CN105525376B - A kind of regenerated celulose fibre and preparation method thereof - Google Patents
A kind of regenerated celulose fibre and preparation method thereof Download PDFInfo
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- CN105525376B CN105525376B CN201510848219.1A CN201510848219A CN105525376B CN 105525376 B CN105525376 B CN 105525376B CN 201510848219 A CN201510848219 A CN 201510848219A CN 105525376 B CN105525376 B CN 105525376B
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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
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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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
Abstract
The invention provides a kind of preparation method of regenerated celulose fibre, it is characterised in that comprises the following steps, dissolves corn cob fiber pulp and chelating agent with NMMO solution first, obtain spinning solution；Then reuse the spinning solution that above-mentioned steps obtain and prepare regenerated celulose fibre.The present invention prepares regenerated celulose fibre using solvent method, raw material using corn cob fiber as Lyocell fiber, sufficiently it make use of agricultural wastes corncob, the effective yoke for solving Lyocell fiber shortage of raw materials, and corn cob fiber element pulp, fibre length is short (length is between 0~0.3mm), the degree of polymerization is uniformly (between 500~600), in dicyandiamide solution can rapid dispersion it is uniform, and pulp surface distributed has substantial amounts of hole, with stronger capillarity, can quick lyosoption, pulp surface is set to be involved in reacting with inside, greatly reduce the reaction time, improve the reaction uniformity.
Description
Technical field
The present invention relates to regenerated fiber technical field, more particularly to a kind of regenerated celulose fibre and preparation method thereof.
Background technology
Regenerated celulose fibre refers to that with natural polymer be raw material, through changing made of chemical method, with original copolymer
Learn the upper essentially identical chemical fibre of composition.Usable fibers element is that raw material is manufactured, the regeneration that structure is cellulose II again simultaneously
Fiber.
In numerous regenerated celulose fibres, it is fine that Lyocell fiber (implying that disappearing fibre) is described as 21 century green
Dimension, it is the regenerated celulose fibre for wet method spinning for solvent with N-methylmorpholine-N- oxides (NMMO).Early in 20
Just there is the thirties in century patent (US92179181) proposition directly to dissolve cellulose with tertiary amine acid oxide excellent to produce performance
In new cellulosic-Lyocell fiber of viscose rayon, it, which is formed, still falls within cellulosic structure, and product abandonment thing is natural
A kind of degraded, it is considered to be the good green fiber of combination property.It has the comfortableness of cotton fiber, polyester fiber it is strong
The soft matter state of degree, the drapability of viscose rayon and silk, it is very popular.Therefore, from the 1970s so far,
At home and abroad under the joint efforts of scientist, apply or disclosed the individual patents up to a hundred about Lyocell fiber.
Bamboo cellulose is utilized as patent " manufacture method of CN1472374A bamboo cellulose fibre by solvent " refer to one kind
Pulp produces the manufacture method of cellulose fiber by solvent method, and its method is：First the bamboo cellulose that the degree of polymerization is 400~1000 is starched
The dregs of rice are cut to the small pieces of specific standard with pulp grinder is cut, and then carrying out dehydration makes moisture content reach 2~4%, then with after concentration
The mixing of NMMO solvents, stirring, are heated to being dissolved at 80~110 DEG C under vacuum, obtain spinning solution.Then should
Spinning solution carries out the processes such as spinning, post processing and obtains the short silk of bamboo fibre or long filament.Patent " CN1420214A solvent method fibers
One kind is refer in the preparation technology of the spinning solution of cellulose fiber " with Cotton Pulp or wood pulps production cellulose fiber by solvent method
Spinning, equipment is simple, be adapted to small lot production, but need to transformation dissolution kettle or polymeric kettle complete reaction.
But it is above-mentioned be related to manufacture method in the prior art, be all with cellulose pulp made of cotton, wood or bamboo pulp
For raw material.But with the high speed development of Lyocell fiber, the agricultural resource such as forest cotton it is increasingly in short supply, people can not be met
To the demand trend of Lyocell fiber raw material.Cellulose pulp is cotton, wood or bamboo pulp used by being additionally, since, fiber
Length is longer (length is generally higher than 0.5mm), and the degree of polymerization is higher, and the poly- effect of conglomeration, bridging, wadding between fiber is obvious, thus
In NMMO dissolving agent process is dissolved in, make NMMO solvents can not quickly, uniformly with pulp hybrid reaction, exist dissolution time it is long,
The technical barriers such as follow-up ropiness energy are influenceed, operability is lacked in actual production process.
Therefore, how to find one kind and be more beneficial for regenerated celulose fibre long-run development, and actual production can be strengthened
The preparation method of middle operability, it has also become the focus and urgent problem to be solved of institute of manufacturer extensive concern in industry.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of regenerated celulose fibre and its preparation side
Method, the regenerated celulose fibre and preparation method of offer of the invention, using corncob be cellulose as raw material, by solvent legal system
Standby regenerated celulose fibre, it is in short supply effectively to solve regenerated celulose fibre raw material, and poor operability in preparation process
The problem of.
