CN107869046B - A kind of silk protein modification method of polyester fabric - Google Patents

Abstract

The present invention provides a method for modifying fibroin of polyester fabric, comprising: A) desizing the polyester fabric to obtain a desizing fabric; B) treating the desizing fabric with sodium hydroxide and washing to obtain an alkali treatment The finished fabric; C) The alkali-treated fabric is immersed in a cross-linking agent solution, and mixed and reacted with silk fibroin with a molecular weight of 1000-5000 Da. In the modification method provided by the present invention, the desizing treated fabric is treated with sodium hydroxide, and the setting of the above-mentioned alkali treatment enables the release of reaction sites on the molecular chain of the polyester fiber; at the same time, the present invention adopts the limited 1000-5000Da molecular weight of silk fibroin. The protein-modified alkali-treated fabric uses the principle of covalent bonding to make the above-mentioned specific small molecular weight silk fibroin firmly introduced into the fiber surface of the polyester fabric, improving the coolness, softness, antistatic properties, and mechanical properties of the polyester fabric. Good, good stability of silk protein.

Description

A kind of silk protein modification method of polyester fabric

technical field

The invention relates to the technical field of textiles, in particular to a method for modifying fibroin of polyester fabrics.

Background technique

Polyester is the fiber with the highest output of textile fibers and the most important raw material for textile products, accounting for more than 70% of the processing volume of textile fibers. Polyester fiber is a chemical synthetic fiber because of its high breaking strength, good light resistance, and rigid products. It is widely used in clothing and home textiles, mainly including coats, curtains, sofa fabrics, car interior accessories, etc., but polyester is a super-hydrophobic fiber with extremely poor hygroscopicity and rigidity, which limits its application in home textiles and some clothing fields. , such as summer cool clothing, underwear and bedding, etc.

The research on silk fibroin-coated polyester has been reported in the prior art, and the polyester fiber or fabric coating is brittle, easy to break and fall off, and will affect the surface structure and even the air permeability of the original fabric. In addition, the silk fibroin coating reported in the literature is low in weight gain, unsatisfactory in water washing resistance, or still very low in moisture regain. So there is no market application.

SUMMARY OF THE INVENTION

In view of this, the technical problem to be solved by the present invention is to provide a method for modifying fibroin of polyester fabric, and the polyester fabric modified by the modification method provided by the present invention has good mechanical properties and good stability.

The invention provides a silk protein modification method for polyester fabrics, comprising:

A) Desizing the polyester fabric to obtain a desizing fabric;

B) the desizing fabric is treated with sodium hydroxide, and washed to obtain the fabric after the alkali treatment;

C) Immerse the alkali-treated fabric in the cross-linking agent solution, and mix and react with silk fibroin with a molecular weight of 1000-5000 Da.

Preferably, the crosslinking agent includes carbodiimide.

Preferably, the mass percentage of the carbodiimide in the silk fibroin is 20% to 40%.

Preferably, the desizing in step A) is specifically a desizing treatment with sodium carbonate; the concentration of the sodium carbonate solution is 6 g/L; the desizing treatment temperature is 90-100°C; the desizing treatment time is 1h.

Preferably, the mass concentration of the sodium hydroxide in step B) is 5% to 30%; the treatment temperature of the sodium hydroxide is 30 to 40° C.; the treatment time of the sodium hydroxide is 1 to 3 hours.

Preferably, the reaction temperature in step C) is 25-35° C.; the reaction time is 1-3 h.

Preferably, the silk fibroin with a molecular weight of 1000-5000 Da is prepared according to the following method:

a) Bombyx mori silk is degummed with sodium carbonate, then added with a neutral salt solution to dissolve, to prepare a silk fibroin solution;

Equilibrate Sephadex G50 and G25 columns for use;

b) adding the silk fibroin solution to Sephadex G50 column of dextran, eluting the silk fibroin with sterile water, and collecting the desalted silk fibroin aqueous solution in separate tubes;

c) Use SDS-PAGE electrophoresis or mass spectrometry for screening step b) Collect silk fibroin below 10 kD in the tube, add it to Sephadex G25 column again, elute silk fibroin with sterile water, collect in separate tubes, and screen to obtain 1000～ 5000Da small molecular weight silk fibroin.

Preferably, the neutral salt solution in step a) is selected from lithium bromide or calcium chloride-ethanol; the dissolving time is 5-7 hours; the concentration of the silk fibroin dissolving solution is 10-50 mg/mL.

Preferably, in the screening step b) in step c), after collecting the silk fibroin below 10 kD in the tube, freeze-drying is further included, and then it is prepared into an aqueous solution of 30-80 mg/mL.

