5-5), atomization drying temperature (130-200° C.), and proportion of graphene oxide in the whole system are all requisite conditions for obtaining a graphene/PCT composite material with uniform dispersion and excellent performance. Compared with neat PCT, the tensile strength is increased by more than 5%, and the modulus is increased by more than 10%, the resistivity is 10.sup.7-10.sup.3Ω m, and the UV protection factor (UPF) is greater than 40 after being spun and woven into a fabric. This example shows only a further preferred result. The tensile strength and modulus are 18% and 39% higher than those of neat PCT, the resistivity is 10.sup.3Ω m, and the UV protection factor (UPF) is greater than 145 after being spun and woven into a fabric.
Example 8-4
(486) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 180° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-50 μm, and the carbon/oxygen ratio is 5.
(487) (2) 100 parts by weight of terephthalic acid, 40 parts by weight of butanediol, 36 parts by weight of propanediol, and 0.02 part by weight of tetrabutyl titanate were fully mixed by stirring, and subjected to an esterification reaction at 240° C. until no water is produced.
(488) (3) 8 parts by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.03 part by weight of tetrabutyl titanate were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs, heated to 260° C. and evacuated to allow the reaction to proceed until no heat is released from the system, and then granulated with water cooling to obtain a graphene/PBT nanocomposite material.
(489) After the above steps, a graphene/PBT/PTT nanocomposite material is obtained.
(490) In addition, through a large number of comparative tests, it is found that the size of graphene oxide (1-50 μm), carbon/oxygen ratio (2.5-5), atomization drying temperature (130-200° C.), and proportion of graphene oxide in the whole system are all requisite conditions for obtaining a graphene/PBT/PTT composite material with uniform dispersion and excellent performance. Compared with/PBT/PTT without graphene, the tensile strength is increased by more than 8%, and the modulus is increased by more than 12%, the resistivity is 10.sup.7-10.sup.3Ω m, and the UV protection factor (UPF) is greater than 30 after being spun and woven into a fabric. This example shows only a further preferred result. The tensile strength and modulus are 27% and 50% higher than those of neat PBT, the resistivity is 10.sup.3Ω m, and the UV protection factor (UPF) is greater than 130 after being spun and woven into a fabric.
Example 8-5
(491) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 1-5 μm, and the carbon/oxygen ratio is 2.5.
(492) (2) 100 parts by weight of terephthalic acid, 125 parts by weight of 1,4-cyclohexanedimethanol, and 0.02 part by weight of tetrabutyl titanate were fully mixed by stirring, and subjected to an esterification reaction at 220° C. until no water is produced.
(493) (3) 0.5 parts by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.1 part by weight of tetrabutyl titanate were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs, heated to 290° C. and evacuated to allow the reaction to proceed until no heat is released from the system, and then granulated with water cooling to obtain a graphene/PCT nanocomposite material.
(494) After the above steps, a graphene/PCT nanocomposite material is obtained. The tensile strength and modulus are 10% and 15% higher than those of neat PCT, the resistivity is 10.sup.6Ω m, and the UV protection factor (UPF) is greater than 50 after being spun and woven into a fabric.
Example 8-6
(495) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 200° C. to obtain graphene oxide microspheres, where the graphene oxide sheet has a size of 40-50 μm, and the carbon/oxygen ratio is 5.
(496) (2) 100 parts by weight of terephthalic acid, 76 parts by weight of butanediol, and 0.03 part by weight of tetrabutyl titanate were fully mixed by stirring, and subjected to an esterification reaction at 235° C. until no water is produced.
(497) (3) 0.1 parts by weight of the pleated graphene oxide microspheres obtained in Step (1) and 0.05 part by weight of tetrabutyl titanate were added to the esterification product obtained in Step (2), incubated with stirring for 3 hrs, heated to 2.55° C. and evacuated to allow the reaction to proceed until no heat is released from the system, and then granulated with water cooling to obtain a graphene/PBT nanocomposite material.
(498) After the above steps, a graphene/PBT nanocomposite material is obtained. The tensile strength and modulus are 15% and 25% higher than those of neat PBT, the resistivity is 10.sup.7Ω m, and the UV protection factor (UPF) is greater than 40 after being spun and woven into a fabric.
Example 9-1
(499) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has a size of 0.3-5 μm and 1 μm on average, the carbon/oxygen ratio is 5, and the moisture content is less than 0.1%.
(500) (2) 3.5 parts by weight of pleated graphene oxide microspheres and 2 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(501) (3) under a nitrogen atmosphere, the dispersion was added to a polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 3 hrs and then under vacuum for 4 hrs to obtain a polymer melt; and finally, the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(502) This material was spun at a high speed, to obtain a yarn roll. Due to the higher amount of graphene added, the yarn has a high UV resistance and a very low percolation threshold.
(503) The properties of the obtained graphene/nylon 6 nanocomposite material are shown in Table 12.
Example 9-2
(504) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has a size of 1-20 μm and 10 μm on average, the carbon/oxygen ratio is 4.2, and the moisture content is less than 0.1%.
