CN107869046A - A kind of fibroin method of modifying of polyester fabric - Google Patents

Abstract

The invention provides a kind of fibroin method of modifying of polyester fabric, including：A) polyester fabric destarch is handled, obtains the fabric of destarch；B the fabric of destarch) is used into naoh treatment, washs, obtains the fabric after alkali process；C) fabric after alkali process is impregnated in cross-linking agent solution, the fibroin albumen hybrid reaction with 1000~5000Da molecular weight.The fabric that method of modifying provided by the invention handles destarch uses naoh treatment, and the setting of above-mentioned alkali process to discharge reaction site on polyester fiber strand；Simultaneously, the present invention is modified the fabric after alkali process using the fibroin albumen of the 1000~5000Da molecular weight limited, the fibroin albumen of above-mentioned specific small-molecular-weight is caused firmly to introduce the fiber surface of polyester fabric using covalently bound principle, nice and cool property, flexibility, the antistatic behaviour of polyester fabric are improved, while mechanical property is good, silk-fibroin stability is good.

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 silk protein 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 crisp products. It is widely used in clothing and home textiles, mainly including coats, curtains, sofa fabrics, car interior accessories, etc. However, polyester is a superhydrophobic fiber with extremely poor hygroscopicity and rigidity, which limits its application in home textiles and certain clothing fields , such as summer cool clothing, underwear and bedding.

The prior art has reported the research on silk fibroin-coated polyester. Polyester fibers or fabrics are brittle, easy to break and fall off after coating, and will affect the surface structure and even air permeability of the original fabric. There are also literature reports that the coating weight gain of silk fibroin is low, the washing resistance is not ideal, or the moisture regain is still very low. So there is no market application.

Contents of the invention

In view of this, the technical problem to be solved by the present invention is to provide a silk protein modification method for polyester fabrics. 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 alkali-treated fabric;

C) Soak 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.

Preferably, the crosslinking agent includes carbodiimide.

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

Preferably, the desizing in step A) is specifically using sodium carbonate desizing treatment; the concentration of the sodium carbonate solution is 6g/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%-30%; the treatment temperature of the sodium hydroxide is 30-40° C.; the treatment time of the sodium hydroxide is 1-3 hours.

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

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

a) degumming the silkworm silk with sodium carbonate, and then adding a neutral salt solution to dissolve it to prepare a silk fibroin solution;

Dextran Sephadex G50 and G25 columns are equilibrated for use;

b) adding the silk fibroin solution into a dextran Sephadex G50 column, eluting the silk fibroin with sterilized water, and collecting the desalted silk fibroin aqueous solution in separate tubes;

c) Use SDS-PAGE electrophoresis or mass spectrometry screening step b) Collect the silk fibroin below 10kD in the tube, add it to the dextran Sephadex G25 column again, elute the silk fibroin with sterilized 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 dissolution time is 5-7 hours; the concentration of the silk fibroin solution is 10-50 mg/mL.

Preferably, the screening step b) in step c) further includes lyophilization after collecting the silk fibroin below 10 kD in the tube, and then formulating it into a 30-80 mg/mL aqueous solution.

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

Compared with the prior art, the present invention provides a silk protein modification method for polyester fabrics, comprising: A) desizing polyester fabrics to obtain desizing fabrics; B) using sodium hydroxide to desizing fabrics treatment to obtain an alkali-treated fabric; C) immersing the alkali-treated fabric in a crosslinking agent solution, and mixing and reacting with silk fibroin with a molecular weight of 1000-5000Da. 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 causes the release of reaction sites on the polyester fiber molecular chain; at the same time, the present invention adopts a limited relative molecular weight of 1000-5000Da And the concentrated distribution of silk fibroin is grafted and modified by alkali treatment. The principle of covalent bonding enables the above-mentioned specific small molecular weight silk fibroin to be 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 alkali-treated fabric;

C) Soak 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.

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

In the invention, the polyester fabric is desizing firstly to obtain the 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 and 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 preferred.

The washing in the present invention is preferably tap water washing, and the present invention does not limit the washing method, as long as those skilled in the art are familiar with it; the present invention does not limit the dehydration method, as long as those skilled in the art are familiar with it; The present invention does not limit the drying method, which is known to those skilled in the art; it may be air drying or drying.