Preferably, the elution flow rate of step b) is 200-400 mL/h; the elution flow rate of step c) is 30-70 mL/h.

Compared with the prior art, the present invention provides a method for modifying fibroin of polyester fabric, comprising: A) desizing the polyester fabric to obtain a desizing fabric; B) using sodium hydroxide for the desizing fabric treatment to obtain an alkali-treated fabric; C) immersing the alkali-treated fabric in a cross-linking agent solution, and mixing and reacting with silk fibroin with a molecular weight of 1000-5000 Da. In the modification method provided by the present invention, the desizing treated fabric is treated with sodium hydroxide, and the setting of the above-mentioned alkali treatment enables the release of reaction sites on the molecular chain of the polyester fiber; at the same time, the limited relative molecular weight of 1000-5000Da is used in the present invention. And the concentrated distribution of the silk fibroin graft modified alkali-treated fabric uses the principle of covalent bonding to make the above-mentioned specific small molecular weight silk fibroin firmly introduced into the fiber surface of the polyester fabric, improving the coolness and softness of the polyester fabric. , Antistatic, good mechanical properties, good stability of silk protein.

Detailed ways

The invention provides a silk protein modification method for polyester fabrics, comprising:

A) Desizing the polyester fabric to obtain a desizing fabric;

B) the desizing fabric is treated with sodium hydroxide, and washed to obtain the fabric after the alkali treatment;

C) Immerse the alkali-treated fabric in the cross-linking agent solution, and mix and react with silk fibroin with a molecular weight of 1000-5000 Da.

The present invention does not limit the polyester fabric, which can be defined as polyester fabric as known to those skilled in the art. In the present invention, the source is not limited, and it may be commercially available.

In the present invention, the polyester fabric is firstly treated by desizing to obtain a desizing fabric.

In the present invention, the desizing treatment preferably adopts sodium carbonate desizing treatment; preferably, the polyester fabric is heated in an aqueous solution of sodium carbonate. The heating method is preferably boiling heating.

The concentration of the sodium carbonate solution is preferably 6 g/L; the desizing treatment temperature is preferably 90-100° C.; the desizing treatment time is preferably 1 h.

After heating, washing, dehydration, and drying are preferably performed.

The washing in the present invention is preferably washing with tap water, and the washing method is not limited in the present invention, and those skilled in the art are well-known; the dehydration method is not limited in the present invention, and those skilled in the art are well-known; The present invention does not limit the drying method, and those skilled in the art are well-known; it can be air-drying or drying.

After drying, a desizing fabric is obtained, and the desizing fabric is treated with sodium hydroxide.

In the present invention, the mass concentration of the sodium hydroxide is preferably 5% to 30%; the treatment temperature of the sodium hydroxide is preferably 30 to 40°C; the treatment time of the sodium hydroxide is preferably 1 to 3h; More preferably, it is 1 to 2 hours.

The present invention does not limit the source of the sodium hydroxide, and it can be commercially available.

After the sodium hydroxide treatment, it is preferably washed and dried.

The washing in the present invention is preferably washing with tap water, and the washing method is not limited in the present invention, as long as those skilled in the art are well-known; the drying method in the present invention is not limited, and those skilled in the art are familiar with it. ; Can be air-dried or tumble dried.

After the fabric is washed and dried, an alkali-treated fabric is obtained.

After the alkali treatment is completed, the alkali-treated fabric is immersed in a cross-linking agent solution, and mixed and reacted with silk fibroin with a molecular weight of 1000-5000 Da to obtain a polyester fabric modified with silk protein.

According to the present invention, the cross-linking agent includes carbodiimide; the cross-linking agent may also include N-acyl succinimide; wherein, the mass percentage of the carbodiimide in silk fibroin is preferably 20% ~40%; more preferably 25%. The mass percentage of the N-acyl succinimide in the silk fibroin is preferably 10%.

According to the present invention, after dipping, the prepared silk fibroin with a molecular weight of 1000-5000 Da is added to carry out the grafting reaction, and the final concentration of the silk fibroin solution is preferably 0.5-5%;

The reaction temperature is preferably 25-35°C; the reaction time is preferably 1-3h.

After the grafting reaction, drying, washing, and drying again are preferred.

The drying in the present invention is preferably air-drying; the washing is preferably water rinsing; the re-drying is preferably air-drying. The present invention does not limit the specific operations of the drying and rinsing, as long as those skilled in the art are well-known.

In the present invention, the silk fibroin is a relatively small molecular weight and concentratedly distributed silk fibroin.

