CN109518294A - A kind of grafting polyvinyl alcohol fiber and preparation method thereof and the textile made of the grafting polyvinyl alcohol fiber - Google Patents
A kind of grafting polyvinyl alcohol fiber and preparation method thereof and the textile made of the grafting polyvinyl alcohol fiber Download PDFInfo
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- CN109518294A CN109518294A CN201811327919.6A CN201811327919A CN109518294A CN 109518294 A CN109518294 A CN 109518294A CN 201811327919 A CN201811327919 A CN 201811327919A CN 109518294 A CN109518294 A CN 109518294A
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- polyvinyl alcohol
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- vinal
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- alcohol fiber
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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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/06—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- 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
-
- 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
Abstract
The invention discloses a kind of grafting polyvinyl alcohol fibers, it is related to vinal field, its key points of the technical solution are that carrying out esterification to polyvinyl alcohol, esterification yield is the 5%~75% of total hydroxyl quantity, so that vinal is while guaranteeing good biological intermiscibility, also improve its mechanical property, thermal stability and water resistance, and then processing easy to produce.Furthermore preparation method simplicity is suitble to planningization production, and the textile being made from it is also substantially pollution-free for environment.
Description
Technical field
The present invention relates to vinal field, in particular to a kind of grafting polyvinyl alcohol fiber and preparation method thereof and
The textile made of the grafting polyvinyl alcohol fiber.
Background technique
With continuing to develop to domestic medical industry now, people are also increasingly for the concern of medical supplies quality
It is high.Also, there are relevant regulations of the relevant departments once according to YY0330-2002 " medical absorbent cotton ", to domestic existing medical de-
Character, pH value, readily oxidizable substance, absorbent time, water absorption, fluorescence, surface reactive material of rouge cotton and products thereof etc. 7 refer to
Mark is examined, and discovery has nonconformance.And lead to underproof basic reason, the natural growth factor of existing cotton,
There are subsequent processing factors again.Medical material is using upper as a result, it would be highly desirable to which a kind of material is identical with cotton, and stability etc. is better than cotton again
Material replace cotton.
Although and having a large amount of terylene, polypropylene fibre, aramid fiber, acrylic fibers, polyamide fibre, compound polyolefin, polyvinyl and spandex on the market etc.
Equal synthetic materials, but due to poor biocompatibility, non-polar material etc., so cannot be used for replacing cotton.
And polyvinyl alcohol is a few one of fibre-forming polymer with hydrophilic radical.Also, it is also mesh
It is preceding it has been found that it is unique there is water-soluble and nontoxic high polymer, alias is polyvinyl alcohol, and molecular structure is-[CH (OH)-
CH2] n-, thus, it is also widely used in the fields such as textile industry, medical.
And general vinal refers to without the processed vinal of acetal, is a kind of in certain temperature
The lower special material that can be dissolved in water of degree.The polyvinyl alcohol textile being process by the special material by spinning, woven fabric, no
Only there is ideal water solution temperature, intensity and elongation and good acidproof, alkaline-resisting, dry heat resistance energy, and be dissolved in nothing after water
Taste, nontoxic, aqueous solution is colorless and transparent, does not generate any pollution, a hundred percent natural decomposition product to environment.
But due to the water solubility of polyvinyl alcohol, thus in the case where not acetal, it is processed into pure vinal
With regard to extremely difficult.Meanwhile on the other hand, vinal is low with thermal stability etc. there is also hygroscopicity, melt-processed difficulty
Disadvantage.
For example, the intensity of polyvinyl alcohol is only the 55%~60% of its dry strength after moisture absorption.And it can hold at 160 DEG C
Beginning intramolecular dehydration, 230 DEG C of whens, start intermolecular dehydration and become fragile.Intramolecular and intermolecular also a large amount of hydrogen due to polyvinyl alcohol
Key exists, and should not process, solution complex forming technology, at high cost.
For this reason, it is necessary to a kind of method of modifying of polyvinyl alcohol be developed, so that vinal is guaranteeing good water
Under the premise of dissolubility temperature, processing is got up also more convenient.
Summary of the invention
The object of the present invention is to provide a kind of grafting polyvinyl alcohol fibers, and not only water-soluble temperature is good, and is also convenient for
Processing, is appropriate for large-scale production, and the textile made by it also has good biological degradability, reduces to ring
The probability of border pollution.
Above-mentioned technical purpose of the invention has the technical scheme that
A kind of grafting polyvinyl alcohol fiber, esterification yield are the 5%~75% of total hydroxyl quantity.
Vinal after over-churning, inside produce ester bond, so that thermal stability and water resistance have
Effect it is improved.Meanwhile still having certain water-soluble temperature, it ensure that its good biological compatibility, in turn
Its manufactured textile can fast decoupled in nature, reduce the pollution to environment.Also, due to ester bond formed it is same
When can consume a large amount of hydroxyl, to also just reduce the quantity of hydrogen bond, processing in this way is got up the poly- second relative to non-grafted mistake
It will convenience more for enol fiber.