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

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

The present invention does not limit the source of the sodium hydroxide, which is commercially available.

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

The washing in the present invention is preferably tap water washing, and the present invention does not limit the washing method, as long as those skilled in the art are familiar with it; the present invention does not limit the drying method, as long as those skilled in the art are familiar with it ;Can be line dried or tumble dry.

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

After the alkali treatment is completed, the alkali-treated fabric is immersed in a crosslinking agent solution, and mixed with silk fibroin with a molecular weight of 1000-5000 Da to obtain a polyester fabric modified by 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 impregnation, the prepared silk fibroin with a molecular weight of 1000-5000 Da is added for 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 1-3 hours.

After the grafting reaction, it is preferable to dry, wash, and dry again.

The drying in the present invention is preferably air drying; the washing is preferably water rinsing; and 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 familiar with it.

In the present invention, the silk fibroin is a silk fibroin with relatively small molecular weight and concentrated distribution.

The present invention creatively adopts the above-mentioned limited small molecular weight silk fibroin to graft and modify the alkali-treated fabric, and utilizes the principle of covalent bonding to make the above-mentioned specific low molecular weight silk fibroin firmly introduced into the fiber surface of the polyester fabric to improve the polyester fabric. The coolness, softness, antistatic and glossiness of the fabric can improve the affinity of the skin, and at the same time, it has good mechanical properties and good stability of silk protein.

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

a) degumming the silkworm silk with sodium carbonate, and then adding a neutral salt solution to dissolve it to prepare a silk fibroin solution;

Dextran Sephadex G50 and G25 columns are equilibrated for use;

b) adding the silk fibroin solution into a dextran Sephadex G50 column, eluting the silk fibroin with sterilized water, and collecting the desalted silk fibroin aqueous solution in separate tubes;

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

In the present invention, firstly, the silkworm silk is degummed with sodium carbonate; preferably, the silkworm silk is put into an aqueous solution of sodium carbonate according to a specific liquor ratio, treated, washed, and dried to obtain the degummed silk.

In the present invention, the silkworm silk is not limited, and silkworm silk well-known to those skilled in the art can be used, which can be commercially available.

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

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

The cleaning of the present invention is preferably deionized water washing, and the present invention does not limit the cleaning method, which is well known to those skilled in the art; after cleaning, it is preferably laxative well known to those skilled in the art; The drying method is not limited, and those skilled in the art can be used; drying in an oven may be used. 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 to 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°C-70°C; more preferably 65°C-70°C; the concentration of the obtained silk fibroin solution is preferably 10-50 mg/mL.

Dextran 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 specifically: dextran Sephadex G50 and G25 are boiled with sterilized deionized water until fully expanded, continuously poured into a hollow column made of glass material, allowed to settle and balance the column material with sterilized deionized water; more preferably Specifically: Put dextran G-50 and G-25 into deionized water respectively, put them in a boiling water bath for 1.5-2 hours, after cooling down at room temperature, drain them with glass rods and put them into an empty glass column, and let them settle naturally for 2-3 hours Finally, the column was pressurized with a peristaltic pump and deionized water with 5 times the column volume was equilibrated three times.

The volume of the preparative column bed in the present invention is preferably 2cm×60cm.

After equilibration, add the silk fibroin solution into the Sephadex G50 column, wash the silk fibroin with sterilized water, and collect the desalted silk fibroin aqueous solution in different tubes.

Preferably specifically: when the equilibrium water drops to the surface of the column material for the last time, add 5-15 mL of a silk fibroin mixed solution with a dissolved concentration of 10-50 mg/mL to the dextran G-50, and when the silk fibroin mixed solution When it completely enters the surface of the column material, continue to elute with sterilized deionized water, the flow rate of the eluent is controlled by a peristaltic pump, and the effluent is collected 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 step b) to collect silk fibroin below 10 kD in the tube.

The present invention does not limit the specific method of the SDS-PAGE electrophoresis or mass spectrometry screening step b) to collect the silk fibroin protein below 10kD in the tube, as long as those skilled in the art are familiar with it.

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

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

Further separation of the molecular weight of the silk fibroin below 10kD is carried out by freeze-drying and then dissolving.