The invention creatively adopts the above-defined small molecular weight silk fibroin to graft modified alkali-treated fabric, and uses the principle of covalent bonding to make the above-mentioned specific small molecular weight silk fibroin firmly introduced into the fiber surface of the polyester fabric, improving the polyester fiber surface. The coolness, softness, antistatic properties and gloss of the fabric improve the affinity of the skin, and at the same time have good mechanical properties and good silk protein stability.

The present invention does not limit the source of the silk fibroin with a molecular weight of 1000-5000 Da, which can be commercially available, and is preferably prepared by the following method:

a) Bombyx mori silk is degummed with sodium carbonate, then added with a neutral salt solution to dissolve, to prepare a silk fibroin solution;

Equilibrate Sephadex G50 and G25 columns for use;

b) adding the silk fibroin solution to Sephadex G50 column of dextran, eluting the silk fibroin with sterile water, and collecting the desalted silk fibroin aqueous solution in separate tubes;

c) Use SDS-PAGE electrophoresis or mass spectrometry for screening step b) Collect silk fibroin below 10 kD in the tube, add it to Sephadex G25 column again, elute silk fibroin with sterile water, collect in separate tubes, and screen to obtain 1000～ 5000Da small molecular weight silk fibroin.

In the present invention, the silkworm silk is first degummed by using sodium carbonate; preferably, the silkworm silk is put into an aqueous sodium carbonate solution according to a specific bath ratio, treated, washed and dried to obtain the degummed silk.

The present invention does not limit the silkworm silk, and the silkworm raw silk well known to those skilled in the art may be commercially available.

The bath ratio of the present invention is preferably 1:50 (g/mL); the mass concentration of the sodium carbonate aqueous solution is preferably 0.2%; the treatment temperature is preferably 98-100°C; the treatment times is preferably 1-5 times; more preferably 2 to 3 times; the treatment time for each time is preferably 30 min.

After the treatment is completed, it is washed and dried to obtain degummed silk.

The cleaning in the present invention is preferably deionized water washing, and the present invention does not limit the cleaning method, and those skilled in the art are familiar with it; The drying method is not limited, and those skilled in the art are well-known; it can be drying in an oven. The drying temperature is preferably 65°C.

The degummed silk is then dissolved in a neutral salt solution to prepare a silk fibroin solution.

In the present invention, the neutral salt solution is preferably selected from lithium bromide or calcium chloride-ethanol; the bath ratio of the silk to the neutral salt solution is preferably 1:15-1:20 (g/mL);

The concentration of the lithium bromide solution is preferably 9-10M; in the calcium chloride-ethanol, the molar ratio of calcium chloride and ethanol is preferably 1:2;

The dissolving time is 5-7 hours; the dissolving temperature is preferably 60-70°C; more preferably 65-70°C; the concentration of the obtained silk fibroin dissolving solution is preferably 10-50 mg/mL.

Sephadex G50 and G25 columns were equilibrated for use. The present invention does not limit the sources of the dextran Sephadex G50 and G25 columns, which may be commercially available or self-made.

Preferably, the specific steps are: boiling the dextran Sephadex G50 and G25 with sterilized deionized water until fully expanded, continuously pouring them into a hollow column made of glass, settling and equilibrating the column material with sterilized deionized water; more preferably Specifically: put dextran G-50 and G-25 into deionized water respectively, take a boiling water bath for 1.5 to 2 hours, and after cooling at room temperature, use a glass rod to drain into a glass empty column, and settle naturally for 2 to 3 hours Then, pressurize the column with a peristaltic pump and equilibrate the column three times with 5 column volumes of deionized water.

The volume of the prepared column bed according to the present invention is preferably 2 cm×60 cm.

After equilibration, the silk fibroin solution was added to a Sephadex G50 dextran column, the silk fibroin was eluted with sterile water, and the desalted silk fibroin aqueous solution was collected in separate tubes.

Preferably, when the equilibrium water drops to the surface of the column material for the last time, add 5 to 15 mL of the silk fibroin mixed solution with a dissolved concentration of 10 to 50 mg/mL to the dextran G-50. When it completely enters the surface of the column material, continue to elute with sterile deionized water. The peristaltic pump controls the flow rate of the eluent, and collects the effluent in separate tubes until the silk fibroin is exhausted.

The elution flow rate is preferably 200-400 mL/h; more preferably 250-350 mL/h.

Use SDS-PAGE electrophoresis or mass spectrometry to screen silk fibroin below 10 kD in the collection tube in step b).

The present invention does not limit the specific manner of collecting silk fibroin below 10 kD in the SDS-PAGE electrophoresis or mass spectrometry screening step b), which is well known to those skilled in the art.

