CN106702515B - Production process of cellulose carbamate fiber filament - Google Patents
Production process of cellulose carbamate fiber filament Download PDFInfo
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- CN106702515B CN106702515B CN201510598807.4A CN201510598807A CN106702515B CN 106702515 B CN106702515 B CN 106702515B CN 201510598807 A CN201510598807 A CN 201510598807A CN 106702515 B CN106702515 B CN 106702515B
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 161
- 239000001913 cellulose Substances 0.000 title claims abstract description 156
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 title claims abstract description 110
- 239000000835 fiber Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000009987 spinning Methods 0.000 claims abstract description 38
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 230000004913 activation Effects 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 222
- 235000010980 cellulose Nutrition 0.000 claims description 154
- 238000004090 dissolution Methods 0.000 claims description 60
- 239000000203 mixture Substances 0.000 claims description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 26
- 239000004202 carbamide Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 21
- 238000005516 engineering process Methods 0.000 claims description 16
- 238000007654 immersion Methods 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 230000000630 rising effect Effects 0.000 claims description 9
- 230000001112 coagulating effect Effects 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- 239000011686 zinc sulphate Substances 0.000 claims description 7
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 239000007832 Na2SO4 Substances 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000002166 wet spinning Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 90
- 238000000034 method Methods 0.000 abstract description 33
- 239000000047 product Substances 0.000 abstract description 10
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000007380 fibre production Methods 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract 1
- 239000011550 stock solution Substances 0.000 abstract 1
- 229920000297 Rayon Polymers 0.000 description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Artificial Filaments (AREA)
Abstract
The invention relates to a production process of cellulose carbamate fiber filaments, belonging to the technical field of cellulose carbamate fiber production. According to the invention, a complete cellulose carbamate fiber filament production process with high completeness is formed through specific steps of cellulose activation, preparation of cellulose carbamate, preparation of a cellulose carbamate solution and spinning, the prepared spinning stock solution has good spinnability, and the final product has good performance, so that the method is very suitable for industrial large-scale production and gives consideration to production cost, production efficiency and product quality.
Description
Technical field
The present invention relates to a kind of production technologies of regenerated celulose fibre, it is more particularly related to a kind of fiber
The production technology of plain carbamate fibre long filament, belongs to cellulose carbamate fibre production technical field.
Background technique
Cellulose fibre is using natural fiber constantly regenerating in nature as chemical fibre made of raw material.Fiber now
The production of cellulose fiber is mainly viscose process, and the product produced is viscose rayon.
Viscose rayon is one kind of regenerated celulose fibre, is one of the chemical fibre of earliest investment industrialized production.It is viscous
The good hygroscopicity of glue fiber, comfortable and easy to wear, spinnability is excellent, and Chang Yumian, hair or various synthetic fibers are blended, interweave, for each
Class clothes and decorative textile product.The high tenacity staple fibre prepared using different raw material and spinning technique, can be used for taking turns
The industrial goods such as warp, conveyer belt.China is the first big producer of viscose rayon at present, but state's cellulose fibres at present
The overwhelming majority is produced also according to traditional old technique, including dipping, squeezing, crushing, aging, yellow, dissolution, maturation, filtering,
Viscose glue is made in the processes such as deaeration, then viscose rayon is made by wet spinning.
In viscose rayon traditional handicraft, the yellowing processes of cellulose will expend a large amount of carbon disulfide, and in spinning rank
Section also gives off the hydrogen sulfide and irretrievable carbon disulfide of suitable share, will cause sizable pollution to environment.Separately
Outside, traditional viscose process is at high cost, and time-consuming for production technology, causes to spend greatly, production efficiency is not but high.