The invention provides a kind of preparation method of regenerated celulose fibre, it is characterised in that comprises the following steps：
1) corn cob fiber pulp and chelating agent after mixed dissolution, are obtained into spinning solution in NMMO solution；
2) spinning solution for again obtaining above-mentioned steps carries out spinning, obtains regenerated celulose fibre.
Preferably, the degree of polymerization of the corn cob fiber pulp is 400~800.
Preferably, it is 80%~95% that first is fine in the corn cob fiber pulp, and whiteness is 70%~90%, ash content 0
~0.5%, moisture is 5%~50%.
Preferably, the quality of the corn cob fiber pulp accounts for the 5%~20% of spinning solution gross mass；The chelating agent
Quality be the corn cob fiber pulp quality 0.1%~0.5%.
Preferably, the chelating agent is carboxylic acid quasi-chelate compound, polycarboxylic acid chelating agent and organic multicomponent phosphonic acid type chelants
In one or more；
Preferably, the carboxylic acid quasi-chelate compound is amino carboxylic acid quasi-chelate compound, hydroxycarboxylic acid quasi-chelate compound and hydroxylamino carboxylic
The one or more of acids chelating agent；
The amino carboxylic acid quasi-chelate compound includes ethylenediamine tetra-acetic acid (EDTA), diethyl pentetic acid (DTPA) and two
One or more in ethylenetriamine pentacetic acid and its salt；The hydroxylamino carboxylic acid quasi-chelate compound includes AEEA three
One or more in acetic acid (HEDTA) and bicine N- (DEG)；The hydroxycarboxylic acid quasi-chelate compound includes citric acid
(CA), the one or more in tartaric acid (TA) and gluconic acid (GA)；
The polycarboxylic acid chelating agent is polyacrylic acid and its sodium salt, polymethylacrylic acid, HPMA, rich horse
One or more in sour (fumaric acid)-propene sulfonic acid EVA.
Preferably, the corn cob fiber pulp is through peracid treatment.
Preferably, the acid treatment is that the corn cob fiber pulp and the mixing of NMMO solution are preceding with acid solution
Reason；
Or during the corn cob fiber pulp and NMMO solution mixed dissolutions, it is passed through sour gas and is handled.
The invention provides a kind of regenerated celulose fibre, it is characterised in that is passed through by corn cob fiber as fibrous raw material
Obtained after preparation.
Present invention also offers a kind of article, it is characterised in that contains the preparation described in claim 1~7 any one
Regenerated celulose fibre prepared by method, or the regenerated celulose fibre described in claim 8~9 any one；
The article includes civilian clothes, home-textile, ultraviolet protection fabric or industrial special protecting clothing.
The invention provides a kind of preparation method of regenerated celulose fibre, it is characterised in that comprises the following steps, first
Corn cob fiber pulp and chelating agent after mixed dissolution, are obtained into spinning solution in NMMO solution；Above-mentioned steps are obtained again
Spinning solution carry out spinning, obtain regenerated celulose fibre.Compared with prior art, the present invention prepares regeneration using solvent method
Cellulose fibre, the raw material using corn cob fiber as Lyocell fiber, sufficiently make use of agricultural wastes corncob, not only
The effective yoke for solving Lyocell fiber shortage of raw materials, the also comprehensive utilization for corncob provide brand-new approach；And
And corn cob fiber element pulp, fibre length is short (length is between 0~0.3mm), and the degree of polymerization is uniform (between 500~600),
In dicyandiamide solution can rapid dispersion it is uniform, and pulp surface distributed has substantial amounts of hole, has stronger capillarity,
Can quick lyosoption, make pulp surface be involved in reacting with inside, greatly reduce the reaction time, it is uniform to improve reaction
Degree, it is not necessary to by the activation procedure of pulp, shorten production procedure, improve production efficiency.In addition, the present invention is preparing spinning
During silk stock solution, by adding chelating agent, the iron ion in corncob pulp is failed, cause so as to avoid iron ion
The spinning solution degree of polymerization acutely declines, and causes difficulty in spinning, easily broken end, makes into the negative effect such as low of silk poor product quality, intensity.
Test result indicates that regenerated celulose fibre preparation method provided by the invention be uniformly dissolved stabilization, dissolution time it is short, the present invention
The preparation method dissolution time of offer is 30~60min, shortens 20~70min compared to wood pulp, follow-up ropiness can be good, made
Standby regenerated celulose fibre elongation at break can reach 17.6%, and dry fracture strength can reach 4.5CN/dtex.
Brief description of the drawings
Fig. 1 is 500 times of SEM photographs of corn cob fiber element pulp provided by the invention；
Fig. 2 is 5000 times of SEM photographs of corn cob fiber element pulp provided by the invention；
Fig. 3 is 5000 times of SEM photographs of the corn cob fiber element pulp in the embodiment of the present invention 1；
Fig. 4 is Lyocell fiber spinning technique general flow chart.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, its source is not particularly limited, commercially buying or according to people in the art
Known to member prepared by conventional method.