In the present invention, the screening step b) collecting the silk fibroin below 10 kD in the tube also includes freeze-drying, and then preparing it into a 30-80 mg/mL aqueous solution. Then, the filtration in the present invention is preferably a 0.45 μm membrane filtration.

The present invention does not limit the specific manner of the freeze-drying, which is well known to those skilled in the art.

The molecular weight of silk fibroin below 10 kD was further separated by lyophilization and then dissolving.

After filtration, the filtered solution was added to a Sephadex G25 column of dextran, and the silk fibroin was eluted with sterile water, collected in separate tubes, and screened to obtain a small molecular weight silk fibroin of 1000-5000 Da.

The flow rate of the elution in the present invention is preferably 30-70 mL/h; more preferably 35-50 mL/h.

After elution, SDS-PAGE electrophoresis or mass spectrometry was used to screen and collect small molecular weight silk fibroin of 1000-5000 Da in the tube, and then freeze-dried for storage.

The present invention can obtain the small molecular weight silk fibroin of 1000-5000 Da in a simpler and more precise manner by adopting the above method.

The present invention does not limit the specific methods of the screening and freeze-drying, as long as those skilled in the art are well-known.

The present invention provides a method for modifying fibroin of polyester fabric, comprising: A) desizing the polyester fabric to obtain a desizing fabric; B) treating the desizing fabric with sodium hydroxide, washing and drying to obtain a Alkali-treated fabric; C) Immerse the alkali-treated fabric in a cross-linking agent solution, and mix and react with silk fibroin with a molecular weight of 1000-5000 Da. In the modification method provided by the present invention, the desizing treated fabric is treated with sodium hydroxide, and the setting of the above-mentioned alkali treatment enables the release of reaction sites on the molecular chain of the polyester fiber; The concentrated distribution of the silk fibroin graft modified alkali-treated fabric uses the principle of covalent bonding to make the above-mentioned specific molecular weight silk fibroin firmly introduced into the fiber surface of the polyester fabric, improving the coolness, softness, and resistance of the polyester fabric. Static and gloss, improve skin affinity, good mechanical properties and good silk protein stability.

The surface of the polyester fabric obtained by the modification of the invention is soft, smooth and cool, and has silk-like skin affinity, and the product is mainly used in the development of high-end underwear, summer clothes and bedding.

The present invention preferably adopts the following method to measure the mechanical properties of the fabric:

The silk fibroin-modified polyester fabric was cut into 15cm×30cm samples, which were measured by a material mechanical property testing machine.

In order to further illustrate the present invention, the fibroin modification method of the polyester fabric provided by the present invention will be described in detail below with reference to the examples.

Example 1

(1) Put the silkworm raw silk into a sodium carbonate aqueous solution with a concentration of 0.2% at a bath ratio of 1:50 (g/mL), and treat it three times at 98 to 100 ° C for 30 minutes each time, and then use deionized water. The silk is fully cleaned, stretched, and dried in an oven to obtain degummed Bombyx mori silk fibroin fibers.

(2) Weigh the degummed Bombyx mori silk fibroin and dissolve it in an aqueous solution of calcium chloride-ethanol with a molar ratio of 1:2 at a bath ratio of 1:20 (g/mL), and dissolve it at 70°C for 5 to 7 hours to obtain Bombyx mori Dissolve the mixed solution.

(3) Weigh dextran G-50 and G-25 and put them in sufficient deionized water, respectively, and boil them in water for 1.5 hours. After cooling at room temperature, use a glass rod to drain into an empty column made of glass material to prepare a column bed volume. 2 cm × 60 cm, and the column was equilibrated three times with deionized water of 5 times the column volume after natural sedimentation for 2 hours.

(4) When the equilibrium water drops to the surface of the column material for the last time, add 5-15ml (10-50mg/ml) of the dissolved silk fibroin mixed solution to the dextran G-50. When the silk fibroin mixed solution completely enters the When it reaches the surface of the column material, continue to elute with sterilized deionized water, and the peristaltic pump controls the flow rate of the eluent to 300 mL/h; the effluent is collected in separate tubes until the silk fibroin is exhausted.

(5) Use SDS-PAGE electrophoresis or mass spectrometry to identify the molecular weight distribution of each tube, mix and freeze-dry the silk fibroin solution with a molecular weight of less than 10kDa, then configure it into an aqueous solution of 30-80mg/ml, and filter with a 0.45μm membrane to remove microparticles .

(6) Similar to step (4), add an appropriate amount of the silk fibroin aqueous solution of step (5) to the column material of G-25, the peristaltic pump controls the flow rate of the eluent to 50 mL/h, and collects the effluent in separate tubes until the silk fibroin is exhausted. , to obtain an aqueous solution of silk fibroin with a molecular weight of 1000-5000 Da, and finally freeze-dried for storage.