(505) (2) 2 parts by weight of pleated graphene oxide microspheres and 2 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(506) (3) under a nitrogen atmosphere, the dispersion was added to a polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 3 hrs and then under vacuum for 4 hrs to obtain a polymer melt; and finally, the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(507) The properties of the obtained graphene/nylon 6 nanocomposite material are shown in Table 12.
Example 9-3
(508) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has a size of 1-40 μm and 20 μm on average, the carbon/oxygen ratio is 3.9, and the moisture content is less than 0.1%.
(509) (2) 0.5 parts by weight of pleated graphene oxide microspheres and 2 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(510) (3) under a nitrogen atmosphere, the dispersion was added to a polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 3 hrs and then under vacuum for 4 hrs to obtain a polymer melt; and finally, the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(511) The properties of the obtained graphene/nylon 6 nanocomposite material are shown in Table 12.
Example 9-4
(512) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 150° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has a size of 20-50 μm and 40 μm on average, the carbon/oxygen ratio is 3, and the moisture content is less than 0.1%.
(513) (2) 0.2 parts by weight of pleated graphene oxide microspheres and 1.5 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(514) (3) under a nitrogen atmosphere, the dispersion was added to a polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 3 hrs and then under vacuum for 4 hrs to obtain a polymer melt; and finally, the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(515) The properties of the obtained graphene/nylon 6 nanocomposite material are shown in Table 12.
Example 9-5
(516) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 160° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has an average size of 50 μm, the carbon/oxygen ratio is 2.5, and the moisture content is less than 0.1%.
(517) (2) 0.01 parts by weight of pleated graphene oxide microspheres and 1 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(518) (3) under a nitrogen atmosphere, the dispersion was added to a polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 3 hrs and then under vacuum for 4 hrs to obtain a polymer melt; and finally, the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(519) The properties of the obtained graphene/nylon 6 nanocomposite material are shown in Table 12.
Example 9-6
(520) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has a size of 1-20 μm and 15 μm on average, the carbon/oxygen ratio is 3.9, and the moisture content is less than 0.1%.
(521) (2) 0.005 parts by weight of pleated graphene oxide microspheres and 1 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(522) (3) under a nitrogen atmosphere, the dispersion was added to a polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 3 hrs and then under vacuum for 4 hrs to obtain a polymer melt; and finally, the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(523) The properties of the obtained graphene/nylon 6 nanocomposite material are shown in Table 13.
Example 9-7
(524) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has a size of 1-20 μm and 15 μm on average, the carbon/oxygen ratio is 3.9, and the moisture content is less than 0.1%.
(525) (2) 4 parts by weight of pleated graphene oxide microspheres and 3 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(526) (3) under a nitrogen atmosphere, the dispersion was added to a polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 3 hrs and then under vacuum for 4 hrs to obtain a polymer melt; and finally, the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(527) The properties of the obtained graphene/nylon 6 nanocomposite material are shown in Table 13.
Example 9-8
(528) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has a size of 0.1-0.8 μm and 0.5 μm on average, the carbon/oxygen ratio is 3.9, and the moisture content is less than 0.1%.
(529) (2) 0.2 parts by weight of pleated graphene oxide microspheres and 1 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(530) (3) under a nitrogen atmosphere, the dispersion was added to a polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 3 hrs and then under vacuum for 4 hrs to obtain a polymer melt; and finally, the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(531) The properties of the obtained graphene/nylon 6 nanocomposite material are shown in Table 13.
Example 9-9
(532) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has a size of 80-120 μm and 100 μm on average, the carbon/oxygen ratio is 3.9, and the moisture content is less than 0.1%.
(533) (2) 0.2 parts by weight of pleated graphene oxide microspheres and 2 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(534) (3) under a nitrogen atmosphere, the dispersion was added to a polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 3 hrs and then under vacuum for 4 hrs to obtain a polymer melt; and finally, the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(535) The properties of the obtained graphene/nylon 6 nanocomposite material are shown in Table 13.
Example 9-10
(536) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has a size of 0.1-0.8 μm and 15 μm on average, the carbon/oxygen ratio is 1.7, and the moisture content is less than 0.1%.
(537) (2) 0.2 parts by weight of pleated graphene oxide microspheres and 2 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(538) (3) under a nitrogen atmosphere, the dispersion was added to a polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 3 hrs and then under vacuum for 4 hrs to obtain a polymer melt; and finally, the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(539) The properties of the obtained graphene/nylon 6 nanocomposite material are shown in Table 13.
Example 9-11
(540) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has a size of 0.1-0.8 μm and 15 μm on average, the carbon/oxygen ratio is 6.5, and the moisture content is less than 0.1%.
(541) (2) 0.2 parts by weight of pleated graphene oxide microspheres and 2 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(542) (3) under a nitrogen atmosphere, the dispersion was added to a polycondenzation reactor, heated to 250-270° C., and reacted under 0.5-1 MPa for 3 hrs and then under vacuum for 4 hrs to obtain a polymer melt; and finally, the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(543) The properties of the obtained graphene/nylon 6 nanocomposite material are shown in Table 13.