After filtering, add the filtered solution to a dextran Sephadex G25 column, elute the silk fibroin with sterilized water, collect in separate tubes, and screen to obtain silk fibroin with a small molecular weight 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, use SDS-PAGE electrophoresis or mass spectrometry to screen and collect small molecular weight silk fibroin of 1000-5000 Da in the collection tube, and then freeze-dry and store.

The present invention can obtain the silk fibroin with a small molecular weight of 1000-5000 Da more simply and more accurately by adopting the above-mentioned method.

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

The invention provides a silk protein modification method for polyester fabrics, comprising: A) desizing the polyester fabrics to obtain desizing fabrics; B) treating the desizing fabrics with sodium hydroxide, washing and drying them to obtain The fabric after alkali treatment; C) soak the fabric after alkali treatment in a crosslinking agent solution, and mix and react with silk fibroin with a molecular weight of 1000-5000Da. 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 causes the release of reaction sites on the molecular chain of the polyester fiber; at the same time, the present invention adopts a method that limits the relative molecular weight of 1000 to 5000Da and is relatively small and Concentratedly distributed silk fibroin is grafted and modified by alkali treatment. Using the principle of covalent bonding, the above-mentioned silk fibroin with a specific molecular weight can be firmly introduced into the fiber surface of polyester fabrics, improving the coolness, softness, and resistance of polyester fabrics. Electrostatic properties and gloss, improve skin affinity, good mechanical properties, good stability of silk protein.

The surface of the polyester fabric obtained after 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-grade underwear, summer clothes and bedding.

The present invention preferably adopts following mode to measure the mechanical property of lining:

Cut the silk fibroin-modified polyester fabric into a 15cm×30cm sample, and use a material mechanical property testing machine to measure it.

In order to further illustrate the present invention, the method for modifying silk protein of polyester fabric provided by the present invention will be described in detail below in conjunction with the examples.

Example 1

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

(2) Weigh the degummed silkworm 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 5-7 hours to obtain silkworm silk Dissolved mixed solution.

(3) Weigh dextran G-50 and G-25 and put them into sufficient deionized water respectively, and put them in a boiling water bath for 1.5 hours. After cooling down at room temperature, drain them with glass rods and put them into an empty glass column to prepare the column bed volume. 2cm×60cm, after 2 hours of natural sedimentation, use a peristaltic pump to pressurize the column, and equilibrate the column with 5 times the column volume of deionized water three times.

(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 has completely entered 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 300mL/h; separate the tubes to collect the effluent 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 less than 10kDa, and then make it into a 30-80mg/ml aqueous solution, and filter it with a 0.45μm membrane to remove microparticles .

(6) Similar to step (4), add an appropriate amount of silk fibroin aqueous solution in step (5) to the G-25 column material, control the flow rate of the eluent to 50mL/h with a peristaltic pump, and collect the effluent in separate tubes until the silk fibroin is exhausted , to obtain a silk fibroin aqueous solution 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, dehydrate and dry it in the air. Then treat the polyester fabric with 10% sodium hydroxide solution at 30°C for 1 to 2 hours, rinse it with tap water and impregnate it in a certain mass concentration of carbodiimide and N-hydroxysuccinimide (the mass is about 25%, 10% of the protein content) in a mixed aqueous solution, soak for about 1 hour, add the silk fibroin dry powder obtained in step 6 (the final mass concentration of silk fibroin is 0.5%) to dissolve, react for 3 hours, take it out to dry, rinse , and then dry.

(8) The polyester fabric modified by silk fibroin is cut into a sample of 15cm×30cm, and the breaking strength measured by a 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 weighing method was 3.1%, which was significantly higher than the weight gain rate of 0.9% in Comparative Example 1. After soaking the silk fibroin-modified fabric in warm water at 37° C. and shaking for 24 hours, it is measured that the dissolution rate of the silk fibroin is less than 5%.

Example 2

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

(2) Weigh the degummed silkworm 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 5-7 hours to obtain silkworm silk Dissolved mixed solution.

