CN116623309B - 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
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- CN116623309B CN116623309B CN202310896447.0A CN202310896447A CN116623309B CN 116623309 B CN116623309 B CN 116623309B CN 202310896447 A CN202310896447 A CN 202310896447A CN 116623309 B CN116623309 B CN 116623309B
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- monomer
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- polymer
- pmia
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- 239000000835 fiber Substances 0.000 title claims abstract description 140
- 238000009987 spinning Methods 0.000 title claims abstract description 117
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000004040 coloring Methods 0.000 title claims abstract description 47
- 229920000642 polymer Polymers 0.000 title claims description 62
- 239000000178 monomer Substances 0.000 claims description 128
- 238000006243 chemical reaction Methods 0.000 claims description 73
- 238000006116 polymerization reaction Methods 0.000 claims description 42
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 40
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 39
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical group ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 31
- LRMDXTVKVHKWEK-UHFFFAOYSA-N 1,2-diaminoanthracene-9,10-dione Chemical group C1=CC=C2C(=O)C3=C(N)C(N)=CC=C3C(=O)C2=C1 LRMDXTVKVHKWEK-UHFFFAOYSA-N 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 17
- 239000003495 polar organic solvent Substances 0.000 claims description 15
- 238000002166 wet spinning Methods 0.000 claims description 15
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 13
- 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 claims description 12
- 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 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 7
- 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 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 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 claims description 5
- 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 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 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 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- -1 polyisophthaloyl Polymers 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 43
- 238000004043 dyeing Methods 0.000 abstract description 40
- 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
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 118
- 239000000243 solution Substances 0.000 description 78
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 27
- 239000000975 dye Substances 0.000 description 26
- 239000002904 solvent Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000047 product Substances 0.000 description 17
- 238000005406 washing Methods 0.000 description 17
- 238000001035 drying Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 239000000049 pigment Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 8
- 239000001110 calcium chloride Substances 0.000 description 8
- 229910001628 calcium chloride Inorganic materials 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 230000018109 developmental process Effects 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 230000001112 coagulating effect Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000017525 heat dissipation Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001263 acyl chlorides Chemical class 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001491 aromatic compounds Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001412 amines Chemical class 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
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000012535 impurity Substances 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
- 239000011159 matrix material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 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
- 230000008901 benefit Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent 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
- 230000008713 feedback mechanism Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 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
- 239000012466 permeate Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 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
- 238000009941 weaving 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- 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
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- 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
- C08G69/28—Preparatory processes
-
- 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
- D01F1/06—Dyes
-
- 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 fiber, which belong to the technical field of textile printing and dyeing. 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
Poly (m-phenylene isophthalamide), PMIA for short, has excellent heat resistance, fiber decomposition temperature up to 500 ℃, long-term use temperature higher than 230 ℃, limiting oxygen index higher than 29, excellent high-temperature acid-base resistance, electrical insulation and good textile processing performance, is widely applied to the fields of protective clothing, high-temperature filter materials, electrical industry and composite materials, and is an indispensable strategic important material in national economic development. However, because the PMIA fiber has a regular molecular structure and high crystallinity and lacks active functional groups on a molecular chain, dye or pigment molecules are difficult to permeate into the structure, and the polymerized PMIA fiber molecules are difficult to combine with the dye or pigment molecules, so that the PMIA fiber and the prepared fabric are difficult to dye, and the PMIA fiber is used as a 'short board' in the field of high-temperature protection.
The existing coloring and dyeing method is to blend pigment or dye with natural color slurry (poly (m-phenylene isophthalamide) solution) of fiber. Pigments are generally inorganic or insoluble organic, exist in the form of particles in the dope fiber, are liable to clog micropores of a spinneret, have large filtration pressure and high breakage rate, and result in low relative strength and elongation at break of the colored fiber product. The dye is generally small organic molecules, cannot resist temperature, and is easy to change color, fade and the like in the high-temperature treatment and use process of fiber products.
In addition, during wet spinning, as the polar solvent and water can be mutually dissolved with dye molecules, the dye is easily dissolved and taken away by the solvent and water, the exhaustion rate is low, and even dyeing cannot be implemented; in addition, small organic molecule dyes are typically dyed in fibers, yarns or fabrics in special solutions containing the dye and specific chemical materials. Dye molecules are immobilized on the fibers by physical bonding, such as absorption, diffusion or adhesion, at a certain temperature and pressure. The bond between the dye molecules and the fibers depends on the physical bond between the dye molecules and the fibers used, for example, PMIA fibers tend to fade or change color due to the weak physical bond between themselves and the dye molecules. In addition, dyeing needs to be performed in a solvent, is energy-consuming, and generates a large amount of wastewater and waste residues.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a polymer coloring method, 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 of a dyed fiber product, poor washing resistance and poor light resistance of a spinneret, and the problems of a large amount of waste water and waste residues generated by printing and dyeing and environmental pollution of the prior art.
