Nano TiO2-doped anti-ultraviolet para-aramid nano paper and preparation method thereof

Abstract

The disclosure discloses nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper and a preparation method thereof. First, nano TiO.sub.2 is selected as an ultraviolet absorbent which has a good absorption effect on ultraviolet rays, and the anti-ultraviolet characteristic of aramid paper-based material can be well improved through addition of nano TiO.sub.2. Second, macroscopic para-aramid fiber is dissolved under the action of a DMSO/KOH system, and the surface of the prepared aramid nano fiber is rich in C═O and N—H. This method is simple in process and does not harm the fiber itself, and can effectively improve the mechanical strength, interface binding performance and processability of a base material. The nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper prepared by the disclosure is simple in preparation process, excellent in material property.

Claims

1. A preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper, comprising the following steps: step 1: mixing γ-aminopropyltriethoxy silane, anhydrous ethanol and water, stirring and adjusting the pH value to 3-5, thereby obtaining a γ-aminopropyltriethoxy silane solution; mixing nano TiO.sub.2, water and anhydrous ethanol and ultrasonically dispersing to obtain a nano TiO.sub.2 dispersion; mixing the nano TiO.sub.2 dispersion with the γ-aminopropyltriethoxy silane solution, stirring, and centrifuging to obtain a first centrifuged product; re-dispersing the first centrifuged product into a mixed solution of water and anhydrous ethanol, and centrifuging again; and repeatedly dispersing the centrifuged product into a mixed solution of water and anhydrous ethanol and centrifuging, repeating the above steps, and drying the final centrifuged product to obtain a powdery modified nano TiO.sub.2; step 2: mixing dimethyl sulfoxide, para-aramid fibrid and KOH to obtain mixed solution A, stirring the mixed solution A at room temperature until the color of the mixed solution A is changed to dark red, so as to obtain a para-aramid fibrid suspension; and step 3: adding water to the para-aramid fibrid suspension and defibering to obtain a defibered para-aramid fibrid suspension; ultrasonically dispersing the powdery modified nano TiO.sub.2 in water to obtain an ultrasonically dispersed nano TiO.sub.2 solution; mixing the ultrasonically dispersed nano TiO.sub.2 solution with the defibered para-aramid fibrid suspension, and stirring to obtain mixed solution B, wherein a mass concentration of nano TiO.sub.2 in the mixed solution B is 2%˜10%; carrying out a suction filtration, squeezing and drying on the mixed solution B to obtain the nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper.

2. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 1, wherein in step 1, a mixing volume ratio of the γ-aminopropyltriethoxy silane, anhydrous ethanol, and water is 1:(85-95):(5-15), respectively.

3. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 2, wherein in step 3, the water added to the para-aramid fibrid suspension is more than 5 times the volume of the para-aramid fibrid suspension.

4. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 1, wherein in step 1, a mixing ratio of the nano TiO.sub.2, anhydrous ethanol, and water is 1 g:(8.8-13.5) mL:(0.7-1.7) mL, respectively.

5. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 4, wherein in step 3, the water added to the para-aramid fibrid suspension is more than 5 times the volume of the para-aramid fibrid suspension.

6. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 1, wherein in step 1, a mixing volume ratio of the nano TiO.sub.2 dispersion to the γ-aminopropyltriethoxy silane solution is 1:(8-10).

7. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 6, wherein in step 3, the water added to the para-aramid fibrid suspension is more than 5 times the volume of the para-aramid fibrid suspension.

8. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 1, wherein in step 1, the centrifuging is performed for 3-10 times.

9. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 8, wherein in step 3, the water added to the para-aramid fibrid suspension is more than 5 times the volume of the para-aramid fibrid suspension.

10. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 1, wherein in step 2: a mixing ratio of dimethyl sulfoxide, para-aramid fibrid, and KOH is (450-550) mL:1 g:(1-2) g, respectively.

11. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 10, wherein in step 3, the water added to the para-aramid fibrid suspension is more than 5 times the volume of the para-aramid fibrid suspension.

12. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 1, wherein in step 2: the stirring the mixed solution A is performed for 7-10 days.

13. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 12, wherein in step 3, the water added to the para-aramid fibrid suspension is more than 5 times the volume of the para-aramid fibrid suspension.