(3) Weigh dextran G-50 and G-25 and put them into sufficient deionized water respectively, and put them in a boiling water bath for 1.5 hours. After cooling down at room temperature, drain them with glass rods and put them into an empty glass column to prepare the column bed volume. 2cm×60cm, after 2 hours of natural sedimentation, use a peristaltic pump to pressurize the column, and equilibrate the column with 5 times the column volume of deionized water three times.

(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 has completely entered 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 300mL/h; separate the tubes to collect the effluent 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 less than 10kDa, and then make it into a 30-80mg/ml aqueous solution, and filter it with a 0.45μm membrane to remove microparticles .

(6) Similar to step (4), add an appropriate amount of silk fibroin aqueous solution in step (5) to the G-25 column material, control the flow rate of the eluent to 50mL/h with a peristaltic pump, and collect the effluent in separate tubes until the silk fibroin is exhausted , to obtain a silk fibroin aqueous solution 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, dehydrate and dry it in the air. Then treat the polyester fabric with 10% sodium hydroxide solution at 30°C for 2 to 3 hours, rinse it with tap water and impregnate it in a certain mass concentration of carbodiimide and N-hydroxysuccinimide (the mass is about 25%, 10% of the protein content) in the mixed aqueous solution, 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 polyester fabric modified by silk fibroin is cut into a sample of 15cm×30cm, and the breaking strength measured by a 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 weighing method was 5.8%, which was significantly higher than the weight gain rate of 0.92% in Comparative Example 2. After soaking the silk fibroin-modified fabric in warm water at 37° C. and shaking for 24 hours, it is measured that the dissolution rate of the silk fibroin is less than 8%.

Example 3

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

(2) Weigh the degummed silkworm 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 5-7 hours to obtain silkworm silk Dissolved mixed solution.

(3) Weigh dextran G-50 and G-25 and put them into sufficient deionized water respectively, and put them in a boiling water bath for 1.5 hours. After cooling down at room temperature, drain them with glass rods and put them into an empty glass column to prepare the column bed volume. 2cm×60cm, after 2 hours of natural sedimentation, use a peristaltic pump to pressurize the column, and equilibrate the column with 5 times the column volume of deionized water three times.

(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 has completely entered 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 300mL/h; separate the tubes to collect the effluent 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 less than 10kDa, and then make it into a 30-80mg/ml aqueous solution, and filter it with a 0.45μm membrane to remove microparticles .

(6) Similar to step (4), add an appropriate amount of silk fibroin aqueous solution in step (5) to the G-25 column material, control the flow rate of the eluent to 50mL/h with a peristaltic pump, and collect the effluent in separate tubes until the silk fibroin is exhausted , to obtain a silk fibroin aqueous solution 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, dehydrate and dry it in the air. Then treat the polyester fabric with 10% sodium hydroxide solution at 30°C for 1 to 2 hours, rinse it with tap water and impregnate it in a certain mass concentration of carbodiimide and N-hydroxysuccinimide (the mass is about 25%, 10% of the protein content) in the mixed aqueous solution, 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 polyester fabric modified by silk fibroin is cut into a sample of 15cm×30cm, and the breaking strength measured by a 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 weighing method was 5.2%, which was significantly higher than the weight gain rate of Comparative Example 2 of 0.92%. After soaking the silk fibroin-modified fabric in warm water at 37° C. and shaking for 24 hours, it is measured that the dissolution rate of the silk fibroin is less than 8%.

Comparative example 1

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

(2) Weigh the degummed silkworm 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 5-7 hours to obtain silkworm silk Dissolved mixed solution.

(3) Weigh dextran G-50 and G-25 and put them into sufficient deionized water respectively, and put them in a boiling water bath for 1.5 hours. After cooling down at room temperature, drain them with glass rods and put them into an empty glass column to prepare the column bed volume. 2cm×60cm, after 2 hours of natural sedimentation, use a peristaltic pump to pressurize the column, and equilibrate the column with 5 times the column volume of deionized water three times.

(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 has completely entered 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 300mL/h; separate the tubes to collect the effluent 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 less than 10kDa, and then make it into a 30-80mg/ml aqueous solution, and filter it with a 0.45μm membrane to remove microparticles .

