CN108624983A - A kind of preparation method of cellulose casein composite fibre - Google Patents
A kind of preparation method of cellulose casein composite fibre Download PDFInfo
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- CN108624983A CN108624983A CN201711494817.9A CN201711494817A CN108624983A CN 108624983 A CN108624983 A CN 108624983A CN 201711494817 A CN201711494817 A CN 201711494817A CN 108624983 A CN108624983 A CN 108624983A
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
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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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Abstract
The invention discloses a kind of preparation methods of cellulose casein composite fibre, include the following steps：A) by casein and cellulose dissolution in ionic liquid aqueous solution, homogeneous blend spinning stoste is made；B) gained spinning solution through filtering, spinning, solidification, stretching, washing, bleach, oil, dry to get the cellulose casein composite fibre；Ionic liquid used is by the connection 1 of 1 butyl, 3 methylimidazole villaumite and 5~15 mass parts of 90~110 mass parts, 4 two [1 (3 methylimidazole)] butyl, two villaumite and two perchlorate of connection 1,4 2 [1 (3 methylimidazole)] butyl of 5~15 mass parts are mixed to get.The present invention realizes casein and is total to the industrialized production that molten symbiosis prepares composite fibre with cellulose, has extremely strong practical value.
Description
Technical field
The present invention relates to a kind of preparation methods of composite fibre, are to be related to a kind of compound fibre of cellulose casein specifically
The preparation method of dimension.
Background technology
Cellulose is that a kind of most wide, content is most polysaccharide is distributed in nature, accounts for 50% or more of plant kingdom's carbon content,
It is most abundant one of the natural organic matter of nature.Cellulose is mainly derived from plant, such as cotton, timber, cotton linter, wheat
Grass, straw, reed, fiber crops, mulberry skin etc., the wherein content of cellulose of cotton are most pure cellulose source naturally close to 100%,
And in general timber, cellulose accounts for 40~50%, also 10~30% hemicellulose and 20~30% lignin.As one
Kind degradable Green biological material, the superior property such as natural fiber is light with its, degradable, inexpensive, high-modulus, high intensity
Can, gradually play an increasingly important role.Therefore, regenerated fiber is made after obtaining native cellulose dissolving in plant, it is real
The regeneration of existing cellulose and functionalization, are an important channels for efficiently using cellulose.
Protein is the peptide chain that amino acid combines, and the amino acid with many needed by human body has good bio-compatible
Property and functions of skin protection and health care, protein is combined with cellulose and prepares composite fibre and can make cellulose fibre that there is comfortable protect
Health-care function, and then obtain the textile fabric of high added value.Traditional composite fibre mainly uses cellulose fibre and protein fiber
Tie up blended method, composite fibre prepared by this method, only by two kinds of fiber blends, actually there is no to cellulose and
The performance of protein itself improves to some extent, and composite fibre performance improvement obtained is limited, and protein in this blend fibre
Additive amount is limited, and firmness is relatively low, and after washing several times, protein content reduces quickly, does not have additional shield substantially
Skin healthcare function.Therefore, the cellulose developed truly is of great significance with protein composite fibre.