14. The preparation method of nano TiO.sub.2-doped anti-ultraviolet para-aramid nano paper according to claim 1, wherein in step 3, the water added to the para-aramid fibrid suspension is more than 5 times the volume of the para-aramid fibrid suspension.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an SEM image of original ANF paper and nano composite paper added with nano TiO.sub.2 according to embodiment 1 of the disclosure;

(2) wherein, (a) is the original ANF paper, and (b) is the nano composite paper added with 4% of nano TiO.sub.2;

(3) FIG. 2 is an XRD image of original ANF paper and nano composite paper added with nano TiO.sub.2 according to embodiment 1 of the disclosure, wherein, (a) refers to the original ANF paper; (b) refers to the composite paper added with 4% of nano TiO.sub.2; (c) refers to nano TiO.sub.2;

(4) FIG. 3 is an FT-IR image of original ANF paper and nano composite paper added with nano TiO.sub.2 according to embodiment 5 of the disclosure, wherein, (a) refers to the original ANF paper, and (b) refers to the nano composite paper added with 2% of nano TiO.sub.2; and

(5) FIG. 4 is a tensile strength graph of original ANF paper and nano composite paper added with nano TiO.sub.2 according to the disclosure, wherein, (a) refers to paper before UV irradiation; (b) refers to paper after UV irradiation.

DESCRIPTION OF THE EMBODIMENTS

(6) The disclosure will be described in detail in combination with drawings and embodiments. The disclosure discloses a nano TiO.sub.2-doped anti-ultrasonic para-aramid nano paper and a preparation method thereof. The para-aramid nano paper is doped with nano TiO.sub.2, the average size of nano TiO.sub.2 is 115 nm, and the surface of the aramid nano fiber in the para-aramid nano paper contains a large number of C═O and N—H functional groups which have certain activity and can be connected with hydroxyl on the surface of nano TiO.sub.2 by means of a hydrogen bond. Raw materials are prepared before preparation, including para-aramid fibrid (ANF), nano TiO.sub.2, potassium hydroxide (KOH), dimethyl sulfoxide (DMSO), γ-aminopropyltriethoxy silane (KH-550), anhydrous ethanol and deionized water; the preparation method specifically comprises the following steps:

(7) Step 1: Modification of Nano TiO.sub.2;

(8) Anhydrous ethanol, deionized water and KH-550 are taken, and mixed (a mixing volume ratio of (85-95):(5-15):1) and stirred at 60-70° C. and then put in a three-neck flask, and the pH value is adjusted to 3-5 with hydrochloric acid and sodium hydroxide solution, so as to obtain KH-550 solution; nano TiO.sub.2, anhydrous ethanol and deionized water are mixed (a mixing ratio of 1 g:(8-13.5) mL:(0.7-1.7) mL) and ultrasonically dispersed for 5 min to obtain ultrasonically dispersed nano TiO.sub.2 suspension; the dispersed nano TiO.sub.2 suspension is poured into the three-neck flask, wherein the mixing volume ratio of the nano TiO.sub.2 suspension to KH-550 solution is 1:(8-10), the nano TiO.sub.2 suspension and the KH-550 solution are stirred for 1 h at a constant speed at 60-70° C. to obtain the mixed solution, the mixed solution is centrifuged to obtained the centrifuged product, and then the centrifuged product is dispersed in the mixed solution of deionized water and anhydrous ethanol again, and the above steps are repeated for several times with total centrifugation for 3-10 times; KH550 on the surface of the modified nano TiO.sub.2 is removed by repeated centrifugation, and the final centrifuged product is dried in a 100° C. oven for 6 hours to obtain the modified nano TiO.sub.2 which is grinded into powder for later user.

(9) Step 2: Preparation of ANF Suspension

(10) According to the proportion of (450-550) mL:1 g:(1:2) g, DMSO, para-aramid fibrid and KOH are mixed to obtain mixed solution A, and then the mixed solution A is stirred at room temperature for 7-10 days until the solution was dark red to obtain ANF suspension.

(11) Step 3: Preparation of Nano TiO.sub.2-Doped Para-Aramid Nano Paper

(12) 1) ANF suspension is taken and defibered by adding water, wherein the addition amount of water is more than 5 times of the volume of ANF suspension, so that DMSO is diluted with water in a solvent;

(13) 2) the powdery modified nano TiO.sub.2 is dispersed in water to obtain the ultrasonically dispersed nano TiO.sub.2 solution; the ultrasonically dispersed nano TiO.sub.2 solution and the defibered ANF suspension are uniformly stirred to obtain mixed solution B; the mass concentration of nano TiO.sub.2 in the mixed solution B is 2%˜10%; the mixed solution B is filtered at reduced, pressed and dried to obtain the nano TiO.sub.2-doped para-aramid nano paper.