The aim of the invention is mainly realized by the following technical scheme:
a method of coloring a polymer comprising the steps of:
step 1: respectively carrying out prepolymerization reaction on a color reaction monomer and a first monomer with a second monomer, and mixing and reacting a prepolymerization product of the prepolymerization reaction to prepare poly m-phenylene isophthalamide color paste; wherein the mass ratio range of the substances of the color reaction monomer and the first monomer is as follows: 0.1-100: 0-99.9;
step 2: mixing the prepared poly m-phenylene isophthalamide color paste with poly m-phenylene isophthalamide unbleached pulp to prepare colored spinning solution, and carrying out pre-spinning slurry pretreatment;
step 3: carrying out wet spinning and precipitation on the colored spinning solution subjected to pretreatment in the step 2 to obtain nascent fibers;
Step 4: and (3) carrying out post-treatment on the nascent fiber obtained in the step (3) to obtain the poly (m-phenylene isophthalamide) coloring yarn.
Preferably, the preparation of the poly m-phenylene isophthalamide color paste in the step 1 comprises the following steps:
s101: placing a chromogenic reaction monomer and a first monomer in two independent reactors, respectively adding a polar solvent for dissolution, adding a second monomer for the first time, and respectively polymerizing to obtain two prepolymer solutions;
s102: mixing the two prepolymer solutions, adding a second monomer for polymerization reaction, adding an acid binding agent after polymerization, and precipitating and separating the acid binding agent and a hydrogen chloride product to obtain color paste.
Preferably, the ratio of the amount of the substances of the color reaction monomer to the first monomer in step 1 is in the range of: 0.1-100: 0-99.9; the mass ratio of the poly m-phenylene isophthalamide color paste to the poly m-phenylene isophthalamide unbleached paste is 1:1-100.
Preferably, the chromogenic reaction monomer is a compound containing two primary amino groups; preferably, the chromogenic reaction monomer is an aromatic compound containing two primary amino groups; preferably, the chromogenic reaction monomer is a diaminoanthraquinone.
Preferably, the diamino anthraquinone is one or more of 1, 4-diamino anthraquinone, 1, 5-diamino anthraquinone, 2, 6-diamino anthraquinone, 1, 5-diamino-4, 8-dihydroxy anthraquinone, 1, 2-diamino anthraquinone and 1, 8-diamino anthraquinone.
A spinning color paste for coloring fiber comprises coloring polymer and polar organic solvent, and is used for preparing spinning solution;
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 of (I) or comprising onlyA prepolymer of units of (II), wherein Aq comprises an anthraquinone functionality.
Preferably, the number ratio of the two structural units (I) and (II) is as follows: 0 to 99.9:0.1 to 100.
A spinning solution for coloring fiber comprises coloring 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 of (I) or comprising onlyA prepolymer of units (II), aq comprising an anthraquinone functionality.
Preferably, the viscosity [ η ] of the dope is: 2.08 to 2.43.
A colored fiber prepared by the above-mentioned polymer coloring method, said colored fiber comprising a polymer having the general formula:；
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 of (I) or comprising onlyA prepolymer of units of (II), aq comprising anthraquinone functionality;
the dynamic viscosity of the colored fiber is 34000-45000/centipoise.
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 the polymer to copolymerize to form the colored polymer through a certain chemical reaction, which is different from the mechanism of blending coloring and graft copolymerization coloring. The color-developing 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 has small filtration pressure, low breakage rate, high relative strength and high elongation at break of the dyed fiber and greatly improves the physical properties of colored fiber products compared with the existing fiber coloring method using particle pigments; 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) The invention adopts the chromogenic monomer and PMIA raw materials to prepare PMIA color paste containing high-concentration chromogenic units, and prepares spinning solution by mixing the PMIA color paste and PMIA unbleached paste according to different proportions, thereby improving the influence on the integral spinnability of the spinning solution when more chromogenic reaction monomers exist, flexibly preparing PMIA dyed fibers with different concentrations and improving the applicability; meanwhile, by synthesizing PMIA color paste, the synthesis reaction scale and the synthesis amount of the colored spinning solution can be reduced, and the PMIA dyeing cost is further reduced.
(3) The invention adopts the steps of respectively prepolymerizing m-phenylenediamine and aminoanthraquinone with acyl chloride raw materials in an independent system, and then mixing and reacting the two prepolymerized raw materials to prepare PMIA color paste containing high-concentration color development units, wherein PMIA molecules are diblock products of the m-phenylenediamine and the aminoanthraquinone respectively. The PMIA color paste prepared by the method has more amino anthraquinone color development units and has higher color forming effect as color paste.
(4) 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.
(5) The invention forms a high molecular chain through the polymerization of the chromogenic monomer, and the high molecular chain is dispersed in a resin matrix at a molecular level, so that the dispersion is uniform, the tinting strength is strong, the dosage of the monomer is small, and the dyeing cost can be saved; the existing blending coloring adjusts the color and shade of the coloring through the addition amount of the pigment, the pigment exists in the polymer in the form of particles, the coloring power is poor, and the required addition amount is large.
(6) 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 designate like parts throughout the drawings;
FIG. 1 is a process flow chart of the three-step color paste method of the 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.
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 breakage 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 polymer main chain is dissolved in a solvent system to form an in-phase solution, so that the defects that in the prior art, the filtering pressure of pigment dyeing on PMIA dyeing is low, the breakage rate is low, and the relative strength and the breakage elongation of the dyed fiber are low are overcome; on the other hand, the color reaction monomer participates in macromolecular chain formation and is dispersed in the resin matrix at a molecular level, so that PMIA is dyed by the organic micromolecule dye, and the color reaction monomer is more uniform in dispersion, stronger in tinting strength, more stable in effect and longer in tinting time.