(7) Boil the woven polyester fabric with 6g/1L sodium carbonate aqueous solution at 100°C for about 1 hour, take it out, wash it repeatedly with tap water, and dehydrate it to dry. Then treat the polyester fabric with 10% sodium hydroxide solution at 30°C for 1 to 2 hours, rinse it with tap water, and then immerse it in a certain mass concentration of carbodiimide and N-hydroxysuccinimide (the mass is about adding silk fibroin, respectively). 25%, 10% of the protein content), soak for about 1 hour, add the dry silk fibroin powder obtained in step 6 (the final mass concentration of silk fibroin is 0.5%) to dissolve, react for 3 hours, take out to dry and rinse , and then dry.

(8) The silk fibroin-modified polyester fabric is cut into a sample of 15cm×30cm, and the breaking strength measured by the material mechanical property testing machine is about 95% of the original fabric, and the elongation at break is about 97% of the original fabric.

(9) The weight gain rate of silk fibroin on the polyester fabric measured by the weighing method is 3.1%, which is significantly higher than the weight gain rate of Comparative Example 1, which is 0.9%. After immersing the silk fibroin-modified fabric in warm water at 37° C. and shaking for 24 hours, the dissolution rate of silk fibroin was measured to be less than 5%.

Example 2

(1) Put the silkworm raw silk into a sodium carbonate aqueous solution with a concentration of 0.2% at a bath ratio of 1:50 (g/mL), and treat it three times at 98 to 100 ° C for 30 minutes each time, and then use deionized water. The silk is fully cleaned, stretched, and dried in an oven to obtain degummed Bombyx mori silk fibroin fibers.

(2) Weigh the degummed Bombyx mori silk fibroin and dissolve it in an aqueous solution of calcium chloride-ethanol with a molar ratio of 1:2 at a bath ratio of 1:20 (g/mL), and dissolve it at 70°C for 5 to 7 hours to obtain Bombyx mori Dissolve the mixed solution.

(3) Weigh dextran G-50 and G-25 and put them in sufficient deionized water, respectively, and boil them in water for 1.5 hours. After cooling at room temperature, use a glass rod to drain into an empty column made of glass material to prepare a column bed volume. 2 cm × 60 cm, and the column was equilibrated three times with deionized water of 5 times the column volume after natural sedimentation for 2 hours.

(4) When the equilibrium water drops to the surface of the column material for the last time, add 5-15ml (10-50mg/ml) of the dissolved silk fibroin mixed solution to the dextran G-50. When the silk fibroin mixed solution completely enters the When it reaches the surface of the column material, continue to elute with sterilized deionized water, and the peristaltic pump controls the flow rate of the eluent to 300 mL/h; the effluent is collected in separate tubes until the silk fibroin is exhausted.

(5) Use SDS-PAGE electrophoresis or mass spectrometry to identify the molecular weight distribution of each tube, mix and freeze-dry the silk fibroin solution with a molecular weight of less than 10kDa, then configure it into an aqueous solution of 30-80mg/ml, and filter with a 0.45μm membrane to remove microparticles .

(6) Similar to step (4), add an appropriate amount of the silk fibroin aqueous solution of step (5) to the column material of G-25, the peristaltic pump controls the flow rate of the eluent to 50 mL/h, and collects the effluent in separate tubes until the silk fibroin is exhausted. , to obtain an aqueous solution of silk fibroin with a molecular weight of 1000-5000 Da, and finally freeze-dried for storage.

(7) Boil the woven polyester fabric with 6g/1L sodium carbonate aqueous solution at 100°C for about 1 hour, take it out, wash it repeatedly with tap water, and dehydrate it to dry. Then treat the polyester fabric with 10% sodium hydroxide solution at 30°C for 2 to 3 hours, rinse it with tap water, and then immerse it in a certain mass concentration of carbodiimide and N-hydroxysuccinimide (the mass is about adding silk fibroin, respectively). 25%, 10% of the protein content), soak for about 1 hour, add the silk fibroin dry powder obtained in step 6 (the final mass concentration of silk fibroin is 1%) to dissolve, react for 3 hours, take it out to dry and rinse , and then dry.

(8) The silk fibroin-modified polyester fabric is cut into a sample of 15cm×30cm, and the breaking strength measured by the material mechanical property testing machine is about 91% of the original fabric, and the elongation at break is about 92% of the original fabric.

(9) The weight gain rate of silk fibroin on the polyester fabric measured by the weighing method is 5.8%, which is significantly higher than that of Comparative Example 2, which is 0.92%. After immersing the silk fibroin-modified fabric in warm water at 37° C. and shaking for 24 hours, the dissolution rate of silk fibroin was measured to be less than 8%.