Example 1

(14) Step 1: 90 mL of anhydrous ethanol, 10 mL of deionized water and 1 mL of KH-550 were taken, mixed and stirred at 60° C. and the put in a three-neck flask, and the pH value was adjusted to about 4 with hydrochloric acid and sodium hydroxide solution; 1 g of nano TiO.sub.2 was weighed and added into mixed solution of 1 mL of deionized water and 9 mL of anhydrous ethanol, the above mixture was ultrasonically dispersed at a high speed for 5 min to obtain ultrasonically dispersed nano TiO.sub.2 suspension; the dispersed nano TiO.sub.2 was poured into the three-neck flask, the mixing volume ratio of nano TiO.sub.2 suspension to KH-550 solution was 1:8, and the mixed solution was obtained after stirring at 60° C. for 1 h at a constant speed. After centrifugation, the above mixed solution was dispersed again in the mixed solution of deionized water and anhydrous ethanol, such the steps were repeated for 5 times, and the above dispersion was dried in an oven at 100° C. for 6 h and then grinded, so that the modified TiO.sub.2 solution was obtained;

(15) Step 2: 500 mL of DMSO solution was taken and added with 1.0 g of para-aramid fibrid and 1.5 g of KOH and then stirred at room temperature for 7 days, until the solution is dark red, and ANF suspension was obtained.

(16) Step 3: 100 mL of ANF solution was taken and added with 500 mL of water to be defibered; the modified TiO.sub.2 solution prepared in step 1 was ultrasonically dispersed in water to obtain the ultrasonically dispersed nano-TiO.sub.2 solution; the ultrasonically dispersed nano TiO.sub.2 solution and the defibered ANF suspension were uniformly stirred to obtain the mixed solution B; the mass concentration of nano TiO.sub.2 in the mixed solution B was 4%; the mixed solution B was filtered at reduced pressure, squeezed and dried to obtain nano TiO.sub.2-doped para-aramid nano paper.

(17) The SEM graph of the nano TiO.sub.2-doped para-aramid nano paper prepared in this embodiment is seen in FIG. 1. It can be seen from FIG. 1 that after adding nano TiO.sub.2, the surface of the paper obviously changes. Some particles and fine fibers are scattered on the surface of the paper, and the surface of the paper becomes rough.

(18) It can be seen from the XRD image in FIG. 2 that there is only one very wide dispersion peak in pure ANF paper, and three characteristic peaks of TiO.sub.2 powder appear in ANF/nano TiO.sub.2 paper, namely, 25.31°, 37.85° and 48.18° in the drawing, which correspond to the reflection peaks of (101), (004) and (200) crystal faces of TiO.sub.2 respectively. It can be shown that nano TiO.sub.2 particles were successfully doped into ANF paper, and the crystal structure of TiO.sub.2 crystal powder in ANF/nano TiO.sub.2 paper is not damaged and kept intact.

(19) It can be seen from FIG. 3 that from the infrared image of ANF, it can be seen that the absorption peak at 3320 cm.sup.−1 is the stretching vibration of the N—H bond, the absorption peak at 1650 cm-1 is the stretching vibration of amide I, and the absorption peak at 1543 cm.sup.−1 is the stretching vibration of amide II. Compared with ANF paper, a large number of hydroxyl groups are present on the surface of nano TiO.sub.2 particles due to the introduction of a large number of nano TiO.sub.2 particles inside the nano composite paper, there is hydrogen bond interaction between these hydroxyl groups and —C═O and —N—H in the ANF molecule, and the existence of hydrogen bond can make the position of the absorption peak in the infrared spectrum changed. It can be seen from the drawing that the hydrogen bond effect makes the stretching vibration absorption band of the N—H bond in the composite paper move to low frequency, which also confirms the existence of TiO.sub.2 in composite paper.

