CN117005056A - Polymer coloring method, spinning color paste, spinning solution and colored fiber - Google Patents
Polymer coloring method, spinning color paste, spinning solution and colored fiber Download PDFInfo
- Publication number
- CN117005056A CN117005056A CN202311062542.7A CN202311062542A CN117005056A CN 117005056 A CN117005056 A CN 117005056A CN 202311062542 A CN202311062542 A CN 202311062542A CN 117005056 A CN117005056 A CN 117005056A
- Authority
- CN
- China
- Prior art keywords
- polysulfonamide
- spinning
- colored
- color paste
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000009987 spinning Methods 0.000 title claims abstract description 222
- 239000000835 fiber Substances 0.000 title claims abstract description 202
- 238000000034 method Methods 0.000 title claims abstract description 82
- 238000004040 coloring Methods 0.000 title claims abstract description 45
- 229920000642 polymer Polymers 0.000 title claims description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 134
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims abstract description 109
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 92
- 239000000178 monomer Substances 0.000 claims abstract description 83
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 76
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 65
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000002156 mixing Methods 0.000 claims abstract description 53
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 13
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 38
- 239000011230 binding agent Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- 239000003495 polar organic solvent Substances 0.000 claims description 23
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 21
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 16
- 239000006227 byproduct Substances 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 abstract description 57
- 238000004043 dyeing Methods 0.000 abstract description 43
- 238000007639 printing Methods 0.000 abstract description 4
- 239000004753 textile Substances 0.000 abstract description 4
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 230000036314 physical performance Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 121
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 52
- 238000005406 washing Methods 0.000 description 40
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 description 34
- 239000000203 mixture Substances 0.000 description 30
- 239000002904 solvent Substances 0.000 description 30
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 29
- 238000001556 precipitation Methods 0.000 description 27
- -1 diformyl chloride Chemical compound 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical group ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 20
- 230000001276 controlling effect Effects 0.000 description 19
- 230000008569 process Effects 0.000 description 19
- 238000002166 wet spinning Methods 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 230000002829 reductive effect Effects 0.000 description 16
- 230000003247 decreasing effect Effects 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 13
- 238000007711 solidification Methods 0.000 description 13
- 230000008023 solidification Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 230000001502 supplementing effect Effects 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000005096 rolling process Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 11
- 239000001110 calcium chloride Substances 0.000 description 11
- 229910001628 calcium chloride Inorganic materials 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- 238000007086 side reaction Methods 0.000 description 10
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 150000007522 mineralic acids Chemical class 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- YSBUANSGDLZTKV-UHFFFAOYSA-N n-phenylcarbamoyl chloride Chemical compound ClC(=O)NC1=CC=CC=C1 YSBUANSGDLZTKV-UHFFFAOYSA-N 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 description 4
- WQOWBWVMZPPPGX-UHFFFAOYSA-N 2,6-diaminoanthracene-9,10-dione Chemical compound NC1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 WQOWBWVMZPPPGX-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000001023 inorganic pigment Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- HSYLKWSCFRLSKB-UHFFFAOYSA-N 1,5-diamino-4,8-dihydroxyanthracene-9,10-dione Chemical compound O=C1C2=C(N)C=CC(O)=C2C(=O)C2=C1C(O)=CC=C2N HSYLKWSCFRLSKB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical group ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 239000012836 macromolecular constituent Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- QWXDVWSEUJXVIK-UHFFFAOYSA-N 1,8-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC(N)=C2C(=O)C2=C1C=CC=C2N QWXDVWSEUJXVIK-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- 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
- D01F1/04—Pigments
-
- 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
- D01F1/06—Dyes
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention relates to a macromolecule coloring method, spinning color paste, spinning solution and colored fibers, belonging to the technical field of textile printing and dyeing, comprising the following steps: mixing a color reaction monomer and diaminodiphenyl sulfone, and then reacting with phenyl diformyl chloride to obtain polysulfonamide color spinning solution color paste, or respectively pre-polymerizing the color reaction monomer and the diaminodiphenyl sulfone with the phenyl diformyl chloride, and mixing and reacting the pre-polymerized products of the pre-polymerization reaction to prepare polysulfonamide color paste; mixing polysulfonamide color paste with polysulfonamide natural color paste, and further spinning to obtain colored polysulfonamide fibers; the invention solves the problems of low relative strength and elongation at break of dyed fiber products caused by high filtering pressure and high breakage rate of the spinneret of the existing dyeing method, improves the filtering performance and spinnability of spinning solution, and has the characteristics of good physical performance and low dyeing cost.
Description
Technical Field
The invention relates to the technical field of textile printing and dyeing, in particular to a polymer coloring method, spinning color paste, spinning solution and colored fibers.
Background
Polysulfonamide has excellent heat resistance, and the fiber decomposition temperature of the polysulfonamide reaches 500 ℃, the long-term use temperature is higher than 250 ℃, the limiting oxygen index is higher than 33, the polysulfonamide has excellent high-temperature acid and alkali resistance, electrical insulation and good textile processing performance, and is widely applied to the fields of protective clothing, high-temperature filter materials, electrical industry and composite materials, thus being an indispensable strategic important material.
The polysulfonamide fiber is often required to be dyed when in use, common dyeing modes comprise pre-spinning dyeing and post-dyeing of the fiber, and the pre-spinning dyeing in the prior art adopts a method of grinding and adding inorganic pigment or insoluble organic matters, because the pigment exists in the fiber in a particle form, micropores of a spinneret are easy to block, normal spinning of the fiber is influenced, the filtering pressure is high, the breakage rate is high, the spinneret plate changing period is short, and the spinning cost is high; the fiber post-dyeing is to dye the spun or woven fiber or fiber fabric by using an organic dye, the post-dyeing material is easy to age and fade at high temperature and in strong ultraviolet environment, so that the polysulfonamide is not firmly dyed, the polysulfonamide is often applied to extreme environments such as high temperature and high radiation, and the dyed polysulfonamide prepared by fiber post-dyeing is difficult to meet the use requirement; meanwhile, the dyeing solution for fiber post-dyeing contains heavy metals and organic pollutants, and a large amount of waste water and waste residues are generated in the dyeing process, so that the environment is seriously polluted.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a polymer coloring method, a spinning color paste, a spinning solution and a colored fiber, which are used for solving the problems of high filtration pressure, high breakage rate, low relative strength and elongation at break and poor light resistance of dyed fiber products, and the problems of large amount of waste water and waste residue generated by printing and dyeing and environmental pollution of the existing coloring method spinneret.
The aim of the invention is mainly realized by the following technical scheme:
a method of coloring a polymer comprising:
mixing a color reaction monomer and diaminodiphenyl sulfone, and then reacting with phenyl diformyl chloride to obtain polysulfonamide color spinning solution color paste, or respectively pre-polymerizing the color reaction monomer and the diaminodiphenyl sulfone with the phenyl diformyl chloride, and mixing and reacting the pre-polymerized products of the pre-polymerization reaction to prepare polysulfonamide color paste; and mixing the polysulfonamide color paste with polysulfonamide natural color paste, and further spinning to obtain the colored polysulfonamide fiber.
Preferably, the preparation of the polysulfonamide colored spinning solution color paste comprises the following steps:
s1101: dissolving a chromogenic reaction monomer and diaminodiphenyl sulfone in a polar organic solvent and uniformly mixing;
s1102: gradually adding phenyl diformyl chloride, and polymerizing to obtain polysulfonamide color paste.
Preferably, the preparation of the polysulfonamide colored spinning solution color paste comprises the following steps:
s2101: dissolving a chromogenic reaction monomer and diaminodiphenyl sulfone in a polar organic solvent;
s2102: adding phenyl diformyl chloride into the mixed system in S2101 for multiple times, performing multiple times of prepolymerization, adding an acid binding agent after each time of prepolymerization, precipitating and separating a reaction product of the acid binding agent and a prepolymerization byproduct, continuing adding phenyl diformyl chloride, and polymerizing to obtain polysulfonamide color paste.
Preferably, the preparation of the polysulfonamide colored spinning solution comprises the following steps:
s3101: placing a chromogenic reaction monomer and diaminodiphenyl sulfone in two independent reactors, respectively adding a polar solvent for dissolution, adding phenyldicarboxyl chloride for the first time, and respectively polymerizing to obtain two prepolymer solutions;
s3102: mixing the two prepolymer solutions, adding phenyl diformyl chloride for the second time, performing post polymerization, adding an acid binding agent after polymerization, and precipitating and separating the acid binding agent and a hydrogen chloride product to obtain polysulfonamide color paste.
The spinning color paste for the colored fibers is prepared by the method and comprises colored polymers and polar organic solvents;
the colored polymer includes:and(III) and (IV) the two structural units are randomly distributed, aq contains anthraquinone functional groups, ac represents m-benzene or p-benzene functional groups, and DS contains diphenyl sulfone structural units.
A spinning solution for coloring fiber is prepared by mixing the color paste and polysulfonamide natural color paste;
the colored polymer includes:and(III) and (IV) the two structural units are randomly distributed, aq contains anthraquinone functional groups, ac represents m-benzene or p-benzene functional groups, and DS contains diphenyl sulfone structural units.
A colored fiber prepared from the above-described spinning solution, said colored fiber comprising two structural units (iii), (iv) randomly distributed:
wherein Aq comprises an anthraquinone functional group, ac is an m-or p-benzene functional group, and DS comprises a diphenyl sulfone structural unit.
The spinning color paste for the colored fibers is prepared by the method and comprises colored polymers and polar organic solvents;
the general formula of the coloring polymer meets the following conditions:
wherein p represents the number of a long chain prepolymer constituting a colored polymer, R p+1 Represents the p+1th long chain prepolymer,
R 1 ，...，R p+1 to only includePrepolymers of units or comprising onlyA prepolymer of units, wherein Aq comprises anthraquinone functionality, ac represents m-or p-benzene functionality, and DS comprises diphenyl sulfone structural units.
The spinning solution for the colored fiber is prepared by mixing the color paste with polysulfonamide natural color paste and comprises colored polymer and polar organic solvent;
The general formula of the coloring polymer meets the following conditions:
wherein p represents the number of a long chain prepolymer constituting a colored polymer, R p+1 Represents the p+1th long chain prepolymer,
R 1 ，...，R p+1 to only includePrepolymers of units or comprising onlyA prepolymer of units, wherein Aq comprises anthraquinone functionality, ac represents m-or p-benzene functionality, and DS comprises diphenyl sulfone structural units.
A colored fiber prepared from the above-described spinning dope, the colored fiber structure satisfying:
wherein p represents the number of a long chain prepolymer constituting a colored polymer, R p+1 Represents the p+1th long chain prepolymer,
R 1 ，...，R p+1 to only includePrepolymers of units or comprising onlyA prepolymer of units, wherein Aq comprises anthraquinone functionality, ac represents m-or p-benzene functionality, and DS comprises diphenyl sulfone structural units.
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) The coloring method of the invention introduces dye molecules into the main chain of polysulfonamide polymers through a certain chemical reaction to copolymerize to form coloring polymers, which is different from the mechanism of blending coloring and graft copolymerization coloring. The color reaction monomer is taken as one of reactants, is copolymerized with other monomers of the fiber to form a polymer main chain, is dissolved in a solvent system to form an in-phase solution, and compared with the existing fiber coloring method using the particle pigment, the color reaction monomer has the advantages of small filtering pressure, low breakage rate, high relative strength and high elongation at break of the dyed fiber, and greatly improves the physical properties of the colored fiber product; the defects of the prior art that micropores of a spinneret are easy to be blocked, the filtration pressure is high, the breakage rate is high, and the relative strength and the breaking elongation of the dyed fiber product are low are overcome; compared with the method of dyeing the fiber after spinning, the dyeing unit structure of the invention is more stable, is not easy to leach out and run off or age, and has obviously improved dyeing durability and light aging resistance.
(2) According to the invention, the polysulfonamide color paste containing the high-concentration color development units is prepared by adopting the color development reaction monomers and polysulfonamide raw materials, and the polysulfonamide color paste and the polysulfonamide unbleached paste are mixed in different proportions to prepare the spinning solution, so that the influence on the whole spinnability of the spinning solution is improved when the color development reaction monomers are more, the polysulfonamide colored fibers with different concentrations can be flexibly prepared, and the applicability is improved; meanwhile, by synthesizing polysulfonamide color paste, the synthesis reaction scale and the synthesis amount of the colored spinning solution can be reduced, and the dyeing cost of polysulfonamide is further reduced.