A kind of preparation method of grafting polyvinyl alcohol fiber,
Polyvinyl alcohol is dissolved in 90~100 DEG C of water and obtains polyvinyl alcohol water solution by the first step, and it is mixed that liquid carboxylic is added
It closes, and is stirred with 500~600rpm revolving speed, mixing stoste is made；
Mixing stoste is warming up to 80~90 DEG C by second step, and acid is added or alkali is esterified, while being turned with 200~300rpm
Speed carries out, and reacts 4~6 hours, obtains the vinal spinning solution of primary esterification；
Third step, when the temperature of the vinal spinning solution of primary esterification is down to 65 DEG C, be added strong oxidizer, simultaneously
It stirs at low speed, reacts 8 hours, obtain vinal spinning solution；
Vinal spinning solution is carried out standing and defoaming processing by the 4th step；
5th step, to deaeration after, vinal spinning solution is carried out into the first coagulating bath by wet process spinneret
Spinning obtains vinal precursor；
Vinal precursor is immersed into the second gelation and carries out drawing-off by the 6th step, cleaned later, dry, coiling
Obtain grafting polyvinyl alcohol fiber.
By using above-mentioned technical proposal, whole preparation process is carried out in 100 DEG C of environment below, thus both
Reduce energy consumption, and can guarantee the safety of production.It is taken off moreover, stand by polyvinyl alcohol spin dope in four steps
Bubble can aid in the abundant termination of esterification in this way, and the use of subsequent cleaning solution can be also reduced after deaeration processing
Amount.
Preferably, raw material polyvinyl alcohol can be by obtaining after polyvinyl acetate ester hydrolysis in the first step.
By using above-mentioned technical proposal, since the glass transition temperature of polyvinyl alcohol is 75~85 DEG C, and polyvinyl acetate
The glass transition temperature of ester is 38 DEG C, thus selects polyvinyl acetate as raw material, is just not required to during feeding early period in this way
It is added being largely ground into after small powder again, to facilitate the operation of early period.Meanwhile it is fine in final polyvinyl alcohol
Acetate group is introduced in dimension, thus can also bring corresponding characteristic into.
Preferably, the mode of polyvinyl acetate ester hydrolysis, includes the following steps,
A, 20~40% polyvinyl acetate are dissolved in 63~75% methanol solutions, form solution A；By 21~35% hydrogen-oxygens
Change sodium to be dissolved into 68~76% methanol solution, forms B solution；
B, according to molar ratio solution A and B solution 1: the ratio of (0.13~0.19) pours into B solution in solution A.Simultaneously in A, B
Enter phthalic anhydride in mixed solution, the additive amount of phthalic anhydride is according to mole A, B mixed solution and an O-phthalic
Acid anhydrides 1: (0.0078~0.0092), in the alcoholysis machine being all added to later, 40~50 DEG C of progress alcoholysis, 30~40 points of alcoholysis
Zhong Hou obtains polyvinyl alcohol.
Preferably, polyvinyl alcohol water solution is heated, its temperature is increased to after carboxylic acid to be added in the first step
72~77 DEG C, be 1.5~2.5 hours to the reaction time.
By using above-mentioned technical proposal, facilitating to mix carboxylic acid and polyvinyl alcohol in stoste in this way can preliminarily be carried out
Esterification, consequently facilitating the efficiency of regulation later period formal esterification process.
Preferably, in the esterification process of second step, the pH value range control for mixing stoste is 0~3 or 12.5~14.
By using above-mentioned technical proposal, the esterification for being conducive to polyvinyl alcohol in this way is accelerated, and then mentions significantly
High production efficiency.
Preferably, strong oxidizer is peroxide in third step.
By using above-mentioned technical proposal, strong oxidizer can cause polyvinyl alcohol and self-crosslinking reaction occurs, and destroy poly-
The regularity of vinyl alcohol interior molecules arrangement, thereby reduces the crystallinity of polyvinyl alcohol.This process makes the nothing in polyvinyl alcohol
Sizing region is more intensive, more fine and close structure is formd, so that the mechanical property of polyvinyl alcohol has obtained effectively
It is promoted.
Moreover, herein be preferably peroxide, compared to trivalent cobalt salt, persulfate, potassium bichromate, potassium permanganate,
Oxygen hydrochlorate and the concentrated sulfuric acid are more friendly for environment.
The self-crosslinking reaction XRD spectra of 1 polyvinyl alcohol with reference to the accompanying drawings, polyvinyl alcohol and peroxide crosslinked polyethylene alcohol
Typical absorption peak appear in 20 °, with the increase of peroxide, the absorption peak strength of cross-linking polyvinyl alcohol is gradually decreased, poly- second
The decline of enol crystallinity.
It is reticulated or three-dimensional polymeric molecule between the line style or branch type macromolecular chain of polyvinyl alcohol after crosslinking with covalent bond connection,
Its physical properties has biggish change, wherein being influenced most significant performance by crosslink density is modulus and hardness, due to
It is crosslinked the sliding between the chain and chain generated between crosslinking points inhibition macromolecular chain, modulus and hardness can be with the increases of crosslink density
And increase.
Also, the oxidisability of peroxide and the reproducibility of carboxylic acid generate vigorous reaction, react away more generations two after carboxylic acid
Carbonoxide and certain salt, for example, (NH4) 2S2O8+K2C2O4=(NH4) 2SO4+2CO2 ↑+K2SO4.