All raw materials of the present invention, its purity is not particularly limited, pure present invention preferably employs analyzing.
The invention provides a kind of preparation method of regenerated celulose fibre, it is characterised in that comprises the following steps：
1) corn cob fiber pulp and chelating agent after mixed dissolution, are obtained into spinning solution in NMMO solution；
2) spinning solution for again obtaining above-mentioned steps carries out spinning, obtains regenerated celulose fibre.
Corn cob fiber pulp and chelating agent after mixed dissolution, are obtained spinning original by the present invention in NMMO solution first
Liquid；The degree of polymerization of the corn cob fiber pulp is preferably 400~800, more preferably 400~750, more preferably 400~
700, more preferably 400~650, optimal is 400~600.In the corn cob fiber pulp, the first fine preferably 80%~
95%, more preferably 83%~92%, most preferably 85%~90%；The whiteness is preferably 70%~90%, more preferably
75%~85%, most preferably 78%~82%；The ash content is preferably 0~0.5%, and more preferably 0.1%~0.4%, most
Preferably 0.2%~0.3%.The corncob is not particularly limited the present invention, with corn well known to those skilled in the art
Core；The other conditions of the corn cob fiber pulp are not particularly limited the present invention, with known to those skilled in the art
Corn cob fiber pulp condition；The corn cob fiber pulp source is not particularly limited the present invention, with ability
Preparation method preparation or commercially available known to field technique personnel, the present invention can preferably be prepared using following methods,
Method one
(1) after corncob is crushed, under the catalytic action of hydrogen peroxide, the organic acid being made up of formic acid and acetic acid is used
Liquid carries out boiling to corncob, controls 120-155 DEG C of boiling temperature, solid-liquid mass ratio 1：5-1：15, reaction time 10-
60min, and obtained reaction solution is subjected to first time separation of solid and liquid；In the organic acid solution, it is 70-95wt% that total acid is dense, institute
The mass ratio for stating acetic acid and formic acid is 1：1-1：19, surplus is water；Hydrogen peroxide accounts for the 1-8wt% of corncob；
(2) solid that the first time separation of solid and liquid obtains is collected, under the catalytic action of hydrogen peroxide, using by first
Acid, the mix acid liquor of acetic acid composition carry out pickling to the solid, control 30-100 DEG C of pickling temperature, solid-liquid mass ratio 1：4-
1：20, and obtained reaction solution is subjected to second of separation of solid and liquid；In the mix acid liquor, dense total acid is 70-95wt%, described
The mass ratio of acetic acid and formic acid is 1：1-1：19, surplus is water；Hydrogen peroxide accounts for the 1-8wt% of corncob；
(3) solid that second of separation of solid and liquid obtains is collected, water-filling of going forward side by side is washed, and it is 25-90 DEG C to control washing temperature,
It is 1-10wt% to starch dense, and obtained washing slurry is carried out into third time separation of solid and liquid；
(4) collect the solid that the third time separation of solid and liquid obtains and screening obtains required screened stock cellulose, through bleaching
After obtain corn cob fiber element pulp.
Method two
By in method one, the pickling of step (2) replaces with alkali cleaning, and actual conditions is 12% sodium hydroxide solution, to step
(1) solid carries out alkali cleaning, 30-100 DEG C of alkali cleaning temperature, alkali cleaning time 10-30min.Other conditions are constant.
Method three
By in method one, the digestion process of step (1) replaces with：Corncob is crushed, it is small to carry out alkali lye boiling 0.5-1.2
When, corn cob fiber element solution is obtained, then carries out separation of solid and liquid.Other conditions are constant.
Referring to Fig. 1, Fig. 1 is 500 times of SEM photographs of corn cob fiber element pulp prepared by the present invention.It is referring to Fig. 2, Fig. 2
5000 times of SEM photographs of corn cob fiber element pulp provided by the invention.
The quality of corn cob fiber pulp of the present invention preferably accounts for the 5%~20% of spinning solution gross mass, more preferably
For 8%~18%, most preferably 10%~15%；The quality of the chelating agent is preferably the corn cob fiber pulp quality
0.1%~0.5%, more preferably 0.2%~0.4%, most preferably 0.25%~0.35%；Chelating agent of the present invention does not have
Especially limitation, with the chelating agent well known to those skilled in the art for being used to go iron ions, the present invention removes effect to improve
One or more in fruit, preferably carboxylic acid quasi-chelate compound, polycarboxylic acid chelating agent and organic multicomponent phosphonic acid type chelants, it is more excellent
Elect carboxylic acid quasi-chelate compound, polycarboxylic acid chelating agent or organic multicomponent phosphonic acid type chelants as, most preferably carboxylic acid quasi-chelate compound or
Polycarboxylic acid chelating agent；The carboxylic acid quasi-chelate compound is preferably amino carboxylic acid quasi-chelate compound, hydroxycarboxylic acid quasi-chelate compound and oxyammonia
The one or more of yl carboxylic acid quasi-chelate compound, more preferably amino carboxylic acid quasi-chelate compound, hydroxycarboxylic acid quasi-chelate compound or hydroxylamino
Carboxylic acid quasi-chelate compound；The polycarboxylic acid chelating agent is preferably polyacrylic acid and its sodium salt, polymethylacrylic acid, the poly- Malaysia of hydrolysis
One or more in acid anhydrides, fumaric acid (fumaric acid)-propene sulfonic acid EVA, more preferably polyacrylic acid and its sodium
Salt, polymethylacrylic acid, HPMA or fumaric acid (fumaric acid)-propene sulfonic acid EVA, it is most preferably poly-
Acrylic acid and its sodium salt, HPMA or fumaric acid (fumaric acid)-propene sulfonic acid EVA.
