阅读说明：本技术 一种碳纳米管接枝聚氨酯改性芳纶防刺纤维合成方法及应用 (Synthesis method and application of carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber ) 是由 赵建海 于 2021-08-10 设计创作，主要内容包括：本发明涉及防穿刺材料,且公开了一种碳纳米管接枝聚氨酯改性芳纶防刺纤维,以碳纳米管表面的二羟乙基官能团作为二醇单体聚合位点,使聚氨酯在碳纳米管表面发生原位聚合,得到碳纳米管接枝聚氨酯,碳纳米管与聚氨酯之间形成三维化学交联网络,增强了碳纳米管与聚氨酯的界面作用力,改善了碳纳米管在聚氨酯中的分散性,显著提高了聚氨酯的交联度和力学强度,通过浸-轧工艺应,将碳纳米管接枝聚氨酯溶液涂敷在芳纶纤维薄膜,碳纳米管接枝在聚氨酯的分子链中,可以有效发挥纳米粒子的增强作用,吸收外界应力和冲击力,使芳纶纤维表现出更大的抗穿刺力和更强的防穿刺性能。(The invention relates to a puncture-proof material and discloses a carbon nano tube grafted polyurethane modified aramid fiber puncture-proof fiber, the dihydroxyethyl functional group on the surface of the carbon nano tube is taken as the polymerization site of the diol monomer, so that the polyurethane is subjected to in-situ polymerization on the surface of the carbon nano tube to obtain the carbon nano tube grafted polyurethane, a three-dimensional chemical crosslinking network is formed between the carbon nano tube and the polyurethane, the interface acting force of the carbon nano tube and the polyurethane is enhanced, the dispersibility of the carbon nano tube in the polyurethane is improved, the crosslinking degree and the mechanical strength of the polyurethane are obviously improved, by the soaking-rolling process, the carbon nano tube grafted polyurethane solution is coated on the aramid fiber film, the carbon nano tube is grafted in the molecular chain of polyurethane, the reinforcing effect of the nano particles can be effectively exerted, and the external stress and impact force are absorbed, so that the aramid fiber has higher puncture resistance and stronger puncture resistance.)

1. A synthetic method of carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber is characterized by comprising the following steps: the synthesis method comprises the following steps:

placing aramid fiber in a carbon nano tube grafted polyurethane solution, treating by a soaking-rolling process, and controlling the coating amount to be 10-25 g/cm²And then drying the treated aramid fiber at the temperature of 80-100 ℃ for 5-20 min, heating to the temperature of 120-140 ℃, and performing thermocuring for 2-4 h to obtain the carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber.

2. The synthesis method of the carbon nanotube grafted polyurethane modified aramid stab-resistant fiber according to claim 1, wherein the synthesis method comprises the following steps: the synthesis method of the carbon nano tube grafted polyurethane solution comprises the following steps:

(1) ultrasonically dispersing an aminated carbon nano tube into N, N-dimethylformamide, adding dihydroxyethyl glycine and a cosolvent, dropwise adding a catalyst p-toluenesulfonic acid, heating for reaction, centrifugally separating after the reaction, and washing the product by using deionized water and acetone in sequence to prepare a dihydroxyethylated carbon nano tube;

(2) the preparation method comprises the following steps of carrying out vacuum dehydration on polycarbonate diol, uniformly mixing the polycarbonate diol with isophorone diisocyanate, a dihydroxyethylated carbon nano tube and acetone, dropwise adding a catalyst dibutyltin dilaurate, heating to 60-75 ℃ in a nitrogen atmosphere, reacting for 4-7 h, reducing the temperature to 35-45 ℃ after the reaction, dropwise adding acetone for dilution, then adding 2, 2-dimethylolpropionic acid, reacting for 1-2 h, and then adding triethylamine for neutralization to obtain a carbon nano tube grafted polyurethane solution.

3. The synthesis method of the carbon nanotube grafted polyurethane modified aramid stab-resistant fiber according to claim 2, wherein the synthesis method comprises the following steps: the mass ratio of the aminated carbon nanotube, the dihydroxyethyl glycine and the p-toluenesulfonic acid in the step (1) is 100:150-400: 6-18.

4. The synthesis method of the carbon nanotube grafted polyurethane modified aramid stab-resistant fiber according to claim 2, wherein the synthesis method comprises the following steps: the cosolvent in the step (1) comprises any one of 1, 4-dioxane, tetrahydrofuran and ethyl acetate, and the volume ratio of the cosolvent to the N, N-dimethylformamide is 40-80: 100.