(3) The invention obtains rich color system by selecting the color reaction monomers with different reactivities to copolymerize with other monomers of the polymer to be dyed to form a high molecular chain; in the prior art, the blending coloring method needs to consider pigment dispersibility, uniformity and pigment and polymer compatibility, so that the pigment selection range is limited.
(4) The invention adopts a process of adding phenyl diformyl chloride twice or more, and after adding a certain amount of phenyl diformyl chloride, introducing an acid binding agent substance to combine with a byproduct of a product, filtering to remove the byproduct, promoting the reaction to proceed forward, and then adding the rest of phenyl diformyl chloride; further, the inorganic acid binding agent is introduced to react with the reaction byproducts, the reaction byproducts are removed through precipitation and filtration, and the new impurities are prevented from being introduced while the reaction byproducts are removed.
(5) The polar solvent used in the spinning process can be recovered by means of reduced pressure distillation and the like, so that the dyeing waste residue and waste water generated in the dyeing process in the prior art are completely avoided, and compared with the existing spinning method, the energy conservation and consumption reduction are realized, and the environmental pollution is reduced.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to refer to like parts throughout the several views.
FIG. 1 is a process flow diagram of the one-step mill base method of the present invention;
FIG. 2 is a flow chart of a two-step mill base process of the present invention;
FIG. 3 is a flow chart of a color paste process for preparing color paste from a color-forming reaction monomer and diamino diphenyl sulfone, respectively, and phenyl diformyl chloride in the present invention.
Detailed Description
The following detailed description of preferred embodiments of the invention is made in connection with the accompanying drawings, which form a part hereof, and together with the description of the embodiments of the invention, are used to explain the principles of the invention and are not intended to limit the scope of the invention.
Technical terms
And (3) hairing: the individual filaments of the filaments break during the winding or weaving process, and the fabric exhibits a protruding or fuzzy appearance at the fiber ends, either locally or diffusely.
Aiming at the defects that pigment exists in a particle form in spinning solution fiber, micropores of a spinneret are easy to be blocked, the filtering pressure is high, the breakage rate is high, the relative strength and the breaking elongation of a dyed fiber product are low, an organic small-molecule dye cannot resist temperature, the color is easy to change and fade in the high-temperature treatment and use process of the fiber product, and the printing and dyeing wastewater is large and difficult to treat, a color reaction monomer with reactivity is selected as one of reactants, and is copolymerized with other monomers of the fiber to form a high-molecular main chain, and the high-molecular main chain is dissolved in a solvent system to form an in-phase solution, so that the defects that the filtering pressure is low, the breakage rate is low, the relative strength and the breaking elongation of the dyed fiber are low in the prior art are overcome; on the other hand, the color reaction monomer participates in macromolecular chain formation, is dispersed in the resin matrix at a molecular level, and is more uniform in dispersion, stronger in coloring power, more stable in effect and longer in coloring time compared with the organic micromolecular dye for dyeing polysulfonamide.
The invention discloses a high polymer coloring method, which comprises the following steps:
step 1: mixing a color reaction monomer and diaminodiphenyl sulfone, and then reacting with phenyl diformyl chloride to obtain polysulfonamide color spinning solution color paste, or respectively pre-polymerizing the color reaction monomer and the diaminodiphenyl sulfone with the phenyl diformyl chloride, and mixing and reacting the pre-polymerized products of the pre-polymerization reaction to prepare polysulfonamide color paste; and mixing the polysulfonamide color paste with polysulfonamide natural color paste, and further spinning to obtain the colored polysulfonamide fiber.
In the invention, dye molecules are introduced into a main chain of a polymer to be copolymerized into a colored polymer through chemical reaction, and the mechanism is different from the mechanism of blending coloring and graft copolymerization coloring: the chromogenic reaction monomer is taken as one of reactants, is copolymerized with other monomers (such as diaminodiphenyl sulfone or phenyldiformyl chloride) of the synthetic fiber to form a high molecular main chain, and is dissolved in a solvent system to form an in-phase solution.
Compared with the fiber coloring method in the prior art using the particle pigment, the coloring method has the characteristics of small filtering pressure, low breakage rate and high relative strength and elongation at break of the dyed fiber, and greatly improves the physical properties of colored fiber products; the defects of high filtering pressure and high breakage rate, which cause low relative strength and elongation at break of dyed fiber products, of micropores which are easy to block a spinneret in the prior art are overcome; meanwhile, the coloring unit directly participates in forming the coloring polymer, so that the structure of the coloring unit is more stable compared with the dye for dyeing, the leaching loss or aging is not easy, and the dyeing durability and the light aging resistance are obviously improved.
It can be understood that the invention prepares spinning color paste by connecting a color reaction monomer as a reaction monomer of the colored polysulfonamide fiber to a polysulfonamide polymer main chain in the reaction, thereby directly preparing colored fiber by the polysulfonamide spinning process, and the fiber can be conveniently processed into colored yarns in the subsequent process to further prepare colored fabrics; or directly preparing non-woven fabrics, and dyeing is not needed in the subsequent use process of the fiber. On the contrary, if the polysulfonamide color paste is used for spinning to obtain the fiber, and the fiber is dyed after spinning or weaving, a dyeing process is needed to be added, and meanwhile, the bath liquid used in the dyeing process is also needed to be treated and then discharged. Compared with the prior art, the invention has no dyeing wastewater, and reduces wastewater discharge after water treatment.
In a possible implementation manner, the preparation of the polysulfonamide colorant in the step 1 can adopt a one-step colorant method, as shown in fig. 1:
s1101: dissolving a chromogenic reaction monomer and diaminodiphenyl sulfone in a polar organic solvent and uniformly mixing;
s1102: gradually adding phenyl diformyl chloride, and polymerizing to obtain polysulfonamide color paste.
The method is characterized in that phenyl diformyl chloride (such as isophthaloyl chloride) is added into a solution of a chromogenic reaction monomer and diaminodiphenyl sulfone to form a local large excess of the chromogenic reaction monomer and the diaminodiphenyl sulfone, so that the main reaction is facilitated, the reaction of a small amount of impurities such as water and the like in a system with the phenyl diformyl chloride is inhibited, side reaction occurs, and the chain extension growth of the polysulfonamide prepolymer is influenced.
Under the condition that the phenyldicarboxyl chloride is sufficient or excessive, the diaminodiphenyl sulfone and the chromogenic reaction monomer can react with the phenyldicarboxyl chloride in a competition mode, and the prepared coloring polymer long chain has a structural unit containing the diaminodiphenyl sulfone-the phenyldicarboxyl chloride and a structural unit containing the chromogenic reaction monomer-the phenyldicarboxyl chloride.
Illustratively, a diaminoanthraquinone (of the formula NH 2 -Aq-NH 2 ) As a chromogenic reactive monomer, diaminodiphenyl sulfone (formula NH 2 -DS-NH 2 ) As examples of diaminodiphenyl sulfone and isophthaloyl chloride as phenylcarbamoyl chloride, the overall reaction is as follows:
the method comprises the steps of carrying out a first treatment on the surface of the Wherein n represents the number of polymer constituent units;represents the polymer constituent unit formed by the reaction of diaminodiphenyl sulfone and phenyl diformyl chloride.
Illustratively, a diaminoanthraquinone (of the formula NH 2 -Aq-NH 2 ) As examples of the color-forming reaction monomer and isophthaloyl chloride as the phenylcarbamoyl chloride and a sufficient amount or an excess of the phenylcarbamoyl chloride, the color-forming reaction monomer, diaminodiphenyl sulfone and the phenylcarbamoyl chloride are reacted as follows:
wherein n represents the number of polymer constituent units;represents a macromolecular constituent unit formed by the reaction of diaminodiphenyl sulfone with phenyldicarboxyl chloride,/for>Representing the polymer composition unit formed by the reaction of the chromogenic reaction monomer and the phenyl diformyl chloride, a represents the number of the polymer structure unit formed by the reaction of the diaminoanthraquinone, n-a represents the number of the polymer structure unit formed by the reaction of the diaminodiphenyl sulfone, and Aq contains anthraquinone functional groups; in the colored fiber, two structural units (I) and (II) are randomly distributed:
specifically, the number ratio of the two structural units (I) to (II) in the color paste is as follows: 0 to 99.9:0.1 to 100.
Specifically, in step S1102, the polymerization reaction for preparing the polyarylsulfone fiber color paste includes a plurality of different reaction stages, and the polymerization reaction temperatures of the reaction stages are different:
the first stage: the preparation method mainly comprises the steps of reacting diaminodiphenyl sulfone, a chromogenic reaction monomer and phenyl diformyl chloride to generate a micromolecular prepolymer and randomly copolymerizing the micromolecular prepolymer to generate a long-chain prepolymer;
And a second stage: with the continued addition of the phenyldicarboxyl chloride, the phenyldicarboxyl chloride reacts with the diamino diphenyl sulfone or the chromophoric reaction monomer end groups of the prepolymer molecules to achieve long chain prepolymer connection and long chain growth.
Specifically, taking phenyl diformyl chloride as m-phenyl diformyl chloride as an example, the main reaction equation in the first stage satisfies:
wherein R represents diaminodiphenyl sulfone or a part other than amino group of a reactive coloring unit; NH (NH) 2 -R-NH 2 Represents diaminodiphenyl sulfone or reactive chromophoric units; m represents the amount of the polymetaphthaloyl structure in the long-chain prepolymer or the amount of phenyl dicarboxylic acid chloride consumed in the first stage.
Specifically, taking isophthaloyl dichloride as an example, the main reaction equation in the second stage satisfies the following conditions:
wherein n represents the number of high molecular structural units in the poly (m-phthaloyl diamino diphenyl sulfone); p represents the consumption of phenyl diformyl chloride in the second stage for preparing polysulfonamide molecules with the number of structural units of n; r is R p+1 Representing the p+1th long chain prepolymer, the number of polymetaphthaloyl structures of different long chain prepolymers may be the same or different.
The phthaloyl chloride groups in the two structural units (I) and (II) and the reaction equation can be replaced by terephthaloyl chloride groups, or m-phthaloyl chloride groups and terephthaloyl chloride groups can be simultaneously present.
Preferably, the polymerization temperature in the first stage is-15 ℃ to 30 ℃, for example, -15 ℃, -10 ℃, -5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃ and 30 ℃, and the polysulfonamide molecules have larger viscosity average molecular weight and better mechanical strength in the range; the reaction time is 0.05 h-1 h.
Further preferably, the polymerization reaction temperature in the first stage is from-5℃to 30℃and may be, for example, -10℃to-5℃and-0℃and 5℃and 10℃and 15℃and 20℃and 25℃and 30 ℃.
Preferably, the second stage polymerization temperature is 31℃to 70℃and may be, for example, 31℃35℃40℃45℃50℃55℃60℃65℃70 ℃; the reaction time is 0.05 h-2 h.
It is noted that the prepolymerization temperature is lower than-15 ℃, the reaction speed is low, and the efficiency of the whole process can be reduced; the post polymerization temperature is higher than 70 ℃, the side reaction is increased, the polysulfonamide molecules are damaged linearly, the molecular weight is lower, the viscosity is lower, the spinnability is reduced, and the fiber strength and the elongation at break are reduced; the post polymerization temperature 1 is higher than the pre polymerization temperature.
The method is characterized in that phenyl diformyl chloride (such as isophthaloyl chloride) is gradually added into a solution of a chromogenic reaction monomer and diaminodiphenyl sulfone to form a local large excess of the chromogenic reaction monomer and the diaminodiphenyl sulfone, so that the method is favorable for carrying out a main reaction, inhibiting a small amount of impurities such as water in a system from reacting with the phenyl diformyl chloride, reducing side reactions, and facilitating the chain extension and growth of a prepolymer in a spinning solution, and a colored polymer with larger molecular weight and polymerization degree is obtained.
It will be appreciated that the gradual addition of the phenyldicarboxylic acid chloride allows the reaction temperature to be readily maintained stable, preventing the reaction from running away due to severe exotherms, while the lower temperature helps to reduce side reactions.
Specifically, the gradual addition of phenyldicarboxyl chloride is achieved by:
the total amount of phenyl diformyl chloride can be divided into equal or unequal parts, and a certain part of phenyl diformyl chloride is added at each time interval, or a continuous feeding device is adopted, and the feeding rate can be changed from 0 to any value meeting the requirement of instantaneous feeding.