In the carboxylic acid quasi-chelate compound, the amino carboxylic acid quasi-chelate compound be specifically as follows ethylenediamine tetra-acetic acid (EDTA),
One or more in diethyl pentetic acid (DTPA) and diethylene-triamine pentaacetic acid and its salt, or ethylenediamine
Tetraacethyl (EDTA), diethyl pentetic acid (DTPA) or diethylene-triamine pentaacetic acid and its salt；The oxyammonia yl carboxylic acid
Quasi-chelate compound is specifically as follows one kind or several in hydroxyethylethylene diamine tri-acetic acid (HEDTA) and bicine N- (DEG)
Kind, or hydroxyethylethylene diamine tri-acetic acid (HEDTA) or bicine N- (DEG)；The hydroxycarboxylic acid chelating
Agent preferably includes the one or more in citric acid (CA), tartaric acid (TA) and gluconic acid (GA), more preferably including citric acid
(CA), tartaric acid (TA) or gluconic acid (GA).
The source of the NMMO solution is not particularly limited the present invention, is prepared in method well known to those skilled in the art
Or it is commercially available, aqueous 10% is concentrated into present invention preferably employs commercially available NMMO solvents (concentration is usually 50% or 60%)~
After 30%, the NMMO solution is obtained.The other conditions of the NMMO solution are not particularly limited the present invention, with this area skill
Condition known to art personnel.
The specific method of the mixing is not particularly limited the present invention, and those skilled in the art can be according to actual feelings
Condition, product requirement and quality control are adjusted, and the present invention is preferably uniformly mixing.Specific side of the present invention to the dissolving
Method is not particularly limited, those skilled in the art can be adjusted according to actual conditions, product requirement and quality control and
Selection, the dissolving of the present invention preferably corn cob fiber pulp can be dissolved in a manner of following three kinds：
Direct dissolution method：Commercially available NMMO solvent concentrations, corncob pulp is added, then heats up, carries out dissolving cellulose.
Indirect dissolution method：Commercially available NMMO solvents (being mostly 50% or 60%), are first mixed, cellulose exists with corncob pulp
It is swelled in solvent, then by depressurizing/vacuumizing removing excess water, dissolves cellulose.
Directly-indirect dissolution method：
Commercially available NMMO solvent concentrations add corncob pulp, then heated up to aqueous 10%~30%, while through over-subtraction
Removing excess water is pressed/vacuumized, dissolves cellulose.
For the present invention to improve the quality of the effect of dissolving and subsequent product, the addition opportunity of preferred sequestrant is that NMMO is molten
When the water content of liquid is 10%~30%, more preferably 13%~30%, more preferably 15%~30%, most preferably 20%~
30%.
The present invention is especially limited without other the specific preparation process of the spinning solution, ripe with those skilled in the art
The preparation method for the spinning solution known, those skilled in the art can be according to actual conditions, product requirement and quality controls
System is adjusted and selected, and the present invention is preferably：
Method one：Take the NMMO aqueous solution, it is 10-30% to be concentrated into water content, by corn cob fiber element pulp, chelating agent and
NMMO solution mixing after concentration, stirring heating, dissolves cellulose, obtains spinning solution.
Method two：The NMMO aqueous solution is taken, corn cob fiber element pulp, chelating agent and NMMO solution are mixed, cellulose exists
It is swelled in solvent, then by depressurizing/vacuumizing removing excess water, dissolves cellulose, obtain spinning solution.
Method three：Take the NMMO aqueous solution, it is 10-30% to be concentrated into water content, by corn cob fiber element pulp, chelating agent and
NMMO solution mixing after concentration, stirring heating, while by depressurizing/vacuumizing removing excess water, dissolve cellulose, obtain
Spinning solution.
The spinning solution that the present invention again obtains above-mentioned steps carries out spinning, obtains regenerated celulose fibre.The present invention is right
The detailed process of the spinning is not particularly limited, and regenerated fiber is prepared with spinning solution spinning well known to those skilled in the art
The process of cellulose fiber, those skilled in the art can be clear from, and other filtering, spinning, wash, oil and dry
Etc. process, be all essential conventional steps, moreover, this is also known to those skilled in the art.
