Degradable elastic fiber and preparation method of knitted textile thereof

Abstract

The invention relates to the technical field of fibers, and discloses a degradable elastic fiber and a preparation method of a knitted textile thereof, nylon resin and modified silk fibroin are mixed, spinning is performed through a melt spinning machine, stretching and heat setting are performed through a drawing machine, and the degradable elastic fiber is obtained. A large number of amido bonds are introduced into the silk fibroin, the compatibility between the silk fibroin and polyamide nylon 66 becomes good, the silk fibroin is evenly dispersed in a nylon fiber matrix, and the fiber has very high elongation at break and breaking strength and has good elastic toughness and strength. The modified silk fibroin contains a large number of hydrophilic amido bonds, quaternary ammonium salt groups and hydroxyl groups, so that the nylon fiber has higher hydrophilicity, the moisture regain is obviously increased, and the silk fibroin has excellent biodegradability and can endow the fiber with certain biodegradability.

Description

Technical Field

[0001] This invention relates to the field of fiber technology, specifically to a method for preparing a biodegradable elastic fiber and its knitted textiles. Background Technology

[0002] Silk fibroin has good biocompatibility and biodegradability, as well as excellent hydrophilicity and numerous active functional groups, making it important in fibers, textiles, and plastics. Nylon fiber has high strength, good flexibility and elasticity, and strong abrasion resistance; however, nylon fiber has low hydrophilicity, resulting in knitted textiles with low moisture regain and poor hygroscopicity.

[0003] Modifying nylon fibers with silk fibroin can impart good biocompatibility, biodegradability, and hydrophilicity. Chinese patent application CN120683658A discloses a flexible nylon-silk fibroin composite fiber membrane with heat and moisture management function and its preparation method. The method involves electrospinning a blend of silk fibroin and nylon 66, resulting in fibers with excellent wet stability. However, the poor compatibility between silk fibroin and nylon affects the fiber's elasticity, strength, and other mechanical properties. Summary of the Invention

[0004] (I) Technical problem to be solved: In view of the shortcomings of the existing technology, the present invention provides a biodegradable elastic fiber, which solves the problems of nylon fiber and its knitted textiles being difficult to biodegrade and having poor hydrophilic and moisture-absorbing properties.

[0005] (II) To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a method for preparing biodegradable elastic fibers: (1) Add 3-dimethylamino-1-propanol and 2-bromoacetamide to isopropanol, stir the reaction, distill under reduced pressure, dissolve the product in an aqueous ethanol solution, recrystallize and purify to obtain 1-propanol acetamamido-N,N-dimethylammonium bromide, the reaction formula is: .

[0006] (2) Add silk fibroin to deionized water, heat and stir, then add sodium hydroxide, ethylene glycol diglycidyl ether, and 1-propanol acetamido-N,N-dimethylammonium bromide. Stir the reaction, pour the solution into a dialysis bag, and dialyze it with deionized water for purification. Dry the solution under vacuum to obtain modified silk fibroin. The reaction formula is: .

[0007] (3) Nylon resin and modified silk fibroin are mixed, spun by a melt spinning machine, stretched by a drawing machine, and heat-set to obtain biodegradable elastic fibers.

[0008] Preferably, in (1), the amount of 3-dimethylamino-1-propanol is 100 parts by weight and the amount of 2-bromoacetamide is 134-160 parts by weight.

[0009] Preferably, the reaction temperature in (1) is 70-85℃ and the reaction time is 24-36h.

[0010] Preferably, the temperature of the stirring reaction in (2) is 50-80℃ and the reaction time is 6-10h.

[0011] Preferably, in (2), the amount of silk fibroin is 100 parts by weight, the amount of sodium hydroxide is 1.4-6 parts by weight, the amount of ethylene glycol diglycidyl ether is 10-35 parts by weight, and the amount of 1-propanol acetamido-N,N-dimethylammonium bromide is 13-54 parts by weight.

[0012] Preferably, in (3), the amount of nylon resin is 75-90 parts by weight and the amount of modified silk fibroin is 10-25 parts by weight.

[0013] Preferably, in (3), the temperature of zones 1-4 of the melt spinning machine is 245-260℃ and the spinning rate is 800-1500m / min.