The carboxylic acid for remaining in polyvinyl alcohol system in this way can prevent excessive ester by reacting removing with peroxide
Change, esterification yield is effectively controlled；Moreover, peroxide can also consume the hydroxyl on part polyethylene alcohol, from
And improve the water resistance of polyvinyl alcohol.
Preferably, the coagulating bath one in the 5th step is 40~44 parts of water, 28~36 parts of urea, 21~31 parts by parts by weight
Sodium chloride mixed dissolution under room temperature environment is made.
Using the sodium chloride aqueous solution of higher concentration as coagulating bath, carries out wet spinning and pass through post-tensioning, be heat-treated
To the vinal with excellent mechanical property.The vinal made from this method is glossy and good resultant force
Performance is learned, breaking strength is up to 0.6GPa, and elongation at break is up to 230%.
Coagulating bath main material of the sodium chloride as polyvinyl alcohol spin dope is not only nontoxic and have significant cost
Advantage.Moreover, because the osmotic pressure of high concentration sodium-chloride water solution is very high, the fiber that polyvinyl alcohol spin dope can be made to spray
Quick solidification improves the output efficiency of spinneret.
And urea also can preferably be polymerize with the hydroxyl of polyvinyl alcohol, be mainly dehydrated between polyvinyl alcohol
Modifying function is played in reaction:
Urea mainly influences the plasticity of vinal, and when urea is added to coagulating bath 3%, fibre property is best.
Preferably, the second gelation in the 6th step is 97.4~99.2 parts of water and 1.08~1.26 parts of Asias by parts by weight
Sodium bisulfate mixed dissolution under room temperature environment is made.
It can be complete with unreacted since sodium hydrogensulfite has stronger reproducibility by using above-mentioned technical proposal
Strong oxidizer have an effect, it is right after avoiding the later period that textile is made to consume the strong oxidizer on vinal
The skin of human body impacts.And sodium hydrogensulfite is also the substance of low toxicity, significantly reduces the pollution to environment.
A kind of textile is made of a kind of above-mentioned grafting polyvinyl alcohol fiber.
The textile made of the application grafting polyvinyl alcohol fiber, not only good mechanical properties, while its have it is relatively strong
Water resistance and good biological compatibility, pollution there is no for environment.
In conclusion the invention has the following advantages:
1, after polyvinyl alcohol is successively carried out esterification and oxidation operation, certain water-soluble temperature and biology both ensure that
Intermiscibility, meanwhile, mechanical property is also improved, and processing easy to produce；
2, strong oxidizer is added in esterification final stage, extra carboxylic acid can not only be removed in this way, to control the progress of esterification
Degree, while the hydroxyl of polyvinyl alcohol can be also oxidized, to improve the water resistance of vinal；
3, using sodium chloride and urea etc. as the raw material of coagulating bath, it can be improved the mechanical property of polyvinyl ester entirety in this way
Energy.
Detailed description of the invention
Fig. 1 is the self-crosslinking reaction XRD spectra of polyvinyl alcohol；
Fig. 2 is the preparation technology flow chart of vinal.
Specific embodiment
Below in conjunction with attached drawing 2, invention is further described in detail.
Embodiment one:
A kind of preparation method of grafting polyvinyl alcohol fiber, includes the following steps:
16Kg polyvinyl alcohol is dissolved in 90 DEG C of 84Kg water and obtains polyvinyl alcohol water solution by the first step, arrives room temperature after cooling
It is added 11Kg formic acid, and afterwards with 550rpm revolving speed stirring 10 minutes, it is then closed and be heated to 75 DEG C, and insulation reaction 2 hours,
Obtain mixing stoste；
165g sodium hydroxide is added in 335g water by second step, forms 30% sodium hydroxide solution.The mixing of the first step is former
Liquid is warming up to 85 DEG C, 30% sodium hydroxide solution is added until pH is 13, and is stirred with 250rpm revolving speed, reaction 5 is small
When, obtain the vinal spinning solution of primary esterification；
73g10% ammonium persulfate is added when the vinal spinning solution temperature of primary esterification is down to 65 DEG C in third step
Solution, the solvent of ammonium persulfate solution are water.Continue to be stirred with 250rpm revolving speed after twenty minutes, is kept for 65 DEG C, reaction 8 is small
When, temperature drops to room temperature later, obtains vinal spinning solution；
Vinal spinning solution is carried out standing and defoaming by the 4th step, and time of repose is 24 hours；
5th step, to deaeration after, by vinal spinning solution by wet-spinning frame with 45m/min spinneret speed
Spinneret enters the first coagulating bath and obtains composite fibre subsequently into drawing-off in the second gelation through supersolidification, drawing-off.It will be compound
Vinal is made by boundling drawing-off, steam drying and thermal finalization in fiber, and esterification yield is the 75% of total hydroxyl quantity.
Wherein, the configuration mode of the first coagulating bath of 100Kg (25 DEG C): water 42Kg, urea 32Kg, sodium chloride 26Kg are mixed
Together, until being completely dissolved, the first coagulating bath is obtained.
The configuration mode of 100Kg the second gelation (25 DEG C): water 98.3Kg, sodium hydrogensulfite 1.17Kg are blended in one
It rises, until being completely dissolved, obtains the second gelation.
