CN106591993B - A kind of gelatin fiber spinning process - Google Patents
A kind of gelatin fiber spinning process Download PDFInfo
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- CN106591993B CN106591993B CN201610976347.9A CN201610976347A CN106591993B CN 106591993 B CN106591993 B CN 106591993B CN 201610976347 A CN201610976347 A CN 201610976347A CN 106591993 B CN106591993 B CN 106591993B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/10—Filtering or de-aerating the spinning solution or melt
- D01D1/103—De-aerating
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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Abstract
The invention discloses a kind of gelatin fiber spinning process, the preparation method includes being mixed with crosslinking agent after being swollen Gelatin in solvent, obtained mixed liquor is added in spinning equipment, as-spun fibre is made, and gelatin fiber finished product is obtained after being post-processed to it.Select transglutaminase as crosslinking agent in the present invention, safe to use, stability is good in water for gelatin fiber obtained, and mechanical property is improved, and biological and medical field is applicable to.
Description
Technical field
The present invention relates to fabric manufacturing area, more particularly to a kind of gelatin fiber spinning process and its product.
Background technology
Gelatin is a kind of peptide molecule polymeric material, is to have good bio-compatible obtained from being hydrolyzed by collagenous portion
Property and degradability and be widely used in food, medicine and other fields.Gelatin fiber mainly uses method of electrostatic spinning to prepare, Yin Qisheng
Produce less efficient, sight is gathered wet spinning process by domestic scholars, and the pure gelatin fiber mechanical strength of wet method spinning is not
It is high, soluble easily in water at normal temperatures, limit the scope of application of gelatin.
In order to improve these performances of gelatin, it is usually necessary to use blending and modifying or the means such as cross-linking modified.Blending and modifying is big
The additive amount of modifying agent is more (as described in CN 105001463A) in molecular material, to be unable to fully embody gelatin materials certainly
The excellent performance of body.Common crosslinking agent generally all has stronger toxicity when cross-linking modified, such as metal ion, formaldehyde, penta 2
Aldehyde, epoxide etc. limit application of the gelatin in biological and medical field, so finding new non-toxic crosslinker becomes one
A new research direction.
Invention content
To solve the above-mentioned problems, present inventor has performed sharp studies, as a result, it has been found that：Using transglutaminase
(TGase enzymes) is modified gelatin fiber as crosslinking agent, and gelatin fiber stability in water and mechanics both can be improved
Performance (fracture strength and elongation at break), and TGase enzyme heat stabilities are strong, safe to use, gelatin fiber obtained can be extensive
Applied to biological and medical field, thereby completing the present invention.
The purpose of the present invention is to provide following aspect：
(1) a kind of spinning process of gelatin fiber, includes the following steps：
Step 1, by Gelatin in solvent, cross-linking agents Ⅰ is added and is mixed；
Step 2, the mixed liquor in step 1 is added in spinning equipment, obtains as-spun fibre.
(2) method according to above-mentioned (1), wherein in step 1, weigh gelatin and be added in solvent, at a set temperature
It is swollen, crosslinking agent is added after the completion of swelling and is crosslinked, the solvent is water, and the weight ratio of gelatin and solvent is 1:1.3
~1:3.0, preferably 1:1.6~1:2.0；And/or
The swelling temperature of gelatin in a solvent is 50~70 DEG C, preferably 55~65 DEG C；
Preferably, the swelling includes first standing swelling and posterior stirring swelling, the time for standing swelling
Time for 0.5~2h, the stirring swelling is 1~3h.
(3) method according to above-mentioned (1) or (2), wherein in step 1, the cross-linking agents Ⅰ turns selected from glutamine
Move any one or more in enzyme, trimethylolpropane, glutaraldehyde or glycerine, preferably transglutaminase；And/or
The mass ratio of cross-linking agents Ⅰ and gelatin is 0.05:100~1:100, preferably 0.1:100~0.5:100；And/or
Cross-linking agents Ⅰ is crosslinked 0.1h~3h with gelatin at 50~70 DEG C, and preferably cross-linking agents Ⅰ is handed over gelatin at 55~65 DEG C
Join 0.5h~1.5h.
(4) method according to one of above-mentioned (1) to (3), wherein in step 2, mixed liquor in step 1 is added
In the head tank of wet-spinning frame, enters in coagulating bath after spinneret, as-spun fibre is obtained after solidification；Wherein,
The temperature of head tank is 50~70 DEG C, preferably 55~65 DEG C；Mixed liquor carries out deaeration, preferably vacuum before spinneret
Deaeration.