Casein is one kind of protein, be mammal includes cow, and the main protein in sheep and people's milk is closed at present
It is less in the report of cellulose casein composite fibre.Since casein is a kind of binding protein of phosphorous calcium, acid labile, pH
It can be precipitated when relatively low, and there is hydrophobicity, be not readily dissolved in water；Meanwhile cellulose due to self assemble state structure the characteristics of, i.e.,
Intramolecular, it is intermolecular there is a large amount of hydrogen bond, while there is higher crystallinity again so that cellulose is in conventional solvent
It is difficult to dissolve in (such as water and most of organic solvents)；And since cellulose and casein belong to natural polymer
Matter, the natural polymer polar group that the two contains have strong interaction, and it is difficult straight also to lead to cellulose and casein
It connects and is dissolved in conventional solvent, cannot achieve the molten symbiosis altogether of the two, therefore current cellulose and casein composite fibre
Casein dissolving is typically prepared by casein stoste using solvent, then casein stoste is blended with viscose, then through wet
Method spinning is prepared into composite fibre, or is dissolved casein and cellulose respectively using solvent, then through wet spinning system
For at composite fibre.During this blending method prepares composite fibre, it will usually use highly basic, N, N- dimethylacetamides
Amine/lithium chloride (DMAc/LiCl), N,N-dimethylformamide/dinitrogen tetroxide (DMF/N2O4), N- methyl-N- oxygen morpholines
(NMMO), dimethyl sulfoxide (DMSO)/tetrabutyl ammonium fluoride (DMSO/TBAF) and and fused salt hydrate (such as LiClO4·3H2O、
LiSCN·2H2O) equal solvent system, such as：Open handsome equal (Zhang Shuai, textile college of Donghua University (China)；Li Faxue, Yu Jianyong,
Modern textile research institute of Donghua University (China)；Biological fiber is blended in regenerated cellulose-casein；World Textile Leader 2011
Year the 4th phase, the 10-12 page) using lithium hydroxide/urea/sulphur urea aqueous solution cosolvent, solubilising casein and cellulose are done, system
The blended fiber of standby casein and cellulose, wherein the mass ratio of casein and cellulose is 10:90, with cellulose fibre phase
Than the crystalline texture and mechanical property of blended fiber are improved.But there are toxicity for the dicyandiamide solution that uses of the blended fiber
By force, of high cost, solvent be difficult to recycle and use during it is unstable the shortcomings of, be unsuitable for industrialized production.
Ionic liquid is a kind of salt existing for room temperature or nearly liquid at room temperature, it has both the mobility and salt of liquid
Chemism, and have many unique properties, as structure can design, liquid journey range is wide, close to zero vapour pressure, can not
It fires, with high thermal stability and chemical stability etc..Ionic liquid is at present in separation process, catalysis, organic synthesis, electrochemistry
Etc. research obtained many progress, and be considered as that there is broad prospect of application in a kind of green syt and clean manufacturing
The green medium of novel environmental close friend.
The study found that ionic liquid can directly dissolve cellulose and protein, such as：Chinese patent
CN200510077288.3 is disclosed prepares bioprotein by solvent mixed dissolution animal wool and cellulosic material of ionic liquid
The fine method of hair；Chinese patent CN200810033113.6 is disclosed using ionic liquid as solvent mixed dissolution cellulose and silk egg
The white method for preparing standby cellulose fibroin composite fiber；Chinese patent CN201510313099.5 is disclosed is with ionic liquid
Solvent dissolves the method that keratin and cellulose prepare composite kerating fiber；Chinese patent CN201610058920.8 is disclosed
The method that fibroin albumen and cellulose prepare composite fibre is dissolved by solvent of ionic liquid；This is also to prepare cellulose and junket egg
White composite fibre provides new method, and Chinese patent CN200710043567.7 discloses molten using ionic liquid as solvent mixing
The method that solution albumen and cellulose prepare protein modified cellulose fibre, and the public affairs respectively in embodiment 5 and embodiment 12
The method that milk casein prepares composite fibre with straw pulp and milk casein with hemp dissolving pulp is opened；Though the above method
The molten symbiosis altogether of the protein and cellulose including casein is so realized, but uses ionic liquid in above-mentioned patent
When (alkyl quaternary ammonium salts, alkyl imidazole salt, alkyl pyrroles's salt etc.) solubilising protein and cellulose, it is molten to be all made of pure ionic liquid
Solve protein and cellulose so that dope viscosity obtained is larger, and spinnability is poor, for spray in follow-up spinning process
The resistance to pressure of filament plate and drawing-off all have a great impact, and are unfavorable for follow-up spinning；Also, inevitably to the fibre of raw material in the above method
Dimension shape characteristic causes damages, and keeps its performance of composite fibre obtained poor, such as：It is made in Chinese patent CN200710043567.7
The protein modified cellulose fibre long filament or short silk obtained, filament number are 1.5~5.0dtex, 2.0~6.2cN/ of intensity
Dtex, wherein the filament number for the composite fibre that milk casein modified straw pulp is prepared in embodiment 5 is
2.0dtex, intensity 4.6cN/dtex；Milk casein is modified the list for the composite fibre that hemp dissolving pulp is prepared in embodiment 12
Silk size is 2.8dtex, intensity 4.2cN/dtex；The above situation causes, although may be implemented including casein at present
Protein and fiber molten symbiosis altogether, but also rest on laboratory stage substantially, also cannot achieve industrialized scale, seriously
Limit the application and development of composite fibre.In addition to this, in the above method, ionic liquid is in solubilising protein (including junket egg
In vain) and when cellulose, dissolution time is longer, usually at 2~48 hours, even as high as 120 hours, also seriously limits its industrialization
Production；And solution temperature is higher, and usually at 100 DEG C or so, even as high as 150 DEG C, energy consumption is higher, is not easy to industrial metaplasia
Production, while casein leads to its non-refractory, therefore, it is necessary to realize casein at a lower temperature due to its special performance
With the molten symbiosis altogether of cellulose, and above-mentioned high temperature is obviously detrimental to casein and the cellulose molten composite fibre for preparing altogether.
