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

A kind of fibroin method of modifying of polyester fabric Download PDF

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Publication number
CN107869046A
CN107869046A CN201711224540.8A CN201711224540A CN107869046A CN 107869046 A CN107869046 A CN 107869046A CN 201711224540 A CN201711224540 A CN 201711224540A CN 107869046 A CN107869046 A CN 107869046A
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China
Prior art keywords
fabric
fibroin
fibroin albumen
destarch
silk
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CN201711224540.8A
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CN107869046B (en
Inventor
王建南
裔洪根
刘山歌
卞香蓥
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Suzhou University
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Suzhou University
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D06L1/14De-sizing
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402Amides imides, sulfamic acids
    • D06M13/432Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/15Proteins or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32Polyesters

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Cosmetics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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 fibroin method of modifying of polyester fabric
Technical field
The present invention relates to textile technology field, more particularly, to a kind of fibroin method of modifying of polyester fabric.
Background technology
Terylene is textile fabric yield highest fiber, is the most important raw material of textile product, and accounting textile fabric is processed More than the 70% of amount, polyester fiber is chemical synthetic fiber, because high with fracture strength, light resistance is good, and it is excellent that product is well-pressed etc. Point and be widely used in and take and household textiles, mainly have overcoat, curtain, sofa fabric, in-car ornaments etc., but terylene category In super-hydrophobicity fiber, hygroscopicity extreme difference, rigidity, limit its application in home textile and some garment industries, as summer cool clothes, Underwear and bedding etc..
Prior art reported the research of fibroin albumen coating polyester, had after progress polyester fiber or fabric coating crisp Property, it is easily rupturable and come off, and the surface texture even gas permeability of original fabric can be influenceed.Also the fibroin albumen of reported in literature applies It is low to cover rate of body weight gain, it is water-fastness undesirable, or regain is still very low.So there is no market application.
The content of the invention
In view of this, the technical problem to be solved in the present invention is the fibroin modification side for providing a kind of polyester fabric Method, polyester fabric mechanical property that method of modifying provided by the invention is modified is good, stability is good.
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, mixed with the fibroin albumen of 1000~5000Da molecular weight Close reaction.
Preferably, the crosslinking agent includes carbodiimides.
Preferably, the mass percent that the carbodiimides accounts for fibroin albumen is 20%~40%.
Preferably, step A) destarch is specially to be handled using sodium carbonate destarch;The concentration of the sodium carbonate liquor is 6g/L;The destarch treatment temperature is 90~100 DEG C;The destarch processing time is 1h.
Preferably, step B) mass concentration of the sodium hydroxide is 5%~30%;The treatment temperature of the sodium hydroxide For 30~40 DEG C;The processing time of the sodium hydroxide is 1~3h.
Preferably, step C) reaction temperature is 25~35 DEG C;The reaction time is 1~3h.
Preferably, the fibroin albumen of 1000~5000Da molecular weight is prepared as follows:
A) silkworm silk is subjected to degumming using sodium carbonate and then adds neutral salt solution dissolving, it is molten to prepare fibroin albumen Solve liquid;
Glucan Sephadex G50 and G25 column equilibrations is stand-by;
B) fibroin albumen lysate is added in glucan Sephadex G50 posts, with sterilizing water elution fibroin albumen, divided Pipe collects the silk fibroin water solution of desalination;
C) using the fibroin albumen of below 10kD in SDS-PAGE electrophoresis or mass spectrum screening step b) collecting pipes, add again In glucan Sephadex G25 posts, with sterilizing water elution fibroin albumen, it is in charge of collection, screening obtains the small of 1000~5000Da Molecular weight fibroin albumen.
Preferably, the step a) neutral salt solutions are selected from lithium bromide or calcium chloride-ethanol;The dissolution time is 5~7 Hour;The fibroin albumen lysate concentration is 10~50mg/mL.
Preferably, also include after below 10kD fibroin albumen in step c) the screening step b) collecting pipes it is lyophilized and After be configured to 30~80mg/mL aqueous solution.