Specifically, the feeding time of the phenyl diformyl chloride is 0.1-4 h, and the polymerization reaction time is 0.1-6 h; the polymerization reaction time is less than 0.1h, and the reaction is insufficient; the polymerization reaction time exceeds 6 hours, side reactions are increased, the molecular weight of the polymer is affected, and the efficiency is low.
In another possible implementation manner, the preparation of the polysulfonamide colored spinning solution in the step 1 can adopt a two-step or multi-step color paste method:
specifically, as shown in fig. 2, the two-step color paste method is to polymerize a color-forming reaction monomer with diaminodiphenyl sulfone and phenyl dicarboxylic acid chloride to prepare a spinning color paste, and further mix the spinning color paste with polysulfonamide natural color paste to prepare a spinning solution, wherein the preparation of the spinning color paste comprises the following steps: and (3) carrying out one-time prepolymerization according to the deficiency of the phenyldicarboxyl chloride, separating an impurity product after each prepolymerization to promote the forward reaction, and further adding the phenyldicarboxyl chloride according to the complete reaction stoichiometric ratio or the near complete reaction stoichiometric ratio and then carrying out polymerization to prepare the polysulfonamide colored spinning solution.
It should be noted that, during the synthesis of polysulfonamide, reaction byproducts are generated simultaneously, and when the reaction byproducts accumulate to a certain extent in the system, the reaction is inhibited from proceeding forward, and the chain growth of polysulfonamide and the final performance of polysulfonamide fibers are affected. According to the invention, a pre-polymerization-post-polymerization process of adding phenyl diformyl chloride twice or more is adopted, when the adding amount of the pre-polyphenyl diformyl chloride reaches 50-95%, an acid binding agent is added to combine with reaction byproducts before further adding the phenyl diformyl chloride, and the combined products are separated from a solution system, so that the aim of promoting forward combination of the reaction is fulfilled.
Illustratively, a diaminoanthraquinone (of the formula NH 2 -Aq-NH 2 ) As examples of the color-forming reaction monomer, diaminodiphenyl sulfone as diaminodiphenyl sulfone and isophthaloyl chloride as phenyldicarboxyl chloride, the overall reaction is as follows:
wherein n represents the number of polymer constituent units;represents a macromolecular constituent unit formed by the reaction of diaminodiphenyl sulfone with phenyldicarboxyl chloride,/for>Representing the polymer composition unit formed by the reaction of the chromogenic reaction monomer and the phenyl diformyl chloride, a represents the number of the polymer structure unit formed by the reaction of the diaminoanthraquinone, n-a represents the number of the polymer structure unit formed by the reaction of the diaminodiphenyl sulfone, and Aq contains anthraquinone functional groups; DS comprises diphenyl sulfone structural units; in the color paste, two structural units (I) and (II) are randomly distributed:
Specifically, the number ratio of the two structural units (I) to (II) in the color paste is as follows: 0 to 99.9:0.1 to 100.
The phthaloyl chloride groups in the two structural units (I) and (II) and the reaction equation can be replaced by terephthaloyl chloride groups, or m-phthaloyl chloride groups and terephthaloyl chloride groups can be simultaneously present.
Specifically, the phenyl diformyl chloride is added twice or more in the step 1, and the method comprises the following steps:
s2101: dissolving a chromogenic reaction monomer and diaminodiphenyl sulfone in a polar organic solvent;
s2102: adding phenyl diformyl chloride into the mixed system in S2101 for multiple times, performing multiple times of prepolymerization, adding an acid binding agent after each time of prepolymerization, precipitating and separating a reaction product of the acid binding agent and a prepolymerization byproduct, continuing adding phenyl diformyl chloride, and polymerizing to obtain polysulfonamide color paste.
Specifically, in the step 1, phenyl diformyl chloride (a two-step color paste method or a multi-step color paste method) is added twice or more, and the addition amount of each phenyl diformyl chloride is as follows: m is M 1 ％：M 2 ％：M 3 ％：…：M n In which M is% n The proportion of the actual added phenyldiformyl chloride to the total phenyldiformyl chloride for the nth time is as follows: m is M n-1 ＞M n The method comprises the steps of carrying out a first treatment on the surface of the The quantity ratio of the first added phenyl diformyl chloride to the second added phenyl diformyl chloride is as follows: 1:0.01 to 1.
It can be understood that impurities such as water and the like are unavoidably present in the reaction system and can react with the phenyl diformyl chloride to generate carboxyl compounds, the substances are difficult to participate in macromolecule chain formation, and the phenyl diformyl chloride part added for the first time is used for impurity consumption; the addition of the phenyl diformyl chloride again is less in quantity, is favorable for controlling the reaction temperature, reduces the occurrence of side reaction, avoids the interference of side reaction products and obtains the chain compound with larger molecular weight.
Specifically, in step S2102, the pre-polymerization is mainly that diaminodiphenyl sulfone, a chromophoric reaction monomer and phenyl dicarboxyl chloride react to generate a small molecular prepolymer, and the small molecular prepolymer is randomly copolymerized to generate a long chain prepolymer, and the phenyl dicarboxyl chloride is taken as m-phthaloyl chloride as an example, and the pre-polymerization main reaction equation is satisfied:
wherein R represents diaminodiphenyl sulfone or a part other than amino group of a reactive coloring unit; NH (NH) 2 -R-NH 2 Represents diaminodiphenyl sulfone or reactive chromophoric units; m represents the number of polyarylsulfone structures in the long chain prepolymer or the number of phenyl dicarboxylic acid dichlorides consumed in the first stage.
Specifically, in step S2102, the post-polymerization is mainly performed by reacting phenyl dicarboxylic acid chloride with diamino diphenyl sulfone or a chromophoric reaction monomer end group of a prepolymer molecule to achieve long-chain prepolymer connection and long-chain growth as phenyl dicarboxylic acid chloride is continuously added; taking phenyl diformyl chloride as m-phthaloyl chloride as an example, the post-polymerization main reaction equation satisfies:
Wherein n represents the number of high molecular structural units in polysulfonamide; p represents the consumption of phenyl diformyl chloride in the second stage for preparing polysulfonamide molecules with the number of structural units of n; r is R p+1 Represents the p+1th long-chain prepolymer, and the number of polyarylsulfone structures of different long-chain prepolymers can be the same or different.
Preferably, the prepolymerization polymerization temperature is from-10℃to 30℃and may be, for example, -10℃to-5℃0℃5℃10℃15℃20℃25℃30 ℃. The polysulfonamide molecules have larger viscosity average molecular weight and better mechanical strength in the range; the reaction time is 0.05 h-1 h.
Further preferably, the prepolymerization polymerization temperature is from-5℃to 30 ℃.
Preferably, the post-polymerization temperature is 31℃to 70℃and may be, for example, 31℃35℃40℃45℃50℃55℃60℃65℃70 ℃; the reaction time is 0.05 h-2 h.
It is noted that the prepolymerization temperature is lower than-10 ℃, the reaction speed is low, and the efficiency of the whole process can be reduced; the post polymerization temperature is higher than 70 ℃, the side reaction is increased, the polysulfonamide molecules are damaged linearly, the molecular weight is lower, the viscosity is lower, the spinnability is reduced, and the fiber strength and the elongation at break are reduced; the post polymerization temperature 1 is higher than the pre polymerization temperature.
Specifically, the mass ratio of the chromogenic reaction monomer in the chromogenic reaction monomer and the diaminodiphenyl sulfone is in the range of: 0.1 to 100 percent.
Specifically, the polar organic solvent in step S2101 may be selected from any one of N-dimethylacetamide, dimethylformamide (DMF), and N-methylpyrrolidone, which has good solubility to the raw material monomer in the range of-20 ℃ to 70 ℃ and does not react with any raw material monomer.
On the one hand, on the basis of the color development reaction monomer in the polymer of the polysulfonamide colored spinning solution, the color of the corresponding color development reaction monomer is shown after spinning; on the other hand, after the compounding of a plurality of different color chromophoric reaction monomers, the mixed color different from any single chromophoric reaction monomer can be generated after spinning.
In another possible implementation manner, the preparation of the polysulfonamide colored spinning solution in the step 1 can adopt a color paste method for preparing color paste by using a color reaction monomer and diaminodiphenyl sulfone and phenyl diformyl chloride respectively:
specifically, as shown in fig. 3, illustratively, step 1 includes:
s3101: placing a chromogenic reaction monomer and diaminodiphenyl sulfone in two independent reactors, respectively adding a polar solvent for dissolution, adding phenyldicarboxyl chloride for the first time, and respectively polymerizing to obtain two prepolymer solutions;
S3102: mixing the two prepolymer solutions, adding phenyl diformyl chloride for the second time, performing post polymerization, adding an acid binding agent after polymerization, and precipitating and separating the acid binding agent and a hydrogen chloride product to obtain polysulfonamide color paste.
Specifically, the mass ratio of the chromogenic reaction monomer in the chromogenic reaction monomer and the diaminodiphenyl sulfone in this embodiment ranges from: 0.1 to 100 percent.
Illustratively, diaminodiphenyl sulfone is used as diaminodiphenyl sulfone and diaminoanthraquinone (of the formula NH 2 -Aq-NH 2 ) For the example of the color reaction monomer and isophthaloyl chloride as the phenylcarbamoyl chloride, diaminodiphenyl sulfone in S3101, the color reaction monomer and an insufficient amount of phenylcarbamoyl chloride are reacted to prepare a prepolymer as follows:
wherein R represents diaminodiphenyl sulfone or a part other than amino group of a reactive coloring unit; NH (NH) 2 -R-NH 2 Represents diaminodiphenyl sulfone or reactive chromophoric units; m represents the number of polyarylsulfone diformyl structures in the long chain prepolymer or the consumption of phenyl diformyl chloride at S3101.
Specifically, taking phenyl diformyl chloride as isophthaloyl dichloride as an example, the main reaction equation of S3102 satisfies:
wherein, p represents the consumption of phenyl diformyl chloride for preparing an polysulfonamide macromolecule in S3102; r is R p+1 The p+1st long-chain prepolymer prepared by S3101 and participating in S3102 reaction can be a prepolymer comprising only The prepolymer of units or comprising only +.>A prepolymer of units; where Aq is the unit of the chromogenic reaction monomer comprising an anthraquinone structure.
The phthaloyl chloride groups in the two structural units (I) and (II) and the reaction equation can be replaced by terephthaloyl chloride groups, or m-phthaloyl chloride groups and terephthaloyl chloride groups can be simultaneously present.
Preferably, the polymerization reaction temperature in S3101 is-10℃to 30℃and may be, for example, -10℃to-5℃to 0℃to 5℃to 10℃to 15℃to 20℃to 25℃to 30 ℃; the polysulfonamide molecules have larger viscosity average molecular weight and better mechanical strength in the range; the reaction time is 0.05 h-1.
Further preferably, the polymerization reaction temperature in S3101 is from-5℃to 30 ℃.
Preferably, the polymerization temperature in S3102 is 31℃to 70℃such as 31℃35℃40℃45℃50℃55℃60℃65℃70 ℃. In S3102, the polymerization temperature is higher than 70 ℃, the linearity of polysulfonamide molecules is destroyed, the molecular weight is lower, the viscosity is lower, the spinnability is reduced, and the fiber strength and the elongation at break are reduced.
Preferably, the reaction time of S3102 is 0.05 h-2 h.
Specifically, S3101, S3102 are less than 0.1h time, insufficient reaction; when S3101 exceeds 1h and S3102 exceeds 2h, side reactions increase, which adversely affect the molecular weight of the polymer and are inefficient.
Specifically, the acid-binding agent in the color paste method for preparing color paste by two or more steps of color paste method, color reaction monomer and diamino diphenyl sulfone and phenyl diformyl chloride respectively comprises an inorganic acid-binding agent and an organic acid-binding agent.
Preferably, the acid-binding agent is an inorganic acid-binding agent.
Specifically, the inorganic acid-binding agent is one or more of ammonia, ammonium carbonate and ammonium bicarbonate.
Specifically, the organic acid-binding agent includes any one of diethylamine and triethylamine.