(5) method according to above-mentioned (4), wherein in step 2, the coagulating bath is the sulphur of 200g/L~430g/L
Acid sodium aqueous solution；And/or
The coagulation bath temperature is 30~50 DEG C, preferably 35~45 DEG C；And/or
The spinning speed of as-spun fibre is 30~100m/min, preferably 60~80m/min；
Preferably, in the coagulating bath further include crosslinking agent II, a concentration of 2% (weight)~10% (weight of crosslinking agent II
Amount), preferably 4% (weight)~6% (weight)；The crosslinking agent II is selected from transglutaminase, trimethylolpropane, penta
Any one or more in dialdehyde or glycerine, preferably transglutaminase.
(6) method according to one of above-mentioned (1) to (5), wherein the method further includes being led to as-spun fibre
Stretch, the drawing-off carries out 2~8 times of drawing-offs at 20~35 DEG C, and draft speed is 120~240m/min, the preferably described drawing-off in
2~4 times of drawing-offs are carried out at 25~30 DEG C, draft speed is 150~200m/min.
(7) method according to above-mentioned (6), wherein the method further includes that the gelatin fiber after making drawing-off is being crosslinked
It is further crosslinked in liquid, obtains finished fiber；And/or
A concentration of 0.5~5% (weight) of the crosslinking bath, 20~35 DEG C of temperature, crosslinking Treatment 0.5h~10h；And/or
Crosslinking agent III is arbitrary in transglutaminase, trimethylolpropane, glutaraldehyde or glycerine in crosslinking bath
It is one or more, preferably transglutaminase.
According to a kind of gelatin fiber spinning process provided by the invention, have the advantages that：
(1) in entire preparation method, using water as solvent, organic solvent is not introduced, it is at low cost, green safe；
(2) entire preparation method is simple for process, and the production equipment used is of less demanding, while easily operated, reduces
Cost, these factors are conducive to the popularization of industrialization；
(3) the gelatin as-spun fibre for using transglutaminase to be prepared as crosslinking agent, with untreated gelatin fibre
Dimension is compared, and water absorption rate can reduce by 35.18%, and fracture strength improves 144.47%, and extension at break improves 73.05%, 700 DEG C
Carbon left is 17.79%, and stability is good in water for as-spun fibre, and mechanical property is improved, and is applicable to after post-processing
Biological and medical field；
(4) by carrying out the drawing-off of reasonable drafting multiple to gelatin fiber, the fracture strength of gelatin fiber is by undrawn
53.71MPa increases to 152.85MPa, improves 184.58%；Elongation at break increases to 8.78 by undrawn 2.99, increases
Add 193.65%, mechanical property is improved；
(5) present invention is crosslinked using three steps, i.e., crosslinking agent is added in spinning solution and is tentatively crosslinked, in coagulating bath
Crosslinking agent is added to be crosslinked again, the fiber after last counter extensioin is further crosslinked in crosslinking is bathed, and the crosslinking of three steps can be into one
Step reduces the water solubility of gelatin fiber, and can improve mechanical property.
Description of the drawings
Fig. 1 is the infrared spectrum that as-spun fibre sample is made in embodiment 4 and comparative example 1 in the present invention；
Fig. 2 is the shear viscosity figure of spinning solution in Examples 1 to 4 and comparative example 1 in the present invention；
Fig. 3 is the TG curves that as-spun fibre sample is made in embodiment 4 and comparative example 1 in the present invention.
Specific implementation mode
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
The object of the present invention is to provide a kind of spinning process of gelatin fiber, include the following steps：
Step 1, by Gelatin in solvent, cross-linking agents Ⅰ is added and is mixed；
Step 2, the mixed liquor in step 1 is added in spinning equipment, obtains as-spun fibre.
In step (1), weighs gelatin and be added in solvent, be swollen at a set temperature, crosslinking is added after the completion of swelling
Agent I is crosslinked, and spinning solution is obtained.
In the present invention, solvent is water.The weight ratio of gelatin and solvent is 1:1.3~1:3.0, weight ratio is less than 1:1.3
Gelatin concentration is high, and viscosity is big, is unfavorable for the quick dissolving of gelatin；Weight ratio is more than 1:When 3.0, concentration is relatively in water for gelatin
Low, addition cross-linking agents Ⅰ post-crosslinking reaction is slow, and excessive water is unfavorable for solidification sizing of the gelatin fiber in follow-up.