(544) In order to systematically explain the improvement on comprehensive performances of the graphene/nylon 6 nanocomposite materials obtained in the present invention over neat nylon 6 materials, the mechanical properties, high temperature resistance, and anti-UV aging resistance of the composite materials obtained in the Examples 9-1-9-5 are listed in Table 12 for comparison. Table 13 compares the performance of the graphene/nylon 6 nanocomposite materials (Examples 9-6-9-11) obtained with the graphene going beyond the technical parameters of the graphene described in the present invention with the composite material (Example 9-3) obtained with a better composition.
(545) TABLE-US-00012 TABLE 12 Example Example Example Example Example Nylon 6 9-1 9-2 9-3 9-4 9-5 Graphene Content (%) 0 3.5 2 0.5 0.2 0.01 0.01-3.5 Average / 1 10 20 40 50 transverse dimension (um) Carbon/oxygen / 5 4.2 3.9 3 2.5 ratio 2.5-5 Tensile yield strength 67.8 75.6 77.6 80.5 79.2 70.2 at 23° C. (MPa) Elastic modulus at 2.48 3.33 3.29 2.99 3.05 2.82 23° C. (GPa) Elongation at break (%) 230 150 180 200 220 175 Bending strength 94.1 107.6 105.7 105.2 104.5 97.2 (MPa) Bending modulus 2.36 2.73 2.62 2.63 2.62 2.43 (GPa) Impact strength 8.6 6.4 7.1 8.9 8.0 8.8 (KJ/m.sup.3) Heat distortion 67 114 104 117 113 70 temperature (° C.) under 0.46 MPa Yield strength (MPa) 43.6 69.9 67.8 68.5 68.6 64.7 after four-week UV aging UV protection factor 3 156 129 98 79 41 (UPF) of fabric Far infrared 0.80 0.94 0.94 0.94 0.94 0.90 emissivity of fabric Surface resistance 10.sup.14 10.sup.5 10.sup.6 10.sup.7 10.sup.12 10.sup.14 High-speed spinnability Yes Yes Yes Yes Yes Yes
(546) TABLE-US-00013 TABLE 13 Example Example Example Example Example Example Example 9-3 9-6 9-7 9-8 9-9 9-10 9-11 Graphene Content(%) 0.5 0.005 4 0.2 0.2 0.2 0.2 0.01-3.5 Average 20 15 15 0.5 100 15 15 transverse dimension (μm) 1-50 Carbon/oxygen 3.9 3.9 3.9 3.9 3.9 1.7 6.5 ratio 2.5-5 Tensile yield strength 80.5 67.7 72.2 72.1 74.6 70.2 74.0 at 23° C. (MPa) Elastic modulus at 2.99 2.55 3.51 2.80 2.96 2.83 2.92 23° C. (GPa) Elongation at break 200 255 51 230 190 185 105 (%) Bending strength 105.2 95.7 99.6 97.7 102.0 100.8 101.4 (MPa) Bending modulus 2.63 2.42 2.93 2.49 2.63 2.47 2.48 (GPa) Impact strength 8.9 8.6 5.2 8.1 8.2 8.5 7.8 (KJ/m.sup.2) Heat distortion 117° C. 75° C. 111° C. 81° C. 150° C. 90° C. 97° C. temperature under 0.46 MPa Yield strength after 68.5 MPa 47.8 MPa 67.7 MPa 51.6 MPa 63.2 MPa 59.3 MPa 63.3 MPa four-week UV aging UV protection factor 98 26 / 39 / 66 / (UPF) of fabric Far infrared 0.94 0.80 / 0.81 / 0.83 / emissivity of fabric Surface resistance 10.sup.7 10.sup.14 / 10.sup.13 / 10.sup.14 / High-speed Yes Yes No Yes No Yes No spinnability
Example 9-12
(547) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has an average size of 5 μm, the carbon/oxygen ratio is 3.9, and the moisture content is less than 0.1%.
(548) (2) 0.2 parts by weight of pleated graphene oxide microspheres and 2 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(549) (3) The dispersion was continuously polymerized in a VK tube, where the polymerization temperature was 260° C., and the polymerization time was 20 hrs; and the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(550) The obtained graphene/nylon 6 nanocomposite material as good performances.
Example 9-13
(551) (1) A single-layer graphene oxide dispersion was dried by atomization drying at a temperature of 130° C. to obtain pleated graphene oxide microspheres, where the graphene oxide sheet has an average size of 3 μm, the carbon/oxygen ratio is 2.5, and the moisture content is less than 0.1%.
(552) (2) 1 part by weight of pleated graphene oxide microspheres and 2 parts by weight of deionized water were added to 100 parts by weight of caprolactam melt, and fully stirred at 80° C. at a high speed (400 rpm) to form a dispersion.
(553) (3) The dispersion was continuously polymerized in a VK tube, where the polymerization temperature was 260° C., and the polymerization time was 20 hrs; and the polymer melt was granulated with water cooling to obtain a graphene/nylon 6 nanocomposite material.
(554) The obtained graphene/nylon 6 nanocomposite material as good performances.