5. The synthesis method of the carbon nanotube grafted polyurethane modified aramid stab-resistant fiber according to claim 2, wherein the synthesis method comprises the following steps: the reaction temperature in the step (1) is 80-110 ℃, and the reaction time is 24-48 h.

6. The synthesis method of the carbon nanotube grafted polyurethane modified aramid stab-resistant fiber according to claim 2, wherein the synthesis method comprises the following steps: in the step (2), the mass ratio of polycarbonate diol, isophorone diisocyanate, dihydroxyethylated carbon nanotubes, dibutyltin dilaurate and 2, 2-dimethylolpropionic acid is 100:45-65:0.5-3:0.2-0.5: 3-8.

7. Use of the carbon nanotube-grafted polyurethane modified aramid stab-resistant fiber according to any one of claims 1 to 6 in a stab-resistant fabric.

Technical Field

The invention relates to a puncture-proof material, in particular to a synthesis method and application of a carbon nanotube grafted polyurethane modified aramid fiber puncture-proof fiber.

Background

The anti-puncture fabric has wide application prospects in the aspects of work protective clothing, sport protection, safety protection and the like, and mainly comprises aramid fibers, polyethylene fibers and the like, wherein the aramid fibers have the advantages of strong molecular rigidity, high strength, large modulus and wide application in the aspect of fiber clothing; the anti-stab performance of the fabric can be improved by compounding high polymer resin, such as epoxy resin, polyurethane and the like, with the aramid fiber fabric, the polyurethane is a high polymer material with high elasticity and strong impact resistance, has good biocompatibility and low toxicity and no irritation, and can be used as fiber fabric to be made into various garment fabrics; the nano materials such as nano silicon dioxide, carbon nano tubes and the like can be prepared into shear thickening liquid, and the puncture-proof capability of the fiber can be effectively enhanced, so that the carbon nano tubes can be combined with polyurethane to carry out surface modification on aramid fibers, and the aramid fiber fabric with excellent puncture-proof performance is obtained.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides the carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber and a synthesis method thereof, and the modified aramid fiber has excellent puncture-resistant performance.

In order to achieve the purpose, the invention provides the following technical scheme: a carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber is synthesized by the following steps:

placing aramid fiber in a carbon nano tube grafted polyurethane solution, treating by a soaking-rolling process, and controlling the coating amount to be 10-25 g/cm²And then drying the treated aramid fiber at the temperature of 80-100 ℃ for 5-20 min, heating to the temperature of 120-140 ℃, and performing thermocuring for 2-4 h to obtain the carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber.

Preferably, the synthesis method of the carbon nanotube grafted polyurethane solution is as follows:

(1) ultrasonically dispersing an aminated carbon nanotube into N, N-dimethylformamide, adding dihydroxyethyl glycine and a cosolvent, dropwise adding a catalyst p-toluenesulfonic acid (TsOH), heating for reaction, performing centrifugal separation after the reaction, and washing the product by using deionized water and acetone in sequence to obtain the dihydroxyethylated carbon nanotube.

(2) The preparation method comprises the following steps of carrying out vacuum dehydration on polycarbonate diol, uniformly mixing the polycarbonate diol with isophorone diisocyanate, a dihydroxyethylated carbon nano tube and acetone, dropwise adding a catalyst dibutyltin dilaurate, heating to 60-75 ℃ in a nitrogen atmosphere, reacting for 4-7 h, reducing the temperature to 35-45 ℃ after the reaction, dropwise adding acetone for dilution, then adding 2, 2-dimethylolpropionic acid, reacting for 1-2 h, and then adding triethylamine for neutralization to obtain a carbon nano tube grafted polyurethane solution.

Preferably, the mass ratio of the aminated carbon nanotube, the dihydroxyethylglycine and the p-toluenesulfonic acid in the step (1) is 100:150-400: 6-18.

Preferably, the cosolvent in the step (1) comprises any one of 1, 4-dioxane, tetrahydrofuran and ethyl acetate, and the volume ratio of the cosolvent to the N, N-dimethylformamide is 40-80: 100.

Preferably, the reaction temperature in the step (1) is 80-110 ℃, and the reaction time is 24-48 h.