Embodiment two:
A kind of preparation method of grafting polyvinyl alcohol fiber, includes the following steps:
16Kg polyvinyl alcohol is dissolved in 90 DEG C of 84Kg water by the first step, and 1.5Kg succinic acid is added after being cooled to room temperature, and
It is then closed and be heated to 72 DEG C, and insulation reaction 1.5 hours with 500rpm revolving speed stirring 10 minutes, obtain mixing stoste；
165g sodium hydroxide is added in 335g water by second step, forms 30% sodium hydroxide solution.The mixing of the first step is former
Liquid is warming up to 80 DEG C, 30% sodium hydroxide solution is added until pH is 14, and is stirred with 200rpm revolving speed, reaction 5 is small
When, obtain the vinal spinning solution of primary esterification；
73g10% ammonium persulfate is added when the vinal spinning solution temperature of primary esterification is down to 60 DEG C in third step
Solution, the solvent of ammonium persulfate solution are water.Continue to carry out after twenty minutes, being kept for 60 DEG C with 200rpm revolving speed, react 10 hours,
Temperature drops to room temperature, obtains vinal spinning solution；
Vinal spinning solution is carried out standing and defoaming by the 4th step, and time of repose is 24 hours；
5th step, to deaeration after, by vinal spinning solution by wet-spinning frame with 10m/min spinneret speed
Spinneret enters the first coagulating bath and obtains composite fibre subsequently into drawing-off in the second gelation through supersolidification, drawing-off.Compound fibre
Vinal is made by boundling drawing-off, steam drying and thermal finalization in dimension, and esterification yield is the 58% of total hydroxyl quantity.
Wherein, the configuration mode of the first coagulating bath of 100Kg (25 DEG C): water 40Kg, urea 28Kg, sodium chloride 21Kg are mixed
Together, until being completely dissolved, the first coagulating bath is obtained.
The configuration mode of 100Kg the second gelation (25 DEG C): water 97.4Kg, sodium hydrogensulfite 1.08Kg are blended in one
It rises, until being completely dissolved, obtains the second gelation.
Embodiment three:
A kind of preparation method of grafting polyvinyl alcohol fiber, includes the following steps:
16Kg polyvinyl alcohol is dissolved in 90 DEG C of 84Kg water by the first step, and 1.5Kg citric acid is added after being cooled to room temperature, and
It is then closed and be heated to 77 DEG C, and insulation reaction 2.5 hours with 600rpm revolving speed stirring 10 minutes；
165g sodium hydroxide is added in 335g water by second step, forms 30% sodium hydroxide solution.The mixing of the first step is former
Liquid is warming up to 90 DEG C, and 30% sodium hydroxide solution is added until pH is 12.5, and is stirred with 300rpm revolving speed, reaction 6
Hour, obtain the vinal spinning solution of primary esterification；
26g60% acyl peroxide is added when the vinal spinning solution temperature of primary esterification is down to 70 DEG C in third step
Solution, the solvent of acyl peroxide solution are water.Continue to be stirred with 300rpm revolving speed after twenty minutes, is kept for 70 DEG C, reaction 12
Hour, temperature drops to room temperature, obtains vinal spinning solution；
Vinal spinning solution is carried out standing and defoaming by the 4th step, and time of repose is 24 hours；
5th step, to deaeration after, by vinal spinning solution by wet-spinning frame with 80m/min spinneret speed
Spinneret enters the first coagulating bath and obtains composite fibre subsequently into drawing-off in the second gelation through supersolidification, drawing-off.It will be compound
Vinal is made by boundling drawing-off, steam drying and thermal finalization in fiber, and esterification yield is the 5% of total hydroxyl quantity.
Wherein, the configuration mode of the first coagulating bath of 100Kg (25 DEG C): water 44Kg, urea 26Kg, sodium chloride 31Kg are mixed
Together, until being completely dissolved, the first coagulating bath is obtained.
The configuration mode of 100Kg the second gelation (25 DEG C): water 99.2Kg, sodium hydrogensulfite 1.26Kg are blended in one
It rises, until being completely dissolved, obtains the second gelation.
Example IV,
A kind of preparation method of grafting polyvinyl alcohol fiber, difference from the first embodiment is that it is propionic acid that it, which selects carboxylic acid, and
Practical 20% sulfuric acid solution replaces 30% sodium hydroxide, and the pH reacted is 3, the ester of final vinal obtained
Rate is the 67% of total hydroxyl quantity.
Embodiment five,
A kind of preparation method of grafting polyvinyl alcohol fiber, the difference with embodiment two are that selection carboxylic acid is tartaric acid,
And practical 20% sulfuric acid solution replace 30% sodium hydroxide, and the pH reacted is 0, final obtained vinal
Esterification yield is the 71% of total hydroxyl quantity.
Embodiment six,
A kind of preparation method of grafting polyvinyl alcohol fiber, difference from the first embodiment is that it is pentamethylene that it, which selects carboxylic acid,
Tetrabasic carboxylic acid, and practical 20% sulfuric acid solution replace 30% sodium hydroxide, and the pH reacted is 1, final obtained polyethylene
The esterification yield of alcohol fiber is the 27% of total hydroxyl quantity.