Meanwhile, in order to further reduce PMIA dyeing cost, PMIA color paste containing a high-concentration color development unit is prepared, when in use, the PMIA color paste and PMIA natural color paste are mixed according to a design proportion, and PMIA fibers with different color depths are obtained after spinning, so that applicability is improved; meanwhile, the synthesis reaction scale and the synthesis amount of the colored spinning solution can be reduced, so that the PMIA dyeing cost is reduced.
Applicants' studies found that: in the PMIA macromolecule chain forming system with the color reaction monomer, the molecular weight of the color reaction monomer (such as amino anthraquinone) is larger, the reactivity is lower than that of m-phenylenediamine which is a PMIA raw material, and the color reaction monomer and the PMIA macromolecule with the color reaction unit are difficult to have larger polymerization degree and molecular weight because of the steric hindrance of the color reaction monomer and the agglomeration synthesis chain containing acyl chloride group are inhibited, so that the mechanical property of the PMIA fiber obtained by spinning is directly influenced; meanwhile, as the activity of the color reaction monomer and the m-phenylenediamine in the competition reaction is weaker, the number of the color reaction monomer actually participating in the reaction is smaller, the number of the color development units on the PMIA polymer is smaller, and the color forming effect of the prepared PMIA color paste is poorer when the prepared PMIA color paste is diluted.
Further, in order to avoid the influence of m-phenylenediamine on aminoanthraquinone, more aminoanthraquinone color development units are arranged on PMIA polymers, so that the PMIA color paste containing high-concentration color development units is prepared by respectively carrying out prepolymerization reaction on m-phenylenediamine and aminoanthraquinone with acyl chloride raw materials in independent systems and then mixing and reacting the two prepolymerized raw materials, wherein PMIA molecules are diblock products of the m-phenylenediamine and the aminoanthraquinone respectively. The PMIA color paste prepared by the method has more amino anthraquinone color development units and has higher color forming effect as color paste.
The invention discloses a high polymer coloring method, which comprises the following steps:
step 1: mixing a color reaction monomer and a first monomer, and adding a second monomer for reaction for two or more times to obtain a color spinning solution color paste of poly m-phenylene isophthalamide; wherein the mass ratio range of the substances of the color reaction monomer and the first monomer is as follows: 0.1-100: 0-99.9;
step 2: mixing the prepared PMIA color paste with PMIA 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 PMIA colored spinning solution subjected to pretreatment in the step 2 to obtain nascent fibers;
step 4: and (3) carrying out post-treatment on the nascent fiber obtained in the step (3) to obtain PMIA colored silk.
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 monomer is used as one of reactants, and is copolymerized with other monomers (such as a first monomer or a second monomer) of the synthetic 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.
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 PMIA fiber to a PMIA polymer main chain in the reaction, thereby realizing the direct preparation of the colored fiber by the PMIA spinning process, and the fibers 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. In contrast, if the fibers are spun from the PMIA natural color pulp, and then dyed after spinning or weaving, a dyeing process is added, and the bath used in the dyeing process is also treated and then discharged. Compared with the prior art, the invention has no dyeing wastewater, and reduces wastewater discharge after water treatment.
Specifically, the method comprises the following steps:
respectively dissolving a chromogenic reaction monomer and a first monomer for preparing the poly (m-phenylene isophthalamide) in a polar organic solvent; the method comprises the steps of (1) adding a color reaction monomer and a first monomer into different containers while stirring to perform prepolymerization on a second monomer for preparing the poly (m-phenylene isophthalamide); mixing the two pre-polymerized products, adding a second monomer for the second time, and performing post-polymerization to obtain PMIA color paste.
It should be noted that; and respectively preparing two pre-polymerized products from the chromogenic reaction monomer and the first monomer and the second monomer in different containers, wherein the two pre-polymerized products respectively comprise a first monomer-second monomer structural unit and a chromogenic reaction monomer-second monomer structural unit.
Specifically, the color paste polymerization method comprises a three-step color paste polymerization method.
Specifically, as shown in fig. 1, illustratively, step 1 includes:
s101: placing a chromogenic reaction monomer and a first monomer in two independent reactors, respectively adding a polar solvent for dissolution, adding a second monomer for the first time, and respectively polymerizing to obtain two prepolymer solutions;
s102: mixing the two prepolymer solutions, adding a second monomer for the second time after mixing, polymerizing, adding an acid binding agent after polymerizing, and precipitating and separating the acid binding agent and a hydrogen chloride product to obtain color paste.
Specifically, the first monomer comprises an amino group and the second monomer comprises a formyl group.
Preferably, the first monomer is m-phenylenediamine and the second monomer is m-phthaloyl 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.
Illustratively, m-phenylenediamine is used as the first monomer, and diaminoanthraquinone (of the formula NH 2 -Aq-NH 2 ) For the example of the color reaction monomer and isophthaloyl dichloride as the second monomer, the first monomer, the color reaction monomer and the insufficient amount of the second monomer in S101 are reacted as follows:
；
wherein R represents a first monomer or a reactive chromonic unit other than an amino group;represents a first monomer or reactive chromonic unit; m represents the number of the polymetaphthaloyl structures in the long chain prepolymer or the second monomer is consumed at S101.