Referring to Fig. 4, Fig. 4 is Lyocell fiber spinning technique general flow chart.
The present invention is especially limited without other the overall preparation method of the regenerated celulose fibre, with art technology
Operating condition known to personnel, those skilled in the art can enter according to actual conditions, product requirement and quality control
Row adjustment and selection, the present invention preferably prepare regenerated celulose fibre using solvent method on the whole, are more preferably specially：
Method one：Take the NMMO aqueous solution, it is 10-30% to be concentrated into water content, by corn cob fiber element pulp, chelating agent and
NMMO solution mixing after concentration, stirring heating, dissolves cellulose, obtains spinning solution.Then spinning solution is filtered,
Regenerated celulose fibre is obtained by dry-jet wet spinning process, coagulating bath is NMMO dilute aqueous solutions (concentration is 5~15%), after shaping
Tow can obtain corn cob fiber cellulose fiber after the postprocessing working procedures such as washing, cut off, oil, drying.
Method two：The NMMO aqueous solution is taken, corn cob fiber element pulp, chelating agent and NMMO solution are mixed, cellulose exists
It is swelled in solvent, then by depressurizing/vacuumizing removing excess water, dissolves cellulose, obtain spinning solution.Then by spinning
Stoste is filtered, regenerated celulose fibre is obtained by dry-jet wet spinning process, and coagulating bath is NMMO dilute aqueous solutions (concentration 5
~15%), the tow after shaping can obtain corn cob fiber element after the postprocessing working procedures such as washing, cut off, oil, drying
Fiber.
Method three：Take the NMMO aqueous solution, it is 10-30% to be concentrated into water content, by corn cob fiber element pulp, chelating agent and
NMMO solution mixing after concentration, stirring heating, while by depressurizing/vacuumizing removing excess water, dissolve cellulose, obtain
Spinning solution.Then spinning solution is filtered, regenerated celulose fibre is obtained by dry-jet wet spinning process, coagulating bath is
NMMO dilute aqueous solutions (concentration be 5~15%), tow after shaping is after the postprocessing working procedures such as washing, cut off, oil, drying
It can obtain corn cob fiber cellulose fiber.
The present invention is the effect of the overall preparation process of raising and the quality of subsequent product, corn cob fiber described in preferred pair
Pulp also includes acid treatment step, and the acid treatment step is not particularly limited the present invention, with known to those skilled in the art
Acid treatment step, the present invention improves the chelate effect of iron ion and chelating agent, and specific steps are more preferably, the corn
Handled before core fibre pulp and the mixing of NMMO solution with acid solution；Or the corn cob fiber pulp and NMMO solution mix
Close in course of dissolution, be passed through sour gas and handled.Sour source in the acid solution is not particularly limited the present invention,
Those skilled in the art can be adjusted and select according to actual conditions, product requirement and quality control, and the present invention is preferably
For nonmetallic strong acid weak base salt, weak acid (such as formic acid, acetic acid)；The present invention is not special to the mode of acid solution processing
Limitation, those skilled in the art can be adjusted and select according to actual conditions, product requirement and quality control, the present invention
Preferably corn cob fiber pulp is impregnated and/or dried in an acidic solution.The present invention is not special to the sour gas
Limitation, those skilled in the art can be adjusted and select according to actual conditions, product requirement and quality control, the present invention
Preferably carbon dioxide；Present invention carbon dioxide that further preferably above-mentioned steps are passed through, in the de-bubble step before follow-up spinning
Remove simultaneously.
Regenerated celulose fibre has been prepared by above-mentioned steps in the present invention, i.e., a kind of corn cob fiber element pulp production
Corn cob fiber regenerated celulose fibre.It is of the invention effectively to utilize the short (length of fibre length in corn cob fiber element pulp
Between 0~0.3mm), the degree of polymerization uniformly (between 500~600), in dicyandiamide solution can rapid dispersion it is uniform, and
Pulp surface distributed has substantial amounts of hole, has stronger capillarity, can quick lyosoption, make pulp surface and it is internal all
Reaction is participated in, the reaction time is greatly reduced, improves the reaction uniformity, it is not necessary to by the activation procedure of pulp, is shortened
Production procedure, improves production efficiency.
In addition, the present invention is aided with the content that chelating agent reduces iron ion in preparation process, iron ion is effectively overcome,
On the one hand the obtained spinning solution degree of polymerization is acutely declined, cause difficulty in spinning, easily broken end, make into silk poor product quality, strong
Low problem is spent, the presence of another aspect iron ion can cause cellulose and solvent NMMO decomposition, produce the centre of explosive
Product, there is the problem of major safety risks.
The invention provides a kind of regenerated celulose fibre, it is characterised in that is passed through by corn cob fiber as fibrous raw material
Obtained after preparation.