[0014] Preferably, in (3), the stretching ratio of S2 is 3-3.5 times.

[0015] Preferably, (3) the heat setting temperature is 90-100℃.

[0016] Preferably, biodegradable elastic fibers can be made into biodegradable moisture-wicking knitted textiles through processes such as knitting and spinning.

[0017] (III) Beneficial technical effects: This invention utilizes ethylene glycol diglycidyl ether as a crosslinking agent. The two epoxy groups are crosslinked with the amino groups of silk fibroin and the hydroxyl groups of 1-propanol acetamido-N,N-dimethylammonium bromide, respectively, to obtain modified silk fibroin containing amide bonds, quaternary ammonium salts and a large number of hydroxyl groups. Then, it is blended and spun with nylon 66 resin to obtain biodegradable elastic fibers. The introduction of a large number of amide bonds into the silk fibroin improves its compatibility with polyamide nylon 66, allowing the silk fibroin to be uniformly dispersed in the nylon fiber matrix, giving the fiber high elongation at break and breaking strength, as well as good elasticity, toughness and strength.

[0018] The silk fibroin of the present invention introduces a large number of hydrophilic amide bonds, quaternary ammonium salt groups and hydroxyl groups, which makes the fiber more hydrophilic and significantly increases the moisture regain. In addition, the silk fibroin has excellent biodegradability and can endow the fiber with certain biodegradability. Detailed Implementation

[0019] To facilitate understanding of the present invention, it will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. Rather, these embodiments or examples are provided to make the disclosure of the present invention more thorough and complete.

[0020] Example 1 (1) Add 50g of 3-dimethylamino-1-propanol and 67g of 2-bromoacetamide to 700mL of isopropanol, heat to 85℃, stir and reflux for 24h, distill under reduced pressure, dissolve the product in an aqueous ethanol solution, recrystallize and purify to obtain 1-propanolacetamido-N,N-dimethylammonium bromide.

[0021] (2) Add 200g of silk fibroin to 3L of deionized water, heat to 60℃, stir, add 2.8g of sodium hydroxide, 20g of ethylene glycol diglycidyl ether, and 26g of 1-propanol acetamido-N,N-dimethylammonium bromide, stir and react for 6h, pour the solution into a dialysis bag, dialyze and purify with deionized water, and dry the solution under vacuum to obtain modified silk fibroin.

[0022] (3) Mix 900g of nylon 66 resin and 100g of modified silk fibroin, and spin them through a melt spinning machine. The temperatures of zones 1-4 are 245℃, 255℃, 260℃, and 260℃, and the spinning rate is 1500m / min. Stretch the fibers using a drawing machine with a stretching ratio of 3 times, and heat set at 100℃ to obtain biodegradable elastic fibers.

[0023] Example 2 (1) Add 50g of 3-dimethylamino-1-propanol and 80g of 2-bromoacetamide to 800mL of isopropanol, heat to 70℃, stir and reflux for 36h, distill under reduced pressure, dissolve the product in an aqueous ethanol solution, recrystallize and purify to obtain 1-propanolacetamido-N,N-dimethylammonium bromide.

[0024] (2) Add 200g of silk fibroin to 3L of deionized water, heat to 80℃, stir, add 5.6g of sodium hydroxide, 35g of ethylene glycol diglycidyl ether, and 60g of 1-propanol acetamido-N,N-dimethylammonium bromide, stir and react for 6h, pour the solution into a dialysis bag, dialyze and purify with deionized water, and vacuum dry the solution to obtain modified silk fibroin.

[0025] (3) Mix 850g of nylon 66 resin and 150g of modified silk fibroin, and spin them through a melt spinning machine. The temperatures of zones 1-4 are 245℃, 255℃, 260℃, and 260℃, and the spinning rate is 1200m / min. Stretch the fibers using a drawing machine with a stretching ratio of 3.5 times, and heat set at 90℃ to obtain biodegradable elastic fibers.

[0026] Example 3 (1) Prepare 1-propanol acetamido-N,N-dimethylammonium bromide according to the method of Example 1.