Preferably, the step b) elution flow rates are 200~400mL/h;Step c) the elution flow rates are 30~70mL/ h。
Compared with prior art, the invention provides a kind of fibroin method of modifying of polyester fabric, including:A) will wash The destarch of synthetic fibre fabric is handled, and obtains the fabric of destarch;B the fabric of destarch) is used into naoh treatment, obtains the face after alkali process Material;C) fabric after alkali process is impregnated in cross-linking agent solution, mixed instead with the fibroin albumen of 1000~5000Da molecular weight Should.The fabric that method of modifying provided by the invention handles destarch uses naoh treatment, and the setting of above-mentioned alkali process causes Reaction site is discharged on polyester fiber strand;Meanwhile the present invention using limit 1000~5000Da relative molecular weights compared with Fabric after small and integrated distribution fibroin albumen graft modification alkali process, is caused above-mentioned specific using covalently bound principle The fibroin albumen of small-molecular-weight firmly introduces the fiber surface of polyester fabric, improves the nice and cool property of polyester fabric, flexibility, anti- Static behaviour, while mechanical property is good, silk-fibroin stability is good.
Embodiment
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, mixed with the fibroin albumen of 1000~5000Da molecular weight Close reaction.
The present invention, without limiting, well known to those skilled in the art can be defined as terylene for the polyester fabric Fabric.The present invention, without limiting, can be commercially available for its source.
The present invention is first handled polyester fabric destarch, obtains the fabric of destarch.
In the present invention, the destarch processing is preferably handled using sodium carbonate destarch;It is preferred that it is specially that polyester fabric exists The heated in water solution of sodium carbonate.The mode of the heating is preferably to boil heating.
The concentration of the sodium carbonate liquor is preferably 6g/L;The destarch treatment temperature is preferably 90~100 DEG C;It is described de- It is preferably 1h to starch processing time.
After heating, preferably wash, be dehydrated, drying.
Washing of the present invention is preferably originally water washing, the present invention for the mode of washing without limiting, ability Known to field technique personnel;The present invention for the dewatering type without limit, it is well known to those skilled in the art i.e. Can;The present invention for the drying mode without limit, it is well known to those skilled in the art;Can be to dry or dry It is dry.
The fabric of destarch is obtained after drying, the fabric of destarch is used into naoh treatment.
In the present invention, the mass concentration of the sodium hydroxide is preferably 5%~30%;The processing temperature of the sodium hydroxide Degree is preferably 30~40 DEG C;The processing time of the sodium hydroxide is preferably 1~3h;More preferably 1~2h.
Source of the invention for the sodium hydroxide is commercially available without limiting.
After naoh treatment, preferably wash, dry.
Washing of the present invention is preferably originally water washing, the present invention for the mode of washing without limiting, ability Known to field technique personnel;The present invention for the drying mode without limit, it is well known to those skilled in the art i.e. Can;Can be to dry or dry.
After fabric washing, drying, the fabric after alkali process is obtained.
After the completion of alkali process, the fabric after alkali process is impregnated in cross-linking agent solution, with 1000~5000Da molecular weight Fibroin albumen hybrid reaction, obtain the modified polyester fabric of silk-fibroin.
According to the present invention, the crosslinking agent includes carbodiimides;The crosslinking agent can also include N- acyl group succinyls Imines;Wherein, the mass percent that the carbodiimides accounts for fibroin albumen is preferably 20%~40%;More preferably 25%. The mass percent that the N- acylsuccinimides account for fibroin albumen is preferably 10%.
According to the present invention, after dipping, the fibroin albumen for adding the 1000~5000Da molecular weight being prepared is grafted Reaction, final silk fibroin protein solution concentration is preferably 0.5-5%;
The reaction temperature is preferably 25~35 DEG C;The reaction time is preferably 1~3h.
After graft reaction, preferably dry, wash, dry again.
Drying of the present invention is preferably to dry;The washing is preferably water rinsing;Described dry again is preferably to dry. The present invention for the concrete operations dried and rinse without restriction, it is well known to those skilled in the art.
In the present invention, the fibroin albumen is that relative molecular weight is smaller and the fibroin albumen of integrated distribution.
Fabric after the fibroin albumen graft modification alkali process of the small-molecular-weight using above-mentioned restriction of the invention, 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, antistatic behaviour and the glossiness of polyester fabric are improved, improves the compatibility of skin, while mechanical property Well, silk-fibroin stability is good.