(20) FIG. 4 shows the change in tensile strength of ANF base paper and ANF/nano TiO.sub.2 paper before and after aging for 72 hours. It can be seen from the drawing that when the addition amount of nano TiO.sub.2 reaches 4%, the fracture stress reaches a peak value, which is increased by 24.49% from the original 113.586 MPa to 141.405 MPa. After UV irradiation, the maximum fracture stress is 149.933 MPa, which is increased by 32.52% compared with ANF base paper and 6.03% compared with that before UV irradiation. The reason may be that under the action of ultraviolet, the amide bond of ANF partially breaks and active groups such as —C═O and —N—H are exposed from the surface of ANF. The hydrogen bond interaction is formed between the active groups and the hydroxyl group on the surface of nano TiO.sub.2, which enhances combination between them and increases the fracture stress of the material. It is also possible that the long-time ultraviolet irradiation causes some small pores on the fiber surface, increases the roughness of the fiber surface, and meanwhile enhances the adhesion of nano TiO.sub.2 on the fiber surface so as to increase the roughness of the fiber surface, thereby improving the friction performance of the fiber, and then improving the mechanical properties of the paper-based materials.

Example 2

(21) Step 1: 85 mL of anhydrous ethanol, 10 mL of deionized water and 1 mL of KH-550 were taken, mixed and stirred at 60° C. and the put in a three-neck flask, the pH value was adjusted to about 4 with hydrochloric acid and sodium hydroxide solution; 1 g of nano TiO.sub.2 was weighed and added into mixed solution of 1.2 mL of deionized water and 10 mL of anhydrous ethanol, the above mixture was ultrasonically dispersed at a high speed for 5 min to obtain ultrasonically dispersed nano TiO.sub.2 suspension; the dispersed nano TiO.sub.2 was poured into the three-neck flask, the mixing volume ratio of nano TiO.sub.2 suspension to KH-550 solution was 1:10, and the mixed solution was obtained after stirring at 70° C. for 1 h at a constant speed. After centrifugation, the above mixed solution was dispersed again in the mixed solution of deionized water and anhydrous ethanol, such the steps were repeated for 3 times, the above dispersion was dried in an oven at 100° C. for 6 h and then grinded, so that the modified TiO.sub.2 solution was obtained;

(22) Step 2: 450 mL of DMSO solution was taken and added with 1.0 g of para-aramid fibrid and 2 g of KOH and then stirred at room temperature for 8 days, until the solution is dark red, and ANF suspension was obtained.

(23) Step 3: 100 mL of ANF solution was taken and added with 600 mL of water to be defibered; the modified TiO.sub.2 solution prepared in step 1 was ultrasonically dispersed in water to obtain the ultrasonically dispersed nano-TiO.sub.2 solution; the ultrasonically dispersed nano TiO.sub.2 solution and the defibered ANF suspension were uniformly stirred to obtain the mixed solution B; the mass concentration of nano TiO.sub.2 in the mixed solution B was 6%; the mixed solution B was filtered at reduced pressure, pressed and dried to obtain nano TiO.sub.2-doped para-aramid nano paper.

Example 3

(24) Step 1: 90 mL of anhydrous ethanol, 15 mL of deionized water and 1 mL of KH-550 were taken, mixed and stirred at 65° C. and the put in a three-neck flask, the pH value was adjusted to about 5 with hydrochloric acid and sodium hydroxide solution; 1 g of nano TiO.sub.2 was weighed and added into mixed solution of 1.7 mL of deionized water and 10 mL of anhydrous ethanol, the above mixture was ultrasonically dispersed at a high speed for 5 min to obtain ultrasonically dispersed nano TiO.sub.2 suspension; the dispersed nano TiO.sub.2 was poured into the three-neck flask, the mixing volume ratio of nano TiO.sub.2 suspension to KH-550 solution was 1:9, and the mixed solution was obtained after stirring at 60° C. for 1 h at a constant speed. After centrifugation, the above mixed solution was dispersed again in the mixed solution of deionized water and anhydrous ethanol, such the steps were repeated for 10 times, and the above dispersion was dried in an oven at 100° C. for 6 h and then grinded, so that the modified TiO.sub.2 solution was obtained;

(25) Step 2: 480 mL of DMSO solution was taken and added with 1.0 g of para-aramid fibrid and 1 g of KOH and then stirred at room temperature for 9 days, until the solution is dark red, and ANF suspension was obtained.

(26) Step 3: 100 mL of ANF solution was taken and added with 800 mL of water to be defibered; the modified TiO.sub.2 solution prepared in step 1 was ultrasonically dispersed in water to obtain the ultrasonically dispersed nano-TiO.sub.2 solution; the ultrasonically dispersed nano TiO.sub.2 solution and the defibered ANF suspension were uniformly stirred to obtain the mixed solution B; the mass concentration of nano TiO.sub.2 in the mixed solution B was 8%; the mixed solution B was filtered at reduced pressure, pressed and dried to obtain nano TiO.sub.2-doped para-aramid nano paper.