Preferably, in the step (2), the mass ratio of the polycarbonate diol to the isophorone diisocyanate to the bis (hydroxyethylated) carbon nanotube to the dibutyltin dilaurate to the 2, 2-dimethylolpropionic acid is 100:45-65:0.5-3:0.2-0.5: 3-8.

Preferably, the carbon nanotube grafted polyurethane modified aramid fiber is applied to a puncture-proof fiber fabric.

The invention has the advantages that:

according to the carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber, the carboxyl of dihydroxyethyl glycine and the amino on the surface of an aminated carbon nanotube are subjected to amidation reaction by taking p-toluenesulfonic acid as a catalyst to obtain a dihydroxyethyl carbon nanotube, and abundant dihydroxyethyl functional groups and amide bonds are introduced to the surface of the carbon nanotube, so that the surface functional modification of the carbon nanotube is realized.

The method comprises the steps of taking a dihydroxyethyl functional group on the surface of a carbon nano tube as a diol monomer polymerization site, carrying out graft copolymerization with polycarbonate diol and isophorone diisocyanate to enable polyurethane to carry out in-situ polymerization on the surface of the carbon nano tube to obtain carbon nano tube grafted polyurethane, connecting the carbon nano tube with the polyurethane through covalent bond bonding, forming good hydrogen bonds with carbamate groups in polyurethane molecular chains through amide groups contained on the surface of the carbon nano tube, forming a three-dimensional chemical crosslinking network between the carbon nano tube and the polyurethane, enhancing the interfacial force between the carbon nano tube and the polyurethane, improving the dispersibility of the carbon nano tube in the polyurethane, obviously improving the crosslinking degree and the mechanical strength of the polyurethane, coating a carbon nano tube grafted polyurethane solution on an aramid fiber film through a dip-rolling process, grafting the carbon nano tube into the molecular chains of the polyurethane, the reinforcing effect of the nano particles can be effectively exerted, and the external stress and impact force are absorbed, so that the aramid fiber has higher puncture resistance and stronger puncture resistance.

Drawings

FIG. 1 is a reaction diagram of an aminated carbon nanotube and dihydroxyethyl glycine;

FIG. 2 is a structural diagram of a carbon nanotube-grafted polyurethane;

fig. 3 is a graph of maximum puncture force performance versus time.

Detailed Description

The invention is further illustrated by the following examples, which are intended to illustrate, but not to limit the invention further. The technical means used in the following examples are conventional means well known to those skilled in the art, and all raw materials are general-purpose materials.

The invention provides a carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber, which comprises the following synthetic methods:

(1) ultrasonically dispersing an aminated carbon nanotube into N, N-dimethylformamide, adding dihydroxyethyl glycine and a cosolvent, wherein the cosolvent comprises any one of 1, 4-dioxane, tetrahydrofuran and ethyl acetate, the volume ratio of the cosolvent to the N, N-dimethylformamide is 40-80:100, dropwise adding a catalyst p-toluenesulfonic acid (TsOH), the mass ratio of the aminated carbon nanotube, the dihydroxyethyl glycine and the p-toluenesulfonic acid is 100:150-400:6-18, heating to 80-110 ℃, reacting for 24-48 h, performing centrifugal separation after reaction, and washing a product by using deionized water and acetone in sequence to obtain the dihydroxyethylated carbon nanotube.

(2) The preparation method comprises the steps of carrying out vacuum dehydration on polycarbonate diol, uniformly mixing the polycarbonate diol with isophorone diisocyanate, a dihydroxyethylated carbon nano tube and acetone, dropwise adding a catalyst dibutyltin dilaurate, heating to 60-75 ℃ in a nitrogen atmosphere, reacting for 4-7 h, reducing the temperature to 35-45 ℃ after the reaction, dropwise adding acetone for dilution, then adding 2, 2-dimethylolpropionic acid, reacting for 1-2 h, and then adding triethylamine for neutralization to obtain the carbon nano tube grafted polyurethane solution, wherein the mass ratio of the polycarbonate diol, the isophorone diisocyanate, the dihydroxyethylated carbon nano tube, the dibutyltin dilaurate and the 2, 2-dimethylolpropionic acid is 100:45-65:0.5-3:0.2-0.5: 3-8.