The present invention for 1000~5000Da molecular weight fibroin albumen source without limit, can be it is commercially available, It is preferred that prepare with the following method:
A) silkworm silk is subjected to degumming using sodium carbonate and then adds neutral salt solution dissolving, it is molten to prepare fibroin albumen Solve liquid;
Glucan Sephadex G50 and G25 column equilibrations is stand-by;
B) fibroin albumen lysate is added in glucan Sephadex G50 posts, with sterilizing water elution fibroin albumen, divided Pipe collects the silk fibroin water solution of desalination;
C) using the fibroin albumen of below 10kD in SDS-PAGE electrophoresis or mass spectrum screening step b) collecting pipes, add again In glucan Sephadex G25 posts, with sterilizing water elution fibroin albumen, it is in charge of collection, screening obtains the small of 1000~5000Da Molecular weight fibroin albumen.
Silkworm silk is carried out degumming by the present invention using sodium carbonate first;It is preferred that it is specially according to specific bath by silkworm silk Than being put into aqueous sodium carbonate, handle, cleaning, be dried to obtain silk after degumming.
For the present invention for the silkworm silk without limiting, silkworm raw silk well known to those skilled in the art can Think commercially available.
Bath raio of the present invention is preferably 1:50(g/mL);The mass concentration of the aqueous sodium carbonate is preferably 0.2%; The treatment temperature is preferably 98~100 DEG C;The number of processes is preferably 1~5 time;More preferably 2~3 times;It is described each Processing time is preferably 30min.
Cleaned after being disposed, be dried to obtain silk after degumming.
It is of the present invention cleaning be preferably deionized water washing, the present invention for the cleaning way without limit, this Known to art personnel;It is preferably well known to those skilled in the art pull loose after cleaning;The present invention is for described dry Dry mode is well known to those skilled in the art without limiting;Can be to be dried in baking oven.The drying temperature is preferably 65℃。
By the silk after degumming and then neutral salt solution dissolving is added, prepares fibroin albumen lysate.
In the present invention, the neutral salt solution is preferably selected from lithium bromide or calcium chloride-ethanol;The silk and neutral salt The bath raio of solution dissolving is preferably 1:15~1:20(g/mL);
The concentration of the lithium-bromide solution is preferably 9~10M;In the calcium chloride-ethanol, mole of calcium chloride and ethanol Than being preferably 1:2;
The dissolution time is 5~7 hours;The solution temperature is preferably 60 DEG C~70 DEG C;More preferably 65 DEG C~70 ℃;The obtained fibroin albumen lysate concentration is preferably 10~50mg/mL.
Glucan Sephadex G50 and G25 column equilibrations is stand-by.The present invention is for the glucan Sephadex G50 Source with G25 posts can be commercially available without limiting, or self-control.
It is preferred that it is specially:The boiling of glucan Sephadex G50 and G25 sterile deionized water is boiled to abundant and expanded, continuously Pour into the hollow column of glass material, standing sedimentation simultaneously balances column material with sterile deionized water;More preferably it is specially:Portugal is gathered Sugared G-50 and G-25 are respectively put into deionized water, 1.5~2h of boiling water bath, are drained after normal temperature cooling with glass bar and are loaded glass In the void column of material, natural subsidence is pressurizeed after 2~3 hours with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
The bed volume of the present invention for preparing is preferably 2cm × 60cm.
After balance, fibroin albumen lysate is added in glucan Sephadex G50 posts, with sterilizing water elution fibroin egg In vain, it is in charge of the silk fibroin water solution for collecting desalination.
It is preferred that it is specially:Last time adds dissolving into glucan G-50 when equilibrium water drops to column material surface Concentration be 10~50mg/mL fibroin albumen 5~15mL of mixed solution, when fibroin albumen mixed solution is completely into post material When expecting surface, continue to be eluted with sterile deionized water, peristaltic pump control eluent flow rate, be in charge of collection efflux, until flowing to end Fibroin albumen.
The elution flow rate is preferably 200~400mL/h;More preferably 250~350mL/h.
Using the fibroin albumen of below 10kD in SDS-PAGE electrophoresis or mass spectrum screening step b) collecting pipes.
Fibroin albumen of the present invention for below 10kD in the SDS-PAGE electrophoresis or mass spectrum screening step b) collecting pipes Concrete mode without limit, it is well known to those skilled in the art.
In the present invention, also include after below 10kD fibroin albumen in the screening step b) collecting pipes lyophilized, then It is configured to 30~80mg/mL aqueous solution.Then filter, filtering of the present invention is preferably the membrane filtration using 0.45 μm.
The present invention for the lyophilized concrete mode without limit, it is well known to those skilled in the art.