Using corn cob fiber as raw material, the present invention is sloughed regenerated celulose fibre provided by the invention using corn ear
Fruit axle-corncob after seed, effectively solve Lyocell fiber raw material and limit its fast-developing bottleneck, while I
The existing corn of producing per year of state is about 1.5 hundred million tons, and the yield of corresponding corncob is estimated also at 40,000,000 tons or so, such substantial amounts of corn
Core, in addition to industrial upper part is used as the products such as furfural, xylitol, largely go out of use.Thus, the corncob that the present invention uses
The not only more cheap wide material sources of price, can also solve corncob after large-area applications as agricultural wastes directly at burning
Reason, the problems such as causing the wasting of resources and environmental pollution.Compared to other raw materials, the regenerated celulose fibre of preparation has preferably by force
Degree, is especially controlled to the content of iron ion, effectively overcomes the defects of corn cob fiber exists as raw material.
Present invention also offers a kind of article, it is characterised in that contains the preparation described in above-mentioned any one technical scheme
Regenerated celulose fibre prepared by method, or the regenerated celulose fibre described in above-mentioned any one technical scheme；
The article preferably includes civilian clothes, home-textile, ultraviolet protection fabric or industrial special protecting clothing.
The invention provides a kind of regenerated celulose fibre and its preparation method and application, and it is fine to prepare regeneration using solvent method
Cellulose fiber, the raw material using corn cob fiber as Lyocell fiber, sufficiently make use of agricultural wastes corncob, does not only have
The yoke for solving Lyocell fiber shortage of raw materials of effect, the also comprehensive utilization for corncob provide brand-new approach；And
Corn cob fiber element pulp, fibre length is short (length is between 0~0.3mm), and the degree of polymerization is uniform (between 500~600),
In dicyandiamide solution can rapid dispersion it is uniform, and pulp surface distributed has substantial amounts of hole, has stronger capillarity, can
Quick lyosoption, make pulp surface be involved in reacting with inside, greatly reduce the reaction time, it is uniform to improve reaction
Degree, it is not necessary to by the activation procedure of pulp, shorten production procedure, improve production efficiency.In addition, the present invention is preparing spinning
During silk stock solution, by adding chelating agent, the iron ion in corncob pulp is failed, cause so as to avoid iron ion
The spinning solution degree of polymerization acutely declines, and causes difficulty in spinning, easily broken end, makes into the negative effect such as low of silk poor product quality, intensity.
Test result indicates that regenerated celulose fibre preparation method provided by the invention be uniformly dissolved stabilization, dissolution time it is short, the present invention
The preparation method dissolution time of offer is 30~60min, shortens 20~70min compared to wood pulp, follow-up ropiness can be good, made
Standby regenerated celulose fibre elongation at break can reach 17.6%, and dry fracture strength can reach 4.5CN/dtex.
In order to further illustrate the present invention, with reference to embodiment to regenerated celulose fibre provided by the invention and its system
Preparation Method and application are described in detail, and protection scope of the present invention is not limited by the following examples.
It is specific in the corn cob fiber pulp containing corn cob fiber pulp in the embodiment of the present invention and comparative example
It is required that being selected within the scope of the following, fine first is 80~95%, and whiteness is 70~90%, and ash content is 0~0.5%, moisture
For 5~50%.
Embodiment 1
Corn cob fiber pulp and chelating agent are dissolved with NMMO solution, obtains spinning solution, is prepared again with the spinning solution
Raw cellulose fibre.
Wherein, corncob pulp accounts for the 12% of total weight of material.Chelating agent (ethylenediamine tetra-acetic acid) addition is cellulose
The 0.1% of pulp.
Referring to Fig. 3, Fig. 3 is 5000 times of SEM photographs of the corn cob fiber element pulp in the embodiment of the present invention 1.
Embodiment 2~15
Embodiment 2-13 is only limitted to the change of corncob pulp content and the change of chelating agent, embodiment 14 with embodiment 1
Corncob pulp impregnated with acetic acid before mixed with NMMO, then dry, add into NMMO solution.In embodiment 15,
After corncob pulp and the mixing of NMMO solution, carbon dioxide is passed through in mixed serum.The carbon dioxide being now passed through,
Removed simultaneously in de-bubble step before spinning.
In embodiment 1~15, addition opportunity of chelating agent is NMMO water content when being 10%~30%, embodiment 1-
15 and documents 1 select corn cob fiber pulp property：It is 80~95% that first is fine in corn cob fiber pulp, and whiteness is
70~90%, ash content is 0~0.5%, and moisture is 5~50%.