Embodiment seven,
A kind of preparation method of grafting polyvinyl alcohol fiber, difference from the first embodiment is that its selection oxygen-containing inorganic acid is
50% concentrated sulfuric acid, the pH for adjusting reaction is 3, and the esterification yield of final vinal obtained is the 46% of total hydroxyl quantity.
Embodiment eight,
A kind of preparation method of grafting polyvinyl alcohol fiber, the difference with embodiment two are that selection oxygen-containing inorganic acid is
Phosphoric acid, the pH for adjusting reaction is 0, and the esterification yield of final vinal obtained is the 58% of total hydroxyl quantity.
Embodiment nine,
A kind of preparation method of grafting polyvinyl alcohol fiber, difference from the first embodiment is that its selection oxygen-containing inorganic acid is
Boric acid, the pH for adjusting reaction is 1, and the esterification yield of final vinal obtained is the 34% of total hydroxyl quantity.
Embodiment ten:
A kind of grafting polyvinyl alcohol fiber, based on the basis of embodiment one, polyvinyl alcohol is obtained by following steps:
A, 30% polyvinyl acetate is dissolved in 70% methanol solution, forms solution A；28% sodium hydroxide is dissolved into
In 72% methanol solution, B solution is formed；
B, B solution is poured into solution A according to the ratio of molar ratio solution A and B solution 1: 0.16.Simultaneously in A, B mixed solution
Middle addition phthalic anhydride, the additive amount of phthalic anhydride are according to mole A, B mixed solution and phthalic anhydride 1:
0.0086.In the alcoholysis machine being added to after addition phthalic anhydride, 45 DEG C of progress alcoholysis alcoholysis 35 minutes, obtain polyethylene
Alcohol.
Embodiment 11:
A kind of grafting polyvinyl alcohol fiber, based on the basis of embodiment two, polyvinyl alcohol is obtained by following steps:
A, 20% polyvinyl acetate is dissolved in 63% methanol solution, forms solution A；21% sodium hydroxide is dissolved into
In 68% methanol solution, B solution is formed；
B, B solution is poured into solution A according to the ratio of molar ratio solution A and B solution 1: 0.13.Simultaneously in A, B mixed solution
Middle addition phthalic anhydride, the additive amount of phthalic anhydride are according to mole A, B mixed solution and phthalic anhydride 1:
0.0078.In the alcoholysis machine being added to after addition phthalic anhydride, 40 DEG C of progress alcoholysis alcoholysis 30 minutes, obtain polyethylene
Alcohol.
Embodiment 12:
A kind of grafting polyvinyl alcohol fiber, based on the basis of embodiment three, polyvinyl alcohol is obtained by following steps:
A, 40% polyvinyl acetate is dissolved in 75% methanol solution, forms solution A；35% sodium hydroxide is dissolved into
In 76% methanol solution, B solution is formed；
B, B solution is poured into solution A according to the ratio of molar ratio solution A and B solution 1: 0.19.Simultaneously in A, B mixed solution
Middle addition phthalic anhydride, the additive amount of phthalic anhydride are according to mole A, B mixed solution and phthalic anhydride 1:
0.0092.In the alcoholysis machine being added to after addition phthalic anhydride, 50 DEG C of progress alcoholysis alcoholysis 40 minutes, obtain polyethylene
Alcohol.
Embodiment 13:
A kind of grafting polyvinyl alcohol fiber, based on the basis of example IV, polyvinyl alcohol is obtained by following steps:
A, 40% polyvinyl acetate is dissolved in 63% methanol solution, forms solution A；21% sodium hydroxide is dissolved into
In 72% methanol solution, B solution is formed；
B, B solution is poured into solution A according to the ratio of molar ratio solution A and B solution 1: 0.16.Simultaneously in A, B mixed solution
Middle addition phthalic anhydride, the additive amount of phthalic anhydride are according to mole A, B mixed solution and phthalic anhydride 1:
0.0092.In the alcoholysis machine being added to after addition phthalic anhydride, 45 DEG C of progress alcoholysis alcoholysis 30 minutes, obtain polyethylene
Alcohol.
Embodiment 14:
A kind of grafting polyvinyl alcohol fiber, based on the basis of example IV, polyvinyl alcohol is obtained by following steps:
A, 30% polyvinyl acetate is dissolved in 70% methanol solution, forms solution A；28% sodium hydroxide is dissolved into
In 76% methanol solution, B solution is formed；
B, B solution is poured into solution A according to the ratio of molar ratio solution A and B solution 1: 0.13.Simultaneously in A, B mixed solution
Middle addition phthalic anhydride, the additive amount of phthalic anhydride are according to mole A, B mixed solution and phthalic anhydride 1:
0.0086.In the alcoholysis machine being added to after addition phthalic anhydride, 40 DEG C of progress alcoholysis alcoholysis 40 minutes, obtain polyethylene
Alcohol.
Embodiment 15:
A kind of grafting polyvinyl alcohol fiber, based on the basis of example IV, polyvinyl alcohol is obtained by following steps:
A, 20% polyvinyl acetate is dissolved in 75% methanol solution, forms solution A；21% sodium hydroxide is dissolved into
In 72% methanol solution, B solution is formed；
B, B solution is poured into solution A according to the ratio of molar ratio solution A and B solution 1: 0.19.Simultaneously in A, B mixed solution
Middle addition phthalic anhydride, the additive amount of phthalic anhydride are according to mole A, B mixed solution and phthalic anhydride 1:
0.0078.In the alcoholysis machine being added to after addition phthalic anhydride, 45 DEG C of progress alcoholysis alcoholysis 30 minutes, obtain polyethylene
Alcohol.