In a preferred embodiment, the weight ratio of gelatin and solvent is 1:1.6~1:2.0.
In the present invention, the swelling is included in the standing swelling and stirring swelling followed by first carried out, described quiet
The time for setting swelling is 0.5~2h, and the time of the stirring swelling is 1~3h, ensure that Gelatin is complete, lysate is equal
It is even.
In the present invention, the swelling temperature of gelatin in a solvent is 50~70 DEG C, preferably 55~65 DEG C.It is big for gelatin
For molecule, temperature increases, and destroys the hydrogen bond of gelatin, is conducive to the swelling of gelatin, and temperature is higher than 70 DEG C, and swelling rate increase is not
Obviously.
In the present invention, the cross-linking agents Ⅰ is selected from transglutaminase, trimethylolpropane, glutaraldehyde or glycerine
In any one or more, preferably transglutaminase.
Transglutaminase (TGase) is a kind of biological enzyme, and the glutamine for capableing of catalytic polypeptide or protein is free
γ-hydroxyamine groups (donor of acyl group) and many primary amino-compounds (receptor of acyl group) between amide transfer reaction, can be with
Peptide bond in gelatin molecule is reacted to the crosslinking realized between gelatin molecule with transglutaminase.TGase enzymes are widely present in
Animal tissue, and harmless, e- (g- glutamy) lysine as people are formed in edible TGase enzymatics always are different
The food of peptide bond uses TGase enzymes to prepare gelatin fiber for crosslinking agent, and the TGase enzymes remained in gelatin fiber will not be right
Body generates harm, and solving to use in current production has stronger toxicity such as metal ion, formaldehyde, glutaraldehyde, epoxidation
Close the problem of object crosslinking agent is brought.
In the present invention, the mass ratio of cross-linking agents Ⅰ and gelatin is 0.05:100~1:100, preferably 0.1:100~0.5:
100.With stirring during cross-linking agents Ⅰ is added and reacts, with the progress of stirring, cross-linking agents Ⅰ is dispersed in rapidly reactant
In system, it is excessive to avoid local concentration, accelerates reaction and carries out.
In the present invention, cross-linking agents Ⅰ and gelatin be crosslinkeds 0.1h~3h at 50~70 DEG C, preferably cross-linking agents Ⅰ and gelatin in
0.5h~1.5h is crosslinked at 55~65 DEG C.
Additive amount, crosslinking temperature and the crosslinking time of cross-linking agents Ⅰ have the mobility of spinning solution important influence.It hands over
The additive amount of connection agent I is fewer or crosslinking temperature is lower, and the speed of cross-linking reaction is slow in spinning solution, needs to expend longer
In the reaction time, if crosslinking time is shorter, the degree of cross linking is too low, and the mobility of spinning solution is strong, is unfavorable for the molding of fiber.
The additive amount of cross-linking agents Ⅰ is more or crosslinking temperature is higher, and the speed of cross-linking reaction is faster in spinning solution, hands over
The uniformity of connection is more difficult to control, if crosslinking time is long, the degree of cross linking is excessively high, and mobility is deteriorated, and enters in follow-up coagulating bath
Filamentous stoste deformation is big, and fibre number unevenness rate is caused to increase.
In step 2, mixed liquor in step 1 (spinning solution) is added in the head tank of wet-spinning frame, spinning solution
By booster pump, filter, metering pump, gooseneck, enter in coagulating bath after spinning head spinneret, nascent fibre is obtained after solidification
Dimension.
In the present invention, the temperature of head tank is 50~70 DEG C, preferably 55~65 DEG C, can be effective in this temperature range
Keep the mobility of spinning solution.
In the present invention, it due to gelatin swelling in a solvent and is stirred to react, a large amount of gas can be contained in spinning solution
Bubble carries out complete deaeration to spinning solution (mixed liquor) before spinneret, avoids bubble from causing the mechanical property of fiber bad
It influences.Preferably, vacuum defoamation is carried out to spinning solution.
In the present invention, the coagulating bath is the aqueous sodium persulfate solution of 200g/L~430g/L.The concentration of coagulating bath influences
The setting rate of as-spun fibre, solidification bath concentration is bigger, and setting rate is faster, and spinning speed can improve, but setting rate mistake
Fiber " core-skin " structure is easily led to soon, and will also result in sulfate crystal precipitation, influences spinning environment, while being also unfavorable for spinning
Stability.