Example 3

(1) Put the silkworm raw silk into a sodium carbonate aqueous solution with a concentration of 0.2% at a bath ratio of 1:50 (g/mL), and treat it three times at 98 to 100 ° C for 30 minutes each time, and then use deionized water. The silk is fully cleaned, stretched, and dried in an oven to obtain degummed Bombyx mori silk fibroin fibers.

(2) Weigh the degummed Bombyx mori silk fibroin and dissolve it in an aqueous solution of calcium chloride-ethanol with a molar ratio of 1:2 at a bath ratio of 1:20 (g/mL), and dissolve it at 70°C for 5 to 7 hours to obtain Bombyx mori Dissolve the mixed solution.

(3) Weigh dextran G-50 and G-25 and put them in sufficient deionized water, respectively, and boil them in water for 1.5 hours. After cooling at room temperature, use a glass rod to drain into an empty column made of glass material to prepare a column bed volume. 2 cm × 60 cm, and the column was equilibrated three times with deionized water of 5 times the column volume after natural sedimentation for 2 hours.

(4) When the equilibrium water drops to the surface of the column material for the last time, add 5-15ml (10-50mg/ml) of the dissolved silk fibroin mixed solution to the dextran G-50. When the silk fibroin mixed solution completely enters the When it reaches the surface of the column material, continue to elute with sterilized deionized water, and the peristaltic pump controls the flow rate of the eluent to 300 mL/h; the effluent is collected in separate tubes until the silk fibroin is exhausted.

(5) Use SDS-PAGE electrophoresis or mass spectrometry to identify the molecular weight distribution of each tube, mix and freeze-dry the silk fibroin solution with a molecular weight of less than 10kDa, then configure it into an aqueous solution of 30-80mg/ml, and filter with a 0.45μm membrane to remove microparticles .

(6) Similar to step (4), add an appropriate amount of the silk fibroin aqueous solution of step (5) to the column material of G-25, the peristaltic pump controls the flow rate of the eluent to 50 mL/h, and collects the effluent in separate tubes until the silk fibroin is exhausted. , to obtain an aqueous solution of silk fibroin with a molecular weight of 1000-5000 Da, and finally freeze-dried for storage.

(7) Boil the woven polyester fabric with 6g/1L sodium carbonate aqueous solution at 100°C for about 1 hour, take it out, wash it repeatedly with tap water, and dehydrate it to dry. Then treat the polyester fabric with 10% sodium hydroxide solution at 30°C for 1 to 2 hours, rinse it with tap water, and then immerse it in a certain mass concentration of carbodiimide and N-hydroxysuccinimide (the mass is about adding silk fibroin, respectively). 25%, 10% of the protein content), soak for about 1 hour, add the silk fibroin dry powder obtained in step 6 (the final mass concentration of silk fibroin is 1%) to dissolve, react for 3 hours, take it out to dry and rinse , and then dry.

(8) The silk fibroin-modified polyester fabric is cut into a sample of 15cm×30cm, and the breaking strength measured by the material mechanical property testing machine is about 97% of the original fabric, and the elongation at break is about 97% of the original fabric.

(9) The weight gain rate of silk fibroin on the polyester fabric measured by the weighing method was 5.2%, which was significantly higher than that of Comparative Example 2, which was 0.92%. After immersing the silk fibroin-modified fabric in warm water at 37° C. and shaking for 24 hours, the dissolution rate of silk fibroin was measured to be less than 8%.

Comparative Example 1

(1) Put the silkworm raw silk into a sodium carbonate aqueous solution with a concentration of 0.2% at a bath ratio of 1:50 (g/mL), and treat it three times at 98 to 100 ° C for 30 minutes each time, and then use deionized water. The silk is fully cleaned, stretched, and dried in an oven to obtain degummed Bombyx mori silk fibroin fibers.

(2) Weigh the degummed Bombyx mori silk fibroin and dissolve it in an aqueous solution of calcium chloride-ethanol with a molar ratio of 1:2 at a bath ratio of 1:20 (g/mL), and dissolve it at 70°C for 5 to 7 hours to obtain Bombyx mori Dissolve the mixed solution.

(3) Weigh dextran G-50 and G-25 and put them in sufficient deionized water, respectively, and boil them in water for 1.5 hours. After cooling at room temperature, use a glass rod to drain into an empty column made of glass material to prepare a column bed volume. 2 cm × 60 cm, and the column was equilibrated three times with deionized water of 5 times the column volume after natural sedimentation for 2 hours.