Coherent detection is carried out to embodiment one to embodiment six, test method is as follows:
1, cytotoxicity experiment:
Experimental method: adding the standard of 1ml cell culture fluid to produce material extract according to 6cm2 surface area, 37 DEG C of extraction 48h, and 4
It DEG C saves stand-by.Third generation human marrow mesenchyme stem cell is extracted, is cell suspension with pancreatin digestion, cell density is adjusted to
1 × 104/ml is inoculated in 96 orifice plates, removes supernatant after cell is adherent after being inoculated with 1d, and material extraction liquid 100 is added in every hole
100 μ l cell culture fluids are added in μ l, the every hole of negative control group；100 μ l cell culture are added in blank control group not inoculating cell
Liquid, to correct OD value.20 μ lMTS solution were added to every hole in the 2nd day, continues after being put into 37 DEG C of incubator 4h, is read with microplate reader
The absorbance value at 490nm is taken, is calculated cell relative growth rate (RGR), RGR=experimental group mean OD value/negative control group
Mean OD value × 100%, the RGR of calculating, by the cytotoxicity of the standards of grading evaluation material to Materials Cell toxicity.
Experimental result: cytotoxicity experiment experimental result shows that cell keeps normal morphology, adherent, proliferation well, according to
Toxicity grading, RGR 89.86% are 1 grade, score as qualification, it was demonstrated that electrospinning chitosan and polyethylene glycol fiber films are without obvious thin
Cellular toxicity.
2, hematotoxicity is tested:
Test method: hemolytic experiment extracts the new fresh rabbit blood of 10ml, is added in the test tube containing 2% potassium oxalate anti-coagulants immediately, from
The middle anticoagulant rabbit blood of extraction 4ml is added 5ml normal saline dilution, is prepared into diluted anticoagulant rabbit blood.Experiment is divided into three groups:
(1) experimental group: 5 sample membranes are respectively taken, is respectively put into the centrifuge tube for the physiological saline that 5 are respectively provided with 10ml and soaks completely
Bubble；
(2) negative control group: 10ml physiological saline is separately added into 5 centrifuge tubes；
(3) positive controls: 10ml distilled water is separately added into 5 centrifuge tubes.
Above-mentioned three groups of centrifuge tubes are placed in the water bath with thermostatic control that temperature is (37 ± 1) DEG C and keep the temperature 30min, then it is each from
The anticoagulant rabbit blood of dilution that 0.2ml has been prepared respectively is added in heart pipe respectively, is uniformly mixed, continues in (37 ± 1) DEG C water bath with thermostatic control
Middle heat preservation 60min.All centrifuge tubes are taken out, Aspirate supernatant 3ml, is placed in spectrophotometer cell after centrifugation, with light splitting
Absorbance value when photometric determination wavelength is 545nm, and record as a result, the average value of 5 Duplicate Samples absorbance values is inhaled for it
Shading value (positive controls absorbance value should be (0.8 ± 0.3), and negative control group absorbance answers < 0.03), hemolysis rate=(real
Test a group absorbance value-negative control group absorbance value)/(positive controls absorbance value-negative control group absorbance value) ×
100%, the light absorption value of negative control group should be (0.8 ± 0.3), and the light absorption value of positive controls answers < 0.03, if material is molten
Blood rate < 5%, it was demonstrated that material meets the haemolysis requirement of material without haemocylolysis.If the hemolysis rate > 5% of material, prompts material
Material has haemocylolysis.
3, line density:
Line density (fineness) index of vinal refers to the weight of fiber unit length.Tekes (tex) is China's line
The legal unit of measurement title of density refers to 1000 meters of long stapled weight in grams.Its calculating formula is as follows:
Ntex=(G/L) × 1000
In formula: Ntex---- line density (tex)；
L---- fibre length (m)
G---- fibre weight (g).
One thousandth, 1/10th and 1,000 times of Tekes (tex) be referred to as milli special (mtex), dtex (dtex) and
Thousand special (ktex).
In the past once using metric count as the fineness index of vinal.Metric count refers to every milligram of polyvinyl alcohol
Length millimeter possessed by fiber, calculating formula are as follows:
Nm=L/G
In formula: Nm---- metric count；
L----- fibre length (mm)；
G---- fibre weight (mg).
4, hygroscopicity indicates that hygroscopic index is regain.Regain refers to that the weight of material contained humidity is dry to material
The percentage of amount.Its calculating formula is as follows:
W=(G-Go)/Go × 100 (%)
In formula: W---- regain (%)；
Go---- material dry measure (g)；
G---- material moisture (g).