In a preferred embodiment, crosslinking agent II is added in coagulating bath, the crosslinking agent II is selected from glutamy
Any one or more in amine transferase, trimethylolpropane, glutaraldehyde or glycerine, preferably transglutaminase.
As-spun fibre of the present invention preferably uses two steps to be crosslinked, i.e., cross-linking agents Ⅰ is added in spinning solution and is tentatively crosslinked,
Crosslinking agent II is added in coagulating bath to be crosslinked again.Crosslinked purpose is that the gelatin into coagulating bath is prevented to be dissolved in again
Water reduces its water solubility, and further improves the mechanical property such as fracture strength and elongation at break of as-spun fibre.
In further preferred embodiment, a concentration of 2% (weight)~10% (weight of the crosslinking agent II in coagulating bath
Amount), within this range, can effectively inhibit the dissolving of gelatin, and avoid crosslinking rate it is too fast caused by it is surface-crosslinked, internal not
The case where crosslinking.Preferably, a concentration of 4% (weight)~6% (weight) of the crosslinking agent II in coagulating bath.
In the present invention, the coagulation bath temperature is 30~50 DEG C, preferably 35~45 DEG C.As coagulation bath temperature is from 30
DEG C 50 DEG C are increased to, the macromolecular chain segment of gelatin is easier free movement, it is easier to be orientated to drawing-off direction, form accurate orderly knot
Structure.However, coagulation bath temperature is excessively high (being more than 50 DEG C), then as-spun fibre setting rate is excessively slow；And temperature is low (being less than 30 DEG C), then
Setting rate is too fast, and crystallinity is inconsistent inside and outside as-spun fibre, unstable mechanical property.
In the present invention, the spinning speed of as-spun fibre is 30~100m/min, preferably 60~80m/min.Wet-spinning
As-spun fibre in silk is in solvent swelling state due to containing big quantity of fluid, and macromolecular has prodigious activity in as-spun fibre
Property, poor mechanical property, and the degree of orientation is very low.As-spun fibre spinning speed is higher than 100m/min, is easy to break as-spun fibre, and
As-spun fibre spinning speed is less than 30m/min, and adhesion is easy to happen between single fiber, can not form the monofilament that can be detached, and viscous
Spinneret phenomenon is serious, and fibre forming is difficult.On the other hand, when in coagulating bath added with crosslinking agent, changing spinning speed can be with
Control crosslinking time can be such that the uniformity of the degree of cross linking inside and outside as-spun fibre improves within the scope of above-mentioned spinning speed.
In a preferred embodiment, the method further includes carrying out drawing-off to as-spun fibre.
Drafting process promotes the supramolecular structure of fiber to change, and the degree of orientation of especially fiber improves a lot.
Crystallinity increases (intrastitial crystalline transition is the variant relatively stablized), leads to the physical mechanics properties such as intensity, the elongation of fiber
It can improve.
In the present invention, the drawing-off carries out 2~8 times of drawing-offs at 20~35 DEG C, and draft speed is 120~240m/
Min, the preferably described drawing-off carry out 2~4 times of drawing-offs at 25~30 DEG C, and draft speed is 150~200m/min.
Drawing temperature is serious less than room temperature fiber frozen glueization, and drawing-off is difficult, and drawing temperature is high, frozen glue strand moisture evaporation amount
Greatly, the plasticization of solvent reduces, and is also unfavorable for stretching, and temperature is required for heating or freezing and expend higher or lower than room temperature
Energy.Drafting multiple is higher, and fiber-wall-element model degree is higher, and fracture strength is higher, but drafting multiple is excessively high, and fiber is broken；It leads
It is low to stretch multiple, fiber stretches deficiency, and the degree of orientation is low, and intensity declines.Draft speed is faster, and stretching tensile stress is bigger, is higher than 240m/
There is lousiness, broken end in fiber when min., and tensile speed is too slow, and fiber-wall-element model is insufficient, and intensity declines, and draw efficiency reduces.
In a preferred embodiment, the method for the present invention further include gelatin fiber after making drawing-off in crosslinked fluid into
The further crosslinking of row, obtains finished fiber.
In the present invention, a concentration of 0.5~5% (weight) of crosslinking agent III, 20~35 DEG C of temperature, at crosslinking during crosslinking is bathed
Manage 0.5h~10h.Crosslinking agent III is in transglutaminase, trimethylolpropane, glutaraldehyde or glycerine in crosslinking bath
Any one or more, preferably transglutaminase.Further crosslinking can significantly improve the heat-resisting water-soluble of gelatin fiber
Property, and mechanical property can be improved.