Therefore, it is increasingly turned to environmentally friendly to the research of viscose rayon technique in recent years and can be improved production effect
Rate reduces on the novel process of production cost, and produces some new forming techniques.Since cellulose basic unit has three
A hydroxyl, it is easy to form intramolecular and intermolecular hydrogen bonding, crystallinity is very high, thus cellulose be difficult to be dissolved in it is general inorganic and
In organic solvent, need using special solvent or by the modified ability of its derivatization it is easy to process with utilize.Cellulose derivatization
Main includes esterification, etherificate and graft copolymerization etc..Wherein, cellulose and urea reaction generate cellulose carbamate,
Process is relatively simple, and good spinning property, environmental pollution is small, resulting fabric function admirable, and urea abundance
And it is nontoxic, price is also relatively cheap, and reaction product cellulose carbamate property is stablized, and can store up under ambient temperature and moisture environment
It deposits for a long time.
State Intellectual Property Office discloses a Publication No. CN104072622A, entitled " cellulose in 2014.10.1
The invention of the preparation of carbamate and its dissolution in low temperature spinning process ", a kind of cellulose carbamate of the disclosure of the invention
Preparation and its dissolution in low temperature spinning process, cellulose is added to sodium hydroxide solution, stirs evenly and impregnates, then will be fine
Dimension element, which takes out, is washed to neutrality, obtains alkalinized celluloses, urea is added, stirs evenly, is put into baking oven and heats, react and do
It is dry, cellulose carbamate is obtained, cellulose carbamate is ground into powder and is added in mixing kettle, and hydrogen-oxygen is added
Change sodium, thiocarbamide, deionized water double solvents, be uniformly mixed；Raw material in mixing kettle after extrusion, deaeration, filtering by
The spinneret orifice of spinneret sprays, and sequentially enters in the first coagulating tank and the second gelation slot and is frozen into solid, using sink
It stretched after washing by filament spinning component, be wound in cellulose carbamate fibre.
Above invention discloses celluloses to prepare cellulose carbamate as raw material with urea, then prepares fiber again
Plain carbamate solution, all processes of last spinning.But the process and it is suitably applied industrialization large-scale production,
The spinning solution spinnability of preparation is poor, and spinning technique by corresponding optimization, does not also cause final products performance bad.
State Intellectual Property Office discloses a Publication No. CN101597336, entitled " cellulose in 2009.12.9
The invention of the microwave synthesis method of carbamate ", a kind of microwave heating synthesis method of fiber carbamate of the disclosure of the invention
Technology.Its method is cellulose to be immersed in aqueous solution of urea that it is made sufficiently to adsorb urea first, and filter, be dried to obtain
Cellulose/urea homogeneous mixture.Then cellulose/urea admixture is placed in heating in micro-wave oven and reacts obtained cellulose
Carbamate.The solvent-free pollution of cellulose carbamate synthetic technology provided by the present invention, does not need to be added organic molten
Agent and any catalyst, reaction speed is fast, and low energy consumption.Synthesized cellulose carbamate product is within the scope of -10~5 DEG C
There is good dissolubility in 6~10wt%NaOH aqueous solution, can prepare stable, transparent and be suitable for industrial spinning and system
The concentrated solution of film.
State Intellectual Property Office discloses a Publication No. CN102691125A in 2012.9.26, entitled " it is a kind of by
The invention of the method that cellulose carbamate prepares regenerated celulose fibre ", the invention are related to one kind by cellulose amino first
The method that acid esters prepares regenerated celulose fibre, this method are to dissolve cellulose carbamate with a kind of solvent compositions,
Solvent compositions are the aqueous solution of the sodium hydroxide containing 6~10wt%, 0.1~3wt% zinc oxide.By a certain amount of cellulose ammonia
Carbamate is dispersed in the solvent compositions, and -10 DEG C are refrigerated under cryogenic conditions and is being not higher than 50 DEG C hereinafter, taking out
Under the conditions of thaw, carry out wet spinning, strand through supersolidification, washing, it is dry after obtain regenerated celulose fibre.This method solves
Cellulose carbamate dissolution is difficult in previous technique and solution this unstable two hang-up, and there is very high industrialization to answer
With value.