Moisture content refers to that contained humidity weight in former polyvinyl alcohol accounts for the percentage of former polyvinyl alcohol moisture.Its calculating formula is such as
Under: M=(G-Go)/G × 100 (%)
5, Qiang Shenxing
The usual available stretch ultimate strength of strong stretching property or specific strength, breaking length and elongation at break table of vinal
Show.Tension failure strength is that fiber is stretched to maximum external force P required when fracture, and unit is newton (N).Due to the fineness of fiber
The strength for influencing fiber can be converted to unit line density fiber institute energy to compare the tensile property of different thicknesses fiber
The maximum external force of receiving, i.e. strength Pt, unit are that ox is every special (N/tex).Calculating formula is as follows:
Pt=P/Ntex
Breaking length is the intensity index indicated with length fashion.Its physical significance is to imagine fiber end to end convergence to suspend in midair
Come, length when it is broken because of self gravity, that is, gravity be equal to strength when fibre length.
For vinal constantly by external force during textile process, certain intensity is that fiber has weaving
One of necessary condition of processing performance, and the higher yarn strength spun of fibre strength is also higher.
The elongation at break of vinal refers to elongation and the percentage of former long ratio when fiber is stretched to fracture
Rate.Calculating formula is as follows:
ε=(La-Lo)/LO × 100 (%)
ε is elongation at break (%) in formula；Fiber when La is tension failure is long；LO is fibre length before stretching.
6, chemical stability
Vinal is soaked in respectively in the acid & alkali liquid and paint that pH is 1 and pH is 14, after 24 hours, re-test
Its above-mentioned mechanical property.
Shown in all test result is as follows tables one and table two:
Table one
Table two
As can be seen that the application grafting polyvinyl alcohol fiber has good biological compatibility, to environment from table one and table two
Pollution is not had substantially.Meanwhile the hygroscopicity of the polyvinyl alcohol of the application is weak, avoid vinal because moisture absorption and
Influence the mechanical property of its own.Furthermore it is also equipped with specific, the made weaving of good acid and alkali-resistance and resistance to grease stain
Product be suitble to carry out in multiple fields using.
Embodiment 16 is to embodiment 12:
A kind of spinning method for genuine of textile, is based respectively on the basis of embodiment one to embodiment six, steps are as follows:
S1, grafting polyvinyl alcohol fiber is under liquid supplementary set pencil state twist processing is carried out to it；
S2, spinning:
1) vinal is loosened into small cotton block or flock and sufficiently and evenly mixed, be made thickness uniformly, shape
Good vinal volume；
2) a point comb carried out by processes such as licker-in, cylinder flat, doffers to the vinal volume of machine under scutching cotton process, removed
It is miscellaneous, be mixed into vinal item and enter cylinder；
3) it is carried out and is closed with 6~8 vinal items, improvement vinal long segment is irregular, polyvinyl alcohol
Ribbon, which elongates to take out, carefully arrives predetermined weight, and further increases straightening of fibers parallel degree, and utilization is simultaneously closed and drawing-off, according to technique
The mixing of vinal item is carried out on drawing frame, circle item is made into the good ripe bar of molding, regular domain is placed on poly- second
In enol fiber bar cylinder；
4) roving-drafting is drawn and attenuated to required fineness, on bobbin；
S3, vinal is spinned after yarn count uniformly glued；
S4, woven fabric: being formed by warp thread and weft yarns, is 28 pieces/inch through density, and weft density is 32 pieces/inch；
After S5, woven fabric by elution repeatedly, sizing, rewinding, sterilizing and according to require to be made hospital gauze, gauze piece, pad of cotion,
Roll of gauze, bandage, operation towel, permanently antistatic clothes and product for civilian use etc. are to get vinal textile.
Wherein, the configuration mode of 100Kg twist auxiliary liquid: water 97Kg, polyvinyl alcohol 3Kg are mixed, until complete
Fully dissolved obtains twist auxiliary liquid.
The configuration mode of glue on 100Kg yarn count: water 94Kg, polyvinyl alcohol 6Kg are mixed, until completely molten
Solution, obtains glue on yarn count.
And the polyvinyl alcohol on yarn count in glue can also (native starch, moves natural plant gum by water-soluble macromolecule
Object glue (casein), the soluble derivative of chitin and alginic acid, carboxymethyl starch, acetic starch, hydroxymethyl cellulose,
Carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl alcohol, 2- acrylamide-2-methyl propane sulfonic, methacrylic acid -2- hydroxyl
Ethyl ester, acrylic acid, methacrylic acid, methacrylate, 4- acryloyl morpholine, acrylamide, vinylpyrrolidone, polyethylene
Acrylate, acrylic acid 3- sulphur methacrylate potassium salt, polyvinyl alcohol, N,N-DMAA, (3- acrylamide propyl) three
Ammonio methacrylate, 2- acrylyl oxy-ethyl-trimethyl salmiac one or any of several, or monomer or friendship by above-mentioned material
Co-product composition.And on yarn count the quality of the water soluble polymer of glue and water than general control be 0.05%-9%.
It is knitted accordingly in addition, the grafting polyvinyl alcohol fiber of the application can also be made up of the production technology of non-woven fabrics
Object, and the production technology of non-woven fabrics is known, so be just no longer explained in detail herein.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the scope of the claims of invention.
Claims (10)
1. a kind of grafting polyvinyl alcohol fiber, it is characterised in that: esterification yield is the 5%~75% of total hydroxyl quantity.