It should be noted that the inorganic acid-binding agent has obvious advantages over the organic acid-binding agent: on one hand, the organic acid-binding agent is dissolved in an polysulfonamide synthetic solvent system and is relatively difficult to separate; on the other hand, the reaction of the organic acid binding agent and hydrochloric acid is reversible, is unstable at high temperature, can be decomposed during heating polymerization, and is difficult to achieve a good acid binding effect; in addition, because polysulfonamide has better crystallinity, the fiber surface is regular and compact after the polysulfonamide is precipitated into filaments, and the interior of the polysulfonamide is difficult to clean thoroughly, so that partial organic acid-binding agent is easy to remain in the polysulfonamide fiber to influence the performance of the polysulfonamide fiber.
The inorganic acid binding agent contains ammonia gas or the decomposition product is ammonia gas, on one hand, ammonia gas and the like are insoluble in a solvent system, and ammonia gas or carbon dioxide generated by heating redundant raw materials is easily separated in a heating and decompression mode and the like, so that the inorganic acid binding agent fully reacts with hydrogen chloride, and meanwhile, redundant ammonia gas residues and raw material impurities are avoided; on the other hand, ammonia gas is insoluble with ammonium chloride which is a hydrogen chloride product and an organic polar solvent system, and is easy to remove in a precipitation mode, so that new impurity introduction is avoided.
In addition, the phenyl diformyl chloride with higher activity is added for multiple times to avoid the decomposition, reaction with impurities and volatilization loss of the phenyl diformyl chloride; on the other hand, the reaction rate is convenient to control by adding for many times, and the uneven reaction degree of the polymerization reaction caused by uneven mass transfer is reduced.
Preferably, the diaminodiphenyl sulfone is one or more of 3,3 '-diaminodiphenyl sulfone (3, 3' -DDS) and 4,4 '-diaminodiphenyl sulfone (4, 4' -DDS), and the phenyldicarboxyl chloride is one or more of terephthaloyl chloride and isophthaloyl chloride.
Specifically, the chromogenic reaction monomer is a compound containing two primary amino groups.
Preferably, the chromogenic reactive monomer is an aromatic compound containing two primary amino groups.
Preferably, the chromogenic reaction monomer is a diaminoanthraquinone. For example, the color-forming reaction monomer may be selected from one or more of 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 2, 6-diaminoanthraquinone, 1, 5-diamino-4, 8-dihydroxyanthraquinone, 1, 2-diaminoanthraquinone, and 1, 8-diaminoanthraquinone.
Preferably, the phenyl dicarboxylic acid chloride is a mixture of terephthaloyl chloride and isophthaloyl chloride, and the molar ratio is 1:0.001 to 0.2.
Specifically, the reactor for obtaining polysulfonamide colored spinning solution can use various types of reactors which have strong material mixing functions, such as a vertical or horizontal kettle type reactor, a screw reactor, a kneader; the aspect ratio of the reactor is more than 1:1 with a jacket or other form of heat sink or heating means to which a cooling or heating liquid is fed.
Specifically, the stirring power of the vertical or horizontal kettle-type reactor is 3 KW/cube-50 KW/cube, the stirring speed is 100 rpm-3000 rpm, and various types of stirring paddles can be used, such as anchor type stirring paddles, paddle type stirring paddles, frame type stirring paddles, multi-layer paddle type stirring paddles, cross type stirring paddles or stirring paddles with composite structures.
Specifically, the screw reactor and various mixing and mixing structural units are used in a combined mode, the rapid rolling state of the solution in the reaction process is maintained, good heat exchange between the inside and the outside is achieved, and rapid polymerization is achieved under the safety condition.
On the one hand, when the radial flow brought by stirring is required to meet the requirement of feeding the phenyldiformyl chloride, substances in different radial areas inside the reaction vessel are uniformly mixed, namely radial mass transfer is realized; on the other hand, the axial flow brought by stirring can meet the requirement that substances in different axial areas inside the reaction vessel are uniformly mixed when the phenyldiformyl chloride is fed, so that the axial mass transfer is realized; in addition, the heat in the internal region of the reaction vessel is transferred to the region exchanging external heat while the mixing of the regions is realized, and the heat is exchanged with external heat, so that the heat transfer and stable temperature control of the regions in the reactor are realized.
Specifically, in order to ensure the spinnability of the spinning solution and the mechanical property of the dyed fibers after the polysulfonamide color paste and polysulfonamide natural color paste are mixed; the mass ratio of the chromogenic reaction monomer to the diaminodiphenyl sulfone in the step 1 is in the range of: 0.1 to 100:0 to 99.9; in the step 2, the mass ratio of the polysulfonamide color paste to the polysulfonamide unbleached paste is 1:1 to 30.
The polymer coloring method further comprises the following steps:
step 2: mixing the prepared polysulfonamide color paste with polysulfonamide natural color paste to prepare colored spinning solution, and carrying out pre-spinning slurry pretreatment;
Step 3: carrying out wet spinning and precipitation on the pretreated polysulfonamide colored spinning solution to obtain nascent fibers;
step 4: and (3) post-treating the primary fiber to obtain the polysulfonamide colored yarn.
Specifically, the pre-spinning slurry pretreatment in step 2 comprises: neutralization, filtration and deaeration.
Specifically, the neutralizing agent is selected from: inorganic base, or organic amine.
Preferably, the inorganic base is one or more of calcium hydroxide, sodium hydroxide, lithium hydroxide and ammonia water.
Specifically, the organic amine is one or more of diethylamine and triethylamine.
Specifically, the filtration pressure is 0.3Mpa to 0.6Mpa.
Specifically, the filtration adopts a closed filter such as a plate-and-frame filter press, a candle filter element filter, a disc filter, a van filter and other precision pressure-resistant filters.
It can be understood that the filtration pressure is related to the density of the spinning solution, the filtration speed and the content of insoluble impurities in the solution, and the inorganic dye in the prior art is insoluble in the spinning solution, so that agglomeration is easy to generate during filtration, and the filtration pressure and the energy consumption of a filtration pump are increased during filtration.
Specifically, vacuum defoaming is adopted for defoaming, and the vacuum degree is 0.1 Kpa-20 Kpa.
Specifically, the spinning pressure of the wet spinning in the step 3 is set to 0.2 to 2MPa, for example, 0.2MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.8MPa, 1.0MPa, 1.2MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.8MPa, 2.0MPa; the spinning temperature is 5-70 ℃, such as 5 ℃, 6 ℃, 8 ℃, 10 ℃, 12 ℃, 14 ℃, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 24 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃; the spin feed rate is 1 m/min to 30 m/min, for example 1 m/min, 2 m/min, 5 m/min, 8 m/min, 10 m/min, 12 m/min, 15 m/min, 18 m/min, 20 m/min, 22 m/min, 25 m/min, 28 m/min, 30 m/min.
Specifically, the aperture of the wet spinning spinneret is 0.04 mm-0.10 mm. For example, the thickness of the material may be 0.04mm, 0.06mm, 0.08mm, or 0.10mm.
Specifically, the precipitation solution used in the precipitation in the step 3 is a mixed solution of the above-mentioned polar organic solvent and an aqueous solution of an alcohol and/or calcium chloride.
In the solution composed of polysulfonamide fibers and the polar organic solvent, the addition of alcohol or calcium chloride is helpful for reducing the solubility of the polysulfonamide fibers in the mixed solution.
Specifically, the mass ratio of the polar organic solvent to the alcohol and/or the aqueous solution of calcium chloride is in the range of 0.2-0.7: from 0.3 to 0.8, in which the spinning precipitate has the highest yield.
Specifically, the post-processing in step 4 includes: plasticizing and stretching, washing, drying and high-temperature heat treatment.
Specifically, the specific method and process conditions for plasticizing and stretching are as follows: the fibers are passed through a plurality of rollers of varying speeds in sequence so that the speed of the fibers as they leave the stretcher is greater than the speed of the fibers as they enter the stretcher, thereby achieving the stretching effect.
In particular, the fibers are immersed in the plasticizing liquid or rinsed by the plasticizing liquid when in two multi-roll machines of different speeds.
Specifically, the plasticizing liquid is a mixed liquid of a polar solvent, inorganic salt and water.
Preferably, the plasticizing liquid is an aqueous solution of DMAC (dimethylacetamide) and calcium chloride, and the mass ratio is as follows: DMAC: calcium chloride: water= (5-40): (0-20): (60-40).
It will be appreciated that the effect of plasticising and stretching is: under the action of plasticizing liquid, the polymer is swelled to a certain extent by the action of solvent, and the polymer can slide mutually to a certain extent under the action of external force, so as to achieve the drawing aim of the molecular in the fiber along the axial orientation of the fiber.
Specifically, the fiber absorbs the plasticizing liquid in the plasticizing and stretching process, so that substances such as polar solvent, inorganic salt and the like remain in the plasticizing liquid; the physical and mechanical properties of the fiber are affected by the substances, and the impurity substances are removed by water washing, the solvent is recovered, so that the material consumption is reduced; the specific method for water washing comprises the following steps: the fiber is washed with water in a multistage countercurrent immersion or leaching mode by using multistage water washing.
Specifically, the specific method and process conditions for drying are as follows: drying the fiber bundles by means of a multi-stage hot roller hot plate or a hot cavity and the like, wherein when the fibers pass through the surface of the heat equipment, heat is transferred from machinery to the fibers, the temperature of the fiber bundles rises, and moisture in the fiber bundles is heated and evaporated, so that the drying effect is achieved; the equipment such as the hot roller or the hot plate can be heated by using an electric resistor, a heating medium (such as heat conducting oil) or steam and the like.
It will be appreciated that drying may remove residual moisture and polar organic solvents.
Specifically, the specific method for high-temperature heat treatment in post-treatment comprises the following steps: and heating the dried fiber by a high-temperature hot cavity device and drawing.
It will be appreciated that the effect of the high temperature heat treatment is: the polymer in the fiber is further oriented along the axial direction of the fiber, so that the physical and mechanical properties are further improved, and the heat resistance of the fiber after being colored is also improved.
Specifically, the post-processing in step 4 includes:
s401, plasticizing and stretching: and (3) carrying out supplementary solidification and multistage stretching on the spinning precipitate obtained in the step (3) in a first plasticizing stretching bath, a second plasticizing stretching bath and a third plasticizing stretching bath in sequence, wherein the concentration of DMAc is decreased in sequence, and the temperature is 60+/-5 ℃, 90+/-5 ℃ and 90+/-5 ℃ respectively. The plasticizing stretching multiple is 3.5-4.5 times. The flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle;
s402, pre-washing and washing: the water washing temperature is 60+/-5 ℃;
s403, drying, heat treatment, oiling and rolling: the fiber is dried at 250 plus or minus 20 ℃ in sequence, and is stretched for 1.1 to 1.5 times in a heat pipe at 350 to 450 ℃ so as to improve the orientation degree and the crystallinity degree of the fiber, and then is oiled and rolled.
The invention discloses a spinning color paste for colored fibers, which comprises colored polymers and a polar organic solvent, and is prepared by a one-step color paste method, a two-step color paste method or a multi-step color paste method and is used for preparing spinning solution by spinning;
The colored polymer includes:and->
(III) and (IV) the two structural units are randomly distributed, aq contains anthraquinone functional groups, ac represents m-benzene or p-benzene functional groups, and DS contains diphenyl sulfone structural units.
Specifically, the number ratio of the two structural units (III) and (IV) is as follows: 0 to 99.9:0.1 to 100.
The invention discloses a spinning color paste of colored fibers, which comprises colored polymers and a polar organic solvent, wherein the colored polymers are prepared by respectively reacting a color reaction monomer and diaminodiphenyl sulfone with phenyl diformyl chloride, and the colored polymers are used for preparing spinning solution by spinning;
the general formula of the coloring polymer meets the following conditions:
wherein p represents the number of a long chain prepolymer constituting a colored polymer, R p+1 Represents the p+1th long chain prepolymer,
R 1 ，...，R p+1 to only includePrepolymers of units or comprising onlyA prepolymer of units, wherein Aq comprises anthraquinone functionality, ac represents m-or p-benzene functionality, and DS comprises diphenyl sulfone structural units.
Specifically, the long-chain prepolymer constituting the colored polymer is the same or different in the kind of constituent units.
Specifically, the number ratio of the two structural units (I) to (II) is as follows: 0 to 99.9:0.1 to 100.