In addition, although the composite fibre prepared after casein and other fiber composites can with the physicochemical property of modified fibre,
But the content of casein is not more Gao Yuegao in composite fibre, such as appoint sea otter etc. (appoint sea otter, Yu Jianyong, Gao Jing, it is different to throw
Expect the performance than Casein modification methods Dralon；Textile journal；In June, 2009, volume 30, the 6th phase, page 19~23) it adopts
Dralon is modified with casein, Casein modification methods Dralon is made, appropriate mass fraction is mentioned in article
So that the intensity of fiber increases, moisture pick-up properties is greatly improved, while having good frictional behaviour for the introducing of casein,
Make it have better taking；Be also mentioned that in composite fibre simultaneously " total casein content is fewer than the content that feeds intake, and
When rate of charge is bigger, the quality of casein loss is bigger, this is because polymerization process there are partial hydrolysis, has trip in spinning process
Caused by being lost from casein, impurity content is improved also with the increase of casein content in fiber, it may be possible to because of junket egg
White polarity is larger, is easier to the impurity such as absorption finish, to be had an impact to fiber composition "；And in fact, although not testing card
The content of casein cannot be higher in light fibers element casein composite fibre, but Chinese patent CN200710043567.7 is implemented
The mass fraction of milk casein and straw pulp compound tense in example 5, milk casein is 4%, milk junket egg in embodiment 12
In vain with hemp dissolving pulp compound tense, the mass fraction of milk casein is 5%, and the cellulose casein sold currently on the market is compound
The content of casein is only up to 8% in fiber, this content that casein in composite fibre is also demonstrated from side to keep compared with
Low content.
In conclusion although casein and cellulose present good development momentum in terms of molten symbiosis altogether at present,
But there are still many deficiencies, also rest on laboratory stage, and in composite fibre casein content it is relatively low, to composite fibre
Property modification it is limited, therefore, it is necessary to develop a kind of preparation method of new cellulose casein composite fibre, to promote
The industrialized production of cellulose and protein composite fibre.
Invention content
In view of the above-mentioned problems existing in the prior art, the object of the present invention is to provide a kind of cellulose casein composite fibres
Preparation method, to promote the industrialized production of cellulose and protein composite fibre.
For achieving the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method of cellulose casein composite fibre, includes the following steps：
A) by casein and cellulose dissolution in ionic liquid aqueous solution, homogeneous blend spinning stoste is made；
B) gained spinning solution through filtering, spinning, solidification, stretching, washing, bleach, oil, dry to get the fiber
Plain casein composite fibre；
Wherein, ionic liquid used is by following components：
1- butyl -3- methylimidazole villaumites：90~110 mass parts；
Join two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl：5~15 mass parts；
Join two perchlorate of 1,4- bis- [1- (3- methylimidazoles)] butyl：5~15 mass parts；
It is mixed to get；Wherein：
Connection two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl chemical structural formula be：
Connection two perchlorate of 1,4- bis- [1- (3- methylimidazoles)] butyl chemical structural formula be：
Preferably, the solution temperature of step a) be 50~100 DEG C (preferably 60~80 DEG C), dissolution time be 5~
30 minutes (preferably 10~25 minutes).