The preparation method of the corn cob fiber pulp is：
Method one
(1) after corncob is crushed, under the catalytic action of hydrogen peroxide, the organic acid being made up of formic acid and acetic acid is used
Liquid carries out boiling to corncob, controls 120-155 DEG C of boiling temperature, solid-liquid mass ratio 1：5-1：15, reaction time 10-
60min, and obtained reaction solution is subjected to first time separation of solid and liquid；In the organic acid solution, it is 70-95wt% that total acid is dense, institute
The mass ratio for stating acetic acid and formic acid is 1：1-1：19, surplus is water；Hydrogen peroxide accounts for the 1-8wt% of corncob；
(2) solid that the first time separation of solid and liquid obtains is collected, under the catalytic action of hydrogen peroxide, using by first
Acid, the mix acid liquor of acetic acid composition carry out pickling to the solid, control 30-100 DEG C of pickling temperature, solid-liquid mass ratio 1：4-
1：20, and obtained reaction solution is subjected to second of separation of solid and liquid；In the mix acid liquor, dense total acid is 70-95wt%, described
The mass ratio of acetic acid and formic acid is 1：1-1：19, surplus is water；Hydrogen peroxide accounts for the 1-8wt% of corncob；
(3) solid that second of separation of solid and liquid obtains is collected, water-filling of going forward side by side is washed, and it is 25-90 DEG C to control washing temperature,
It is 1-10wt% to starch dense, and obtained washing slurry is carried out into third time separation of solid and liquid；
(4) collect the solid that the third time separation of solid and liquid obtains and screening obtains required screened stock cellulose, through bleaching
After obtain corn cob fiber element pulp.
Method two
By in method one, the pickling of step (2) replaces with alkali cleaning, and actual conditions is 12% sodium hydroxide solution, to step
(1) solid carries out alkali cleaning, 30-100 DEG C of alkali cleaning temperature, alkali cleaning time 10-30min.Other conditions are constant.
Method three
By in method one, the digestion process of step (1) replaces with：Corncob is crushed, it is small to carry out alkali lye boiling 0.5-1.2
When, corn cob fiber element solution is obtained, then carries out separation of solid and liquid.Other conditions are constant.
The property for the corn cob fiber element pulp that comparative example 2 selects：It is 83% that first is fine in corn cob fiber pulp, and whiteness is
65%, ash content 1.2%, moisture 8%.
Comparative example 3-4 replaces with corn cob fiber element pulp the wood pulps that the degree of polymerization is 700.
Comparative example 5-6 replaces with corn cob fiber element pulp the Cotton Pulp that the degree of polymerization is 700.
Performance detection is carried out to the regenerated celulose fibre prepared by above-described embodiment and comparative example, testing result is specifically shown in
Table 1 below, table 1 are the condition and performance data of embodiment 1~15 and comparative example.
The condition and performance data of the embodiment 1~15 of table 1 and comparative example
Applicant states that the present invention illustrates the process of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of preparation method of regenerated celulose fibre, it is characterised in that comprise the following steps：
1) corn cob fiber pulp and chelating agent after mixed dissolution, are obtained into spinning solution in NMMO solution；
The step 1) is specially：
During by NMMO solvent concentrations to aqueous 10%~30%, chelating agent and corncob pulp are added, is passed through sour gas progress
Processing, then heats up, while by depressurizing/vacuumizing removing excess water, dissolves cellulose, obtain spinning solution；
2) spinning solution for again obtaining above-mentioned steps carries out spinning, obtains regenerated celulose fibre.
2. preparation method according to claim 1, it is characterised in that the degree of polymerization of the corn cob fiber pulp is 400
~800.
3. preparation method according to claim 1, it is characterised in that in the corn cob fiber pulp first it is fine for 80%~
95%, whiteness is 70%~90%, and ash content is 0~0.5%, and moisture is 5%~50%.
4. preparation method according to claim 1, it is characterised in that the quality of the corn cob fiber pulp accounts for spinning original
The 5%~20% of liquid gross mass；The quality of the chelating agent is the 0.1%~0.5% of the corn cob fiber pulp quality.
5. preparation method according to claim 1, it is characterised in that the chelating agent is carboxylic acid quasi-chelate compound, polycarboxylic acids
One or more in quasi-chelate compound and organic multicomponent phosphonic acid type chelants.
6. preparation method according to claim 5, it is characterised in that the carboxylic acid quasi-chelate compound chelates for aminocarboxylic acids
The one or more of agent, hydroxycarboxylic acid quasi-chelate compound and hydroxylamino carboxylic acid quasi-chelate compound；
The amino carboxylic acid quasi-chelate compound includes ethylenediamine tetra-acetic acid (EDTA), diethyl pentetic acid (DTPA) and two sub- second
One or more in base pentaacetic acid and its salt；The hydroxylamino carboxylic acid quasi-chelate compound includes hydroxyethylethylene diamine tri-acetic acid
And the one or more in bicine N- (DEG) (HEDTA)；The hydroxycarboxylic acid quasi-chelate compound includes citric acid
(CA), the one or more in tartaric acid (TA) and gluconic acid (GA)；
The polycarboxylic acid chelating agent is polyacrylic acid and its sodium salt, polymethylacrylic acid, HPMA, fumaric acid
One or more in (fumaric acid)-propene sulfonic acid EVA.
7. preparation method according to claim 1, it is characterised in that the corn cob fiber pulp is through peracid treatment.
8. preparation method according to claim 7, it is characterised in that the acid treatment be the corn cob fiber pulp and
Handled before the mixing of NMMO solution with acid solution.