2. a kind of preparation method of grafting polyvinyl alcohol fiber as described in claim 1, it is characterised in that:
Polyvinyl alcohol is dissolved in 90~100 DEG C of water and obtains polyvinyl alcohol water solution by the first step, and liquid carboxylic is added or contains
Oxygen inorganic acid is mixed, and is stirred with 500~600rpm revolving speed, and mixing stoste is made；
Mixing stoste is warming up to 80~90 DEG C by second step, and acid is added or alkali is esterified, while being turned with 200~300rpm
Speed is stirred, and is reacted 4~6 hours, is obtained the vinal spinning solution of primary esterification；
Third step, when the temperature of the vinal spinning solution of primary esterification is down to 60~70 DEG C, be added strong oxidizer,
It stirs at low speed simultaneously, reacts 8~12 hours, obtain vinal spinning solution；
Vinal spinning solution is carried out standing and defoaming processing by the 4th step；
5th step, to deaeration after, vinal spinning solution is carried out into the first coagulating bath by wet process spinneret
Spinning obtains vinal precursor；
Vinal precursor is immersed into the second gelation and carries out drawing-off by the 6th step, cleaned later, dry, coiling
Obtain grafting polyvinyl alcohol fiber.
3. a kind of preparation method of grafting polyvinyl alcohol fiber according to claim 1, it is characterised in that: first step Central Plains
Expect that polyvinyl alcohol can be by obtaining after polyvinyl acetate ester hydrolysis.
4. a kind of preparation method of grafting polyvinyl alcohol fiber according to claim 3, it is characterised in that: polyvinyl acetate
The mode of ester hydrolysis, includes the following steps,
20~40% polyvinyl acetate are dissolved in 63~75% methanol solutions, solution A is formed；By 21~35% hydroxides
Sodium is dissolved into 68~76% methanol solution, forms B solution；
According to molar ratio solution A and B solution 1: the ratio of (0.13~0.19) pours into B solution in solution A；
Enter phthalic anhydride in A, B mixed solution simultaneously, the additive amount of phthalic anhydride is molten according to mole A, B mixing
Liquid and phthalic anhydride 1: (0.0078~0.0092), in the alcoholysis machine being all added to later, 40~50 DEG C of progress alcoholysis,
Alcoholysis 30~after forty minutes, obtain polyvinyl alcohol.
5. a kind of preparation method of grafting polyvinyl alcohol fiber according to claim 2, it is characterised in that: in the first step to
It is added after carboxylic acid, polyvinyl alcohol water solution is heated, its temperature is made to be increased to 72~77 DEG C, be 1.5 to the reaction time
~2.5 hours.
6. a kind of preparation method of grafting polyvinyl alcohol fiber according to claim 2, it is characterised in that: the ester of second step
During change, the pH value range control for mixing stoste is 0~3 or 12.5~14.
7. a kind of preparation method of grafting polyvinyl alcohol fiber according to claim 2, it is characterised in that: strong in third step
Oxidant is peroxide.
8. a kind of preparation method of grafting polyvinyl alcohol fiber according to claim 2, it is characterised in that: in the 5th step
It is molten that coagulating bath one by parts by weight is that 40~44 parts of water, 28~36 parts of urea, 21~31 parts of sodium chloride mix under room temperature environment
Solution is made.
9. a kind of preparation method of grafted polyethylene fiber according to claim 2, it is characterised in that: in the 6th step
It is molten that two coagulating baths by parts by weight are that 97.4~99.2 parts of water and 1.08~1.26 parts of sodium hydrogensulfites mix under room temperature environment
Solution is made.
10. a kind of textile, it is characterised in that: a kind of grafting polyvinyl alcohol fiber described in claims 1 or 2 is made.
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| CN110578178A (en) * | 2019-10-11 | 2019-12-17 | 振德医疗用品股份有限公司 | device and method for washing polyvinyl alcohol fibers at low temperature |
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| CN113073395A (en) * | 2021-04-01 | 2021-07-06 | 许玉华 | Graphene modified high-water-absorption fiber and preparation method thereof |
| CN113501897A (en) * | 2021-07-19 | 2021-10-15 | 南京信息工程大学 | Method for synthesizing polyvinyl formate and wet spinning thereof |
| CN115748251A (en) * | 2022-09-28 | 2023-03-07 | 青岛格诚经纬生物科技有限公司 | Processing method for improving spinnability of alginate fibers and application |
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| CN112442771B (en) * | 2020-11-13 | 2022-03-08 | 浙江羊绒世家服饰股份有限公司 | Water-soluble fiber and high count cashmere yarn spinning process |
| CN113073395A (en) * | 2021-04-01 | 2021-07-06 | 许玉华 | Graphene modified high-water-absorption fiber and preparation method thereof |
| CN113501897A (en) * | 2021-07-19 | 2021-10-15 | 南京信息工程大学 | Method for synthesizing polyvinyl formate and wet spinning thereof |
| CN113501897B (en) * | 2021-07-19 | 2023-08-25 | 南京信息工程大学 | Synthesis method of polyvinyl formate and wet spinning method thereof |
| CN115748251A (en) * | 2022-09-28 | 2023-03-07 | 青岛格诚经纬生物科技有限公司 | Processing method for improving spinnability of alginate fibers and application |
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