State Intellectual Property Office discloses a Publication No. CN103980368A, a kind of entitled " liquid in 2014.8.13
The invention of the method that solid phase reaction prepares cellulose carbamate ", the invention using cellulose pulp or through overactivation at
The cellulose pulp and urea of reason are raw material, sub- in dimethylformamide (DMF) or dimethyl acetamide (DMAc), dimethyl
The higher boilings such as sulfone (DMSO), N-Methyl pyrrolidone (NMP) are non-proton and intensive polar solvent in carry out esterification synthetic fibers
Plain carbamate.It during liquid and solid phase reaction method prepares cellulose carbamate, selects that solvent toxicity is small, easy recycling, makes
Preparation process is easy, environmental protection, safely and controllably, obtained cellulose carbamate can be dissolved in NaOH solution formed it is good steady
Fixed solution can be used for the preparation of regenerated celulose fibre or film etc..
Above-mentioned three patents are directed to certain links and step in entire cellulose carbamate fibre production, still
It is all not involved with entire technical process, cannot achieve industrialization large-scale production.
Summary of the invention
Present invention seek to address that the technique of existing production cellulose carbamate fibre can not adapt to industrialization on a large scale
The problem of production, a kind of production technology of cellulose carbamate fibre long filament is provided, which is suitble to industrialization extensive
Production, the spinning solution good spinnability of preparation, final products performance are good.
In order to achieve the above-mentioned object of the invention, specific technical solution is as follows:
A kind of production technology of cellulose carbamate fibre long filament, it is characterised in that: comprise the following steps that:
A, the activation of cellulose
First cellulose is added in sodium hydroxide solution and is impregnated, basification is carried out, after being disposed, filtration washing,
Alkalinized celluloses are dried in vacuo again, obtain activated cellulose；
B, the preparation of cellulose carbamate
The liquid ammonia solution of urea is added into activated cellulose, is taken out after immersion and is placed in drying in vacuum oven, then adopted
With microwave heating, esterification is carried out, cellulose carbamate is obtained；
C, the preparation of cellulose carbamate solution
Cellulose carbamate is added in sodium hydroxide solution, first time mixed dissolution is carried out；Again to mixture
Middle addition sodium hydroxide solution carries out second of mixed dissolution；Third time is added sodium hydroxide solution into mixture, carries out the
Mixed dissolution three times obtains cellulose carbamate solution, i.e. spinning solution after rising to room temperature；
D, spinning
Cellulose carbamate fibre long filament is made by wet spinning in spinning solution in step C.
In step A of the present invention, the cellulose is the linter pulp of the degree of polymerization 400~600.
In step A of the present invention, the mass concentration 15~20% of the sodium hydroxide solution, the sodium hydroxide with
The volume ratio of cellulose dosage is (4~6): 1.
In step A of the present invention, the time of the immersion is 1~2h, temperature is 5~15 DEG C.
In step A of the present invention, the vacuum drying time is 1~3h, temperature is 40~60 DEG C.
In step B of the present invention, the activated cellulose and urea are 1:(2~4 in mass ratio), the liquefied ammonia of urea is molten
The concentration of liquid is 20~40%.
In step B of the present invention, the heating power of the microwave heating be 500~800W, heating the reaction time be 1~
3h。
In step C of the present invention, the preparation of the cellulose carbamate solution specifically:
Cellulose carbamate is added in the sodium hydroxide solution that concentration is 6~8% at -5~0 DEG C, carries out the
Mixed once dissolution；The sodium hydroxide solution that concentration is 8~10% is added into mixture at -10~-5 DEG C, carries out second
Mixed dissolution；It is 10~12% sodium hydroxide solutions that concentration is added into mixture at -15~-10 DEG C, carries out third time mixing
Dissolution, obtains cellulose carbamate solution, i.e. spinning solution after rising to room temperature.
In step C of the present invention, in the first time mixed dissolution, the sodium hydroxide solution and cellulose amino of addition
The liquid-solid ratio of formic acid esters is (10~12): 1, in second of mixed dissolution, and the sodium hydroxide solution and cellulose of addition
The liquid-solid ratio of carbamate is (12~14): 1, in the third time mixed dissolution, and the sodium hydroxide solution of addition and fine
The liquid-solid ratio for tieing up plain carbamate is (14~16): 1.