Specifically, taking the second monomer as isophthaloyl dichloride as an example, the main reaction equation of S102 satisfies:
；
Wherein p represents the amount of the second monomer consumed for preparing one PMIA polymer at S102;representation of S101 preparationThe p+1th long-chain prepolymer involved in the S102 reaction may be one comprising +.>A prepolymer of units (I) or comprising only +.>A prepolymer of units (II); where Aq is the unit of the chromogenic reaction monomer comprising an anthraquinone structure.
Preferably, the polymerization reaction temperature in S101 is-20 ℃, and PMIA molecules have larger viscosity average molecular weight and better mechanical strength in the range; the reaction time is 0.05h to 1h.
Further preferably, the polymerization reaction temperature in S101 is-5-20 ℃; for example, it may be-20 ℃, -15 ℃, -10 ℃, -5 ℃, 0 ℃, 5 ℃, 10 ℃, 15 ℃ and 20 ℃.
Preferably, the polymerization temperature in S102 is 20℃to 50℃such as 20℃25℃30℃35℃40℃45℃50 ℃. In S102, the polymerization temperature is higher than 50 ℃, the linearity of PMIA 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, S102, the reaction time is 0.05 h-2 h.
Specifically, S101 and S102 are less than 0.1h, and the reaction is insufficient; s101 exceeds 1h, S102 exceeds 2h, side reactions are increased, the molecular weight of the polymer is affected, and the efficiency is low.
Preferably, the polymerization temperature is monitored, and the feed rate is adjusted according to the polymerization temperature to ensure that the polymerization temperature does not exceed the set temperature range.
Further preferably, in the polymerization reaction temperature monitoring, a temperature control feedback mechanism for the continuous feeding device is arranged, so that the automatic feeding of the polymerization reaction temperature in a controllable range is realized by automatically adjusting the feeding rate according to the temperature.
Specifically, the temperature is higher than a preset target temperature, the feeding is reduced or stopped, and the heat dissipation rate of a heat dissipation device on the reactor is increased (such as the cooling water temperature is reduced and the water flow speed is increased); the temperature is lower than the preset target temperature, the feeding speed is improved, the heat dissipation rate of a heat dissipation device on the reactor is reduced, and a heating device is opened for heating if necessary, so that the feeding quantity is adjusted by utilizing temperature feedback.
Specifically, the mass ratio of the chromogenic reaction monomer in the chromogenic reaction monomer and the first monomer ranges from: 0.1% -100%.
Specifically, the polar organic solvent in step S101 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 60 ℃ and does not react with any raw material monomer.
Specifically, in the step S102, the mass concentration of PMIA in the poly (m-phenylene isophthalamide) color paste is 17% -22%.
On the one hand, PMIA molecules with color reaction monomers are contained in PMIA colored color paste polymerized to form PMIA colored color paste, and the color of the corresponding color reaction monomers is presented after spinning based on the color reaction monomers; 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.
Specifically, the reactor for obtaining the color slurry of poly (m-phenylene isophthalamide) (PMIA) can use various types of reactors, which have strong material mixing functions, such as a vertical or horizontal kettle type reactor, a screw reactor, and 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 to 50 KW/cube, the stirring speed is 100rpm to 3000rpm, and the stirring paddles can be selected from various types 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 composite structure stirring paddles.
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 of the second monomer, substances in different radial areas inside the reaction vessel are uniformly mixed, namely radial mass transfer is realized; on the other hand, when the axial flow brought by stirring can meet the requirement of feeding the second monomer, substances in axially different areas inside the reaction vessel are uniformly mixed, namely, 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, step 101 includes: neutralizing and filtering the prepolymer solution before mixing; the pretreatment of the slurry before spinning in the step 2 comprises the following steps: 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, triethylamine and tetraethyl ethylenediamine.
Specifically, the colored polymer in the colored spinning solution prepared by the invention has good solubility, good fluidity during filtration, and the filtration pressure is 0.3-0.5 mpa.
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 solution to be filtered, the filtration speed and the content of insoluble impurities in the solution, and inorganic dye in the prior art is insoluble in the solution to be filtered, so that agglomeration is easy to occur 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, in the step 2, the mass ratio of PMIA color paste to PMIA unbleached paste is 1:1-100, so that better spinnability is realized.
Specifically, the spinning pressure of the wet spinning in the step 3 is set to be 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 and 2.0MPa; the spinning temperature is 5-40 ℃, such as 5 ℃, 6 ℃, 8 ℃, 10 ℃, 12 ℃, 14 ℃, 15 ℃, 18 ℃, 20 ℃, 22 ℃, 24 ℃, 25 ℃, 28 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃ and 40 ℃; 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.
The addition of alcohol or calcium chloride to the solution of PMIA fibers and polar organic solvent helps to reduce the solubility of PMIA 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: 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= (5-30): (0-20): (70:50).
It will be appreciated that the effect of plasticising and stretching is: under the action of plasticizing liquid, the polymers are swelled to a certain extent under the action of solvent, so that the polymers can slide mutually to a certain extent under the action of external force, and the aim of stretching the molecules in the fibers along the axial direction of the fibers is fulfilled.
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.
The invention discloses a spinning color paste of colored fibers, which comprises colored polymers and a polar organic solvent, wherein the colored polymers and the polar organic solvent 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 of (I) or comprising onlyA prepolymer of units of (II), wherein Aq comprises an anthraquinone functionality.