(3) Placing aramid fiber in a carbon nano tube grafted polyurethane solution, treating by a soaking-rolling process, and controlling the coating amount to be 10-25 g/cm²And then drying the treated aramid fiber at 80-100 ℃ for 5-20 min, heating to 120-140 ℃ and performing thermocuring for 2-4 h to obtain the carbon nanotube grafted polyurethane modified aramid fiber stab-resistant fiber which is applied to the stab-resistant fiber fabric.

Example 1

(1) Ultrasonically dispersing 0.5 g of aminated carbon nano tube into 20 mL of N, N-dimethylformamide, adding 0.75 g of dihydroxyethylglycine and 8 mL of cosolvent 1, 4-dioxane, dropwise adding 0.03 g of catalyst p-toluenesulfonic acid, heating to 80 ℃, reacting for 24 hours, centrifugally separating after the reaction, and washing the product by using deionized water and acetone in sequence to obtain the dihydroxyethylated carbon nano tube.

(2) Vacuum dehydrating 2 g of polycarbonate diol, uniformly mixing with 0.9 g of isophorone diisocyanate, 0.01 g of dihydroxyethylated carbon nano tube and acetone, dropwise adding 0.004 g of catalyst dibutyltin dilaurate, heating to 60 ℃ in a nitrogen atmosphere, reacting for 4 hours, reducing the temperature to 35 ℃ after reaction, dropwise adding acetone for dilution, then adding 0.06 g of 2, 2-dimethylolpropionic acid, reacting for 1 hour, and then adding triethylamine for neutralization to obtain the carbon nano tube grafted polyurethane solution.

(3) Placing aramid fiber in a carbon nano tube grafted polyurethane solution, treating by a soaking-rolling process, and controlling the coating amount to be 10 g/cm²Then drying the treated aramid fiber at 80 ℃ for 5 min, then heating to 120 ℃, and thermally curing for 2 h to obtain the aramid fiberThe carbon nanotube grafted polyurethane modified aramid fiber is used as stab-resistant fiber.

Example 2

(1) Ultrasonically dispersing 0.5 g of aminated carbon nanotube into 20 mL of N, N-dimethylformamide, adding 1.2 g of dihydroxyethylglycine and 10 mL of cosolvent tetrahydrofuran, dropwise adding 0.05 g of catalyst p-toluenesulfonic acid, heating to 100 ℃, reacting for 24 h, centrifugally separating after the reaction, and washing the product by using deionized water and acetone in sequence to obtain the dihydroxyethylated carbon nanotube.

(2) Vacuum dehydrating 2 g of polycarbonate diol, uniformly mixing with 1 g of isophorone diisocyanate, 0.025 g of dihydroxyethylated carbon nano tube and acetone, dropwise adding 0.006 g of catalyst dibutyltin dilaurate, heating to 65 ℃ in a nitrogen atmosphere, reacting for 5 hours, reducing the temperature to 40 ℃ after reaction, dropwise adding acetone for dilution, then adding 0.08 g of 2, 2-dimethylolpropionic acid, reacting for 1.5 hours, and then adding triethylamine for neutralization to obtain the carbon nano tube grafted polyurethane solution.

(3) Placing aramid fiber in a carbon nano tube grafted polyurethane solution, treating the aramid fiber through a soaking-rolling process, and controlling the coating amount to be 15 g/cm²And then drying the treated aramid fiber at 90 ℃ for 15 min, heating to 130 ℃, and thermally curing for 3 h to obtain the carbon nanotube grafted polyurethane modified aramid stab-resistant fiber.

Example 3

(1) Ultrasonically dispersing 0.5 g of aminated carbon nanotube into 20 mL of N, N-dimethylformamide, adding 1.6 g of dihydroxyethylglycine and 12 mL of cosolvent ethyl acetate, dropwise adding 0.07 g of catalyst p-toluenesulfonic acid, heating to 100 ℃, reacting for 36 h, centrifugally separating after reaction, and washing a product by using deionized water and acetone in sequence to obtain the dihydroxyethylated carbon nanotube.

(2) Vacuum dehydrating 2 g of polycarbonate diol, uniformly mixing with 1.2 g of isophorone diisocyanate, 0.04 g of dihydroxyethylated carbon nano tube and acetone, dropwise adding 0.008 g of catalyst dibutyltin dilaurate, heating to 70 ℃ in a nitrogen atmosphere, reacting for 6 h, reducing the temperature to 40 ℃ after reaction, dropwise adding acetone for dilution, then adding 0.13 g of 2, 2-dimethylolpropionic acid, reacting for 1.5 h, and then adding triethylamine for neutralization to obtain the carbon nano tube grafted polyurethane solution.