Using it is lyophilized then dissolve by the way of carry out below 10kD fibroin albumen molecular weight further separation.
After filtering, solution after filtering is added in glucan Sephadex G25 posts, with sterilizing water elution fibroin albumen, divided Pipe is collected, and screening obtains 1000~5000Da small-molecular-weight fibroin albumen.
The flow velocity of elution of the present invention is preferably 30~70mL/h;More preferably 35~50mL/h.
After elution, using the small-molecular-weight fibroin egg of 1000~5000Da in SDS-PAGE electrophoresis or mass spectrum screening collecting pipe In vain, then freeze and preserve.
The present invention can the easier small-molecular-weight fibroin egg for more accurately obtaining 1000~5000Da using aforesaid way In vain.
The present invention for the screening and lyophilized concrete mode without limiting, it is well known to those skilled in the art i.e. Can.
The invention provides a kind of fibroin method of modifying of polyester fabric, including:A) polyester fabric destarch is handled, Obtain the fabric of destarch;B the fabric of destarch) is used into naoh treatment, washing and drying, 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.This The fabric that the method for modifying that invention provides handles destarch uses naoh treatment, and the setting of above-mentioned alkali process make it that terylene is fine Reaction site is discharged on dimension strand;Meanwhile the present invention is smaller using restriction 1000~5000Da relative molecular weights and collects Fabric after the fibroin albumen graft modification alkali process of middle distribution, causes above-mentioned specified molecular weight using covalently bound principle Fibroin albumen firmly introduces the fiber surface of polyester fabric, improve the nice and cool property of polyester fabric, flexibility, antistatic behaviour and Glossiness, improve the compatibility of skin, while mechanical property is good, silk-fibroin stability is good.
It is the modified obtained polyester fabric soft surface of the present invention, smooth, refrigerant, there is soyeux skin compatibility, Product is mainly used in high-grade underwear, the summer hangs out and the exploitation of bedding.
The mechanical property of fabric is measured present invention preferably employs following manner:
The polyester fabric that fibroin albumen is modified is cut into 15cm × 30cm sample, using material mechanical performance testing machine Measure.
In order to further illustrate the present invention, the fibroin of polyester fabric provided by the invention is changed with reference to embodiments Property method is described in detail.
Embodiment 1
(1) silkworm raw silk is pressed 1:50 (g/mL) bath raio is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~ Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:20 (g/mL) bath raio is dissolved in mol ratio 1:2 calcium chloride-ethanol The aqueous solution in, 70 DEG C dissolving 5~7 hours bombyx mori silk fibroin dissolving mixed solution.
(3) glucan G-50 and G-25 are weighed to be respectively put into the deionized water of abundance, boiling water bath 1.5 hours, treats normal temperature Drained and loaded in the void column of glass material with glass bar after cooling, prepare bed volume 2cm × 60cm, natural subsidence is after 2 hours Pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
(4) for the last time when equilibrium water drops to column material surface, the fibroin egg of dissolving is added into glucan G-50 White 5~15ml of mixed solution (10~50mg/ml), when fibroin albumen mixed solution is completely into column material surface, continue Eluted with sterile deionized water, peristaltic pump control eluent flow rate 300mL/h;It is in charge of collection efflux, until flowing to end fibroin egg In vain.
(5) using the molecular weight distribution of SDS-PAGE electrophoresis or each pipe of Mass Spectrometric Identification, by fibroin of the molecular weight less than 10kDa Protein solution is freeze-dried mixed, is then configured to the 30~80mg/ml aqueous solution, and microparticle is removed with 0.45 μm of membrane filtration.
(6) similar step (4), the silk fibroin water solution of appropriate step (5), peristaltic pump control are added to G-25 column material Eluent flow rate 50mL/h processed, is in charge of collection efflux, until flowing to end fibroin albumen, obtains the silk of 1000~5000Da molecular weight The fibroin aqueous solution, finally freeze and preserve.
(7) weaving polyester fabric is boiled with 6g/1L aqueous sodium carbonate at 100 DEG C and boiled 1 hour or so, taken out with certainly Water repeatedly dry by washes clean, dehydration.Then with handling polyester fabric 1~2 hour at 10% 30 DEG C of sodium hydroxide solution, Be impregnated in after tap water rinse is clean certain mass concentration carbodiimides and n-hydroxysuccinimide (quality respectively may be about Add the 25% of fibroin albumen quality, in mixed aqueous solution 10%), impregnate 1 hour or so, add the fibroin that step 6 obtains After protein dry powder (fibroin albumen final mass concentration is 0.5%) dissolving, 3h is reacted, taking-up is dried, rinsed, drying again.