Embodiment
The present invention is further described below by way of specific example.But these examples are only exemplary, not to this
The protection domain of invention constitutes any restrictions.
Raw material and its source are in the present invention：Gelatin (Beijing University of Chemical Technology, food-grade)；Transglutaminase (Taixing
Dong Sheng food science and technologies Co., Ltd of city, food-grade)；Sodium sulphate (Zhongyan Dongxing Salt Chemical Co., Ltd., technical grade).
Embodiment 1
Step 1, it weighs 110g gelatin to be added in the beaker for filling 190ml water, is stood in 60 DEG C of water-baths and be swollen 2h, then with
110r/min stirrings 3h obtains gelatin solution；The TGase enzymes of 10mL 0.011g/mL are added into gelatin solution (for gelatin quality
0.1%), at 60 DEG C stir 1h obtain spinning solution；
Step 2, spinning solution is added to the original fluid container of spinning-drawing machine, original fluid container temperature 60 C, from micropore after vacuum defoamation 2h
The spinning head of diameter 0.09mm enters solidification in coagulating bath and obtains as-spun fibre, and coagulating bath is containing 5% (weight) TGase enzymes
The aqueous sodium persulfate solution of 430g/L, coagulation bath temperature are 40 DEG C, and spinning speed is 80m/min, obtains the as-spun fibre of gelatin, sample
Product number is 1#.
Embodiment 2~4
Operating procedure is same as Example 1, differs only in the TGase enzymes for changing the step and being added into gelatin solution in 1
Amount, the TGase enzymes for being separately added into 10mL 0.0165g/mL, 0.022g/mL and 0.0275g/mL (are respectively gelatin quality
0.15%, 0.20% and 0.25%), obtained gelatin as-spun fibre number consecutively be 2# (embodiment 2), 3# (embodiment 3) and
4# (embodiment 4).
Embodiment 5~7
Operating procedure is same as Example 3, differs only in spin as-spun fibre in 25 DEG C and stretches speed for 180m/min, divides
It is other to 2 times, 3 times and 4 times of drawing of fiber, obtained gelatin fiber number consecutively be 5# (embodiment 5) and 6# (embodiment 6) and 7#
(embodiment 7).
Embodiment 8~10
Operating procedure is same as Example 3, differs only in and is carried out with 3 times of 180m/min progress in 25 DEG C to as-spun fibre
Drawing-off, by the gelatin fiber after drawing-off when it is 2%, 3% and 4% to be crosslinked bath concentration (mass fraction of TGase enzymes), in 25 DEG C
Under crosslinking bathe in crosslinking Treatment 1.0h, obtain gelatin fiber finished product number consecutively be 8# (embodiment 8) and 9# (embodiment 9) and
10# (embodiment 10).
Comparative example 1
Operating procedure is same as Example 1, differs only in step 1 " TGase enzymes are added not into gelatin solution ", obtains
To finished gelatin fiber number be D1#.
Embodiment and comparative example conditions correlation is as shown in table 1：
1 embodiment and comparative example conditions correlation of table
Experimental example
Rheology testing：Using 200 solution rotating rheometers of Bohlin Gemini HR Nano, shear rate is
20s-1。
Examination of infrared spectrum：Using the NicoletNexus670 type infrared lights of Thermo Nicolet Company companies
Spectrometer, scanning range：500-4000cm-1。
Water absorption rate test：Take 10cm fiber samples in vacuum drying oven 50 DEG C of dryings until constant weight.Weigh m1After be put into
In 50ml distilled water, 10min is impregnated under room temperature (25 DEG C).The moisture that fiber surface is blotted with filter paper, weigh m2, then by sample
Being put into vacuum drying oven 50 DEG C, drying to constant weight, and weigh m3；The measurement of water absorption rate, which repeats five times, to be averaged, wherein：
Water absorption rate/%=(m2-m3)/m3。
TG is tested：After sample dries 3h under 60 DEG C of vacuum conditions, using the Netzsch TG of German Nai Chi companies
The TG thermogravimetric analyzers of 209F1 types measure its thermal stability, heating rate：10 DEG C/min, N2Atmosphere is enclosed.
Mechanics Performance Testing：The fracture strength of gelatin fiber is tested using U.S.'s Instron universal testing machines and is broken
Split elongation.It is 20mm, 25 DEG C of experimental temperature, drafting rate 20mm/min that sample, which accommodates length,.