In step D, in the spinning process, the composition and ratio of coagulating bath are Na to the present invention2SO4 230~245g/
L, ZnSO48~12g/L, H2SO4110~140g/L.
Bring advantageous effects of the present invention:
1, it is extensive can not to adapt to industrialization for the technique that the present invention solves existing production cellulose carbamate fibre
The problem of production.The present invention provides a kind of production technology of cellulose carbamate fibre long filament, is walked by specific technique
Rapid and technological parameter, forms the higher intact fibre element carbamate fibre long filament production process of a completeness, preparation
Spinning solution good spinnability, final products performance is good, is very suitable to industrialization large-scale production, takes into account production cost, production effect
Rate and product quality.
2, currently preferred, cellulose in step is the linter pulp of the degree of polymerization 400~600.The first of linter pulp is fine
It is high to tie up cellulose content, and selects above-mentioned polymerization scope, is more favorable for the dissolution of cellulose, the quality of final products is enabled to mention
It is high.
3, currently preferred, the mass concentration 15~20% of sodium hydroxide solution in step, the hydroxide
The volume ratio of sodium and cellulose dosage is (4~6): 1.The selection of above-mentioned special process parameter area is so that cellulose activation degree
Height guarantees enough alkali concentrations.
4, currently preferred, the time of immersion in step is 1~2h, and temperature is 5~15 DEG C.Above-mentioned specific work
The selection of skill parameter area dissolves out the hemicellulose in cellulose pulp preferably, it is ensured that the uniformity of alkali cellulose.
5, currently preferred, the vacuum drying time in step is 1~3h, and temperature is 40~60 DEG C.Above-mentioned spy
The selection of fixed process parameters range is so that the moisture content after dry in alkali cellulose can effectively reduce alkali cellulose lower than 10%
Oxidative degradation.
6, currently preferred, activated cellulose and urea in stepb is 1:(2~4 in mass ratio), the liquid of urea
The concentration of ammonia solution is 20~40%.The selection of above-mentioned specific process parameters range is so that nitrogenous in cellulose carbamate
Amount is 3% or so, and the dissolubility of cellulose carbamate is good, and the spinnability of stoste is also more preferable.
7, currently preferred, the heating power of microwave heating in stepb is 500~800W, heats the reaction time
For 1~3h.The selection of above-mentioned specific process parameters range reactant can be heated rapidly to range of reaction temperature 140~
160 DEG C, esterification is carried out, controls the nitrogen content of reaction product cellulose carbamate 2~4%.
8, currently preferred, in step C, the preparation of the cellulose carbamate solution specifically: will be fine
It ties up plain carbamate to be added at -5~0 DEG C in the sodium hydroxide solution that concentration is 6-8%, carries out first time mixed dissolution；
The sodium hydroxide solution that concentration is 8~10% is added into mixture at -10~-5 DEG C, carries out second of mixed dissolution；-
It is 10~12% sodium hydroxide solutions that concentration is added at 15~-10 DEG C into mixture, carries out third time mixed dissolution, rises to often
Cellulose carbamate solution, i.e. spinning solution are obtained after temperature.With the dissolution of cellulose carbamate, hydrogen in mixed liquor
Oxidation na concn gradually decreases, and sodium hydroxide is added by segmentation, makes the concentration of sodium hydroxide more evenly, and course of dissolution is viscous
Degree gradually increases, and gradually decreases the dissolution that temperature is more favorable for cellulose carbamate.