(6) Similar to step (4), add an appropriate amount of silk fibroin aqueous solution in step (5) to the G-25 column material, control the flow rate of the eluent to 50mL/h with a peristaltic pump, and collect the effluent in separate tubes until the silk fibroin is exhausted , to obtain a silk fibroin aqueous solution 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 taking out and washing it repeatedly with tap water. In the aqueous solution, continue to act at room temperature for the same time as in Examples 1 to 4, take it out to dry, rinse, and then dry.

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

Comparative example 2

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

(2) Weigh the degummed silkworm 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 5-7 hours to obtain silkworm silk Dissolved mixed solution.

(3) Weigh dextran G-50 and G-25 and put them into sufficient deionized water respectively, and put them in a boiling water bath for 1.5 hours. After cooling down at room temperature, drain them with glass rods and put them into an empty glass column to prepare the column bed volume. 2cm×60cm, after 2 hours of natural sedimentation, use a peristaltic pump to pressurize the column, and equilibrate the column with 5 times the column volume of deionized water three times.

(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 has completely entered 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 300mL/h; separate the tubes to collect the effluent 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 less than 10kDa, and then make it into a 30-80mg/ml aqueous solution, and filter it with a 0.45μm membrane to remove microparticles .

(6) Similar to step (4), add an appropriate amount of silk fibroin aqueous solution in step (5) to the G-25 column material, control the flow rate of the eluent to 50mL/h with a peristaltic pump, and collect the effluent in separate tubes until the silk fibroin is exhausted , to obtain a silk fibroin aqueous solution 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 and wash it repeatedly with tap water, and soak it in the silk fibroin obtained in step 6 with a mass concentration of 1%. In the aqueous solution, continue to act at room temperature for the same time as in Examples 1-4, take it out to dry, rinse, and then dry in the air.

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

Comparative example 3

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

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

(3) Pour the silkworm fibroin solution into the dialysis bag. The wall of the dialysis bag is a semipermeable membrane with a molecular weight cut-off of 12.0-16.0kDa. 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 the purified silk fibroin aqueous solution (preparation of conventional silk fibroin aqueous solution), and then freeze-dry save.

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

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

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

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. A method for modifying silk protein of polyester fabric, characterized in that, 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 alkali-treated fabric; C) Soak 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. 2. The method of claim 1, wherein the crosslinking agent comprises carbodiimide. 3. The method according to claim 2, characterized in that the mass percentage of the carbodiimide in the silk fibroin is 20%-40%. 4. method according to claim 1, is characterized in that, step A) described desizing is specially to adopt sodium carbonate desizing treatment; The concentration of described sodium carbonate solution is 6g/L; Described desizing treatment temperature is 90-100° C.; the desizing treatment time is 1 h. 5. The method according to claim 1, wherein 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 hydrogen The treatment time of sodium oxide is 1~3h. 6 . The method according to claim 1 , characterized in that, in step C), the reaction temperature is 25-35° C.; the reaction time is 1-3 hours. 7. The method according to claim 1, characterized in that the silk fibroin with a molecular weight of 1000-5000 Da is prepared according to the following method: a) degumming the silkworm silk with sodium carbonate, and then adding a neutral salt solution to dissolve it to prepare a silk fibroin solution; Dextran Sephadex G50 and G25 columns are equilibrated for use; b) adding the silk fibroin solution into a dextran Sephadex G50 column, eluting the silk fibroin with sterilized water, and collecting the desalted silk fibroin aqueous solution in separate tubes; c) Use SDS-PAGE electrophoresis or mass spectrometry screening step b) Collect the silk fibroin below 10kD in the tube, add it to the dextran Sephadex G25 column again, elute the silk fibroin with sterilized water, collect in separate tubes, and screen to obtain 1000~ 5000Da small molecular weight silk fibroin. 8. The method according to claim 7, wherein the neutral salt solution in step a) is selected from lithium bromide or calcium chloride-ethanol; the dissolution time is 5 to 7 hours; the silk fibroin dissolves The liquid concentration is 10-50mg/mL. 9. The method according to claim 7, characterized in that the screening step b) in step c) further comprises freeze-drying and then preparing a 30-80 mg/mL aqueous solution after collecting the silk fibroin protein below 10 kD in the tube. 10. The method according to claim 7, characterized in that the elution flow rate in step b) is 200-400 mL/h; the elution flow rate in step c) is 30-70 mL/h.