Preferably, the mass fraction of the ionic liquid aqueous solution be 20~98%, further preferred 50~
98%.
Preferably, the preparation of the ionic liquid, includes the following steps：
First make 1- butyl -3- methylimidazole villaumites and connection two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl and connection 1,4-
Two [1- (3- methylimidazoles)] butyl, two perchlorate is measured according to the ratio to be uniformly mixed, and is then stirred to react 5 at 110~130 DEG C
~15 hours.
Preferably, the preparation of two villaumite of the connection Isosorbide-5-Nitrae-two [1- (3- methylimidazoles)] butyl includes following step
Suddenly：Under 65~85 DEG C, inert gas shielding, N- methylimidazoles are added dropwise in Isosorbide-5-Nitrae-dichloroetane, are then refluxed for reaction 12
~72 hours.
As further preferred scheme, the molar ratio of Isosorbide-5-Nitrae-dichloroetane and N- methylimidazoles is 1:1~1:1.5.
As further preferred scheme, the inert gas is nitrogen or argon gas.
Preferably, the preparation of two perchlorate of the connection Isosorbide-5-Nitrae-two [1- (3- methylimidazoles)] butyl includes such as
Lower step：
To first two villaumite of Isosorbide-5-Nitrae-two [1- (3- methylimidazoles)] butyl be joined and lithium perchlorate is soluble in water, then 75~85
It is stirred to react at DEG C 12~48 hours, is cooled to room temperature, continue stirring at room temperature 5~15 hours.
As further preferred scheme, join mole of Isosorbide-5-Nitrae-two [1- (3- methylimidazoles)] butyl two villaumite and lithium perchlorate
Than being 1:1~1:1.5.
Preferably, the casein includes milk casein and goat milk casein, and protein content >=
90wt%.
Preferably, the cellulose be selected from wood pulps, Cotton Pulp, bamboo pulp, the mulberry root bark pulp dregs of rice, straw pulp,
Any one in the reed pulp dregs of rice, the multitudinous slurry dregs of rice or hemp dissolving pulp, content of cellulose >=90wt%, the degree of polymerization >=500.
Preferably, the content of casein accounts for 1~55wt% of cellulose and casein total amount.
Preferably, the mass ratio of the total amount and ionic liquid aqueous solution of cellulose and casein is 1:3~1:20.
Preferably, in step b), spinning is carried out using dry-jet wet-spinning spinning technique, the temperature of spinning solution is 50
~100 DEG C (preferably 60~80 DEG C), spinning speed are 60~150 ms/min.
The dry-jet wet-spinning spinning technique refers to forming dynamic analysis of spinning after squeezing out spinning solution by spinning head, wet
First one-step forming in cold air.Clammy air refers to that temperature is 5~25 DEG C, the air that relative humidity is 60~95%.
Preferably, in step b), the coagulating bath that when solidification uses is made of ionic liquid and water, and temperature is 0~
20 DEG C (preferably 5~15 DEG C), the wherein mass percent of ionic liquid are 1~20%.
Compared with prior art, the present invention has following conspicuousness advantageous effect：
The present invention is by 1- butyl -3- methylimidazole villaumites, connection two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl and connection
Two perchlorate of Isosorbide-5-Nitrae-two [1- (3- methylimidazoles)] butyl carries out compounding and a kind of novel ionic liquid, the ionic liquid is made
Aqueous solution can be 50~100 DEG C in solution temperature, dissolution time is that casein and cellulose are realized under conditions of 5~30 minutes
Altogether it is molten, not only saved cost, improved production efficiency, also achieved the dissolution in low temperature of casein, avoid to casein
Performance causes to damage, while dope viscosity obtained is relatively low, is conducive to spinning, but also will not be to raw material in subsequent technique
Fibrous characteristic causes damages, and when to make its filament number of composite fibre obtained be 1.67dtex, fracture strength can reach
3.2cN/dtex has excellent mechanical performance, is also conducive to scale spinning, and spinneret hole count is by the traditional experiment room stage when spinning
60~100 holes be promoted to 14000~30000 holes, realize industrialized production；Especially, the junket in the composite fibre of preparation
The content of albumen is improved to 55%, substantially increases modification of the casein to composite fibre performance；In addition, the preparation work of the present invention
Skill needs not move through deaeration step and can be prepared by composite fibre, economical and practical, and preparation process is simple, of low cost, without using appointing
What organic solvent, it is environmental-friendly pollution-free, it is not necessarily to special installation and harsh conditions, it is easy to accomplish industrialized production has extremely strong
Practical value.