9, currently preferred, in the first time mixed dissolution in step C, the sodium hydroxide solution and cellulose of addition
The liquid-solid ratio of carbamate is (10~12): 1；In second of mixed dissolution, the sodium hydroxide solution and fibre of addition
The liquid-solid ratio for tieing up plain carbamate is (12~14): 1；In the third time mixed dissolution, the sodium hydroxide solution of addition
Liquid-solid ratio with cellulose carbamate is (14~16): 1；With the dissolution of raw material, the viscosity of mixed liquor is gradually risen, with
Above-mentioned special parameter increases the amount of sodium hydroxide, and conducive to the dissolution of cellulose carbamate, segmentation, which is added, can accelerate cellulose
The solution rate of carbamate.
10, in step D, in the spinning process, the composition and ratio of coagulating bath are Na to the present invention2SO4 230~
245g/L, ZnSO48~12g/L, H2SO4110~140g/L.The selection of above-mentioned specific process parameters range is for fiber
What plain carbamate solution (spinning solution) optimized, cellulose carbamate can rapid shaping, final long filament produces
The performance of product is more preferable.
Specific embodiment
Embodiment 1
A kind of production technology of cellulose carbamate fibre long filament, comprises the following steps that:
A, the activation of cellulose
First cellulose is added in sodium hydroxide solution and is impregnated, basification is carried out, after being disposed, filtration washing,
Alkalinized celluloses are dried in vacuo again, obtain activated cellulose；
B, the preparation of cellulose carbamate
The liquid ammonia solution of urea is added into activated cellulose, is taken out after immersion and is placed in drying in vacuum oven, then adopted
With microwave heating, esterification is carried out, cellulose carbamate is obtained；
C, the preparation of cellulose carbamate solution
Cellulose carbamate is added in sodium hydroxide solution, first time mixed dissolution is carried out；Again to mixture
Middle addition sodium hydroxide solution carries out second of mixed dissolution；Third time is added sodium hydroxide solution into mixture, carries out the
Mixed dissolution three times obtains cellulose carbamate solution, i.e. spinning solution after rising to room temperature；
D, spinning
Cellulose carbamate fibre long filament is made by wet spinning in spinning solution in step C.
The cellulose carbamate fibre long filament similar performance being prepared through above-mentioned technique is in viscose fiber filament, energy
Meet the requirement of viscose fiber filament, and without residual sulphur, dye uniformity is better than viscose fiber filament.In addition, cellulose
The production process of carbamate fibre long filament does not use CS2, do not generate SO2、H2The toxic and harmful gas such as S are greener than viscose rayon
Colour circle is protected.
The index parameter for the cellulose carbamate fibre long filament that this technique is prepared and the finger of viscose fiber filament
Mark parameter is shown in Table 1.
Table 1
| Project | Cellulose carbamate fibre | Viscose rayon |
| Dry breaking strength >= | 1.65 | 1.70 |
| Dry elongation at break >= | 19% | 18% |
| The dry extension at break coefficient of variation≤ | 8.0% | 10% |
| Line density deviation | ±2.0 | ±2.5 |
| The line density coefficient of variation≤ | 3.0% | 3.0% |
| Monofilament radical deviation≤ | 3.0 | 3.0% |
| Residual sulfur content (mg/100g)≤ | 0 | 10 |
| Dye uniformity (gray card grade) >= | 4 | 3 |
Embodiment 2
On the basis of embodiment 1:
Preferably, in step, the cellulose is the linter pulp of the degree of polymerization 400.
Preferably, in step, the mass concentration 15% of the sodium hydroxide solution, the sodium hydroxide and fiber
The volume ratio of plain dosage is 4:1.
Preferably, in step, the time of the immersion is 1h, and temperature is 5 DEG C.
Preferably, in step, the vacuum drying time is 1h, and temperature is 40 DEG C.
Embodiment 3
On the basis of embodiment 1:
Preferably, in step, the cellulose is the linter pulp of the degree of polymerization 600.
Preferably, in step, the mass concentration 20% of the sodium hydroxide solution, the sodium hydroxide and fiber
The volume ratio of plain dosage is 6:1.
Preferably, in step, the time of the immersion is 2h, and temperature is 15 DEG C.
Preferably, in step, the vacuum drying time is 3h, and temperature is 60 DEG C.