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 of colored fibers, which 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 of (I) or comprising onlyA prepolymer of units (II), aq comprising an anthraquinone functionality.
Specifically, the long-chain prepolymer constituting the colored polymer is the same or different in the kind of constituent units.
Preferably, the concentration of PMIA colored polymer mass in the spinning solution is 17-22%.
Preferably, the viscosity [ η ] of the dope is: 2.08 to 2.43.
[ eta ] represents the relative viscosity, the dynamic viscosity of spinning solution and the dynamic viscosity ratio of the solvent in the spinning solution.
Specifically, the polar organic solvent may be any one of N-dimethylacetamide, dimethylformamide (DMF), and N-methylpyrrolidone.
Specifically, the mass ratio of the chromogenic reaction monomer to the first monomer ranges from: 0.1-100: 0-99.9, and the mass ratio of PMIA color paste to PMIA unbleached pulp is 1:1-100.
In one particular embodiment of the present invention, a colored fiber is disclosed comprising a fiber having the general formula:；
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 of (I) or comprising onlyA prepolymer of units (II), aq comprising an anthraquinone functionality.
Specifically, the long-chain prepolymer constituting the colored polymer is the same or different in the kind of constituent units.
Optionally, the colored fibers are prepared by the polymer coloring method.
Specifically, PMIA colored spinning solution is prepared by reacting a colored reaction monomer, a first monomer and a second monomer, and colored spinning solution is further spun to obtain colored fibers.
Specifically, the first monomer comprises an amino group and the second monomer comprises a formyl group.
Preferably, the first monomer is m-phenylenediamine and the second monomer is m-phthaloyl 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, one or more of 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 2, 6-diaminoanthraquinone, 1, 5-diamino-4, 8-dihydroxyanthraquinone, 1, 2-diaminoanthraquinone, 1, 8-diaminoanthraquinone may be selected.
Specifically, the hydrodynamic viscosity of spinning solution of the fiber is 34000-45000/centipoise; the glass transition temperature of the colored fiber is 270-275 ℃; the relative strength of the fiber is 4.0-4.80 cN/dtex; the breaking elongation of the fiber is 25% -30%; the light fastness is 4-5 grades; the washing fastness grade is 4-5.
In order to better illustrate the present invention, the following examples and comparative examples are further provided.
Example 1
(1) Preparing colored color paste: 1, 5-diaminoanthraquinone and m-phenylenediamine are mixed according to a molar ratio of 10:46, respectively adding 553ml of N-dimethylacetamide solvent and 1047ml of N-dimethylacetamide solvent, placing in different reactors for prepolymerization, introducing enough ammonia gas to remove hydrogen chloride after the prepolymerization of diaminoanthraquinone and m-phenylenediamine, filtering, mixing, adding m-phthaloyl chloride for the second time, and performing a post-polymerization to obtain color paste with super-constant concentration; the amount of the total substances of the isophthaloyl dichloride, the diaminoanthraquinone and the m-phenylenediamine is the same, and the mass ratio of the first time to the second time of adding the isophthaloyl dichloride is 9:1, and the isophthaloyl dichloride is added twice in 2 hours; wherein, the first time of adding isophthaloyl dichloride into a reactor of diaminoanthraquinone and m-phenylenediamine respectively for prepolymerization, 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 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 PMIA unbleached pulp with the same mass concentration according to the following weight percentage of 1:30 mass percent to obtain PMIA colored spinning solution.
(3) Filtering PMIA colored spinning solution, filtering at 0.45Mpa and defoaming, then wet spinning at 20 ℃ and spinning feeding rate of 6 m/min under the spinning pressure or the pressure of each spinning area of 0.55Mpa, wherein the spinning process is smooth without filoplume, and the nascent 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 45:25:30).
(4) And (3) plasticizing and stretching the nascent fiber by 3 times, washing with water, drying at 120 ℃ and performing high-temperature heat treatment at 370 ℃ to directly obtain the corresponding PMIA colored silk.
Example 2
(1) 1, 4-diaminoanthraquinone and m-phenylenediamine are mixed according to 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, introducing enough ammonia gas to remove hydrogen chloride after the prepolymerization of diaminoanthraquinone and m-phenylenediamine, filtering, mixing, adding m-phthaloyl chloride for the second time, and performing post polymerization to obtain color paste with super-constant concentration; the amount of the total substances of the isophthaloyl dichloride, the diaminoanthraquinone and the m-phenylenediamine is the same, and the mass ratio of the first and the second isophthaloyl dichloride is 9:1 in 2 hours, wherein the first isophthaloyl dichloride is respectively added into the reactor of the diaminoanthraquinone and the m-phenylenediamine for prepolymerization, 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 20 ℃ 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 PMIA unbleached pulp with the same mass concentration according to the following weight percentage of 1:5 mass ratio to obtain PMIA colored spinning solution.
(3) Filtering PMIA colored spinning solution, filtering at a filtering pressure of 0.37Mpa and defoaming, then wet spinning at a spinning pressure or a pressure of each spinning area of 0.67Mpa, a spinning temperature of 26 ℃ 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 without any broken filaments in a smooth spinning process. Wherein the aperture of the spinning nozzle is 0.04mm; wherein the coagulating bath is an N-dimethylacetamide solution, the mass percentage concentration of the coagulating bath is 40 percent, and the temperature is 30 ℃.