The invention discloses a spinning solution for colored fibers, which is prepared from color paste prepared by a one-step color paste method, a two-step color paste method or a multi-step color paste method and polysulfonamide natural color paste, comprises colored polymers and polar organic solvents, and is used for preparing the colored fibers by spinning;
The colored polymer includes:and
(III) and (IV) the two structural units are randomly distributed, aq contains anthraquinone functional groups, ac represents m-benzene or p-benzene functional groups, and DS contains diphenyl sulfone structural units.
Specifically, the mass concentration of polysulfonamide coloring polymer in the spinning solution is 12-18%.
Specifically, the viscosity [ η ] of the spinning solution: 2.3 to 2.8.
[ eta ] represents the relative viscosity, the dynamic viscosity of spinning solution and the dynamic viscosity ratio of the solvent in the spinning solution.
The invention discloses a spinning solution of colored fibers, which is prepared from color paste prepared from a color reaction monomer and diaminodiphenyl sulfone which are respectively prepared from phenyl diformyl chloride and polysulfonamide natural color paste, and comprises colored polymers and a polar organic solvent, wherein the colored polymers and the polar organic solvent are used for preparing the colored fibers by spinning;
the general formula of the coloring polymer meets the following conditions:
wherein p represents the number of a long chain prepolymer constituting a colored polymer, R p+1 Represents the p+1th long chain prepolymer,
R 1 ，...，R p+1 to only includePrepolymers of units or comprising onlyA prepolymer of units, wherein Aq comprises anthraquinone functionality, ac represents m-or p-benzene functionality, and DS comprises diphenyl sulfone structural units.
Specifically, the mass concentration of polysulfonamide coloring polymer in the spinning solution is 12-18%.
Specifically, the viscosity [ η ] of the spinning solution: 2.4 to 2.65.
Specifically, the polar organic solvent may be any one of N-dimethylacetamide, dimethylformamide (DMF), and N-methylpyrrolidone.
In one specific embodiment of the invention, a colored fiber is disclosed, prepared from a spinning solution comprising a mill base prepared by a one-step mill base process, a two-step mill base process, or a multi-step mill base process,
the colored fiber comprises two structural units (III) and (IV) which are randomly distributed:
wherein Aq comprises an anthraquinone functional group, ac is an m-or p-benzene functional group, and DS comprises a diphenyl sulfone structural unit.
Specifically, the dynamic viscosity of the fiber is 20000 to 60000/centipoise, and the glass transition temperature of the colored fiber is 285 to 310 ℃; the dynamic viscosity of the fiber is 25000-51000 centipoise; the relative strength of the fiber is in the range of 2.45cN/dtex to 3.55 cN/dtex; the breaking elongation of the fiber is 23-31%; the light color fastness is 3.5-4 grade; the washing fastness grade is 4-5.
In one specific embodiment of the invention, a colored fiber is disclosed, which is prepared from a spinning solution of color paste prepared by adopting a color reaction monomer and diaminodiphenyl sulfone and phenyl diformyl chloride respectively, and comprises a colored polymer, wherein the general formula of the colored polymer satisfies:
Wherein p represents the number of a long chain prepolymer constituting a colored polymer, R p+1 Represents the p+1th long chain prepolymer,
R 1 ，...，R p+1 to only includePrepolymers of units or comprising onlyA prepolymer of units, wherein Aq comprises anthraquinone functionality, ac represents m-or p-benzene functionality, and DS comprises diphenyl sulfone structural units.
Specifically, the glass transition temperature of the colored fibers is in the range of 285 ℃ to 310 ℃; the dynamic viscosity of the fiber is 25000-50000 centipoise; the relative strength of the fiber is in the range of 2.80cN/dtex to 3.05 cN/dtex; the breaking elongation of the fiber is 25% -30%; the light color fastness is 3.5-4 grade; the washing fastness grade is 4-5.
In order to better illustrate the invention, the following examples and comparative examples are further provided:
example 1
(1) Preparing colored color paste: 1, 5-diaminoanthraquinone and diaminodiphenyl sulfone are mixed according to a molar ratio of 10:46, adding into proper amount of N-dimethylacetamide solvent, wherein the mole ratio of 3,3'-DDS and 4,4' -DDS in diaminodiphenyl sulfone is 1:3, a step of; the same amount of terephthaloyl chloride and isophthaloyl chloride mixture (molar ratio 9:1) as the total substances of 1, 4-diaminoanthraquinone and diaminodiphenyl sulfone was added in two portions over 2 hours, the first and second mass ratios being 19:1, controlling the polymerization reaction temperature and time at-5 ℃ in the pre-polymerization stage, controlling the post-polymerization stage at 31 ℃ for 1h, and controlling the solute mass concentration in the color paste to be 16.1%.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:30 mass ratio to obtain polysulfonamide colored spinning solution;
(3) Filtering the polysulfonamide colored spinning solution, wherein the filtering pressure is 0.45Mpa, defoaming, then carrying out wet spinning at the spinning pressure or the pressure of each spinning area of 0.55Mpa, the spinning temperature of 60 ℃ and the spinning feeding rate of 6 m/min, wherein the spinning process is smooth without hairline basically, and the primary fiber is obtained by precipitation. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water ((the mass ratio is 50:15:35)).
(4) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is 65 ℃, 90 ℃ and 95 ℃ respectively; plasticizing stretching multiple is 4.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing at 65 ℃; the fiber is dried at 250 ℃ and stretched for 1.1 times in a heat pipe at 350 ℃ in sequence, so that the orientation degree and the crystallinity of the fiber are improved, and then the corresponding polysulfonamide colored yarn is obtained by oiling and rolling.
Example 2
(1) 1, 4-diaminoanthraquinone and diaminodiphenyl sulfone were mixed in a molar ratio of 95:5, adding the mixture into a proper amount of N-dimethylacetamide solvent, wherein the molar ratio of 3,3'-DDS and 4,4' -DDS in diaminodiphenyl sulfone is 1:3, a step of; the terephthaloyl chloride and isophthaloyl chloride mixture (molar ratio 1:0.01) with the same amount of the total materials of diaminoanthraquinone and diaminodiphenyl sulfone were added in four times within 2 hours, and the mass ratio of the first time, the second time, the third time and the fourth time was 60:30:8:2, adding enough ammonium carbonate to remove hydrogen chloride after 90% of reaction is finished, then continuously adding the rest of phenyl diformyl chloride to obtain color paste with extra-normal concentration, controlling the polymerization temperature and time at-5 ℃ in a pre-polymerization stage, controlling the polymerization stage at 31 ℃ for 1h, and controlling the solute mass concentration in the color paste at 23%.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:5, mixing the materials according to the mass ratio to obtain polysulfonamide colored spinning solution;
(3) Filtering polysulfonamide colored spinning solution, filtering at a filtering pressure of 0.37Mpa and defoaming, then carrying out wet spinning at a spinning pressure or a pressure of each spinning area of 0.67Mpa, a spinning temperature of 60 ℃ and a spinning feeding rate of 6.5 m/min, cooling at 30 ℃ for 2min after wet spinning to solidify into filaments, and obtaining the nascent fiber by precipitation without any broken filaments in a smooth spinning process. Wherein the aperture of the spinning nozzle is 0.04mm; wherein the precipitation solution is N-dimethylacetamide solution, the mass percentage concentration is 40 percent, and the temperature is 30 ℃.
(4) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is respectively 60 ℃, 90 ℃ and 95 ℃; plasticizing stretching multiple is 3.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing with water at 60 ℃; the fiber is dried at 270 ℃ and stretched 11.5 times in a heat pipe at 450 ℃ in sequence to improve the orientation degree and the crystallinity of the fiber, and then the corresponding polysulfonamide colored yarn is obtained by oiling and rolling.
Example 3
(1) 2, 6-diamino anthraquinone and diamino diphenyl sulfone are mixed according to the mole ratio of 0.5:99.5, 176.406g total, to a suitable amount of N-dimethylacetamide solvent, wherein the molar ratio of 3,3'-DDS, 4' -DDS in diaminodiphenyl sulfone is 1:3, a step of; the terephthaloyl chloride and isophthaloyl chloride mixture (molar ratio 1:0.2) with the same amount of total diaminoanthraquinone and diaminodiphenyl sulfone substances were added six times in 2 hours, and the mass ratio of the first time, the second time, the third time, the fourth time, the fifth time and the sixth time was 65:15:10:5:3:2, adding 95% of ammonia gas to remove hydrogen chloride after reaction, then continuously adding the rest of phenyl diformyl chloride to react to obtain color paste with extra-normal concentration, controlling the polymerization temperature and time at 20 ℃ in a prepolymerization stage, controlling the polymerization stage at 50 ℃ for 1h, and controlling the solute mass concentration in the color paste at 16.1% in a post-polymerization stage.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:1.5 mass percent to obtain polysulfonamide colored spinning solution;
(3) Filtering the polysulfonamide colored spinning solution, wherein the filtering pressure is 0.50Mpa, defoaming, then carrying out wet spinning at the spinning pressure or the pressure of each spinning area of 0.50Mpa, the spinning temperature of 60 ℃ and the spinning feeding rate of 5.6 per minute, smoothly removing the hairline during the spinning process, and precipitating to obtain the nascent fiber. Wherein the aperture of the spinning jet is 0.10mm, and the precipitation solution is a mixed solution of N-dimethylacetamide and water (50:15:35).
(4) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is 65 ℃, 90 ℃ and 95 ℃ respectively; plasticizing stretching multiple is 4.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing at 65 ℃; the fiber is dried at 230 ℃ and stretched for 1.2 times in a heat pipe at 350 ℃ in sequence, so that the orientation degree and the crystallinity of the fiber are improved, and then the corresponding polysulfonamide colored filaments are obtained by oiling and rolling.
Example 4
(1) Preparing a colored spinning solution: 1, 5-diamino-4, 8-dihydroxyanthraquinone and diaminodiphenyl sulfone are mixed according to a molar ratio of 0.5:99.5, adding into proper amount of N-dimethylacetamide solvent, wherein the mole ratio of 3,3'-DDS and 4,4' -DDS in diaminodiphenyl sulfone is 1:3, a step of; the same amount of the total materials of the diaminoanthraquinone and the diaminodiphenyl sulfone as that of the mixture of the terephthaloyl chloride and the isophthaloyl chloride (the mol ratio is 9:1) is added into the mixture of the diaminoanthraquinone and the diaminodiphenyl sulfone in two times in 2 hours, and the mass ratio of the first time to the second time is 19:1, introducing enough ammonia gas to remove hydrogen chloride before adding the monomers for the second time, then adding the rest phenyl diformyl chloride to react to obtain color paste with extra-normal concentration, controlling the polymerization temperature and time at-5 ℃ in a pre-polymerization stage, controlling the polymerization stage at 31 ℃ for 1h, and controlling the solute mass concentration in the color paste to be 16.1%.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:1 mass ratio to obtain polysulfonamide colored spinning solution;
(3) Filtering polysulfonamide colored spinning solution, filtering at a filtering pressure of 0.40Mpa and defoaming, then wet spinning at a spinning pressure or a pressure of each spinning area of 0.55Mpa, a spinning temperature of 60 ℃ and a spinning feeding rate of 5.3/min, wherein the spinning process is smooth without hairline basically, and precipitating to obtain the nascent fiber. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water (the mass ratio is 50:15:35).
(4) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is 65 ℃, 90 ℃ and 95 ℃ respectively; plasticizing stretching multiple is 4.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing at 65 ℃; the fiber is dried at 250 ℃ and stretched for 1.1 times in a heat pipe at 350 ℃ in sequence, so that the orientation degree and the crystallinity of the fiber are improved, and then the corresponding polysulfonamide colored yarn is obtained by oiling and rolling.