Embodiment 4
On the basis of embodiment 1:
Preferably, in step, the cellulose is the linter pulp of the degree of polymerization 500.
Preferably, in step, the mass concentration 17.5% of the sodium hydroxide solution, the sodium hydroxide and fibre
The volume ratio for tieing up plain dosage is 5:1.
Preferably, in step, the time of the immersion is 1.5h, and temperature is 10 DEG C.
Preferably, in step, the vacuum drying time is 2h, and temperature is 50 DEG C.
Embodiment 5
On the basis of embodiment 1:
Preferably, in step, the cellulose is the linter pulp of the degree of polymerization 450.
Preferably, in step, the mass concentration 19% of the sodium hydroxide solution, the sodium hydroxide and fiber
The volume ratio of plain dosage is 4.2:1.
Preferably, in step, the time of the immersion is 1.3h, and temperature is 12 DEG C.
Preferably, in step, the vacuum drying time is 1.6h, and temperature is 56 DEG C.
Embodiment 6
On the basis of embodiment 1:
Preferably, in stepb, the activated cellulose and urea are 1:2 in mass ratio, the liquid ammonia solution of urea
Concentration is 20%.
Preferably, in stepb, the heating power of the microwave heating is 500W, and the heating reaction time is 1h.
Embodiment 7
On the basis of embodiment 1:
Preferably, in stepb, the activated cellulose and urea are 1:4 in mass ratio, the liquid ammonia solution of urea
Concentration is 40%.
Preferably, in stepb, the heating power of the microwave heating is 800W, and the heating reaction time is 3h.
Embodiment 8
On the basis of embodiment 1:
Preferably, in stepb, the activated cellulose and urea are 1:3 in mass ratio, the liquid ammonia solution of urea
Concentration is 30%.
Preferably, in stepb, the heating power of the microwave heating is 650W, and the heating reaction time is 2h.
Embodiment 9
On the basis of embodiment 1:
Preferably, in stepb, the activated cellulose and urea are 1:3.5, the liquid ammonia solution of urea in mass ratio
Concentration be 21%.
Preferably, in stepb, the heating power of the microwave heating is 600W, and the heating reaction time is 2.5h.
Embodiment 9
On the basis of embodiment 1:
Preferably, in step C, the preparation of the cellulose carbamate solution specifically:
Cellulose carbamate is added in the sodium hydroxide solution that concentration is 6% at -5 DEG C, is carried out mixed for the first time
Close dissolution；The sodium hydroxide solution that concentration is 8% is added into mixture at -10 DEG C, carries out second of mixed dissolution；- 15
It is 10% sodium hydroxide solution that concentration is added at DEG C into mixture, carries out third time mixed dissolution, obtains fiber after rising to room temperature
Plain carbamate solution, i.e. spinning solution.
Preferably, in step C, in the first time mixed dissolution, the sodium hydroxide solution and cellulose ammonia of addition
The liquid-solid ratio of carbamate is 10:1；In second of mixed dissolution, the sodium hydroxide solution and cellulose amino of addition
The liquid-solid ratio of formic acid esters is 12:1；In the third time mixed dissolution, the sodium hydroxide solution and cellulose amino first of addition
The liquid-solid ratio of acid esters is 14:1.
Embodiment 10
On the basis of embodiment 1:
Preferably, in step C, the preparation of the cellulose carbamate solution specifically:
Cellulose carbamate is added in the sodium hydroxide solution that concentration is 8% at 0 DEG C, is carried out mixed for the first time
Close dissolution；The sodium hydroxide solution that concentration is 10% is added into mixture at -5 DEG C, carries out second of mixed dissolution；- 10
It is 12% sodium hydroxide solution that concentration is added at DEG C into mixture, carries out third time mixed dissolution, obtains fiber after rising to room temperature
Plain carbamate solution, i.e. spinning solution.