Specific implementation mode
Technical solution of the present invention is described in further detail and completely with reference to embodiment, application examples and comparative example.
Embodiment 1
One, join the preparation of two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl：
At nitrogen protection, 80 DEG C, 1.2mol N- methylimidazoles are slowly added dropwise in 1mol Isosorbide-5-Nitraes-dichloroetane, are dripped
After adding, back flow reaction 72 hours, reaction was completed, and reaction solution is cooled to room temperature, and products therefrom is washed with ether to remove not
The raw material of reaction obtains white solid matter, and as joining Isosorbide-5-Nitrae-two [1- (3- methylimidazoles)] butyl two villaumite, (HPLC purity is
98.8%, yield 88%).
Two, join the preparation of two perchlorate of 1,4- bis- [1- (3- methylimidazoles)] butyl：
1mol is joined into two villaumite of Isosorbide-5-Nitrae-two [1- (3- methylimidazoles)] butyl and 1.2mol lithium perchlorates are dissolved in 1L water, so
It is stirred to react 36 hours, is cooled to room temperature at 80 DEG C afterwards, continue stirring 12 hours at room temperature, reaction solution is dispersed in equal volume
Chloroform in, separation, chloroform mutually washes with water, until water phase, without chlorion, chloroform is mutually concentrated under reduced pressure, and obtains water white transparency liquid
Body as joins two perchlorate of Isosorbide-5-Nitrae-two [1- (3- methylimidazoles)] butyl (HPLC purity is 98.9%, yield 78%).
Three, the preparation of ionic liquid：
By 100g 1- butyl -3- methylimidazole villaumites, 10g connection two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl and
10g joins two perchlorate of Isosorbide-5-Nitrae-two [1- (3- methylimidazoles)] butyl after mixing, is stirred to react at 120 DEG C 12 hours,
Reaction was completed, is cooled to room temperature to get the ionic liquid.
Four, the preparation of composite fibre：
A) by ion liquid dissolving in deionized water, configuration obtains the ionic liquid aqueous solution of 80wt%, for use；It will
The milk caseins (protein content 92%) of 0.5 mass parts and 9.5 mass parts Cotton Pulp (content of cellulose 99%,
The degree of polymerization be 600) be uniformly mixed, be added 100 mass parts, 80wt% ionic liquid aqueous solution in, at 70 DEG C stir 25 points
Clock obtains the spinning solution of stable uniform；
B) through filtering, (traditional preparation method spinning solution will pass through filtering to gained spinning solution, deaeration could be spun
Silk, processing step is complex), (spinneret hole count is 20000 holes, and spinning solution temperature is 70 DEG C, is spun for porous spinneret spinning
Silk speed is 100 ms/min) afterwards, be immersed in the coagulating bath of the ionic liquid containing 10wt% and solidify, coagulation bath temperature is 15 DEG C,
After 3.5 times stretch, then through washing, bleach, oil, dry to get cellulose casein composite fibre.