Influence of the 1 TGase enzymes of experimental example to gelatin molecule structure
In the present invention, fiber sample is made in vacuum drying oven after 60 DEG C of dry 3h in embodiment 4 and comparative example 1, is carried out
IR spectrum scanning, the results are shown in Figure 1.
As seen from Figure 1, the D1# gelatin as-spun fibres of TGase enzymes are not added in 1630cm-1The absorption peak at place belongs to bright
C=O stretching vibrations in glue amido bond, i.e. amide Ⅰ；1522cm-1Belong to II band of amide, is N-H flexural vibrations peaks；
1233cm-1It is then C-N stretching vibrations, Amide Ⅲ band.The amide A bands of gelatin are in 3287cm-1Left and right appearance corresponds to gelatin
N-H stretching vibrations and O-H stretching vibrations vibration, absorb peak position and absorption intensity and hydrogen bond association degree and three spiral knots
Structure order degree is closely related.
In the 4# gelatin fiber middle peak of spectrograms of addition 0.0275g/mL (additive amount is the 0.25% of gelatin quality) TGase enzymes
Position and the D1# samples for not adding TGase enzymes do not have a significant change, and amide A bands, I band and II peak intensity with characteristic absorption peak
Degree reduces.Remitted its furys of the amide A with absorption peak, this is because with after TGase enzyme reactions ,-the NH in gelatin chains2Quantity
It reduces；The absorption peak of II band of amide I band and amide after the reaction peak intensity decline, this may with react after-NH2Number is reduced,
The number reduction that gelatin molecule interchain forms hydrogen bond is related.
The reaction equation that amido in TGase enzymatic gelatin chains reacts is：
Glu-CO-NH2+RNH2→Glu-CO-NHR+NH3
Influence of the 2 TGase enzymes of experimental example to spinning solution rheological characteristic
The molecular weight of gelatin has great influence to the rheological property of spinning solution and the spinnability of gelatin.From INFRARED SPECTRUM
Map analysis show that TGase enzymes are reacted with the amino in gelatin chains.In mutually synthermal and polymer concentration, gather
The shear viscosity of polymer solution is related with the molecular weight of polymer.Spinning solution in Examples 1 to 4 and comparative example 1 is flowed
Become test, determines influence of the TGase enzymes to gelatine molecular weight.
From figure 2 it can be seen that when temperature is 60 DEG C, the additive amounts of TGase enzymes from 0 increase to 0.0275g/mL when gelatin
The shear viscosity of stoste is gradually increased to 25Pas from 6Pas, illustrates that TGase enzymes and the amido of gelatin molecule interchain have occurred
Cross-linking reaction makes the molecular weight of gelatin increase, and increases with the increase of TGase enzyme concentrations within the scope of 0~0.0275g/mL.
The increase of gelatine molecular weight is conducive to improve the mechanical property of gelatin fiber.
Influence of the 3 TGase enzymes of experimental example to water imbibition
Water absorption rate can indirectly reflect the crosslinking degree of material.To difference TGase enzymes in Examples 1 to 4 and comparative example 1
Gelatin fiber prepared by additive amount carries out water absorption rate measurement, and the results are shown in Table 2.
From Table 2, it can be seen that containing a large amount of hydrophilic radical in gelatin, hygroscopic swelling in water at room temperature is inhaled
Water rate is 901%.With the increase of TGase enzyme additive amounts, the water absorption rate of gelatin fiber continuously decreases, and works as the dense of TGase enzymes
The water absorption rate of degree fiber when be 0.0275g/mL (additive amount is the 0.25% of gelatin quality) is minimum, is 584%, relative to not adding
The gelatin fiber water absorption rate of TGase enzymes is added to reduce by 35.18%.This is because as TGase enzyme contents increase, gelatin molecule interchain
Crosslinking degree increases and hydrophilic radical reduction causes hydrone to be difficult to penetrate into, and cannot be formed in conjunction with water.The reduction of water absorption rate has
Conducive to stable structure of the gelatin fiber in water environment.
Table 2 is crosslinked front and back gelatin fiber water absorption rate
Influence of the 4 TGase enzymes of experimental example to thermal stability
The thermal stability of gelatin fiber processes it and performance has large effect.By embodiment 4 and comparative example 1
Obtained fiber sample measures TG curves after 60 DEG C of dry 3h in a vacuum.