(8) polyester fabric that fibroin albumen is modified is cut into 15cm × 30cm sample, tried using material mechanical performance The machine of testing measures 95% or so that fracture strength is original fabric, and elongation at break is 97% or so of original fabric.
(9) the fibroin albumen rate of body weight gain 3.1% on polyester fabric is measured using weight method, is significantly higher than the increasing of comparative example 1 Rate 0.9% again.The fabric that fibroin albumen is modified is impregnated in after being vibrated 24 hours in 37 DEG C of warm water, measures the molten of fibroin albumen Mistake rate is less than 5%.
Embodiment 2
(1) silkworm raw silk is pressed 1:50 (g/mL) bath raio is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~ Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:20 (g/mL) bath raio is dissolved in mol ratio 1:2 calcium chloride-ethanol The aqueous solution in, 70 DEG C dissolving 5~7 hours bombyx mori silk fibroin dissolving mixed solution.
(3) glucan G-50 and G-25 are weighed to be respectively put into the deionized water of abundance, boiling water bath 1.5 hours, treats normal temperature Drained and loaded in the void column of glass material with glass bar after cooling, prepare bed volume 2cm × 60cm, natural subsidence is after 2 hours Pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
(4) for the last time when equilibrium water drops to column material surface, the fibroin egg of dissolving is added into glucan G-50 White 5~15ml of mixed solution (10~50mg/ml), when fibroin albumen mixed solution is completely into column material surface, continue Eluted with sterile deionized water, peristaltic pump control eluent flow rate 300mL/h;It is in charge of collection efflux, until flowing to end fibroin egg In vain.
(5) using the molecular weight distribution of SDS-PAGE electrophoresis or each pipe of Mass Spectrometric Identification, by fibroin of the molecular weight less than 10kDa Protein solution is freeze-dried mixed, is then configured to the 30~80mg/ml aqueous solution, and microparticle is removed with 0.45 μm of membrane filtration.
(6) similar step (4), the silk fibroin water solution of appropriate step (5), peristaltic pump control are added to G-25 column material Eluent flow rate 50mL/h processed, is in charge of collection efflux, until flowing to end fibroin albumen, obtains the silk of 1000~5000Da molecular weight The fibroin aqueous solution, finally freeze and preserve.
(7) weaving polyester fabric is boiled with 6g/1L aqueous sodium carbonate at 100 DEG C and boiled 1 hour or so, taken out with certainly Water repeatedly dry by washes clean, dehydration.Then with handling polyester fabric 2~3 hours at 10% 30 DEG C of sodium hydroxide solution, Be impregnated in after tap water rinse is clean certain mass concentration carbodiimides and n-hydroxysuccinimide (quality respectively may be about Add the 25% of fibroin albumen quality, in mixed aqueous solution 10%), impregnate 1 hour or so, add the fibroin that step 6 obtains After protein dry powder (fibroin albumen final mass concentration is 1%) dissolving, 3h is reacted, taking-up is dried, rinsed, drying again.
(8) polyester fabric that fibroin albumen is modified is cut into 15cm × 30cm sample, tried using material mechanical performance The machine of testing measures 91% or so that fracture strength is original fabric, and elongation at break is 92% or so of original fabric.
(9) the fibroin albumen rate of body weight gain 5.8% on polyester fabric is measured using weight method, is significantly higher than the increasing of comparative example 2 Rate 0.92% again.The fabric that fibroin albumen is modified is impregnated in after being vibrated 24 hours in 37 DEG C of warm water, measures fibroin albumen Dissolve-loss ratio is less than 8%.
Embodiment 3
(1) silkworm raw silk is pressed 1:50 (g/mL) bath raio is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~ Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:20 (g/mL) bath raio is dissolved in mol ratio 1:2 calcium chloride-ethanol The aqueous solution in, 70 DEG C dissolving 5~7 hours bombyx mori silk fibroin dissolving mixed solution.