Example 5
(1) Preparing a colored spinning solution: 1, 5-diaminoanthraquinone and diaminodiphenyl sulfone are mixed according to a molar ratio of 20:80, adding into a proper amount of N-dimethylacetamide solvent, wherein the molar ratio of 3,3'-DDS and 4,4' -DDS in diaminodiphenyl sulfone is 1:3, a step of; the same amount of the total materials of the diaminoanthraquinone and the diaminodiphenyl sulfone as that of the mixture of the terephthaloyl chloride and the isophthaloyl chloride (the mol ratio is 9:1) is added into the mixture of the diaminoanthraquinone and the diaminodiphenyl sulfone in two times in 2 hours, and the mass ratio of the first time to the second time is 19:1, introducing enough ammonia gas to remove hydrogen chloride before adding the monomers for the second time, then adding the rest phenyl diformyl chloride to react to obtain color paste with extra-normal concentration, controlling the polymerization temperature and time at-5 ℃ in a pre-polymerization stage, controlling the polymerization stage at 31 ℃ for 1h, and controlling the solute mass concentration in the color paste to be 16.1%.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:100 mass percent to obtain polysulfonamide colored spinning solution;
(3) Filtering the polysulfonamide colored spinning solution, wherein the filtering pressure is 0.40Mpa, defoaming, then carrying out wet spinning at the spinning pressure or the pressure of each spinning area of 0.55Mpa, the spinning temperature of 60 ℃ and the spinning feeding rate of 5.5/min, and obtaining the nascent fiber by precipitation without hairline in the smooth spinning process. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water (the mass ratio is 50:15:35).
(4) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is 65 ℃, 90 ℃ and 95 ℃ respectively; plasticizing stretching multiple is 4.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing at 65 ℃; the fiber is dried at 250 ℃ and stretched for 1.1 times in a heat pipe at 350 ℃ in sequence, so that the orientation degree and the crystallinity of the fiber are improved, and then the corresponding polysulfonamide colored yarn is obtained by oiling and rolling.
Example 6
(1) Preparing a colored spinning solution: 1, 5-diaminoanthraquinone and diaminodiphenyl sulfone are mixed according to a molar ratio of 0.1:99.9, adding into proper amount of N-dimethylacetamide solvent, wherein the mole ratio of 3,3'-DDS and 4,4' -DDS in diaminodiphenyl sulfone is 1:3, a step of; the same amount of terephthaloyl chloride and isophthaloyl chloride mixture (molar ratio 9:1) as the total materials of diaminoanthraquinone and diaminodiphenyl sulfone was added in two portions over 2 hours, the mass ratio of the first time and the second time being 19:1, introducing enough ammonia gas to remove hydrogen chloride before adding the monomers for the second time, then adding the rest phenyl diformyl chloride to react to obtain the color paste with extra-normal concentration, controlling the polymerization reaction temperature and time at-20 ℃ in the first stage, controlling the polymerization reaction time at 31 ℃ in the second stage, and controlling the solute mass concentration in the color paste at 16.1 percent.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:1 mass ratio to obtain polysulfonamide colored spinning solution;
(3) Filtering polysulfonamide colored spinning solution, wherein the filtering pressure is 0.39Mpa, defoaming, and then carrying out wet spinning at the spinning pressure or the pressure of each spinning area of 0.55Mpa, the spinning temperature of 60 ℃ and the spinning feeding rate of 5.5/min, wherein the spinning process is smooth without hairline and precipitation, thus obtaining the nascent fiber. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide and water (the mass ratio is 50:15:35).
(4) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is 65 ℃, 90 ℃ and 95 ℃ respectively; plasticizing stretching multiple is 4.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing at 65 ℃; the fiber is dried at 250 ℃ and stretched 1.1 times in a heat pipe at 350 ℃ in sequence to improve the orientation degree and the crystallinity of the fiber, and then the fiber is oiled and wound.
Example 7
The preparation method of polysulfonamide colored fibers is the same as that of the embodiment 1, and the only difference is that: the 1, 5-diaminoanthraquinone light-emitting colouring monomer in example 1 was replaced by a molar ratio of 1:1, 5-diaminoanthraquinone, 2, 6-diaminoanthraquinone.
Example 8
The preparation method of polysulfonamide colored fibers is the same as that of the embodiment 1, and the only difference is that: 1, 5-diaminoanthraquinone and diaminodiphenyl sulfone were set to 50 in molar ratio: 50.
example 9
The preparation method of polysulfonamide colored fibers is the same as that of the embodiment 1, and the only difference is that: molar ratio of 3,3'-DDS, 4' -DDS 1:5.
example 10
The preparation method of polysulfonamide colored fibers is the same as that of example 1, and the only difference is that the molar ratio of 3,3'-DDS to 4,4' -DDS is 1:2.
example 11
Polysulfonamide colored fibers were prepared by the method disclosed in example 1, wherein the difference from example 1 is that: the preparation of the spinning slurry does not adopt an acid binding agent to treat the by-products after the prepolymerization.
Example 12
(1) Preparing colored color paste: 1, 5-diaminoanthraquinone and diaminodiphenyl sulfone are mixed according to a molar ratio of 10:46, respectively adding 553ml of N-dimethylacetamide solvent and 1047ml of N-dimethylacetamide solvent, placing the mixture in different reactors for prepolymerization, and carrying out prepolymerization on diaminoanthraquinone (3, 3'-DDS, 4' -DDS in diaminodiphenyl sulfone, the molar ratio of 1:3) and a mixture of terephthaloyl chloride and isophthaloyl chloride (the molar ratio of 9:1), introducing sufficient ammonia gas to remove hydrogen chloride, filtering, mixing, adding the rest of the mixture of the diacid chloride, and carrying out postpolymerization to obtain color paste with super-constant concentration; the amount of the mixture of the diformyl chloride and the total substance of the diaminoanthraquinone and the diaminodiphenyl sulfone is the same, and the mass ratio of the mixture of the diformyl chloride to the total substance of the diaminoanthraquinone and the diaminodiphenyl sulfone is 9:1, adding the mixture twice in 2 hours; wherein, the first time of adding the diformyl chloride mixture into a diaminoanthraquinone and diaminodiphenyl sulfone reactor for prepolymerization reaction respectively, and the molar ratio is 10:46; in the first stage, the polymerization reaction temperature and time are controlled at-5 ℃ for 1h, in the second stage, the temperature is controlled at 31 ℃ for 1h, and the mass concentration of solute in the color paste is controlled to be 17% according to the requirement.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:30 mass ratio to obtain polysulfonamide colored spinning solution;
(3) Filtering the polysulfonamide colored spinning solution, wherein the filtering pressure is 0.45Mpa, defoaming, then carrying out wet spinning at the spinning pressure or the pressure of each spinning area of 0.55Mpa, the spinning temperature of 60 ℃ and the spinning feeding rate of 6 m/min, wherein the spinning process is smooth without hairline basically, and the primary fiber is obtained by precipitation. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water (the mass ratio is 50:15:35).
(4) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is 65 ℃, 90 ℃ and 95 ℃ respectively; plasticizing stretching multiple is 4.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing at 65 ℃; the fiber is dried at 250 ℃ and stretched 1.1 times in a heat pipe at 350 ℃ in sequence to improve the orientation degree and the crystallinity of the fiber, and then the fiber is oiled and wound.
Example 13
(1) 1, 4-diaminoanthraquinone and diaminodiphenyl sulfone were mixed in a molar ratio of 95:5, respectively adding 553ml of N-dimethylacetamide solvent and 1047ml of N-dimethylacetamide solvent, placing the mixture in different reactors for prepolymerization, and carrying out prepolymerization on diaminoanthraquinone (3, 3'-DDS, 4' -DDS in diaminodiphenyl sulfone, the molar ratio of 1:3) and terephthaloyl chloride and isophthaloyl chloride mixture (the molar ratio of 9:1), introducing sufficient ammonia gas to remove hydrogen chloride, filtering, mixing, adding the diacid chloride for the second time, and carrying out postpolymerization to obtain color paste with super-constant concentration; the amount of the diformyl chloride is the same as the total amount of the diaminoanthraquinone and the diaminodiphenyl sulfone, and the mass ratio of the diformyl chloride added for the first time to the second time within 2 hours is 9:1, wherein the first time of adding the diformyl chloride is respectively added into a diaminoanthraquinone and diaminodiphenyl sulfone reactor for prepolymerization reaction, and the molar ratio is 95:5, a step of; in the first stage, the polymerization reaction temperature and time are controlled at-5 ℃ for 1h, in the second stage, the temperature is controlled at 31 ℃ for 1h, and the mass concentration of solute in the color paste is controlled to be 22% according to the requirement.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:5, mixing the materials according to the mass ratio to obtain polysulfonamide colored spinning solution;
(3) Filtering polysulfonamide colored spinning solution, filtering at a filtering pressure of 0.37Mpa and defoaming, then carrying out wet spinning at a spinning pressure or a pressure of each spinning area of 0.67Mpa, a spinning temperature of 60 ℃ and a spinning feeding rate of 6.5 m/min, cooling at 30 ℃ for 2min after wet spinning, and solidifying into filaments, wherein the spinning process is smooth and basically free of filaments, thus obtaining the nascent fiber. Wherein the aperture of the spinning nozzle is 0.04mm; wherein the precipitation solution is N-dimethylacetamide solution, the mass percentage concentration is 40 percent, and the temperature is 30 ℃.
(4) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is 65 ℃, 90 ℃ and 95 ℃ respectively; plasticizing stretching multiple is 4.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing at 65 ℃; the fiber is dried at 230 ℃ and stretched for 1.2 times in a heat pipe at 350 ℃ in sequence, so that the orientation degree and the crystallinity of the fiber are improved, and then the corresponding polysulfonamide colored filaments are obtained by oiling and rolling.
Example 14
(1) Preparing a colored spinning solution: 2, 6-diamino anthraquinone and diamino diphenyl sulfone are mixed according to the mole ratio of 0.5:99.5, respectively adding 553ml of N-dimethylacetamide solvent and 1047ml of N-dimethylacetamide solvent, placing the mixture in different reactors for prepolymerization, and carrying out prepolymerization on diaminoanthraquinone (3, 3'-DDS, 4' -DDS in diaminodiphenyl sulfone, the mol ratio of 1:3) and a mixture of terephthaloyl chloride and isophthaloyl chloride (mol ratio of 9:1), introducing enough ammonia gas to remove hydrogen chloride, filtering, mixing, adding the diacid chloride for the second time, and carrying out postpolymerization to obtain color paste with super-constant concentration; the amount of the diformyl chloride and the total substance of the diaminoanthraquinone and the diaminodiphenyl sulfone is the same, and the mass ratio of the diformyl chloride added for the first time to the second time is 9:1, wherein the first time of adding the diformyl chloride is respectively added into a diaminoanthraquinone reactor and a diaminodiphenyl sulfone reactor for prepolymerization reaction, and the molar ratio is 0.5:99.5; in the first stage, the polymerization reaction temperature and time are controlled at 20 ℃ for 1h, in the second stage, the temperature is controlled at 50 ℃ for 1h, and the mass concentration of solute in the color paste is controlled to be 17% according to the requirement.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:1.5 mass percent to obtain polysulfonamide colored spinning solution;
(3) Filtering the polysulfonamide colored spinning solution, wherein the filtering pressure is 0.50Mpa, defoaming, then carrying out wet spinning at the spinning pressure or the pressure of each spinning area of 0.50Mpa, the spinning temperature of 60 ℃ and the spinning feeding rate of 5.6 per minute, smoothly removing the hairline during the spinning process, and precipitating to obtain the nascent fiber. Wherein the aperture of the spinning jet is 0.10mm, and the precipitation solution is a mixed solution of N-dimethylacetamide and water (50:15:35).
(4) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is 65 ℃, 90 ℃ and 95 ℃ respectively; plasticizing stretching multiple is 4.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing at 65 ℃; the fiber is dried at 250 ℃ and stretched for 1.1 times in a heat pipe at 350 ℃ in sequence, so that the orientation degree and the crystallinity of the fiber are improved, and then the corresponding polysulfonamide colored yarn is obtained by oiling and rolling.