As shown in figure 3, all there are one the weightless mistakes lost in conjunction with water between 50 DEG C to 250 DEG C for D1# and 4# gelatin fibers
Journey.Gelatin fiber occurs drastically weightless between 200 DEG C~350 DEG C, and weightless process variances are little.At 530 DEG C~700 DEG C
When, 4# cross-linked gelatin fiber weightlessness tends towards stability, and D1# gelatin fibers are acutely weightless again.At 700 DEG C, the uncrosslinked gelatin of D1#
The carbon left of fiber is close to 0, and the final carbon left of 1# cross filaments is 17.79%, adds the gelatin fiber after TGase enzymes
Thermal stability improve.
The influence to mechanical property is crosslinked after 5 TGase enzymes of experimental example, drawing-off and drawing-off again
Mechanical property, especially drawing-off intensity and elongation at break are to limit the important indicator of fiber applications.To that will implement
Example 4 and comparative example 1 are made carries out Mechanics Performance Testing without draft fiber sample, the results are shown in Table 3.
As shown in Table 3, it is all shown as after first increasing with the increase fracture strength and elongation at break of TGase enzyme additive amounts
Reduce.When a concentration of 0.022g/mL (additive amount 0.20%), fracture strength reaches maximum value, is increased to by 21.97MPa
53.71MPa, fracture strength improves 144.47%, this is because with the crosslinking journey for increasing gelatin molecule of TGase enzyme additive amounts
Degree increases, and molecular weight increases and stress strand increases.However, as TGase enzyme additive amounts continue growing the disconnected of gelatin fiber
Resistance to spalling rate reduces, and causes the fiber surface degree of cross linking excessive this is because TGase enzyme additive amounts are excessive, internal crosslinking is less in fibre
Stress concentration is generated in Wiki body makes gelatin fiber be broken powerful reduction.
The surface of gelatin fiber and internal crosslinking journey when TGase enzyme concentrations are 0.011g/mL (additive amount 0.10%)
Spend approximately the same, fibre structure is uniform, and elongation at break is up to 3.98%, compared with the gelatin fiber without TGase enzymatic treatments
(2.30%) extension at break improves 73.05%, and when TGase enzyme additive amounts continue growing, fiber surface crosslinking degree is excessive, shape
At network structure so that gelatin chains can not free displacement under the effect of external force and relatively, material fragility increase, break
Split elongation reduction.
The gelatin fiber mechanical performance data of 3 difference TGase enzyme additive amounts of table
The obtained fiber sample in embodiment 3,5,6 and 7 is subjected to Mechanics Performance Testing, the results are shown in Table 4.
If table 4 can be seen that the increase with drafting multiple, the fracture strength of gelatin fiber gradually increases, when drawing-off times
Fracture strength is maximum when number is 4 times, increases to 152.85MPa by undrawn 53.71MPa, intensity is approximately the 3 of non-stretched fiber
Times, 184.58% is improved, this is because as drafting multiple increases, the crystallinity and the macromolecular chain degree of orientation of fiber increase therewith
Greatly, the fracture strength of gelatin fiber is made to increase；The elongation at break of draft fiber is bigger than undrawn fiber, elongation at break by
Undrawn 2.99 increase to 8.78, increase 193.65%, and the cross-linked network structure mainly due to undrawn fiber is weak, fiber
Embrittlement, elongation at break is low, as drafting multiple improves, cross-linked network structure enhancing, elongation increase, but when draw ratio after
Continuous when increasing up to 4 times, fiber is fully orientated, and elongation at break declines again.
Mechanical performance data before and after 4 drawing-off of table
Embodiment 6 and 8~10 obtained fiber sample of embodiment are subjected to Mechanics Performance Testing, the results are shown in Table 5.
Crosslinked mechanical performance data again before and after 5 drawing-off of table
As shown in Table 5, fracture strength with crosslinking bathe in TGase enzyme concentrations increase and first increases and then decreases.Work as crosslinking
It is 158.5MPa that fracture strength, which reaches maximum value, when TGase enzyme concentrations are 3% in bath, this is because gelatin fiber molecule after crosslinking
The reason of amount increases.When TGase enzyme concentrations continue to increase, the fracture strength of gelatin fiber reduces, when TGase enzyme concentrations increase
It is reduced to 124.8MPa to fracture strength when 4%.This may be since the crosslinking points that the degree of cross linking increases gelatin molecule increase, in addition
Crosslinked inhomogeneities makes to be easy to happen stress concentration when fiber stress.Elongation at break the result shows that, crosslinked bath processing
Afterwards, elongation at break is more untreated is significantly improved, as the increase extension at break of TGase enzyme concentrations takes the lead in dropping after increasing
It is low, it is gradually decrease to 14.56% after first increasing to 27.80% by 8.78, this is because what the bigger gelatin molecule of the degree of cross linking generated
Crosslinking points are more, caused by the mobility reduction of gelatin molecule.