(4) And (3) plasticizing and stretching the nascent fiber by 2.5 times, washing, drying at 125 ℃ and performing high-temperature heat treatment at 370 ℃ to directly obtain the corresponding PMIA colored silk.
Example 3
(1) Preparing a colored spinning solution: 2, 6-diaminoanthraquinone and m-phenylenediamine are mixed according to the molar ratio of 0.5:99.5, respectively adding 553ml of N-dimethylacetamide solvent and 1047ml of N-dimethylacetamide solvent, placing in different reactors for prepolymerization, introducing enough ammonia gas to remove hydrogen chloride after the prepolymerization of diaminoanthraquinone and m-phenylenediamine, filtering, mixing, adding m-phthaloyl chloride for the second time, and carrying out the post-polymerization to obtain color paste with super-constant concentration; the amount of the total substances of the isophthaloyl dichloride, the diaminoanthraquinone and the m-phenylenediamine is the same, the mass ratio of the first time to the second time of adding the isophthaloyl dichloride is 9:1, wherein the first time of adding the isophthaloyl dichloride is respectively added into a reactor of the diaminoanthraquinone and the m-phenylenediamine for prepolymerization, 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 PMIA unbleached pulp with the same mass concentration according to the following weight percentage of 1: mixing in a mass ratio of 1.5 to obtain PMIA colored spinning solution.
(3) Filtering PMIA colored spinning solution, filtering at 0.50Mpa and defoaming, then wet spinning at 22 ℃ and spinning feeding rate of 5.6/min under the spinning pressure or the pressure of each spinning area of 0.50Mpa, wherein the spinning process is smooth without filoplume, and the nascent fiber is obtained by precipitation. Wherein the aperture of the spinning jet is 0.10mm, and the precipitation solution is a mixed solution of N-dimethylacetamide and water (45:25:30).
(4) And (3) plasticizing and stretching the nascent fiber by 2.5 times, washing with water, drying at 120 ℃ and performing high-temperature heat treatment at 370 ℃ to directly obtain the corresponding PMIA colored silk.
Example 4
(1) 1, 5-diamino-4, 8-dihydroxyanthraquinone and m-phenylenediamine are mixed according to the molar ratio of 0.5:99.5, respectively adding 553ml of N-dimethylacetamide solvent and 1047ml of N-dimethylacetamide solvent, placing in different reactors for prepolymerization, introducing enough ammonia gas to remove hydrogen chloride after the prepolymerization of diaminoanthraquinone and m-phenylenediamine, filtering, mixing, adding m-phthaloyl chloride for the second time, and carrying out the post-polymerization to obtain color paste with super-constant concentration; the amount of the total substances of the isophthaloyl dichloride, the diaminoanthraquinone and the m-phenylenediamine is the same, and the mass ratio of the first and the second isophthaloyl dichloride is 9:1 in 2 hours, wherein the first isophthaloyl dichloride is respectively added into the reactor of the diaminoanthraquinone and the m-phenylenediamine for prepolymerization, 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 PMIA (PMIA) unbleached pulp with the same mass concentration according to the mass ratio of 1:1 to obtain PMIA colored spinning solution.
(3) Filtering PMIA colored spinning solution, filtering at 0.40Mpa and defoaming, and wet spinning at 20 deg.C and 5.3/min at 0.55Mpa in spinning pressure or spinning area to obtain 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 45:25:30).
(4) And (3) plasticizing and stretching the nascent fiber by 2.5 times, washing with water, drying at 120 ℃ and carrying out 365 ℃ high-temperature heat treatment to directly obtain the corresponding PMIA colored silk.
Example 5
(1) Preparing a colored spinning solution: 1, 5-diaminoanthraquinone and m-phenylenediamine are mixed according to a molar ratio of 20:80, respectively adding 553ml of N-dimethylacetamide solvent and 1047ml of N-dimethylacetamide solvent, placing in different reactors for prepolymerization, introducing enough ammonia gas to remove hydrogen chloride after the prepolymerization of diaminoanthraquinone and m-phenylenediamine, filtering, mixing, adding m-phthaloyl chloride for the second time, and performing a post-polymerization reaction to obtain color paste with super-constant concentration; the amount of the total substances of the isophthaloyl dichloride, the diaminoanthraquinone and the m-phenylenediamine is the same, and the mass ratio of the first and the second isophthaloyl dichloride is 9:1 in 2 hours, wherein the first isophthaloyl dichloride is respectively added into a reactor of the diaminoanthraquinone and the m-phenylenediamine for prepolymerization, 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 20 ℃ for 1h, and the mass concentration of solute in the color paste is controlled to be 17% according to the requirement.
(2) And mixing the obtained color paste with PMIA (PMIA) unbleached pulp with the same mass concentration according to the mass ratio of 1:100 to obtain PMIA colored spinning solution.
(3) Filtering PMIA colored spinning solution, filtering at 0.40Mpa and defoaming, then wet spinning at 25 ℃ and spinning feeding rate of 5.5/min under the spinning pressure or the pressure of each spinning area of 0.55Mpa, wherein the spinning process is smooth without filoplume, and the nascent 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 45:25:30).