Example 15
(1) 1, 5-diamino-4, 8-dihydroxyanthraquinone and diaminodiphenyl sulfone are mixed according to a molar ratio of 0.5:99.5, respectively adding 553ml of N-dimethylacetamide solvent and 1047ml of N-dimethylacetamide solvent, placing the mixture in different reactors for prepolymerization, and carrying out prepolymerization on diaminoanthraquinone (3, 3'-DDS, 4' -DDS in diaminodiphenyl sulfone, the mol ratio of 1:3) and a mixture of terephthaloyl chloride and isophthaloyl chloride (mol ratio of 9:1), introducing enough ammonia gas to remove hydrogen chloride, filtering, mixing, adding the diacid chloride for the second time, and carrying out postpolymerization to obtain color paste with super-constant concentration; the amount of the diformyl chloride is the same as the total amount of the diaminoanthraquinone and the diaminodiphenyl sulfone, and the mass ratio of the diformyl chloride added for the first time to the second time within 2 hours is 9:1, wherein the first time of adding the diformyl chloride is respectively added into a diaminoanthraquinone reactor and a diaminodiphenyl sulfone reactor for prepolymerization reaction, and the molar ratio is 0.5:99.5; in the first stage, the polymerization reaction temperature and time are controlled at-5 ℃ for 1h, in the second stage, the temperature is controlled at 20 ℃ for 1h, and the mass concentration of solute in the color paste is controlled to be 17% according to the requirement.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:1 mass ratio to obtain polysulfonamide colored spinning solution;
(3) Filtering polysulfonamide colored spinning solution, wherein the filtering pressure is 0.40Mpa, defoaming, and then carrying out wet spinning at the spinning pressure or the pressure of each spinning area of 0.55Mpa, the spinning temperature of 60 ℃ and the spinning feeding rate of 5.3/min, wherein the spinning process is smooth without hairline and precipitation, thus obtaining the nascent fiber. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water (the mass ratio is 50:15:35).
(4) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is 65 ℃, 90 ℃ and 95 ℃ respectively; plasticizing stretching multiple is 4.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing at 65 ℃; the fiber is dried at 250 ℃ and stretched for 1.1 times in a heat pipe at 350 ℃ in sequence, so that the orientation degree and the crystallinity of the fiber are improved, and then the corresponding polysulfonamide colored yarn is obtained by oiling and rolling.
Example 16
(1) Preparing a colored spinning solution: 1, 5-diaminoanthraquinone and diaminodiphenyl sulfone are mixed according to a molar ratio of 20:80, respectively adding 553ml of N-dimethylacetamide solvent and 1047ml of N-dimethylacetamide solvent, placing the mixture in different reactors for prepolymerization, and carrying out prepolymerization on diaminoanthraquinone (3, 3'-DDS, 4' -DDS in diaminodiphenyl sulfone, the mol ratio of 1:3) and terephthaloyl chloride and isophthaloyl chloride mixture (mol ratio of 9:1), introducing sufficient ammonia gas to remove hydrogen chloride, filtering, mixing, adding the diacid chloride for the second time, and carrying out postpolymerization to obtain color paste with super-constant concentration; the amount of the diformyl chloride is the same as the total amount of the diaminoanthraquinone and the diaminodiphenyl sulfone, and the mass ratio of the diformyl chloride added for the first time to the second time within 2 hours is 9:1, wherein the first time of adding isophthaloyl dichloride into a diaminoanthraquinone reactor and a diaminodiphenyl sulfone reactor for prepolymerization reaction respectively, and the molar ratio is 20:80; in the first stage, the polymerization reaction temperature and time are controlled at-5 ℃ for 1h, in the second stage, the temperature is controlled at 31 ℃ for 1h, and the mass concentration of solute in the color paste is controlled to be 17% according to the requirement.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:100 mass percent to obtain polysulfonamide colored spinning solution;
(3) Filtering the polysulfonamide colored spinning solution, wherein the filtering pressure is 0.40Mpa, defoaming, then carrying out wet spinning at the spinning pressure or the pressure of each spinning area of 0.55Mpa, the spinning temperature of 60 ℃ and the spinning feeding rate of 5.5/min, and obtaining the nascent fiber by precipitation without hairline in the smooth spinning process. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide, calcium chloride and water (the mass ratio is 50:15:35).
(3) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is 65 ℃, 90 ℃ and 95 ℃ respectively; plasticizing stretching multiple is 4.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing at 65 ℃; the fiber is dried at 250 ℃ and stretched for 1.1 times in a heat pipe at 350 ℃ in sequence, so that the orientation degree and the crystallinity of the fiber are improved, and then the corresponding polysulfonamide colored yarn is obtained by oiling and rolling.
Example 17
(1) Preparing a colored spinning solution: 1, 5-diaminoanthraquinone and diaminodiphenyl sulfone are mixed according to a molar ratio of 0.1:99.9, respectively adding 553ml of N-dimethylacetamide solvent and 1047ml of N-dimethylacetamide solvent, placing the mixture in different reactors for prepolymerization, and carrying out prepolymerization on diaminoanthraquinone (3, 3'-DDS, 4' -DDS in diaminodiphenyl sulfone, the mol ratio of 1:3) and a mixture of terephthaloyl chloride and isophthaloyl chloride (mol ratio of 9:1), introducing enough ammonia gas to remove hydrogen chloride, filtering, mixing, adding the diacid chloride for the second time, and carrying out postpolymerization to obtain color paste with super-constant concentration; the amount of the diformyl chloride and the total substance of the diaminoanthraquinone and the diaminodiphenyl sulfone is the same, and the mass ratio of the diformyl chloride added for the first time to the second time is 9:1, wherein the first time of adding the diformyl chloride is respectively added into a diaminoanthraquinone reactor and a diaminodiphenyl sulfone reactor for prepolymerization reaction, and the molar ratio is 0.1:99.9; in the first stage, the polymerization reaction temperature and time are controlled at-20 ℃ for 1h, in the second stage, the temperature is controlled at 31 ℃ for 1h, and the mass concentration of solute in the color paste is controlled to be 17% according to the requirement.
(2) Mixing the obtained color paste with polysulfonamide unbleached pulp with the same mass concentration according to the following weight percentage of 1:1 mass ratio to obtain polysulfonamide colored spinning solution;
(3) Filtering polysulfonamide colored spinning solution, wherein the filtering pressure is 0.39Mpa, defoaming, and then carrying out wet spinning at the spinning pressure or the pressure of each spinning area of 0.55Mpa, the spinning temperature of 60 ℃ and the spinning feeding rate of 5.5/min, wherein the spinning process is smooth without hairline and precipitation, thus obtaining the nascent fiber. Wherein the aperture of the spinning jet is 0.06mm, and the precipitation solution is a mixed solution of N-dimethylacetamide and water (the mass ratio is 50:15:35).
(4) Sequentially carrying out supplementary solidification and multistage stretching on the spinning precipitate in a first plasticizing stretching bath tank, a second plasticizing stretching bath tank and a third plasticizing stretching bath tank, wherein the concentration of DMAc is sequentially decreased, and the temperature is 65 ℃, 90 ℃ and 95 ℃ respectively; plasticizing stretching multiple is 4.5 times; the flow direction of the supplementing liquid is opposite to the advancing direction of the silk bundle; pre-washing and washing at 65 ℃; the fiber is dried at 250 ℃ and stretched for 1.1 times in a heat pipe at 350 ℃ in sequence, so that the orientation degree and the crystallinity of the fiber are improved, and then the corresponding polysulfonamide colored yarn is obtained by oiling and rolling.
Example 18
The preparation method of polysulfonamide colored fibers is the same as that of example 12, and the only difference is that: 1, 5-diaminoanthraquinone and diaminodiphenyl sulfone were set to 50 in molar ratio: 50.
Comparative example 1
Comparative example 1 discloses a preparation method of polysulfonamide colored fiber, which is different from example 1 in that: when the colored paste is prepared, the non-dyed polysulfonamide fiber is further prepared without adding a color reaction monomer (namely, the molar ratio of the color reaction monomer to the diaminodiphenyl sulfone is 0:100).
Comparative example 2 (inorganic dye dyeing method)
A preparation method of polysulfonamide colored fibers comprises the following steps:
(1) Grinding: adding nano-scale inorganic pigment lead yellow into ball milling and dispersing, wherein the maximum particle diameter after ball milling is lower than 180nm;
(2) Preparing a dyeing solution: 4800ml of dimethylacetamide is put into a ball mill circulation system, the ball mill is started to circulate, 6g of inorganic pigment is added into the ball mill for circulation grinding in three times, and the mass ratio of the inorganic pigment to the N-dimethylacetamide solvent is 1:800, mixing and stirring, adding a dispersing agent, and placing the mixed solution on an ultrasonic oscillator for oscillation to obtain a uniform dyeing solution;
(3) Preparing a spinning solution: 113.50g of diaminodiphenyl sulfone is dissolved in 10670ml of N-dimethylacetamide solvent, cooled, 213.10g of isophthaloyl dichloride is added for low-temperature solution polymerization, calcium hydroxide is used for neutralization, polysulfonamide spinning solution is obtained, defoaming is carried out, wherein the mass percentage concentration of salt is 8%, and the mass percentage concentration of polysulfonamide is 20%;
(4) Mixing solution: adding the dyeing solution and the spinning solution into an extruder head for mixing, wherein the mass ratio of the dyeing solution to the spinning solution is 1:650, a step of;
(5) Filtering pressure is 0.80Mpa before spinning, wet spinning, finding out broken filaments and broken finger lines in the spinning process, and then stretching, washing, drying, curling, cutting and packaging to obtain polysulfonamide colored fibers. Wherein the wet spinning adopts a precipitation solution to treat into filaments, the precipitation solution is an N-dimethylacetamide solution, the mass percentage concentration of the solution is 40%, and the temperature is 30 ℃; the stretching temperature was 280℃and the stretching ratio was 2.5 times.
Comparative example 3 (organic dyeing method)
The polysulfonamide colorant was colored as described in example 1 with reference to CN202011083100.7, and the dye of comparative example 2 was replaced with an equivalent amount of 1, 5-diaminoanthraquinone as compared to the CN202011083100.7 regimen, and the dyed fiber was a colorless polysulfonamide fiber prepared in comparative example 1, consisting of the following steps:
A. deoiling: adding 8.5g/L sodium hydroxide into polysulfonamide fibers, degreasing for 20min at 95 ℃, washing with water, and drying;
B. pretreatment: placing the polysulfonamide fiber treated in the step A into an N-methyl pyrrolidone solvent, wherein the bath ratio is 1:15, soaking for 60min at 60 ℃; then washing for 30min at 80 ℃, and drying in an oven at 80 ℃ for later use;
C. Dyeing: b, placing the polysulfonamide fiber treated in the step B into high-temperature dye liquor for dyeing; the formula of the dye liquor comprises the following steps: 3% of 1, 5-diaminoanthraquinone, N-diethyl-3-methylbenzamide with the concentration of 30g/L and sodium chloride with the concentration of 30 g/L; dyeing conditions: ph=3 (acetic acid adjustment), temperature 140 ℃, time 60min, bath ratio 1:15;
D. post-treatment: placing the polysulfonamide fiber treated in the step C into 2g/L soap solution, washing for 30min, dehydrating and drying to obtain dyed polysulfonamide fiber.
Comparative example 4
Polysulfonamide colored fibers were prepared by the method disclosed in example 1, wherein the difference from example 1 is that: the polysulfonamide color paste is produced, and the polymerization temperature in the second stage is controlled at 80 ℃.
Comparative example 5
Polysulfonamide colored fibers were prepared by the method disclosed in example 1, wherein the difference from example 1 is that: the polysulfonamide colored color paste is produced, and the polymerization temperature in the first stage is controlled at-30 ℃.
Comparative example 6
Polysulfonamide colored fibers were prepared by the method disclosed in example 1, wherein the difference from example 1 is that: the polysulfonamide colored spinning solution is produced, and the temperature is controlled at 30 ℃ in the whole polymerization process.
Comparative example 7
Polysulfonamide colored fibers were prepared by the method disclosed in example 1, wherein the difference from example 1 is that: the polysulfonamide colored spinning slurry is generated, and the acid binding agent is replaced by equivalent diethylamine.
Comparative example 8
Polysulfonamide colored fibers were prepared by the method disclosed in example 12, wherein the difference from example 12 is that: the polysulfonamide color paste is produced, and the polymerization temperature in the second stage is controlled at 70 ℃.
Comparative example 9
Polysulfonamide colored fibers were prepared by the method disclosed in example 12, wherein the difference from example 12 is that: the polysulfonamide colored color paste is produced, and the polymerization temperature in the first stage is controlled at-30 ℃.
Comparative example 10
Polysulfonamide colored fibers were prepared by the method disclosed in example 12, wherein the difference from example 12 is that: the polysulfonamide colored spinning solution is produced, and the temperature is controlled at 30 ℃ in the whole polymerization process.