9. the regenerated celulose fibre prepared by a kind of preparation method as described in claim 1~8 any one, its feature exist
In being obtained by corn cob fiber as fibrous raw material after preparation.
10. a kind of article, it is characterised in that the regeneration prepared containing the preparation method described in claim 1~8 any one is fine
Cellulose fiber, or the regenerated celulose fibre described in claim 9；
The article includes civilian clothes, home-textile, ultraviolet protection fabric or industrial special protecting clothing.
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| CN201510848219.1A CN105525376B (en) | 2015-11-27 | 2015-11-27 | A kind of regenerated celulose fibre and preparation method thereof |
| PCT/CN2016/107317 WO2017088826A1 (en) | 2015-11-27 | 2016-11-25 | Regenerated cellulose fiber and method preparing the same and article manufactured from the same |
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| CN105525376B (en) * | 2015-11-27 | 2018-03-27 | 济南圣泉集团股份有限公司 | A kind of regenerated celulose fibre and preparation method thereof |
| CN106757464B (en) * | 2016-11-15 | 2019-03-08 | 天津捷盛东辉保鲜科技有限公司 | Food oxydating resistance cellulose acetate nanofiber preservative film |
| US20200055961A1 (en) * | 2017-04-21 | 2020-02-20 | China Agricultural University | Preparation of oxidized cellulose, and application of oxidized cellulose in washing and drug loading |
| KR101904771B1 (en) * | 2017-09-22 | 2018-10-05 | 오영세 | The lyocell fibers and The method for produce it |
| EP3511451A1 (en) * | 2018-01-15 | 2019-07-17 | Lenzing Aktiengesellschaft | Method for reusing a mixed textile containing cellulose and synthetic plastic |
| CN113005533B (en) * | 2021-03-22 | 2022-03-15 | 太原理工大学 | Method for removing iron ions in seed hemp pulp |
| TWI825401B (en) * | 2021-03-23 | 2023-12-11 | 聚隆纖維股份有限公司 | Lyocell fiber with recycled cellulose |
| CN114214784A (en) * | 2021-12-10 | 2022-03-22 | 湖南俏妃卫生用品有限公司 | Preparation method of bamboo fiber and corn fiber bi-component non-woven fabric |
| CN114892296B (en) * | 2022-05-23 | 2023-06-06 | 东华大学 | Method for spinning high-performance Lyocell fibers by compounding waste cotton regenerated pulp |
| CN116356441A (en) * | 2023-03-02 | 2023-06-30 | 东华大学 | Preparation method of regenerated cellulose fiber based on corncob |
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| US3033698A (en) * | 1959-10-23 | 1962-05-08 | Eastman Kodak Co | Cellulose acetate spinning solutions and process of spinning fine denier filaments |
| ZA834139B (en) * | 1982-06-08 | 1984-03-28 | Courtaulds Plc | Polymer solutions |
| WO1997033018A1 (en) * | 1996-03-06 | 1997-09-12 | Mitsubishi Rayon Co., Ltd. | Fibril based fibers, method of manufacturing same, spinning nozzle used in same, and moldings obtained therefrom |
| CN1129680C (en) * | 2001-04-30 | 2003-12-03 | 许炯 | Process for production of LYOCELL fiber with bamboo material |
| DE10331342B4 (en) * | 2003-07-11 | 2009-03-12 | Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. | Thermostable molding or spinning mass |
| DE102004024029A1 (en) * | 2004-05-13 | 2005-12-08 | Zimmer Ag | Lyocell method and apparatus with metal ion content control |
| US20060070711A1 (en) * | 2004-09-30 | 2006-04-06 | Mengkui Luo | Low pH treatment of pulp in a bleach sequence to produce pulp having low D.P. and low copper number for use in lyocell manufacture |
| DE102006033591B4 (en) * | 2006-07-18 | 2008-10-16 | Thüringisches Institut für Textil- und Kunststoff-Forschung e.V. | Process for stabilizing the spinning solution in the production of cellulosic composite moldings |
| CN103541022B (en) * | 2013-11-06 | 2016-04-20 | 济南圣泉集团股份有限公司 | Porous corn cob fiber and preparation method thereof |
| CN104004207B (en) * | 2014-05-21 | 2018-01-02 | 中国科学院过程工程研究所 | Ionic liquid prepares corn cob fiber cellulosic material or the method for blended fiber material |
| KR101695354B1 (en) * | 2015-03-26 | 2017-01-12 | (주)세왕섬유 | Method of preparing knitted fabric comprising cellulose fiber |
| CN105525376B (en) * | 2015-11-27 | 2018-03-27 | 济南圣泉集团股份有限公司 | A kind of regenerated celulose fibre and preparation method thereof |
| CN105648561B (en) * | 2016-04-01 | 2018-05-18 | 山东嘉成赛尔新材料技术有限公司 | A kind of preparation method of solvent method corn cob fiber cellulose fiber |
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