[0027] (2) Add 200g of silk fibroin to 4L of deionized water, heat to 50℃, stir, add 7.5g of sodium hydroxide, 52g of ethylene glycol diglycidyl ether, and 83g of 1-propanol acetamido-N,N-dimethylammonium bromide, stir and react for 10h, pour the solution into a dialysis bag, dialyze and purify with deionized water, and vacuum dry the solution to obtain modified silk fibroin.

[0028] (3) Mix 800g of nylon 66 resin and 200g of modified silk fibroin, and spin them through a melt spinning machine. The temperatures of zones 1-4 are 245℃, 255℃, 260℃ and 255℃, respectively. The spinning rate is 800m / min. Stretch the fibers using a drawing machine with a stretching ratio of 3.5 times. Heat set at 100℃ to obtain biodegradable elastic fibers.

[0029] Example 4 (1) Prepare 1-propanol acetamido-N,N-dimethylammonium bromide according to the method of Example 1.

[0030] (2) Add 200g of silk fibroin to 4L of deionized water, heat to 70℃, stir, add 12g of sodium hydroxide, 70g of ethylene glycol diglycidyl ether, and 108g of 1-propanol acetamido-N,N-dimethylammonium bromide, stir and react for 9h, pour the solution into a dialysis bag, dialyze and purify with deionized water, and vacuum dry the solution to obtain modified silk fibroin.

[0031] (3) Mix 750g of nylon 66 resin and 250g of modified silk fibroin, and spin them through a melt spinning machine. The temperatures of zones 1-4 are 245℃, 255℃, 260℃ and 255℃, respectively. The spinning rate is 800m / min. Stretch the fibers using a stretching machine with a stretching ratio of 3 times. Heat set at 90℃ to obtain biodegradable elastic fibers.

[0032] Comparative Example 1 (1) Mix 900g of nylon 66 resin and 100g of silk fibroin, and spin them through a melt spinning machine. The temperatures of zones 1-4 are 245℃, 255℃, 260℃, and 260℃, and the spinning rate is 1500m / min. Stretch the fibers using a drawing machine with a stretching ratio of 3 times, and heat set at 100℃ to obtain the fibers.

[0033] Comparative Example 2 (1) Add 200g of silk fibroin to 3L of deionized water, heat to 60℃, stir, add 2.8g of sodium hydroxide, 20g of ethylene glycol diglycidyl ether and 26g of hydroxyacetamide, stir and react for 6h, pour the solution into a dialysis bag, dialyze and purify with deionized water, and vacuum dry the solution to obtain modified silk fibroin.

[0034] (2) Mix 900g of nylon 66 resin and 100g of modified silk fibroin, and spin them through a melt spinning machine. The temperatures of zones 1-4 are 245℃, 255℃, 260℃, and 260℃, and the spinning rate is 1500m / min. Stretch the fibers using a drawing machine with a stretching ratio of 3 times, and heat set at 100℃ to obtain biodegradable elastic fibers.

[0035] Comparative Example 3 (1) Add 50g of 3-dimethylamino-1-propanol and 67g of 1-bromopropane to 700mL of isopropanol, heat to 85℃, stir and reflux for 24h, distill under reduced pressure, wash the product with petroleum ether, and dry to obtain 1-propanolpropyl-N,N-dimethylammonium bromide, with the structural formula: .

[0036] (2) Add 200g of silk fibroin to 3L of deionized water, heat to 60℃, stir, add 2.8g of sodium hydroxide, 20g of ethylene glycol diglycidyl ether, and 26g of 1-propanol propyl-N,N-dimethylammonium bromide, stir for 6h, pour the solution into a dialysis bag, dialyze to deionized water for purification, and vacuum dry the solution to obtain modified silk fibroin.

[0037] (3) Mix 900g of nylon 66 resin and 100g of modified silk fibroin, and spin them through a melt spinning machine. The temperatures of zones 1-4 are 245℃, 255℃, 260℃, and 260℃, and the spinning rate is 1500m / min. Stretch the fibers using a drawing machine with a stretching ratio of 3 times, and heat set at 100℃ to obtain biodegradable elastic fibers.