The polysulfonamide spinning solution and the polysulfonamide fiber prepared in the examples and the comparative examples are tested, wherein the light fastness grade adopts the standard of GB/T8426-1998 textile color fastness test light fastness-sunlight; the viscosity of the spinning solution adopts relative viscosity [ eta ]: the ratio of the dynamic viscosity of the spinning solution to the dynamic viscosity of the pure solvent at the same temperature is shown in Table 1:
TABLE 1 data relating to the properties of the spinning solutions and fibers of examples 1-11 and comparative examples 1-7
TABLE 2 data relating to the properties of the dope and fiber of examples 12-18 and comparative examples 8-10
/>
Conclusion of the test:
as can be seen from Table 1, the mass ratio of the color-forming reaction monomer to the diaminodiphenyl sulfone in examples 1 to 11 was within the range of: 0.1 to 100:0 to 99.9 mass ratio of polysulfonamide color paste to polysulfonamide unbleached paste is 1: when the viscosity is within the range of 1 to 30, the viscosity [ eta ] of the spinning solution is prepared: 2.3 to 2.80, the spinning solution has good spinnability, the color of the fiber can be regulated based on different color reaction monomers, and the spinning process has no broken filaments and broken finger lines, compared with the existing inorganic dye dyeing method, the invention obviously improves the phenomena of broken filaments and broken finger lines, and the relative strength and elongation at break performance indexes of the colored fiber prepared by the method of the invention in the embodiment 1 are obviously improved compared with the conventional pigment coloring of the comparative example 2 and the comparative example 3.
As can be seen from Table 1, the colored fibers prepared in examples 1 to 11 have a glass transition temperature in the range of 285℃to 310 ℃; the dynamic viscosity of the fiber is 25000-51000 centipoise; the relative strength of the fiber is in the range of 2.45cN/dtex to 3.55 cN/dtex; the breaking elongation of the fiber is 23-31%; the light color fastness is 3.5-4 grade; the washing fastness grade is 4-5.
As can be seen from Table 2, the mass ratio of the color-forming reaction monomer to the diaminodiphenyl sulfone in examples 12 to 18 was in the range of: 0.1 to 100:0 to 99.9 mass ratio of polysulfonamide color paste to polysulfonamide unbleached paste is 1: 1-30, preparing the viscosity [ eta ] of the spinning solution: 2.4 to 2.65, the spinning solution has good spinnability, and the glass transition temperature of the prepared colored fiber is in the range of 285 to 310 ℃; the dynamic viscosity of the fiber is 25000-50000 centipoise; the relative strength of the fiber is in the range of 2.80cN/dtex to 3.05 cN/dtex; the breaking elongation of the fiber is 25% -30%; the light color fastness is 3.5-4 grade; the washing fastness grade is 4-5. Wherein, different color forming effect is provided by different color forming reaction monomers, and the combination of different color forming reaction monomers can prepare a new color forming effect different from any color forming reaction monomers.
As can be seen from comparative examples 1 and 2, the dyeing scheme of the invention has a remarkable improvement in the relative strength and light fastness of the fiber compared with the conventional dyeing with inorganic dye, wherein the relative strength of the fiber is increased from 2.30cN/dtex to 3.55cN/dtex, the elongation at break of the fiber is increased to 31%, the filtration pressure before spinning is reduced from 0.8Mpa to 0.55Mpa, and the filtration energy consumption is greatly reduced.
As can be seen from comparative examples 1 and 3, the dyeing scheme of the present invention is significantly improved in both the relative strength and the light fastness grade of the fiber compared with the conventional organic dye dyeing, wherein the relative strength of the fiber is increased from 2.90cN/dtex to 3.55cN/dtex, the light fastness grade is increased from 3 grade to 4 grade, and the washing fastness grade is increased from 3.5 grade to 5 grade.
As is clear from comparative examples 1 and 4 and comparative examples 12 and 8, the second stage polymerization temperature was higher than 70℃and the molecular weight of the colored fibers was decreased due to the increase of side reactions and the decrease of polymerization degree, resulting in the decrease of spinnability, the occurrence of broken fingerline, the relative strength of fibers and the significant decrease of elongation at break of fibers; meanwhile, as is clear from comparative examples 1 and 5 and comparative examples 12 and 9, too low a polymerization temperature also affects the final polymerization degree, the relative strength of the fiber is lowered, and the polymerization temperature is in the range of-10 to 70 ℃, and the relative strength of the prepared colored fiber and the elongation at break of the fiber are in a good range. As is clear from comparative examples 1 and 6 and comparative examples 12 and 10, the relative strength of the colored fibers and the elongation at break of the fibers, which were not prepared through the low-temperature polymerization stage at 30℃or less, were significantly deteriorated.
As can be seen from comparative examples 1 and 11, the coloration schemes of the present invention provide a significant improvement in both the relative strength and elongation at break of the fibers over the non-acid binding agent scheme.
Comparative examples 1 and 7 show that the fibers prepared using the inorganic acid-binding agent have superior relative strength and elongation at break.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. A method of coloring a polymer, comprising:
mixing a color reaction monomer and diaminodiphenyl sulfone, and then reacting with phenyl diformyl chloride to obtain polysulfonamide color spinning solution color paste, or respectively pre-polymerizing the color reaction monomer and the diaminodiphenyl sulfone with the phenyl diformyl chloride, and mixing and reacting the pre-polymerized products of the pre-polymerization reaction to prepare polysulfonamide color paste; and mixing the polysulfonamide color paste with polysulfonamide natural color paste, and further spinning to obtain the colored polysulfonamide fiber.
2. The method for coloring polymers according to claim 1, wherein the preparation of the polysulfonamide colored spinning liquid color paste comprises the following steps:
S1101: dissolving a chromogenic reaction monomer and diaminodiphenyl sulfone in a polar organic solvent and uniformly mixing;
s1102: gradually adding phenyl diformyl chloride, and polymerizing to obtain polysulfonamide color paste.
3. The method for coloring polymers according to claim 1, wherein the preparation of the polysulfonamide colored spinning liquid color paste comprises the following steps:
s2101: dissolving a chromogenic reaction monomer and diaminodiphenyl sulfone in a polar organic solvent;
s2102: adding phenyl diformyl chloride into the mixed system in S2101 for multiple times, performing multiple times of prepolymerization, adding an acid binding agent after each time of prepolymerization, precipitating and separating a reaction product of the acid binding agent and a prepolymerization byproduct, continuing adding phenyl diformyl chloride, and polymerizing to obtain polysulfonamide color paste.
4. The method of claim 1, wherein the preparation of the polysulfonamide colorant spin dope comprises:
s3101: placing a chromogenic reaction monomer and diaminodiphenyl sulfone in two independent reactors, respectively adding a polar solvent for dissolution, adding phenyldicarboxyl chloride for the first time, and respectively polymerizing to obtain two prepolymer solutions;
s3102: mixing the two prepolymer solutions, adding phenyl diformyl chloride for the second time, performing post polymerization, adding an acid binding agent after polymerization, and precipitating and separating the acid binding agent and a hydrogen chloride product to obtain polysulfonamide color paste.
5. A spin paste for colored fibers, prepared by the method of claim 2 or 3, comprising a colored polymer and a polar organic solvent;
the colored polymer includes:
(III) and (IV) the two structural units are randomly distributed, aq contains anthraquinone functional groups, ac represents m-benzene or p-benzene functional groups, and DS contains diphenyl sulfone structural units.
6. A spinning solution for coloring fibers, which is characterized by being prepared by mixing the color paste of claim 5 with polysulfonamide natural color paste;
the colored polymer includes:
(III) and (IV) the two structural units are randomly distributed, aq contains anthraquinone functional groups, ac represents m-benzene or p-benzene functional groups, and DS contains diphenyl sulfone structural units.
7. A colored fiber prepared from the dope of claim 6, said colored fiber comprising two structural units (iii), (iv) randomly distributed:
wherein Aq comprises an anthraquinone functional group, ac is an m-or p-benzene functional group, and DS comprises a diphenyl sulfone structural unit.
8. A spin color paste for colored fibers, prepared by the method of claim 4, comprising a colored polymer and a polar organic solvent;
the general formula of the coloring polymer meets the following conditions:
Wherein p represents the number of a long chain prepolymer constituting a colored polymer, R p+1 Represents the p+1th long chain prepolymer, R 1 ，...，R p+1 To only includePrepolymers of units or comprising onlyA prepolymer of units, wherein Aq comprises anthraquinone functionality, ac represents m-or p-benzene functionality, and DS comprises diphenyl sulfone structural units.
9. A spinning solution for coloring fibers, which is characterized by being prepared by mixing the color paste of claim 8 with polysulfonamide natural color paste and comprising coloring polymers and polar organic solvents;
the general formula of the coloring polymer meets the following conditions:
wherein p represents the number of a long chain prepolymer constituting a colored polymer, R p+1 Represents the p+1th long chain prepolymer, R 1 ，...，R p+1 To only includePrepolymers of units or comprising onlyA prepolymer of units, wherein Aq comprises anthraquinone functionality, ac represents m-or p-benzene functionality, and DS comprises diphenyl sulfone structural units.
10. A colored fiber prepared from the dope of claim 9, wherein the colored fiber structure satisfies:
wherein p represents the number of a long chain prepolymer constituting a colored polymer, R p+1 Represents the p+1th long chain prepolymer, R 1 ，...，R p+1 To only includePrepolymers of units or comprising onlyA prepolymer of units, wherein Aq comprises anthraquinone functionality, ac represents m-or p-benzene functionality, and DS comprises diphenyl sulfone structural units.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311062542.7A CN117005056A (en) | 2023-08-22 | 2023-08-22 | Polymer coloring method, spinning color paste, spinning solution and colored fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311062542.7A CN117005056A (en) | 2023-08-22 | 2023-08-22 | Polymer coloring method, spinning color paste, spinning solution and colored fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117005056A true CN117005056A (en) | 2023-11-07 |
Family
ID=88565498
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311062542.7A Pending CN117005056A (en) | 2023-08-22 | 2023-08-22 | Polymer coloring method, spinning color paste, spinning solution and colored fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117005056A (en) |
-
2023
- 2023-08-22 CN CN202311062542.7A patent/CN117005056A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100531989B1 (en) | Process for producing meta-aromatic polyamide fiber | |
| CA2255686C (en) | Wet spinning process for aramid polymer containing salts and fiber produced from this process | |
| CN101735455B (en) | Method for preparing special aromatic polyoxadiazole and flame-retardant high-temperature resistant polyoxadiazole fiber thereof | |
| CN104119534B (en) | One birdss of the same feather flock together hydroxyl to phenylene Benzo-dioxazole polymer and its preparation and application | |
| CN103409854A (en) | Production method of carbon fiber | |
| WO2001061086A1 (en) | Meta-form wholly aromatic polyamide fiber and process for producing the same | |
| CN103113576B (en) | Batch polymerization method of aramid 1313 | |
| EP0246634B1 (en) | Heat resistant organic synthetic fibers and process for producing the same | |
| CA1118546A (en) | Wholly aromatic polyamide composition | |
| CN107814928B (en) | Modified polyisophthaloyl metaphenylene diamine easy to dye by cationic dye and preparation method and application thereof | |
| WO2021036574A1 (en) | Modified easily dyeable meta-aramid and preparation method therefor | |
| CN108048946B (en) | Hydrophilic flame-retardant polyester fiber material and preparation method thereof | |
| CN117005056A (en) | Polymer coloring method, spinning color paste, spinning solution and colored fiber | |
| CN116623309B (en) | Polymer coloring method, spinning color paste, spinning solution and colored fiber | |
| CN117004018A (en) | Polymer coloring method, spinning solution and colored fiber | |
| CN116837490A (en) | Polymer coloring method, spinning color paste, spinning solution and colored fiber | |
| CN110724262B (en) | Ternary light-resistant liquid crystal copolymer containing oxazole structure and preparation and application thereof | |
| CN100549248C (en) | The wet spinning process of improved aramid polymer containing salts | |
| CN116837483A (en) | Polymer coloring method, spinning solution and colored fiber | |
| CN116988184A (en) | Polymer coloring method, spinning color paste, spinning solution and colored fiber | |
| CN116837484A (en) | Polymer coloring method, spinning solution and colored fiber | |
| CN114059178A (en) | Simplified and improved process for producing acrylic fibers | |
| CN112135859A (en) | Multi-mixed composite salt monomer and multi-polybenzoxadiazole liquid crystal polymer with antioxidant stability and preparation and application thereof | |
| CN117966294A (en) | Fiber and preparation method thereof | |
| CN113355764B (en) | Method for preparing colored meta-aramid fiber by one-step method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |