Graphene-modified elastomer material and its preparation method

Abstract

A graphene-modified elastomer material and its preparation method. The elastomer material comprises a first component and a second component; the first component comprises isocyanate prepolymer obtained through reaction of polyol and isocyanate, and the isocyanate prepolymer has a —NCO content of 22-30%; the second component comprises the following components in parts by weight: 60-90 parts of polyetheramine, 1-10 parts of liquid amine chain extender, 1-5 parts of polytetrahydrofuran ether polyol, and 1-5 parts of graphenes. Through adjusting the —NCO content of the isocyanate prepolymer, increasing the hard segment content, and combining with the components in the second component, the invention ensures the elasticity of the polymer while improving its mechanical properties such as hardness and bending strength.

Claims

1. A graphene-modified elastomer material, comprising a first component and a second component; the first component comprises isocyanate prepolymer obtained through reaction of polyol and isocyanate, and the isocyanate prepolymer has a —NCO content of 22-30 wt %; the second component comprises the following components in parts by weight: 60-90 parts of polyetheramine, 1-5 parts of graphene, 1-10 parts of liquid amine chain extender, and 1-5 parts of polytetrahydrofuran ether polyol.

2. The graphene-modified elastomer material according to claim 1, wherein the graphene is at least one selected from the group consisting of surface-pretreated graphene, surface-pretreated biomass graphene, and surface-pretreated graphene oxide.

3. The graphene-modified elastomer material according to claim 2, wherein a surface pretreatment comprises: a surface graft coupling agent of graphene and/or biomass graphene and/or graphene oxide; the surface graft coupling agent is a silane coupling agent; a mass of the surface graft coupling agent is 1-5% of the graphene.

4. The graphene-modified elastomer material according to claim 3, wherein the graphene is the surface-pretreated graphene oxide.

5. The graphene-modified elastomer material according to claim 1, wherein a functionality ratio of the first component to the second component is 1:(1-1.05).

6. The graphene-modified elastomer material according to claim 1, wherein the polytetrahydrofuran ether polyol has a number average molecular weight of 1,000 to 2,000.

7. The graphene-modified elastomer material according to claim 1, wherein the liquid amine chain extender is at least one selected from the group consisting of diethyl methane diamine, dimethyl toluene diamine, and dialkethylene diamine.

8. A preparation method of the graphene-modified elastomer material according to claim 1, comprising the following steps: heating and dehydrating the polyol, reacting with isocyanates at 50-90° C. for 2-3 h, and defoaming to obtain the first component; mixing polytetrahydrofuran ether polyol and graphene uniformly, adding polyether amine and liquid amine chain extender, mixing them and heating to 50-90° C., and stirring for 20-50 min to obtain the second component.

9. The preparation method of the graphene-modified elastomer material according to claim 8, wherein the polytetrahydrofuran ether polyol and the graphene are mixed and stirred uniformly at a rotational speed of 1,000-1,200 rpm for a stirring time of 15-30 min.

10. The preparation method of the graphene-modified elastomer material according to claim 8, wherein the first component and the second component are heated to 55-70° C., adjusted to have a pressure of 30-40 MPa, mixed with a supergravity mixing method, and sprayed to obtain the graphene-modified elastomer material.

11. The preparation method of the graphene-modified elastomer material according to claim 8, wherein the graphene is at least one selected from the group consisting of surface-pretreated graphene, surface-pretreated biomass graphene, and surface-pretreated graphene oxide.

12. The preparation method of the graphene-modified elastomer material according to claim 11, wherein a surface pretreatment comprises: a surface graft coupling agent of graphene and/or biomass graphene and/or graphene oxide; the surface graft coupling agent is a silane coupling agent; a mass of the surface graft coupling agent is 1-5% of the graphene.

13. The preparation method of the graphene-modified elastomer material according to claim 12, wherein the graphene is the surface-pretreated graphene oxide.

14. The preparation method of the graphene-modified elastomer material according to claim 8, wherein a functionality ratio of the first component to the second component is 1:(1-1.05).