After tested, the cellulose casein composite fibre that the present embodiment is prepared is in the feelings that filament number is 1.67dtex
Under condition, fracture strength is 2.2cN/dtex or so.And it tests and shows：Under equal conditions, using the 1- butyl -3- of 80wt%
Methylimidazole villaumite, connection two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl or 1,4- bis- [1- (3- methylimidazoles)] butyl two
When the single ionic liquid aqueous solution solubilising casein and Cotton Pulp of perchlorate, need the stirring 3~5 at 110~130 DEG C small
Shi Caineng obtains the spinning solution of stable uniform, and in the case where filament number is all 1.67dtex, and comparison obtained is multiple
Its fracture strength of condensating fiber is only 1.3cN/dtex or so, illustrates the preparation process using the present embodiment, not only realizes fiber
The molten symbiosis altogether of element and casein, and the composite fibre better mechanical property prepared；
In addition, the present embodiment by using the ionic liquid, is realized removes dissolving junket using ionic liquid aqueous solution
Albumen and cellulose, and in fact casein and cellulose are all not readily dissolved in water, the water of addition is actually to be unfavorable for cellulose
(this is also that organic solvent, such as DMSO is added to promote cellulose dissolution in traditional ionic liquid with the dissolving of casein
Reason)；In addition, the application can also reduce the viscosity of spinning solution, be advantageously implemented height simultaneously by the way that water is added in dissolution system
Hole spinneret；Also, solution temperature is significantly reduced, and dissolution time significantly shortens.
Due to the composite fibre better mechanical property that the present embodiment is prepared, the viscosity of spinning solution is relatively low, so that
Spinneret hole count can reach 20000 holes when the present embodiment spinning, and spinning speed can be 100 ms/min, realize industrialization
Production.
The mass fraction of the present embodiment step a) intermediate ion liquid aqueous solutions can be 20~98%, remaining condition is constant.
Solution temperature can be 50~100 DEG C in the present embodiment step a), and dissolution time can be 5~30 minutes, remaining
Condition is constant.
In the present embodiment step a) Cotton Pulp can be wood pulps, it is bamboo pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, multitudinous
The slurry dregs of rice or hemp dissolving pulp, remaining condition are constant.
Spinning hole count can be 14000~30000 holes in the present embodiment step b), remaining condition is constant, spinning solution temperature
Degree can be 50~100 DEG C, and spinning speed can be 60~150 ms/min, remaining condition is constant.
Coagulating bath can be the ionic liquid aqueous solution of 1~20wt% in the present embodiment step b), and solidification bath temperature can be 0
~20 DEG C, remaining condition is constant.
It can be 1.5~4 times of stretchings to be stretched in the present embodiment step b), remaining condition is constant.
Embodiment 2
The present embodiment the difference is that only with embodiment 1：By the milk caseins of 1 mass parts, (protein content is
92%) with the Cotton Pulp of 9 mass parts (content of cellulose 99%, the degree of polymerization 600) be uniformly mixed, remaining content with implementation
It is identical described in example 1.
After tested, the cellulose that the present embodiment is prepared is 1.67dtex's in filament number with casein composite fibre
In the case of, fracture strength is 2.8cN/dtex or so.And it tests and shows：Under equal conditions, using the 1- butyl-of 80wt%
3- methylimidazole villaumites, connection two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl or 1,4- bis- [1- (3- methylimidazoles)] butyl
When the single ionic liquid aqueous solution solubilising casein and Cotton Pulp of two perchlorate, need to stir 3~5 at 110~130 DEG C
Hour can just obtain the spinning solution of stable uniform, and in the case where filament number is all 1.67dtex, comparison obtained
Its fracture strength of composite fibre is only 1.4cN/dtex or so.
Embodiment 3
The present embodiment the difference is that only with embodiment 1：By the milk caseins of 2 mass parts, (protein content is
92%) with the Cotton Pulp of 8 mass parts (content of cellulose 99%, the degree of polymerization 600) be uniformly mixed, remaining content with implementation
It is identical described in example 1.
After tested, the cellulose that the present embodiment is prepared is 1.67dtex's in filament number with casein composite fibre
In the case of, fracture strength is 3.2cN/dtex or so.And it tests and shows：Under equal conditions, using the 1- butyl-of 80wt%
3- methylimidazole villaumites, connection two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl or 1,4- bis- [1- (3- methylimidazoles)] butyl
When the single ionic liquid aqueous solution solubilising casein and Cotton Pulp of two perchlorate, need to stir 3~5 at 110~130 DEG C
Hour can just obtain the spinning solution of stable uniform, and in the case where filament number is all 1.67dtex, comparison obtained
Its fracture strength of composite fibre is only 1.5cN/dtex or so.