It is described the invention in detail above in association with detailed description and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention
In the range of.Scope of protection of the present invention is subject to the appended claims.
Claims (12)
1. a kind of spinning process of gelatin fiber, includes the following steps：
Step 1, it weighs gelatin to be added in solvent, be swollen at a set temperature, crosslinking agent I is added after the completion of swelling thereto
It is crosslinked, the solvent is water；
Step 2, the mixed liquor in step 1 is added in the head tank of wet-spinning frame, coagulating bath, solidification is entered after spinneret
After obtain as-spun fibre；
In step 1, the cross-linking agents Ⅰ is transglutaminase；The cross-linking agents Ⅰ is crosslinked 0.1h with gelatin at 50~70 DEG C
~3h；
In step 2, the coagulating bath is 200g/L~430g/L aqueous sodium persulfate solutions；
Crosslinking agent II is also added in coagulating bath, the crosslinking agent II is transglutaminase；Crosslinking agent II is in coagulating bath
In a concentration of 2% weight~10% weight；
The method further includes carrying out drawing-off to the as-spun fibre that step 2 obtains, and the drawing-off carries out 2~8 at 20~35 DEG C
Times drawing-off, draft speed are 120~240m/min,
The method further includes that the gelatin fiber after making drawing-off is further crosslinked in crosslinking is bathed, and obtains finished fiber；
A concentration of 0.5~5% weight of the crosslinking bath, 20~35 DEG C of temperature, crosslinking Treatment 0.5h~10h；In being bathed with crosslinking
Crosslinking agent III is transglutaminase.
2. according to the method described in claim 1, it is characterized in that, in step 1,
The weight ratio of gelatin and solvent is 1:1.3~1:3.0；With
The swelling temperature of gelatin in a solvent is 50~70 DEG C；
The swelling includes standing swelling and stirring swelling, and the time for standing swelling is 0.5~2h, the stirring swelling
Time is 1~3h.
3. according to the method described in claim 2, it is characterized in that, in step 1,
The weight ratio of gelatin and solvent is 1:1.6~1:2.0；
The swelling temperature of gelatin in a solvent is 55~65 DEG C.
4. method according to claim 1 to 3, which is characterized in that in step 1, the matter of the cross-linking agents Ⅰ and gelatin
Amount is than being 0.05:100~1:100.
5. according to the method described in claim 4, it is characterized in that, in step 1, the mass ratio of the cross-linking agents Ⅰ and gelatin is
0.1:100~0.5:100.
6. method according to claim 1 to 3, which is characterized in that in step 1, the cross-linking agents Ⅰ is with gelatin in 55
0.5h~1.5h is crosslinked at~65 DEG C.
7. method according to claim 1 to 3, which is characterized in that in step 2,
The temperature of head tank is 50~70 DEG C；
Mixed liquor carries out deaeration before spinneret.
8. the method according to the description of claim 7 is characterized in that in step 2,
The temperature of head tank is 55~65 DEG C；
Mixed liquor carries out vacuum defoamation before spinneret.
9. method according to claim 1 to 3, which is characterized in that in step 2,
The coagulation bath temperature is 30~50 DEG C；With
The spinning speed of as-spun fibre is 30~100m/min.
10. according to the method described in claim 9, it is characterized in that, in step 2,
The coagulation bath temperature is 35~45 DEG C；
The spinning speed of as-spun fibre is 60~80m/min.
11. method according to claim 1 to 3, which is characterized in that in step 2, crosslinking agent II is in coagulating bath
The weight of a concentration of 4% weight~6%.
12. method according to claim 1 to 3, which is characterized in that the drawing-off carries out 2~4 at 25~30 DEG C
Times drawing-off, draft speed are 150~200m/min.
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| CN113818095B (en) * | 2021-08-27 | 2022-11-04 | 东华大学 | Wet spinning method capable of preparing degradable gelatin hydrogel fiber in large scale based on Hofmeister effect |
| CN115559009B (en) * | 2022-10-31 | 2024-03-26 | 得福乐(南通)科技有限公司 | Collagen filament with collagen microfiber structure and preparation method thereof |
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