15. The preparation method of the graphene-modified elastomer material according to claim 8, wherein the polytetrahydrofuran ether polyol has a number average molecular weight of 1,000 to 2,000.

16. The preparation method of the graphene-modified elastomer material according to claim 8, wherein the liquid amine chain extender is at least one selected from the group consisting of diethyl methane diamine, dimethyl toluene diamine, and dialkethylene diamine.

17. The graphene-modified elastomer material according to claim 6, wherein the polytetrahydrofuran ether polyol has the number average molecular weight of 1,000 to 1,500.

18. The graphene-modified elastomer material according to claim 6, wherein the polytetrahydrofuran ether polyol has the number average molecular weight of 1,000.

19. The preparation method of the graphene-modified elastomer material according to claim 15, wherein the polytetrahydrofuran ether polyol has the number average molecular weight of 1,000 to 1,500.

20. The preparation method of the graphene-modified elastomer material according to claim 15, wherein the polytetrahydrofuran ether polyol has the number average molecular weight of 1,000.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) The technical solutions of the invention will be clearly and completely described below in combination with the specific embodiments, but those skilled in the art will understand that the embodiments described below are a part of the embodiments of the invention, and not exhaustive. Such embodiments are intended to illustrate the invention and not to limit the scope of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without creative efforts fall within the scope of protection of the invention. Conditions not specifically specified in the embodiments are conventional conditions or the conditions recommended by the manufacturers. Reagents or instruments used whose manufacturers are not indicated are commercially available conventional products.

(2) The information about some reagents used in the embodiments of the invention is as follows:

(3) Polyether triol, manufacturer: Bayer, model: ARCOL-5613;

(4) Polyether glycol, manufacturer: Bayer, model: ARCOL-1011;

(5) Polyether triamine, manufacturer: Hubei Qifei Pharmaceutical Chemical Co., Ltd., model: H362005;

(6) Polyether diamine, manufacturer: Huntsman, model: T-3000;

(7) Polytetrahydrofuran ether polyol, manufacturer: Mitsubishi Chemical, model: PTMG-1000;

(8) Graphene oxide, manufacturer: Shandong Leadernano Tech Co., Ltd.

Embodiment 1

(9) The elastomer material of this embodiment comprises the first component and the second component.

(10) The first component comprises isocyanate prepolymer obtained through reaction of polyether polyol with methyl isocyanate, p-phenylene diisocyanate and triphenylmethane isocyanate, and the isocyanate prepolymer has a —NCO content of 25%;

(11) The second component comprises the following components in parts by weight: 18 parts of polyether triamine, 56 parts of polyether diamine, 5 parts of diethyl methane diamine, 3 parts of polytetrahydrofuran ether polyol, and 3 parts of surface-pretreated graphene oxide.

(12) The preparation method of the elastomer material comprises the following steps:

(13) (1) Mix 30 g of polyether triol and 100 g of polyether diol uniformly, heat to 100-120° C. for dehydration for 2-3 h, then cool to 70° C., add 1 g of methyl isocyanate, 135 g of p-phenylene diisocyanate, 35 g of triphenylmethane isocyanate, react for 2-3 h under heat insulation conditions, and defoam and cool to obtain the first component with a —NCO content of 25±1%;

(14) (2) Add 18 parts of polyether triamine, 56 parts of polyether diamine, 5 parts of diethyl methane diamine, 3 parts of polytetrahydrofuran ether polyol, and 3 parts of surface-pretreated graphene oxide into the stirring vessel, heat to 70° C., and stir uniformly for 30 min at the stirring speed of 400-500 rpm/min to obtain the second component;

(15) The preparation method of the surface-pretreated graphene oxide comprises: carrying out ultrasonic dispersion of graphene oxide in absolute ethanol, preparing the coupling agent KH-560 into water solution with a mass fraction of 2%, adding hydrochloric acid to adjust the pH to 5, and adding it to the dispersed graphene oxide. After ultrasonic treatment, carry out reflux and reaction at 70° C. for 4 h, filter, rinse and dry it to obtain surface pre-treated graphene oxide;

(16) (3) Weigh the first component and the second component at the reactive functionality ratio of 1:1.02 (the first component to the second component), mix the first component and the second component with a supergravity reactor, heat to 62° C., adjust the pressure to 36 MPa, keep the flow rate of 0.183 L/min, and spray onto the surface of the substrate to obtain the elastomer material.