Embodiment 4
The present embodiment the difference is that only with embodiment 1：By the milk caseins of 4 mass parts, (protein content is
92%) with the Cotton Pulp of 6 mass parts (content of cellulose 99%, the degree of polymerization 600) be uniformly mixed, remaining content with implementation
It is identical described in example 1.
After tested, the cellulose that the present embodiment is prepared is 1.67dtex's in filament number with casein composite fibre
In the case of, fracture strength is 2.7cN/dtex or so.And it tests and shows：Under equal conditions, using the 1- butyl-of 80wt%
3- methylimidazole villaumites, connection two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl or 1,4- bis- [1- (3- methylimidazoles)] butyl
When the single ionic liquid aqueous solution solubilising casein and Cotton Pulp of two perchlorate, need to stir 3~5 at 110~130 DEG C
Hour can just obtain the spinning solution of stable uniform, and in the case where filament number is all 1.67dtex, comparison obtained
Its fracture strength of composite fibre is only 1.2cN/dtex or so.
Embodiment 5
The present embodiment the difference is that only with embodiment 1：By the milk casein (protein content of 5.5 mass parts
For 92%) with the Cotton Pulp of 4.5 mass parts (content of cellulose 99%, the degree of polymerization 600) be uniformly mixed, remaining content with
It is identical described in embodiment 1.
After tested, the cellulose that the present embodiment is prepared is 1.67dtex's in filament number with casein composite fibre
In the case of, fracture strength is 2.2cN/dtex or so.And it tests and shows：Under equal conditions, using the 1- butyl-of 80wt%
3- methylimidazole villaumites, connection two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl or 1,4- bis- [1- (3- methylimidazoles)] butyl
When the single ionic liquid aqueous solution solubilising casein and Cotton Pulp of two perchlorate, need to stir 3~5 at 110~130 DEG C
Hour can just obtain the spinning solution of stable uniform, and in the case where filament number is all 1.67dtex, comparison obtained
Its fracture strength of composite fibre is only 1.0cN/dtex or so.
By embodiment 1 to embodiment 5 as it can be seen that preparation process using the present invention, in particular by the present invention it is compound from
Sub- liquid dissolves cellulose and casein, and the composite fibre being prepared is under identical filament number, using this hair
The fracture strength for the composite fibre that bright compound ion liquid is prepared is compare composite fibre fracture strength twice or so,
Illustrate preparation process using the present invention, not only realizes the molten symbiosis altogether of cellulose and casein, and the compound fibre prepared
The mechanical performance of dimension is more preferable, and especially, in composite fibre prepared by the present invention, the content of casein can be improved to 55%, though
When right casein additive amount is 20%, composite fibre performance obtained is best, when 55% additive amount, composite fibre performance under
Drop, still, even 55% additive amount, composite fibre is in the case where filament number is all 1.67dtex, fracture strength
2.2N/dtex can be reached, be still better than when the comparison optimal additive amount of composite fibre attainable 1.4~1.5 fracture strength,
To overcome the defect that casein content cannot be excessively high in previous composite fibre.
In summary：The present invention by 1- butyl -3- methylimidazole villaumites, connection 1,4- bis- [1- (3- methylimidazoles)] butyl two
Villaumite and connection two perchlorate of Isosorbide-5-Nitrae-two [1- (3- methylimidazoles)] butyl carry out compounding and a kind of novel ionic liquid are made, and obtain
To ionic liquid the molten symbiosis altogether of casein and cellulose may be implemented, can be used for preparing the compound fibre of cellulose casein
Dimension, cellulose casein composite fibre obtained have excellent mechanical performance, and in the preparation process of composite fibre, no
Pure ionic liquid need to be used, you can realize the molten altogether of casein and cellulose, and significantly reduce solution temperature, shorten
Dissolution time (and under identical solution temperature, with the increase of casein additive amount, dissolution time can also shorten therewith), carries
High dissolved efficiency, reduces production cost, improves production efficiency, and the use of ionic liquid aqueous solution compared to it is pure from
For sub- liquid, obtained dope viscosity is relatively low, and can be adjusted according to the needs the concentration of ionic liquid aqueous solution, Jin Erling
It is living to adjust dope viscosity so that spinning solution is easy to spinning, and spinneret hole count can reach 14000~30000 holes when spinning,
Spinning speed can be 60~150 ms/min, realize industrialized production；In addition, the present invention preparation process need not move through it is de-
Bubble step can be prepared by composite fibre, and processing step is relatively simple, economical and practical, and preparation process is simple, of low cost, without making
It is environmental-friendly pollution-free with any organic solvent, it is not necessarily to special installation and harsh conditions, it is easy to accomplish industrialized production has
Extremely strong practical value achieves conspicuousness progress and unexpected effect in terms of existing technologies.