(4) When the equilibrium water drops to the surface of the column material for the last time, add 5-15ml (10-50mg/ml) of the dissolved silk fibroin mixed solution to the dextran G-50. When the silk fibroin mixed solution completely enters the When it reaches the surface of the column material, continue to elute with sterilized deionized water, and the peristaltic pump controls the flow rate of the eluent to 300 mL/h; the effluent is collected in separate tubes until the silk fibroin is exhausted.

(5) Use SDS-PAGE electrophoresis or mass spectrometry to identify the molecular weight distribution of each tube, mix and freeze-dry the silk fibroin solution with a molecular weight of less than 10kDa, then configure it into an aqueous solution of 30-80mg/ml, and filter with a 0.45μm membrane to remove microparticles .

(6) Similar to step (4), add an appropriate amount of the silk fibroin aqueous solution of step (5) to the column material of G-25, the peristaltic pump controls the flow rate of the eluent to 50 mL/h, and collects the effluent in separate tubes until the silk fibroin is exhausted. , to obtain an aqueous solution of silk fibroin with a molecular weight of 1000-5000 Da, and finally freeze-dried for storage.

(7) Boil the woven polyester fabric with 6g/1L sodium carbonate aqueous solution at 100°C for about 1 hour, take out the silk fibroin obtained in step 6 with a mass concentration of 0.5% after repeated washing with tap water. In the aqueous solution, the room temperature continued to act for the same time as in Examples 1 to 4, and it was taken out to dry, rinsed, and then air-dried.

(8) The weight gain rate of silk fibroin on the polyester fabric was measured by weighing method to be 0.9%, and the hot water dissolution rate of silk fibroin was about 25%.

Comparative Example 2

(1) Put the silkworm raw silk into a sodium carbonate aqueous solution with a concentration of 0.2% at a bath ratio of 1:50 (g/mL), and treat it three times at 98 to 100 ° C for 30 minutes each time, and then use deionized water. The silk is fully cleaned, stretched, and dried in an oven to obtain degummed Bombyx mori silk fibroin fibers.

(2) Weigh the degummed Bombyx mori silk fibroin and dissolve it in an aqueous solution of calcium chloride-ethanol with a molar ratio of 1:2 at a bath ratio of 1:20 (g/mL), and dissolve it at 70°C for 5 to 7 hours to obtain Bombyx mori Dissolve the mixed solution.

(3) Weigh dextran G-50 and G-25 and put them in sufficient deionized water, respectively, and boil them in water for 1.5 hours. After cooling at room temperature, use a glass rod to drain into an empty column made of glass material to prepare a column bed volume. 2 cm × 60 cm, and the column was equilibrated three times with deionized water of 5 times the column volume after natural sedimentation for 2 hours.

(4) When the equilibrium water drops to the surface of the column material for the last time, add 5-15ml (10-50mg/ml) of the dissolved silk fibroin mixed solution to the dextran G-50. When the silk fibroin mixed solution completely enters the When it reaches the surface of the column material, continue to elute with sterilized deionized water, and the peristaltic pump controls the flow rate of the eluent to 300 mL/h; the effluent is collected in separate tubes until the silk fibroin is exhausted.

(5) Use SDS-PAGE electrophoresis or mass spectrometry to identify the molecular weight distribution of each tube, mix and freeze-dry the silk fibroin solution with a molecular weight of less than 10kDa, then configure it into an aqueous solution of 30-80mg/ml, and filter with a 0.45μm membrane to remove microparticles .

(6) Similar to step (4), add an appropriate amount of the silk fibroin aqueous solution of step (5) to the column material of G-25, the peristaltic pump controls the flow rate of the eluent to 50 mL/h, and collects the effluent in separate tubes until the silk fibroin is exhausted. , to obtain an aqueous solution of silk fibroin with a molecular weight of 1000-5000 Da, and finally freeze-dried for storage.

(7) Boil the woven polyester fabric with 6g/1L sodium carbonate aqueous solution at 100°C for about 1 hour, take out the silk fibroin obtained in step 6 with a mass concentration of 1% after repeatedly washing it with tap water. In the aqueous solution, the room temperature continued to act for the same time as in Examples 1 to 4, and it was taken out to dry, rinsed, and then air-dried.

(8) The weight gain rate of silk fibroin on the polyester fabric was measured by weighing method to be 0.92%, and the hot water dissolution rate of silk fibroin was about 25%.

Comparative Example 3

(1) Put the silkworm raw silk into a sodium carbonate aqueous solution with a concentration of 0.2% at a bath ratio of 1:50 (g/mL), and treat it three times at 98 to 100 ° C for 30 minutes each time, and then use deionized water. The silk is fully cleaned, stretched, and dried in an oven to obtain degummed Bombyx mori silk fibroin fibers.