(3) And (3) plasticizing and stretching the nascent fiber, washing with water, drying at 120 ℃ and performing 370 mu high-temperature heat treatment to directly obtain the corresponding PMIA colored silk.
Example 6
(1) Preparing a colored spinning solution: 1, 5-diaminoanthraquinone and m-phenylenediamine are mixed according to the molar ratio of 0.1:99.9, respectively adding 553ml of N-dimethylacetamide solvent and 1047ml of N-dimethylacetamide solvent, placing in different reactors for prepolymerization, introducing enough ammonia gas to remove hydrogen chloride after the prepolymerization of diaminoanthraquinone and m-phenylenediamine, filtering, mixing, adding m-phthaloyl chloride for the second time, and carrying out the post-polymerization to obtain color paste with super-constant concentration; the amount of the total substances of the isophthaloyl dichloride, the diaminoanthraquinone and the m-phenylenediamine is the same, the mass ratio of the first time to the second time of adding the isophthaloyl dichloride is 9:1, wherein the first time of adding the isophthaloyl dichloride is respectively added into a reactor of the diaminoanthraquinone and the m-phenylenediamine for prepolymerization, 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 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 PMIA (PMIA) unbleached pulp with the same mass concentration according to the mass ratio of 1:1 to obtain PMIA colored spinning solution.
(3) Filtering PMIA colored spinning solution, filtering at 0.39Mpa and defoaming, and wet spinning at 25 deg.C and 5.5/min at 0.55Mpa in spinning pressure or spinning area to obtain 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 45:25:30).
(4) Plasticizing and stretching, washing, drying and high-temperature treatment are carried out on the nascent fiber to directly obtain the corresponding PMIA colored silk; wherein the hot stretching temperature is 280 ℃, and the hot stretching multiple is 2.5 times.
Example 7
The preparation of PMIA colored fibers was the same as in example 1, the only difference being 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 of PMIA colored fibers was the same as in example 1, the only difference being that: the molar ratio of 1, 5-diaminoanthraquinone to m-phenylenediamine is set to be 50:50.
Comparative example 1
Comparative example 1 discloses a method for preparing PMIA colored fibers, which is different from example 1 in that: when the colored spinning solution is prepared, the non-dyed PMIA fibers are further prepared without adding a color reaction monomer (namely, the molar ratio of the color reaction monomer to the m-phenylenediamine is 0:100).
Comparative example 2 (inorganic dye dyeing method)
A preparation method of PMIA 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 m-phenylenediamine is dissolved in 10670ml of N-dimethylacetamide solvent, cooled, 213.10g of m-phthaloyl chloride is added for low-temperature solution polymerization, calcium hydroxide is used for neutralization, and a poly-m-phthaloyl m-phenylenediamine spinning solution is obtained for defoaming, wherein the mass percentage concentration of salt is 8%, and the mass percentage concentration of poly-m-phthaloyl m-phenylenediamine 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 PMIA colored fibers. Wherein wet spinning adopts a coagulating bath to treat into filaments, the coagulating bath is an N-dimethylacetamide solution, the mass percentage concentration of the coagulating bath 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 PMIA was colored according to the method of example 1 of CN202011083100.7, and the dye of comparative example 2 was replaced with an equivalent amount of 1, 5-diaminoanthraquinone as compared with the CN202011083100.7, and the dyed fiber was a colorless PMIA fiber prepared by comparative example 1, consisting of the following steps:
A. deoiling: adding 8.5g/L sodium hydroxide into PMIA fiber, degreasing for 20min at 95 ℃, washing with water and drying;
B. pretreatment: placing the PMIA fiber treated in the step A in 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 standby;
C. Dyeing: placing the PMIA fibers treated in the step B into a 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 PMIA fibers treated in the step C in 2g/L soap solution, washing for 30min, dehydrating and drying to obtain dyed PMIA fibers.
Comparative example 4
The PMIA colored fibers were produced by the method disclosed in example 1, wherein the difference from example 1 was that: PMIA colored color paste is produced, and the polymerization temperature is controlled at 60 ℃.
Comparative example 5
The PMIA colored fibers were produced by the method disclosed in example 1, wherein the difference from example 1 was that: PMIA colored color paste is produced, and the polymerization temperature is controlled at-30 ℃.
Comparative example 6
The PMIA colored fibers were produced by the method disclosed in example 1, wherein the difference from example 1 was that: the PMIA colored spinning solution is produced, and the temperature is controlled at 30 ℃ in the whole polymerization process.
PMIA spinning solutions and PMIA fibers prepared in examples 1 to 8 and comparative examples 1 to 6 were tested, wherein the light fastness grade was the standard of light fastness-sunlight for the GB/T8426-1998 textile color fastness test; the relative viscosity [. Eta. ] is used as the viscosity of the spinning solution, 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 tables 1 and 2:
TABLE 1 spinning-phase related data
TABLE 2 data relating to fiber properties
Conclusion of the test
As can be seen from tables 1 and 2, the mass ratio ranges of the substances of the color reaction monomer and the first monomer in examples 1 to 8 are as follows: 0.1-100: when the mass ratio of PMIA color paste to PMIA unbleached pulp is within the range of 0-99.9 and 1:1-100, preparing the viscosity [ eta ] of the spinning solution: 2.08-2.43, 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.