Preferably, in step C, in the first time mixed dissolution, the sodium hydroxide solution and cellulose ammonia of addition
The liquid-solid ratio of carbamate is 12:1；In second of mixed dissolution, the sodium hydroxide solution and cellulose amino of addition
The liquid-solid ratio of formic acid esters is 14:1；In the third time mixed dissolution, the sodium hydroxide solution and cellulose amino first of addition
The liquid-solid ratio of acid esters is 16:1.
Embodiment 11
On the basis of embodiment 1:
Preferably, in step C, the preparation of the cellulose carbamate solution specifically:
Cellulose carbamate is added in the sodium hydroxide solution that concentration is 7% at -2.5 DEG C, is carried out for the first time
Mixed dissolution；The sodium hydroxide solution that concentration is 9% is added into mixture at -7.5 DEG C, carries out second of mixed dissolution；
It is 11% sodium hydroxide solution that concentration is added into mixture at -12.5 DEG C, third time mixed dissolution is carried out, after rising to room temperature
Obtain cellulose carbamate solution, i.e. spinning solution.
Preferably, in step C, in the first time mixed dissolution, the sodium hydroxide solution and cellulose ammonia of addition
The liquid-solid ratio of carbamate is 11:1；In second of mixed dissolution, the sodium hydroxide solution and cellulose amino of addition
The liquid-solid ratio of formic acid esters is 13:1；In the third time mixed dissolution, the sodium hydroxide solution and cellulose amino first of addition
The liquid-solid ratio of acid esters is 15:1.
Embodiment 12
On the basis of embodiment 1:
Preferably, in step C, the preparation of the cellulose carbamate solution specifically:
Cellulose carbamate is added in the sodium hydroxide solution that concentration is 7.6% at -2 DEG C, is carried out for the first time
Mixed dissolution；The sodium hydroxide solution that concentration is 9.5% is added into mixture at -8 DEG C, carries out second of mixed dissolution；
It is 11.5% sodium hydroxide solution that concentration is added into mixture at -14 DEG C, third time mixed dissolution is carried out, after rising to room temperature
Obtain cellulose carbamate solution, i.e. spinning solution.
Preferably, in step C, in the first time mixed dissolution, the sodium hydroxide solution and cellulose ammonia of addition
The liquid-solid ratio of carbamate is 10.5:1；In second of mixed dissolution, the sodium hydroxide solution and cellulose ammonia of addition
The liquid-solid ratio of carbamate is 13.5:1；In the third time mixed dissolution, the sodium hydroxide solution and cellulose ammonia of addition
The liquid-solid ratio of carbamate is 14.5:1.
Embodiment 13
On the basis of embodiment 1:
Preferably, in step D, in the spinning process, the composition and ratio of coagulating bath are Na2SO4 230g/L,
ZnSO48g/L, H2SO4 110g/L。
Embodiment 14
On the basis of embodiment 1:
Preferably, in step D, in the spinning process, the composition and ratio of coagulating bath are Na2SO4 245g/L,
ZnSO412g/L, H2SO4 140g/L。
Embodiment 15
On the basis of embodiment 1:
Preferably, in step D, in the spinning process, the composition and ratio of coagulating bath are Na2SO4 237.5g/L
ZnSO410g/L, H2SO4 125g/L。
Embodiment 16
On the basis of embodiment 1:
Preferably, in step D, in the spinning process, the composition and ratio of coagulating bath are Na2SO4 240g/L,
ZnSO411g/L, H2SO4 130g/L。
Claims (6)
1. a kind of production technology of cellulose carbamate fibre long filament, it is characterised in that: comprise the following steps that:
A, the activation of cellulose
First cellulose is added in sodium hydroxide solution and is impregnated, basification is carried out, after being disposed, filtration washing, then will
Alkalinized celluloses vacuum drying, obtains activated cellulose；The cellulose is the linter pulp of the degree of polymerization 400~600；Described
The volume ratio of the mass concentration 15~20% of sodium hydroxide solution, the sodium hydroxide and cellulose dosage is 4~6:1；It is described
Immersion time be 1~2h, temperature be 5~15 DEG C；The vacuum drying time is 1~3h, and temperature is 40~60 DEG C；
B, the preparation of cellulose carbamate
The liquid ammonia solution of urea is added into activated cellulose, is taken out after immersion and is placed in drying in vacuum oven, then using micro-
Wave heating carries out esterification, obtains cellulose carbamate；
C, the preparation of cellulose carbamate solution
Cellulose carbamate is added in sodium hydroxide solution, first time mixed dissolution is carried out；Add again into mixture
Enter sodium hydroxide solution, carries out second of mixed dissolution；Sodium hydroxide solution is added into mixture for third time, carries out third time
Mixed dissolution obtains cellulose carbamate solution, i.e. spinning solution after rising to room temperature；
D, spinning
Cellulose carbamate fibre long filament is made by wet spinning in spinning solution in step C.