Finally need indicated herein be：The part preferred embodiment that the above is only the present invention, should not be understood as to this hair
The limitation of bright protection domain, those skilled in the art's the above according to the present invention make some it is nonessential improvement and
Adjustment all belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of cellulose casein composite fibre, includes the following steps：
A) by casein and cellulose dissolution in ionic liquid aqueous solution, homogeneous blend spinning stoste is made；
B) gained spinning solution through filtering, spinning, solidification, stretching, washing, bleach, oil, dry to get the cellulose junket
Protein composite fiber；
It is characterized in that, ionic liquid used is by following components：
1- butyl -3- methylimidazole villaumites：90~110 mass parts；
Join two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl：5~15 mass parts；
Join two perchlorate of 1,4- bis- [1- (3- methylimidazoles)] butyl：5~15 mass parts；
It is mixed to get；Wherein：
Connection two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl chemical structural formula be：
Connection two perchlorate of 1,4- bis- [1- (3- methylimidazoles)] butyl chemical structural formula be：
2. preparation method according to claim 1, it is characterised in that：The mass fraction of the ionic liquid aqueous solution is 20
~98%.
3. preparation method according to claim 1, it is characterised in that：Solution temperature in step a) is 50~100 DEG C, molten
It is 5~30 minutes to solve the time.
4. preparation method according to claim 1, which is characterized in that the preparation of the ionic liquid includes the following steps：
First make 1- butyl -3- methylimidazole villaumites and connection two villaumite of 1,4- bis- [1- (3- methylimidazoles)] butyl and connection 1,4- bis-
Two perchlorate of [1- (3- methylimidazoles)] butyl is measured according to the ratio to be uniformly mixed, then it is stirred to react 5 at 110~130 DEG C~
15 hours.
5. preparation method according to claim 4, which is characterized in that described connection Isosorbide-5-Nitrae-two [1- (3- the methylimidazoles)] fourth
The preparation of two villaumite of base includes the following steps：Under 65~85 DEG C, inert gas shielding, N- methylimidazoles are added dropwise to Isosorbide-5-Nitrae-two
In chlorobutane, it is then refluxed for reaction 12~72 hours.
6. preparation method according to claim 4, which is characterized in that described connection Isosorbide-5-Nitrae-two [1- (3- the methylimidazoles)] fourth
The preparation of two perchlorate of base includes the following steps：
To first two villaumite of Isosorbide-5-Nitrae-two [1- (3- methylimidazoles)] butyl be joined and lithium perchlorate is soluble in water, then at 75~85 DEG C
It is stirred to react 12~48 hours, is cooled to room temperature, continue stirring at room temperature 5~15 hours.
7. preparation method according to claim 1, it is characterised in that：The cellulose is selected from wood pulps, Cotton Pulp, bamboo
Any one in pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, the multitudinous slurry dregs of rice or hemp dissolving pulp, content of cellulose >=
90wt%, the degree of polymerization >=500.
8. preparation method according to claim 1, it is characterised in that：The content of casein accounts for cellulose and casein total amount
1~55wt%.
9. preparation method according to claim 1, it is characterised in that：The total amount of cellulose and casein and ionic liquid water
The mass ratio of solution is：1:3~1:20.
10. preparation method according to claim 1, it is characterised in that：In step b), using dry-jet wet-spinning spinning technique into
The temperature of row spinning, spinning solution is 50~100 DEG C, and spinning speed is 60~150 ms/min.
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| CN110344131A (en) * | 2019-07-19 | 2019-10-18 | 嘉兴学院 | A kind of sericin modification regeneration cellulose fibre and preparation method thereof |
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