(3) Placing aramid fiber in a carbon nano tube grafted polyurethane solution, treating by a soaking-rolling process, and controlling the coating amount to be 20 g/cm²And then drying the treated aramid fiber at 90 ℃ for 15 min, heating to 130 ℃, and thermally curing for 3 h to obtain the carbon nanotube grafted polyurethane modified aramid stab-resistant fiber.

Example 4

(1) Ultrasonically dispersing 0.5 g of aminated carbon nano tube into 20 mL of N, N-dimethylformamide, adding 2 g of dihydroxyethylglycine and 16 mL of cosolvent 1, 4-dioxane, dropwise adding 0.09 g of catalyst p-toluenesulfonic acid, heating to 110 ℃, reacting for 48 hours, centrifugally separating after the reaction, and washing the product by using deionized water and acetone in sequence to obtain the dihydroxyethylated carbon nano tube.

(2) Vacuum dehydrating 2 g of polycarbonate diol, uniformly mixing with 1.3 g of isophorone diisocyanate, 0.06 g of dihydroxyethylated carbon nano tube and acetone, dropwise adding 0.01 g of catalyst dibutyltin dilaurate, heating to 75 ℃ in a nitrogen atmosphere, reacting for 7 h, reducing the temperature to 45 ℃ after reaction, dropwise adding acetone for dilution, then adding 0.16 g of 2, 2-dimethylolpropionic acid, reacting for 2 h, and then adding triethylamine for neutralization to obtain the carbon nano tube grafted polyurethane solution.

(3) Placing aramid fiber in a carbon nano tube grafted polyurethane solution, treating by a soaking-rolling process, and controlling the coating amount to be 25 g/cm²And then drying the treated aramid fiber at 100 ℃ for 20 min, heating to 140 ℃, and thermally curing for 4 h to obtain the carbon nanotube grafted polyurethane modified aramid stab-resistant fiber.

Comparative example 1

(1) Vacuum dehydrating 2 g of polycarbonate diol, uniformly mixing with 1 g of isophorone diisocyanate, 0.01 g of carbon nano tube and acetone, dropwise adding 0.005 g of dibutyltin dilaurate serving as a catalyst, heating to 60 ℃ in a nitrogen atmosphere, reacting for 7 hours, reducing the temperature to 45 ℃ after the reaction, dropwise adding acetone for diluting, then adding 0.08 g of 2, 2-dimethylolpropionic acid, reacting for 2 hours, and then adding triethylamine for neutralizing to obtain the carbon nano tube-polyurethane solution.

(2) Placing aramid fiber in a carbon nano tube-polyurethane solution, treating by a soaking-rolling process, and controlling the coating amount to be 10 g/cm²And then drying the treated aramid fiber at 100 ℃ for 20 min, heating to 120 ℃, and thermally curing for 2 h to obtain the carbon nanotube-polyurethane modified aramid stab-resistant fiber.

Comparative example 2

(1) Vacuum dehydrating 2 g of polycarbonate diol, uniformly mixing the polycarbonate diol with 0.9 g of isophorone diisocyanate and acetone, dropwise adding 0.004 g of dibutyltin dilaurate serving as a catalyst, heating to 60 ℃ in a nitrogen atmosphere, reacting for 7 hours, reducing the temperature to 45 ℃ after the reaction, dropwise adding acetone for diluting, then adding 0.06 g of 2, 2-dimethylolpropionic acid, reacting for 1 hour, and then adding triethylamine for neutralizing to obtain a polyurethane solution.

(2) Placing aramid fiber in polyurethane solution, treating by soaking-rolling process, and controlling coating amount to be 10 g/cm²And then drying the treated aramid fiber at 80 ℃ for 5 min, heating to 140 ℃, and thermally curing for 4 h to obtain the polyurethane modified aramid fiber stab-resistant fiber.

The carbon nano tube grafted polyurethane modified aramid fiber stab-resistant fiber is prepared into a block-shaped membrane material with the specification of 5 cm multiplied by 0.2 cm, and the dynamic stab-resistant performance is tested according to GA 68-2008 police stab-resistant clothing. The performance ratio of the maximum piercing force is shown in fig. 3.

Finally, it should be noted that: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; it will be understood by those skilled in the art that the present invention may be modified and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.