Method of preparing vinyl collagen microsphere polyamide fiber composite material

Patent metadata

Field	Value
Publication number	US-11746232-B2
Application number	US-202117498181-A
Country	US
Kind code	B2
Filing date	Oct 11, 2021
Priority date	Jan 4, 2021
Publication date	Sep 5, 2023
Grant date	Sep 5, 2023

Abstract

A method of preparing a vinyl collagen microsphere polyamide fiber composite material includes the following steps: step 1: modifying a collagen with methacrylic anhydride to obtain a vinyl collagen, then emulsifying and cross-linking the vinyl collagen to obtain vinyl collagen microspheres; step 2: treating a polyamide fiber substrate with formaldehyde to obtain a hydroxylated polyamide fiber substrate, treating the hydroxylated polyamide fiber with (3-mercaptopropyl)trimethoxysilane (MPS) to obtain a sulfhydrylated polyamide fiber substrate; and step 3: modifying the sulfhydrylated polyamide fiber substrate with the vinyl collagen microspheres to obtain the vinyl collagen microsphere polyamide fiber composite material.

First claim

The invention claimed is:

1. A method of preparing a vinyl collagen microsphere polyamide fiber composite material, comprising the following steps:
step 1: modifying a collagen with methacrylic anhydride to obtain a vinyl collagen, then emulsifying and cross-linking the vinyl collagen to obtain vinyl collagen microspheres;
step 2: treating a polyamide fiber substrate with formaldehyde to obtain a hydroxylated polyamide fiber substrate, treating the hydroxylated polyamide fiber substrate with (3-mercaptopropyl)trimethoxysilane (MPS) to obtain a sulfhydrylated polyamide fiber substrate; and
step 3: modifying the sulfhydrylated polyamide fiber substrate with the vinyl collagen microspheres to obtain the vinyl collagen microsphere polyamide fiber composite material.

2. The method according to claim 1 , wherein the step 1 comprises:
step 1.1: adding the collagen and a phosphate buffer solution into a flask, heating at 70° C. and stirring until the collagen is completely dissolved, lowering to 50° C., after 20 minutes adding methacrylic anhydride, reacting for 2 hours, wherein a volume ratio of methacrylic anhydride:the phosphate buffer solution is 3:500, dialyzing for 24 hours, freeze-drying for 12-24 hours to obtain the vinyl collagen, and storing the vinyl collagen in a desiccator for later use, wherein a ratio of the collagen:the phosphate buffer solution is 1 g:10 ml; and
step 1.2: preparing a vinyl collagen aqueous solution with a concentration of 15% to 40% (wt/wt), adding a liquid paraffin and a surfactant in a volume ratio of 50:1 into a three-necked flask and mixing, placing the three-necked flask in a water bath, stirring at 400-1200 rpm and heating the water bath to 60° C. at the speed of 1° C./min, after 10 minutes adding the vinyl collagen aqueous solution to the liquid paraffin and the surfactant, a volume ratio of the vinyl collagen aqueous solution to the liquid paraffin being 1:4-8, emulsifying for 20 minutes, transferring the three-necked flask to an ice bath at 0-10° C., after 15 minutes adding a glutaraldehyde aqueous solution and cross-linking for 2 hours, the glutaraldehyde aqueous solution added being 0.4%-1% (vol/vol) of the liquid paraffin, adding isopropanol, the isopropanol added being 1/10 (vol/vol) of the liquid paraffin, stirring for 10 minutes, stopping the cross-linking, centrifugating, washing with isopropanol, acetone, and water 3 times to remove impurities, freeze-drying to obtain the vinyl collagen microspheres;
wherein the glutaraldehyde aqueous solution has a concentration of 25% (wt/wt).

3. The method according to claim 2 , wherein, in the step 1.1, a pH of the phosphate buffer solution is 7.4.

4. The method according to claim 2 , wherein the step 1.2 further comprises: heating to 60° C. under agitation to aid solubility to obtain the vinyl collagen aqueous solution.

5. The method according to claim 1 , wherein the step 2 comprises:
step 2.1: ultrasonically cleaning the polyamide fiber substrate with acetone for 0.5 hour, the polyamide fiber substrate being a 55-mm-diameter polyamide fiber fabric disc, mixing a 85% (wt) phosphoric acid solution and a 40% (wt) formaldehyde solution at a volume ratio of 3:100 to obtain a solution A, immersing the polyamide fiber substrate in the solution A, reacting at 60° C. for 15 hours, rinsing the polyamide fiber substrate with water to obtain the hydroxylated polyamide fiber substrate;
step 2.2: mixing (3-mercaptopropyl)trimethoxysilane and isopropanol in a volume ratio of 7:1000 to obtain a solution B, placing the hydroxylated polyamide fiber substrate prepared in the step 2.1 into the solution B, reacting under nitrogen atomosphere at 70° C. for 12 hours, washing with isopropanol, and drying at 60° C. to obtain the sulfhydrylated polyamide fiber substrate.

6. The method according to claim 1 , wherein the step 3 comprises:
step 3.1: immersing the sulfhydrylated polyamide fiber substrate prepared in a 5 mmol/L tris(2-carboxyethyl)phosphine hydrochloride solution for 1 hour to obtain a product A; and
step 3.2: preparing a vinyl collagen microspheres aqueous solution with a concentration of 2%-18% (wt/wt), adding a photoinitiator to obtain a solution C, a weight ratio of the photoinitiator:the vinyl collagen microspheres aqueous solution being 0.006%-0.01%, immersing the product A prepared in the step 3.1 into the solution C, sonicating for 30 minutes, reacting under a UV lamp for 3-7 hours to obtain the vinyl collagen microsphere polyamide fiber composite material.

Assignees

• Xu Na
• Xing Yanmei
• Wang Xuechuan
• Univ Shaanxi Science & Tech

Inventors

• Xu Na
• Xing Yanmei
• Wang Xuechuan

Classifications

• C08L77/00 Primary

  Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain (of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08); Compositions of derivatives of such polymers · CPC title

• C08J3/247

  Heating methods · CPC title

• C08L89/06

  derived from leather or skin {, e.g. gelatin} · CPC title

• D06M10/001

  Treatment with visible light, infrared or ultraviolet, X-rays · CPC title

• D06M13/127

  Mono-aldehydes, e.g. formaldehyde; Monoketones · CPC title