Example 4

(27) Step 1: 95 mL of anhydrous ethanol, 5 mL of deionized water and 1 mL of KH-550 were taken, mixed and stirred at 60° C. and the put in a three-neck flask, the pH value was adjusted to about 3 with hydrochloric acid and sodium hydroxide solution; 1 g of nano TiO.sub.2 was weighed and added into mixed solution of 0.7 mL of deionized water and 13.5 mL of anhydrous ethanol, the above mixture was ultrasonically dispersed at a high speed for 5 min to obtain ultrasonically dispersed nano TiO.sub.2 suspension; the dispersed nano TiO.sub.2 was poured into the three-neck flask, the mixing volume ratio of nano TiO.sub.2 suspension to KH-550 solution was 1:8, and the mixed solution was obtained after stirring at 60° C. for 1 h at a constant speed. After centrifugation, the above mixed solution was dispersed again in the mixed solution of deionized water and anhydrous ethanol, such the steps were repeated for 6 times, and the above dispersion was dried in an oven at 100° C. for 6 h and then grinded, so that the modified TiO.sub.2 solution was obtained;

(28) Step 2: 470 mL of DMSO solution was taken and added with 1.0 g of para-aramid fibrid and 1.5 g of KOH and then stirred at room temperature for 10 days, until the solution is dark red, and ANF suspension was obtained.

(29) Step 3: 100 mL of ANF solution was taken and added with 600 mL of water to be defibered; the modified TiO.sub.2 solution prepared in step 1 was ultrasonically dispersed in water to obtain the ultrasonically dispersed nano-TiO.sub.2 solution; the ultrasonically dispersed nano TiO.sub.2 solution and the defibered ANF suspension were uniformly stirred to obtain the mixed solution B; the mass concentration of nano TiO.sub.2 in the mixed solution B was 2%; the mixed solution B was filtered at reduced pressure, pressed and dried to obtain nano TiO.sub.2-doped para-aramid nano paper.

Example 5

(30) Step 1: 88 mL of anhydrous ethanol, 10 mL of deionized water and 1 mL of KH-550 were taken, mixed and stirred at 60° C. and the put in a three-neck flask, the pH value was adjusted to about 4 with hydrochloric acid and sodium hydroxide solution; 1 g of nano TiO.sub.2 was weighed and added into mixed solution of 1 mL of deionized water and 8.8 mL of anhydrous ethanol, the above mixture was ultrasonically dispersed at a high speed for 5 min to obtain ultrasonically dispersed nano TiO.sub.2 suspension; the dispersed nano TiO.sub.2 was poured into the three-neck flask, the mixing volume ratio of nano TiO.sub.2 suspension to KH-550 solution was 1:10, and the mixed solution was obtained after stirring at 60° C. for 1 h at a constant speed. After centrifugation, the above mixed solution was dispersed again in the mixed solution of deionized water and anhydrous ethanol, such the steps were repeated for 6 times, the above dispersion was dried in an oven at 100° C. for 6 h and then grinded, so that the modified TiO.sub.2 solution was obtained;

(31) Step 2: 550 mL of DMSO solution was taken and added with 1.0 g of para-aramid fibrid and 2 g of KOH and then stirred at room temperature for 8 days, until the solution is dark red, and ANF suspension was obtained.

(32) Step 3: 100 mL of ANF solution was taken and added with 600 mL of water to be defibered; the modified TiO.sub.2 solution prepared in step 1 was ultrasonically dispersed in water to obtain the ultrasonically dispersed nano-TiO.sub.2 solution; the ultrasonically dispersed nano TiO.sub.2 solution and the defibered ANF suspension were uniformly stirred to obtain the mixed solution B; the mass concentration of nano TiO.sub.2 in the mixed solution B was 10%; the mixed solution B was filtered at reduced pressure, pressed and dried to obtain nano TiO.sub.2-doped para-aramid nano paper.

(33) The above descriptions are only preferred embodiments of the disclosure but not intended to limit the disclosure. Any modifications, equivalent substitutions, improvements and the like made without departing from the spirit and principle of the disclosure are all included within the scope of protection of the disclosure.