(3) glucan G-50 and G-25 are weighed to be respectively put into the deionized water of abundance, boiling water bath 1.5 hours, treats normal temperature Drained and loaded in the void column of glass material with glass bar after cooling, prepare bed volume 2cm × 60cm, natural subsidence is after 2 hours Pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
(4) for the last time when equilibrium water drops to column material surface, the fibroin egg of dissolving is added into glucan G-50 White 5~15ml of mixed solution (10~50mg/ml), when fibroin albumen mixed solution is completely into column material surface, continue Eluted with sterile deionized water, peristaltic pump control eluent flow rate 300mL/h;It is in charge of collection efflux, until flowing to end fibroin egg In vain.
(5) using the molecular weight distribution of SDS-PAGE electrophoresis or each pipe of Mass Spectrometric Identification, by fibroin of the molecular weight less than 10kDa Protein solution is freeze-dried mixed, is then configured to the 30~80mg/ml aqueous solution, and microparticle is removed with 0.45 μm of membrane filtration.
(6) similar step (4), the silk fibroin water solution of appropriate step (5), peristaltic pump control are added to G-25 column material Eluent flow rate 50mL/h processed, is in charge of collection efflux, until flowing to end fibroin albumen, obtains the silk of 1000~5000Da molecular weight The fibroin aqueous solution, finally freeze and preserve.
(7) weaving polyester fabric is boiled with 6g/1L aqueous sodium carbonate at 100 DEG C and boiled 1 hour or so, taken out with certainly Water repeatedly dry by washes clean, dehydration.Then with handling polyester fabric 1~2 hour at 10% 30 DEG C of sodium hydroxide solution, Be impregnated in after tap water rinse is clean certain mass concentration carbodiimides and n-hydroxysuccinimide (quality respectively may be about Add the 25% of fibroin albumen quality, in mixed aqueous solution 10%), impregnate 1 hour or so, add the fibroin that step 6 obtains After protein dry powder (fibroin albumen final mass concentration is 1%) dissolving, 3h is reacted, taking-up is dried, rinsed, drying again.
(8) polyester fabric that fibroin albumen is modified is cut into 15cm × 30cm sample, tried using material mechanical performance The machine of testing measures 97% or so that fracture strength is original fabric, and elongation at break is 97% or so of original fabric.
(9) the fibroin albumen rate of body weight gain 5.2% on polyester fabric is measured using weight method, is significantly higher than the increasing of comparative example 2 Rate 0.92% again.The fabric that fibroin albumen is modified is impregnated in after being vibrated 24 hours in 37 DEG C of warm water, measures fibroin albumen Dissolve-loss ratio is less than 8%.
Comparative example 1
(1) silkworm raw silk is pressed 1:50 (g/mL) bath raio is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~ Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:20 (g/mL) bath raio is dissolved in mol ratio 1:2 calcium chloride-ethanol The aqueous solution in, 70 DEG C dissolving 5~7 hours bombyx mori silk fibroin dissolving mixed solution.
(3) glucan G-50 and G-25 are weighed to be respectively put into the deionized water of abundance, boiling water bath 1.5 hours, treats normal temperature Drained and loaded in the void column of glass material with glass bar after cooling, prepare bed volume 2cm × 60cm, natural subsidence is after 2 hours Pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
(4) for the last time when equilibrium water drops to column material surface, the fibroin egg of dissolving is added into glucan G-50 White 5~15ml of mixed solution (10~50mg/ml), when fibroin albumen mixed solution is completely into column material surface, continue Eluted with sterile deionized water, peristaltic pump control eluent flow rate 300mL/h;It is in charge of collection efflux, until flowing to end fibroin egg In vain.
(5) using the molecular weight distribution of SDS-PAGE electrophoresis or each pipe of Mass Spectrometric Identification, by fibroin of the molecular weight less than 10kDa Protein solution is freeze-dried mixed, is then configured to the 30~80mg/ml aqueous solution, and microparticle is removed with 0.45 μm of membrane filtration.
(6) similar step (4), the silk fibroin water solution of appropriate step (5), peristaltic pump control are added to G-25 column material Eluent flow rate 50mL/h processed, is in charge of collection efflux, until flowing to end fibroin albumen, obtains the silk of 1000~5000Da molecular weight The fibroin aqueous solution, finally freeze and preserve.
(7) weaving polyester fabric is boiled with 6g/1L aqueous sodium carbonate at 100 DEG C and boiled 1 hour or so, taken out with certainly Water repeatedly after washes clean, be impregnated in the aqueous solution for the fibroin albumen that the step 6 that mass concentration is 0.5% obtains, room temperature Continuous action and the same time of embodiment 1~4, taking-up are dried, rinsed, drying again.