(2) Weigh the degummed silk fibroin and dissolve it in a 9.3M lithium bromide aqueous solution at a liquor ratio of 1:15 (g/mL), and dissolve it at 65°C for 5-7 hours to obtain a mixed solution of silk fibroin dissolved.

(3) Pour the Bombyx mori fibroin solution into a dialysis bag, the wall of the dialysis bag is a semi-permeable membrane, and the molecular weight cut-off is in the range of 12.0-16.0kDa, and the dialysis bag filled with the Bombyx mori fibroin solution is placed in deionized water. In the container, replace the water in the container with new deionized water or pure water every 2 hours, and continue dialysis for 3 days to obtain purified silk fibroin aqueous solution (preparation of conventional silk fibroin aqueous solution), and then freeze-dried save.

(4) Boil the woven polyester fabric with 6g/1L sodium carbonate aqueous solution for about 1 hour, take out and wash with tap water, dehydrate, air dry or dry, and then treat the polyester fabric with 10% sodium hydroxide solution at 30°C For 1 to 2 hours, after rinsing, immerse in a mixed aqueous solution of carbodiimide and N-hydroxysuccinimide with a certain mass concentration (about 25% and 10% of the amount of silk fibroin added) for 1 hour. After adding the lyophilized silk fibroin in step 3 (the final mass concentration of silk fibroin is 1%) to dissolve, react for 3 hours, then take it out to dry, rinse and dry again.

(5) The silk fibroin-modified polyester fabric is cut into a sample of 15cm×30cm, and the breaking strength measured by the material mechanical property testing machine is about 94% of the original fabric, and the elongation at break is about 97% of the original fabric.

(6) The weight gain rate of silk fibroin on the polyester fabric was measured by the weighing method, which was 1.4%. The silk fibroin-modified fabric was immersed in warm water at 37°C and shaken for 24 hours, and the dissolution and loss of silk fibroin was measured. rate is less than 10%.

The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.

Claims (8)

1. a silk protein modification method of polyester fabric, is characterized in that, comprises: A) Desizing the polyester fabric to obtain a desizing fabric; B) the desizing fabric is treated with sodium hydroxide solution, washed, and obtains the fabric after alkali treatment; C) immersing the alkali-treated fabric in a cross-linking agent solution, and reacting with silk fibroin with a molecular weight of 1000-5000 Da; the cross-linking agent includes carbodiimide; The silk fibroin with a molecular weight of 1000-5000 Da is prepared according to the following method: a) Bombyx mori silk is degummed with sodium carbonate, then added with a neutral salt solution to dissolve, to prepare a silk fibroin solution; Equilibrate Sephadex G50 and G25 columns for use; b) adding the silk fibroin solution to Sephadex G50 column of dextran, eluting the silk fibroin with sterile water, and collecting the desalted silk fibroin aqueous solution in separate tubes; c) Use SDS-PAGE electrophoresis or mass spectrometry for screening step b) Collect silk fibroin below 10 kD in the tube, add it to Sephadex G25 column again, elute silk fibroin with sterile water, collect in separate tubes, and screen to obtain 1000～ 5000Da small molecular weight silk fibroin. 2 . The method according to claim 1 , wherein the carbodiimide accounts for 20% to 40% by mass of silk fibroin. 3 . 3. method according to claim 1, is characterized in that, step A) described desizing is specially adopting sodium carbonate solution desizing treatment; The concentration of described sodium carbonate solution is 6g/L; Described desizing treatment temperature The temperature is 90-100°C; the desizing treatment time is 1h. 4. The method according to claim 1, wherein the mass concentration of the sodium hydroxide solution in step B) is 5% to 30%; the treatment temperature of the sodium hydroxide solution is 30 to 40°C; The treatment time of the sodium hydroxide solution is 1～3h. 5 . The method according to claim 1 , wherein the reaction temperature in step C) is 25-35° C.; the reaction time is 1-3 h. 6 . 6. The method according to claim 1, wherein the neutral salt in step a) is selected from lithium bromide or calcium chloride-ethanol; the dissolution time is 5-7 hours; the silk fibroin solution The concentration is 10～50mg/mL. 7 . The method according to claim 1 , wherein in the screening step b) in step c), after collecting the silk fibroin below 10 kD in the tube, the method further comprises freeze-drying and then preparing an aqueous solution of 30-80 mg/mL. 8 . 8 . The method according to claim 1 , wherein the elution flow rate of step b) is 200-400 mL/h; the elution flow rate of step c) is 30-70 mL/h. 9 .