In examples 1 to 8, the mass ratio of the color reaction monomer to the first monomer was in the range of: 0.1-100: 0-99.9, wherein the mass ratio of PMIA color paste to PMIA unbleached pulp is 1:1-100, and the glass transition temperature of the prepared colored fiber is 270-275 ℃; the dynamic viscosity of the fiber is 34000-45000 centipoise; the relative strength of the fiber is in the range of 4.18 cN/dtex to 4.8 cN/dtex; the breaking elongation of the fiber is 25% -30%; the light fastness is 4-5 grades; the washing fastness grade is 4-5. Wherein, different chromophoric monomers have different color forming effects, and different chromophoric monomer combinations can prepare new color forming effects different from any chromophoric monomer.
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 3.3cN/dtex to 4.4cN/dtex, the elongation at break of the fiber is increased to 25%, and the filtration pressure is reduced from 0.80Mpa to 0.45Mpa before spinning, thereby greatly reducing the filtration energy consumption.
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 3.5 cN/dtex to 4.4cN/dtex, the elongation at break is increased from 20% to 25%, and the light fastness grade is increased from 2-3 to 4.
As is clear from comparative examples 1 and 4, the second stage polymerization temperature is higher than 50 ℃, and the molecular weight of the colored fiber is reduced due to the increase of side reactions and the reduction of polymerization degree, so that the spinnability is reduced, the broken fingerline phenomenon occurs, and the relative strength of the fiber and the elongation at break of the fiber are obviously reduced; meanwhile, as is clear from comparative examples 1 and 5, too low a polymerization reaction temperature also affects the final polymerization degree, the relative strength of the fiber is lowered, the polymerization reaction temperature is in the range of-20 ℃ to 50 ℃, and the relative strength of the prepared colored fiber and the elongation at break of the fiber are in good ranges. Comparative examples 1 and 6 show that the relative strength and elongation at break of the colored fibers prepared in comparative example 6, which was not subjected to the low-temperature polymerization stage at 20℃or less, were significantly deteriorated.
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 (8)
1. A method of coloring a polymer, comprising the steps of:
step 1: respectively carrying out prepolymerization reaction on a color reaction monomer and a first monomer with a second monomer, and mixing and reacting a prepolymerization product of the prepolymerization reaction to prepare poly m-phenylene isophthalamide color paste; wherein the mass ratio range of the substances of the color reaction monomer and the first monomer is as follows: 0.1-100: 0-99.9; the chromogenic reaction monomer is diaminoanthraquinone; the first monomer is m-phenylenediamine and the second monomer is m-phthaloyl chloride;
step 2: mixing the poly m-phenylene isophthalamide color paste prepared in the step 1 with poly m-phenylene isophthalamide unbleached paste to prepare colored spinning solution, and carrying out pre-spinning slurry pretreatment;
step 3: carrying out wet spinning and precipitation on the colored spinning solution subjected to pretreatment in the step 2 to obtain nascent fibers;
step 4: post-treating the nascent fiber obtained in the step 3 to obtain a poly m-phenylene isophthalamide coloring yarn;
The preparation of the poly m-phenylene isophthalamide color paste in the step 1 comprises the following steps:
s101: placing a chromogenic reaction monomer and a first monomer in two independent reactors, respectively adding a polar solvent for dissolution, adding a second monomer for the first time, and respectively polymerizing to obtain two prepolymer solutions; the polymerization reaction temperature in S101 is-20 ℃;
s102: mixing the two prepolymer solutions, adding a second monomer for polymerization reaction, adding an acid-binding agent after polymerization, and precipitating and separating the acid-binding agent and a hydrogen chloride product to obtain the color paste of the polyisophthaloyl metaphenylene diamine colored spinning solution; the polymerization reaction temperature in S102 is 20-50 ℃.
2. The method of coloring polymers according to claim 1, wherein the mass ratio of the color-forming reactive monomer to the first monomer in the step 1 is in the range of: 0.1-100: 0-99.9; in the step 2, the mass ratio of the poly m-phenylene isophthalamide color paste to the poly m-phenylene isophthalamide unbleached paste is 1:1-100.
3. The method for coloring polymer according to claim 2, wherein the color-forming reaction monomer is diaminoanthraquinone, and the diaminoanthraquinone is 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.
4. A spinning paste for coloring fibers, characterized in that the spinning paste is prepared by the polymer coloring method of any one of claims 1 to 3, comprising coloring polymers and polar organic solvents, and is used for preparing spinning solution;
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 of (I) or comprising onlyA prepolymer of units of (II), wherein Aq comprises an anthraquinone functionality.
5. The spinning mill base of claim 4, wherein the ratio of the number of structural units of (I) to (II) is: 0 to 99.9:0.1 to 100.
6. A dope for colored fibers, characterized by being prepared by the polymer coloring method according to any one of claims 1 to 3, 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 of (I) or comprising onlyA prepolymer of units (II), aq comprising an anthraquinone functionality.
7. The dope of claim 6, wherein the viscosity of the dope: 2.08 to 2.43.
8. A colored fiber prepared by the polymer coloring method according to any one of claims 1 to 3, said colored fiber comprising a polymer having a general formula 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 of (I) or comprising onlyA prepolymer of units of (II), aq comprising anthraquinone functionality;
the dynamic viscosity of the colored fiber spinning solution is 34000-45000/centipoise.
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