(8) the fibroin albumen rate of body weight gain 0.9% on polyester fabric, the hot water dissolve-loss ratio of fibroin albumen are measured using weight method About 25%.
Comparative example 2
(1) silkworm raw silk is pressed 1:50 (g/mL) bath raio is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~ Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:20 (g/mL) bath raio is dissolved in mol ratio 1:2 calcium chloride-ethanol The aqueous solution in, 70 DEG C dissolving 5~7 hours bombyx mori silk fibroin dissolving mixed solution.
(3) glucan G-50 and G-25 are weighed to be respectively put into the deionized water of abundance, boiling water bath 1.5 hours, treats normal temperature Drained and loaded in the void column of glass material with glass bar after cooling, prepare bed volume 2cm × 60cm, natural subsidence is after 2 hours Pressurizeed with peristaltic pump, the deionized water balance pillar of 5 times of column volumes three times.
(4) for the last time when equilibrium water drops to column material surface, the fibroin egg of dissolving is added into glucan G-50 White 5~15ml of mixed solution (10~50mg/ml), when fibroin albumen mixed solution is completely into column material surface, continue Eluted with sterile deionized water, peristaltic pump control eluent flow rate 300mL/h;It is in charge of collection efflux, until flowing to end fibroin egg In vain.
(5) using the molecular weight distribution of SDS-PAGE electrophoresis or each pipe of Mass Spectrometric Identification, by fibroin of the molecular weight less than 10kDa Protein solution is freeze-dried mixed, is then configured to the 30~80mg/ml aqueous solution, and microparticle is removed with 0.45 μm of membrane filtration.
(6) similar step (4), the silk fibroin water solution of appropriate step (5), peristaltic pump control are added to G-25 column material Eluent flow rate 50mL/h processed, is in charge of collection efflux, until flowing to end fibroin albumen, obtains the silk of 1000~5000Da molecular weight The fibroin aqueous solution, finally freeze and preserve.
(7) weaving polyester fabric is boiled with 6g/1L aqueous sodium carbonate at 100 DEG C and boiled 1 hour or so, taken out with certainly Water repeatedly after washes clean, be impregnated in the aqueous solution for the fibroin albumen that the step 6 that mass concentration is 1% obtains, room temperature is held Continuous effect and the same time of embodiment 1~4, taking-up are dried, rinsed, drying again.
(8) the fibroin albumen rate of body weight gain 0.92% on polyester fabric, the molten mistake of hot water of fibroin albumen are measured using weight method Rate about 25%.
Comparative example 3
(1) silkworm raw silk is pressed 1:50 (g/mL) bath raio is put into the aqueous sodium carbonate that concentration is 0.2%, in 98~ Silk three times, 30 minutes per treatment, is then fully cleaned up, pulled loose by 100 DEG C of processing with deionized water, is placed in baking oven and is done It is dry, obtain the bombyx mori silk fibroin fiber after degumming.
(2) bombyx mori silk fibroin after degumming is weighed by 1:15 (g/mL) bath raio is dissolved in 9.3M lithium bromide water solutions, and 65 DEG C dissolving 5~7 hours bombyx mori silk fibroin dissolving mixed solution.
(3) bombyx mori silk fibroin lysate being poured into bag filter, bag filter wall is pellicle, molecular cut off is 12.0~ 16.0kDa scopes, the bag filter for being filled with bombyx mori silk fibroin lysate is placed in the container for filling deionized water, every 2 hours The water in container is changed with new deionized water or pure water, persistently dialyses 3 days, obtains the silk fibroin protein aqueous solution after purification (preparation of conventional silk fibroin water solution), then freeze and preserve.
(4) weaving polyester fabric is boiled 1 hour or so with 6g/1L aqueous sodium carbonate boiling, taking-up originally water washing, It is dehydrated, dries or dries, then with polyester fabric is handled at 10% 30 DEG C of sodium hydroxide solution 1~2 hour, is impregnated after rinsing In the carbodiimides and n-hydroxysuccinimide of certain mass concentration, (quality, which respectively may be about, adds fibroin albumen quality 25%th, in mixed aqueous solution 10%), impregnate 1 hour or so, add lyophilized fibroin albumen (the final matter of fibroin albumen of step 3 After concentration is measured 1%) to dissolve, 3h is reacted, taking-up is dried, rinsed, drying again.