Embodiment 2

(17) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that the —NCO content of the first component—isocyanate prepolymer is 22%;

(18) The preparation method of the first component comprises: mixing 30 g of polyether triol and 100 g of polyether diol uniformly, heating to 100-120° C. for dehydration for 2-3 h, then cooling to 70° C., adding 0.8 g of methyl isocyanate, 110 g of p-phenylene diisocyanate, and 30 g of triphenylmethane isocyanate, reacting for 2-3 h under heat insulation conditions, and defoaming and cooling to obtain the first component with a —NCO content of 22±1%.

Embodiment 3

(19) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that the —NCO content of the first component—isocyanate prepolymer is 30%;

(20) The preparation method of the first component comprises: mixing 30 g of polyether triol and 100 g of polyether diol uniformly, heating to 100-120° C. for dehydration for 2-3 h, then cooling to 70° C., adding 1.5 g of methyl isocyanate, 220 g of p-phenylene diisocyanate, and 55 g of triphenylmethane isocyanate, reacting for 2-3 h under heat insulation conditions, and defoaming and cooling to obtain the first component with a —NCO content of 30±1%.

Embodiment 4

(21) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that the first component comprises isocyanate prepolymer obtained through reaction of polyether polyol with p-phenylene diisocyanate, and the isocyanate prepolymer has a —NCO content of 25%;

(22) The preparation method of the first component comprises:

(23) Mixing 30 g of polyether triol and 100 g of polyether diol uniformly, heating to 100-120° C. for dehydration for 2-3 h, then cooling to 70° C., adding 150 g of p-phenylene diisocyanate, reacting for 2-3 h under heat insulation conditions, and defoaming and cooling to obtain the first component with a —NCO content of 25±1%.

Embodiment 5

(24) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that the first component comprises isocyanate prepolymer obtained through reaction of polyether polyol with methyl isocyanate, p-phenylene diisocyanate and triphenylmethane isocyanate, and the isocyanate prepolymer has a —NCO content of 25%;

(25) The preparation method of the first component comprises: Mixing 30 g of polyether triol and 100 g of polyether diol uniformly, heating to 100-120° C. for dehydration for 2-3 h, then cooling to 70° C., adding 1 g of methyl isocyanate, 100 g of p-phenylene diisocyanate, and 125 g of triphenylmethane isocyanate, reacting for 2-3 h under heat insulation conditions, and defoaming and cooling to obtain the first component with a —NCO content of 25±1%.

Embodiment 6

(26) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that the first component comprises isocyanate prepolymer obtained through reaction of polyether polyol with methyl isocyanate, p-phenylene diisocyanate and triphenylmethane isocyanate, and the isocyanate prepolymer has a —NCO content of 25%;

(27) The preparation method of the first component comprises: Mixing 120 g of polyether diol uniformly, heating to 100-120° C. for dehydration for 2-3 h, then cooling to 70° C., adding 1 g of methyl isocyanate, 100 g of p-phenylene diisocyanate, and 125 g of triphenylmethane isocyanate, reacting for 2-3 h under heat insulation conditions, and defoaming and cooling to obtain the first component with a —NCO content of 25±1%.

Embodiment 7

(28) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that the second component comprises the following components in parts by weight: 37 parts of polyether triamine, 37 parts of polyether diamine, 5 parts of diethyl methane diamine, 3 parts of polytetrahydrofuran ether polyol, and 3 parts of surface-pretreated graphene oxide.

Embodiment 8

(29) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that the second component comprises the following components in parts by weight: 74 parts of polyether diamine, 5 parts of diethyl methane diamine, 3 parts of polytetrahydrofuran ether polyol, and 3 parts of surface-pretreated graphene oxide.

Embodiment 9

(30) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that the second component comprises the following components in parts by weight: 15 parts of polyether triamine, 45 parts of polyether diamine, 1 parts of diethyl methane diamine, 1 part of polytetrahydrofuran ether polyol, and 1 part of surface-pretreated graphene oxide.