2. a kind of production technology of cellulose carbamate fibre long filament according to claim 1, it is characterised in that:
In step B, the activated cellulose and urea are 1:2~4 in mass ratio, and the concentration of the liquid ammonia solution of urea is 20~40%.
3. a kind of production technology of cellulose carbamate fibre long filament according to claim 1, it is characterised in that:
In step B, the heating power of the microwave heating is 500~800W, and the heating reaction time is 1~3h.
4. a kind of production technology of cellulose carbamate fibre long filament according to claim 1, it is characterised in that:
In step C, the preparation of the cellulose carbamate solution specifically:
Cellulose carbamate is added in the sodium hydroxide solution that concentration is 6~8% at -5~0 DEG C, is carried out for the first time
Mixed dissolution；The sodium hydroxide solution that concentration is 8~10% is added into mixture at -10~-5 DEG C, carries out second and mixes
Dissolution；It is 10~12% sodium hydroxide solutions that concentration is added into mixture at -15~-10 DEG C, mix for the third time molten
Solution, obtains cellulose carbamate solution, i.e. spinning solution after rising to room temperature.
5. a kind of production technology of cellulose carbamate fibre long filament according to claim 1 or 4, feature exist
In: in step C, in the first time mixed dissolution, the sodium hydroxide solution of addition and the liquid of cellulose carbamate
Gu than being 10~12:1；In second of mixed dissolution, the sodium hydroxide solution of addition and cellulose carbamate
Liquid-solid ratio is 12~14:1；In the third time mixed dissolution, the sodium hydroxide solution and cellulose carbamate of addition
Liquid-solid ratio be 14~16:1.
6. a kind of production technology of cellulose carbamate fibre long filament according to claim 1, it is characterised in that:
In step D, in the spinning process, the composition and ratio of coagulating bath are Na2SO4 230~245g/L, ZnSO48~12g/
L, H2SO4110~140g/L.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104957A (en) * | 2007-08-20 | 2008-01-16 | 中国科学院新疆理化技术研究所 | Process for preparing cellulose carbamate fibre |
| CN102691125A (en) * | 2012-06-19 | 2012-09-26 | 武汉大学 | Method for preparing regenerated cellulose fibers with cellulose carbamate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104957A (en) * | 2007-08-20 | 2008-01-16 | 中国科学院新疆理化技术研究所 | Process for preparing cellulose carbamate fibre |
| CN102691125A (en) * | 2012-06-19 | 2012-09-26 | 武汉大学 | Method for preparing regenerated cellulose fibers with cellulose carbamate |
Non-Patent Citations (1)
| Title |
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| "尿素嵌入法生产纤维素氨基甲酸酯新工艺";哈丽丹•买买提等;《纤维素科学与技术》;20060630;第14卷(第2期);第35-40页 * |
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Application publication date: 20170524 Assignee: Yibin Siliya Technology Innovation Co.,Ltd. Assignor: YIBIN GRACE GROUP Co.,Ltd. Contract record no.: X2024510000017 Denomination of invention: Production process of cellulose carbamate fiber filament Granted publication date: 20181214 License type: Common License Record date: 20240830 |