(5) polyester fabric that fibroin albumen is modified is cut into 15cm × 30cm sample, tried using material mechanical performance The machine of testing measures 94% or so that fracture strength is original fabric, and elongation at break is 97% or so of original fabric.
(6) the fibroin albumen rate of body weight gain 1.4% on polyester fabric, the fabric that fibroin albumen is modified are measured using weight method It is impregnated in after being vibrated 24 hours in 37 DEG C of warm water, the dissolve-loss ratio for measuring fibroin albumen is less than 10%.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (10)

  1. A kind of 1. fibroin method of modifying of polyester fabric, it is characterised in that 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, mixed instead with the fibroin albumen of 1000~5000Da molecular weight Should.
  2. 2. according to the method for claim 1, it is characterised in that the crosslinking agent includes carbodiimides.
  3. 3. according to the method for claim 2, it is characterised in that the carbodiimides accounts for the mass percent of fibroin albumen For 20%~40%.
  4. 4. the destarch is specially using at sodium carbonate destarch according to the method for claim 1, it is characterised in that step A) Reason;The concentration of the sodium carbonate liquor is 6g/L;The destarch treatment temperature is 90~100 DEG C;The destarch processing time is 1h。
  5. 5. according to the method for claim 1, it is characterised in that step B) mass concentration of the sodium hydroxide for 5%~ 30%;The treatment temperature of the sodium hydroxide is 30~40 DEG C;The processing time of the sodium hydroxide is 1~3h.
  6. 6. the reaction temperature is 25~35 DEG C according to the method for claim 1, it is characterised in that step C);It is described anti- It is 1~3h between seasonable.
  7. 7. according to the method for claim 1, it is characterised in that the fibroin albumen of 1000~5000Da molecular weight according to It is prepared by following method:
    A) silkworm silk is subjected to degumming using sodium carbonate and then adds neutral salt solution dissolving, prepare fibroin albumen lysate;
    Glucan Sephadex G50 and G25 column equilibrations is stand-by;
    B) fibroin albumen lysate is added in glucan Sephadex G50 posts, with sterilizing water elution fibroin albumen, is in charge of receipts Collect the silk fibroin water solution of desalination;
    C) using the fibroin albumen of below 10kD in SDS-PAGE electrophoresis or mass spectrum screening step b) collecting pipes, Portugal is added again and is gathered In sugared Sephadex G25 posts, with sterilizing water elution fibroin albumen, it is in charge of collection, screening obtains 1000~5000Da small molecule Measure fibroin albumen.
  8. 8. according to the method for claim 7, it is characterised in that the step a) neutral salt solutions are selected from lithium bromide or chlorination Calcium-ethanol;The dissolution time is 5~7 hours;The fibroin albumen lysate concentration is 10~50mg/mL.
  9. 9. according to the method for claim 7, it is characterised in that below 10kD in step c) the screening step b) collecting pipes Fibroin albumen after also include it is lyophilized, be then configured to 30~80mg/mL aqueous solution.
  10. 10. according to the method for claim 7, it is characterised in that the step b) elution flow rates are 200~400mL/h;Step Rapid c) described elution flow rate is 30~70mL/h.
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CN108642878A (en) * 2018-04-19 2018-10-12 中原工学院 A method of arranging polyester fabric using fibroin albumen and gamma-polyglutamic acid self-assembly
CN111793981A (en) * 2020-07-10 2020-10-20 温州厚德服饰有限公司 Moisture permeable cotton-padded clothes
CN112853748A (en) * 2020-12-23 2021-05-28 南通雅文纺织品有限公司 Production process of soft fabric for quilt cover

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108642878A (en) * 2018-04-19 2018-10-12 中原工学院 A method of arranging polyester fabric using fibroin albumen and gamma-polyglutamic acid self-assembly
CN108642878B (en) * 2018-04-19 2020-11-27 中原工学院 Method for finishing polyester fabric by using silk fibroin and gamma-polyglutamic acid self-assembly
CN111793981A (en) * 2020-07-10 2020-10-20 温州厚德服饰有限公司 Moisture permeable cotton-padded clothes
CN112853748A (en) * 2020-12-23 2021-05-28 南通雅文纺织品有限公司 Production process of soft fabric for quilt cover

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