Embodiment 10

(31) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that the second component comprises the following components in parts by weight: 25 parts of polyether triamine, 65 parts of polyether diamine, 10 parts of diethyl methane diamine, 5 parts of polytetrahydrofuran ether polyol, and 5 parts of surface-pretreated graphene oxide.

Embodiment 11

(32) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that diisocyanate in the first component is 4,4′-diphenylmethane diisocyanate.

Embodiment 12

(33) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that diisocyanate in the first component is toluene diisocyanate.

Embodiment 13

(34) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that surface-pretreated graphene is used to replace surface-pretreated graphene oxide;

(35) The method of surface pretreatment is similar to that in Embodiment 1, except that after surface-pretreated graphene oxide is obtained, chemical reduction is performed to obtain surface-pretreated graphene.

Embodiment 14

(36) This embodiment refers to the elastomer material and its preparation method of Embodiment 1, except that surface-pretreated biamoss graphene is used to replace surface-pretreated graphene oxide; and the same method of surface pretreatment is adopted.

Comparative Example 1

(37) The comparative example refers to the preparation method of Embodiment 1, except that the —NCO content of the first component—isocyanate prepolymer is 18%;

(38) The preparation method of the first component comprises: mixing 30 g of polyether triol and 100 g of polyether diol uniformly, heating to 100-120° C. for dehydration for 2-3 h, then cooling to 70° C., adding 0.6 g of methyl isocyanate, 83 g of p-phenylene diisocyanate, and 22 g of triphenylmethane isocyanate, reacting for 2-3 h under heat insulation conditions, and defoaming and cooling to obtain the first component with a —NCO content of 18±1%.

Comparative Example 2

(39) The comparative example refers to the preparation method of Embodiment 1, except that the second component comprises the following components in parts by weight: 18 parts of polyether triamine, 56 parts of polyether diamine, 15 parts of diethyl methane diamine, and 3 parts of surface-pretreated graphene oxide.

Comparative Example 3

(40) The comparative example refers to the preparation method of Embodiment 1, except that the second component is not added with surface-pretreated graphene oxide.

Comparative Example 4

(41) The comparative example refers to the preparation method of Embodiment 1, except that the second component is not added with polytetrahydrofuran ether polyol.

Experimental Example 1

(42) In order to compare and explain the properties of the elastomer materials obtained in the embodiments and comparative examples of the invention, the following property tests were conducted for elastomer materials obtained in the embodiments and comparative examples, and the test results are shown in Table 1.

(43) TABLE-US-00001 TABLE 1 Propety test results of different elastomer materials Test items Shore hardness Bending strength (D) (kgf/cm.sup.2) Test method ASTM D2240 ASTM D790 Embodiment 1 83 203 Embodiment 2 79 195 Embodiment 3 85 200 Embodiment 4 78 194 Embodiment 5 80 194 Embodiment 6 82 193 Embodiment 7 79 191 Embodiment 8 78 186 Embodiment 9 73 190 Embodiment 10 80 195 Embodiment 11 75 197 Embodiment 12 74 194 Embodiment 13 85 202 Embodiment 14 80 199 Comparative example 1 70 181 Comparative example 2 72 192 Comparative example 3 66 182 Comparative example 4 69 186

(44) As can be seen from the above table, the invention adjusts the —NCO content of isocyanate prepolymer to increase the hard segment content, thus reducing the soft segment content, increasing the content of urea bonds in the elastomer and the rigid chain segments, and improving the hardness and bending strength; meanwhile, the elasticity of the polymer is ensured.

(45) At the same time, graphenes are added to the second component, and grafted into the elastomer material, thus effectively improving the hardness and bending strength of the material.

(46) Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the invention and not to limit them; although the invention has been described in detail with reference to the embodiments, those skilled in the art should understand that the technical solutions described in the embodiments may be modified, or some or all of the technical features thereof may be equivalently substituted; however, such modifications or substitutions will not essentially make the corresponding technical solutions depart from the scope of technical solutions of the embodiments of the invention.