[0038] Table 1 Fiber Performance Tests

[0039] In Comparative Example 1, the nylon 66 resin and silk fibroin showed poor compatibility, resulting in low elongation at break and tensile strength, as well as poor elasticity, toughness, and strength. Example 1 utilized ethylene glycol diglycidyl ether as a crosslinking agent, reacting 1-propanol acetamido-N,N-dimethylammonium bromide with the amino and hydroxyl groups of silk fibroin. This introduced a large number of amide bonds, quaternary ammonium salt groups, and hydroxyl groups into the silk fibroin. The amide bonds improved the compatibility between silk fibroin and polyamide nylon 66, allowing the silk fibroin to be uniformly dispersed in the nylon fiber matrix, maintaining good elasticity, toughness, and strength, and exhibiting higher elongation at break and tensile strength. Furthermore, the introduction of numerous hydrophilic amide bonds, quaternary ammonium salt groups, and hydroxyl groups into the silk fibroin increased the fiber's hydrophilicity and significantly increased moisture regain.

[0040] Comparative Example 2 utilizes the cross-linking reaction of silk fibroin with the hydroxyl groups of ethylene glycol diglycidyl ether and hydroxyacetamide to obtain modified silk fibroin that does not contain quaternary ammonium salt groups and has a lower moisture regain rate.

[0041] Comparative Example 3 involved cross-linking silk fibroin with ethylene glycol diglycidyl ether and the hydroxyl groups of 1-propanol propyl-N,N-dimethylammonium bromide. The resulting modified silk fibroin did not contain amide bonds, had poor compatibility with nylon 66 resin, and exhibited lower fiber elongation at break and breaking strength, as well as a lower moisture regain than in Example 1.

[0042] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing biodegradable elastic fibers, characterized in that, The preparation method is as follows: S1. Add silk fibroin to deionized water, heat and stir, then add sodium hydroxide, ethylene glycol diglycidyl ether, and 1-propanol acetamido-N,N-dimethylammonium bromide. Stir the reaction, pour the solution into a dialysis bag, dialyze and purify, and vacuum dry the solution to obtain modified silk fibroin. S2. Nylon resin and modified silk fibroin are mixed, spun through a melt spinning machine, stretched through a drawing machine, and heat-set to obtain biodegradable elastic fibers.

2. The method for preparing biodegradable elastic fibers according to claim 1, characterized in that, The temperature of the stirring reaction in S1 is 50-80℃, and the reaction time is 6-10h.

3. The method for preparing biodegradable elastic fibers according to claim 1, characterized in that, In S1, the amount of silk fibroin is 100 parts by weight, the amount of sodium hydroxide is 1.4-6 parts by weight, the amount of ethylene glycol diglycidyl ether is 10-35 parts by weight, and the amount of 1-propanol acetamido-N,N-dimethylammonium bromide is 13-54 parts by weight.

4. The method for preparing biodegradable elastic fibers according to claim 1, characterized in that, The preparation method of 1-propanol acetamido-N,N-dimethylammonium bromide is as follows: 100 parts by weight of 3-dimethylamino-1-propanol and 134-160 parts by weight of 2-bromoacetamide are added to isopropanol, the mixture is stirred and reacted, and the product is distilled under reduced pressure and recrystallized to obtain 1-propanol acetamido-N,N-dimethylammonium bromide.

5. The method for preparing biodegradable elastic fibers according to claim 4, characterized in that, In the preparation method of 1-propanol acetamido-N,N-dimethylammonium bromide, the reaction temperature is 70-85℃ and the reaction time is 24-36h.

6. The method for preparing biodegradable elastic fibers according to claim 1, characterized in that, The amount of nylon resin in S2 is 75-90 parts by weight, and the amount of modified silk fibroin is 10-25 parts by weight.

7. The method for preparing biodegradable elastic fibers according to claim 1, characterized in that, The temperature of zones 1-4 of the melt spinning machine in S2 is 245-260℃, and the spinning rate is 800-1500m / min.

8. The method for preparing biodegradable elastic fibers according to claim 1, characterized in that, The stretching ratio in S2 is 3-3.5 times, and the heat setting temperature is 90-100℃.

9. A biodegradable elastic fiber obtained by the preparation method according to any one of claims 1-8.

10. A knitted textile made of the biodegradable elastic fiber as described in claim 9.

Images