CN115976677B - Method for preparing colored meta-aramid fiber by adopting reactive stock solution coloring technology - Google Patents
Method for preparing colored meta-aramid fiber by adopting reactive stock solution coloring technology Download PDFInfo
- Publication number
- CN115976677B CN115976677B CN202211565819.3A CN202211565819A CN115976677B CN 115976677 B CN115976677 B CN 115976677B CN 202211565819 A CN202211565819 A CN 202211565819A CN 115976677 B CN115976677 B CN 115976677B
- Authority
- CN
- China
- Prior art keywords
- spinning
- diazonium salt
- meta
- aramid fiber
- fiber
- 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.)
- Active
Links
- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004040 coloring Methods 0.000 title claims abstract description 19
- 238000005516 engineering process Methods 0.000 title claims abstract description 13
- 239000011550 stock solution Substances 0.000 title claims abstract description 11
- 239000012954 diazonium Substances 0.000 claims abstract description 61
- 238000009987 spinning Methods 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 42
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 41
- 239000007787 solid Substances 0.000 claims abstract description 41
- 239000000835 fiber Substances 0.000 claims abstract description 36
- -1 aromatic amine diazonium salt Chemical class 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000002166 wet spinning Methods 0.000 claims abstract description 9
- 238000002788 crimping Methods 0.000 claims abstract description 6
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LXQOQPGNCGEELI-UHFFFAOYSA-N 2,4-dinitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O LXQOQPGNCGEELI-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- XTEGVFVZDVNBPF-UHFFFAOYSA-N naphthalene-1,5-disulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1S(O)(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LOCWBQIWHWIRGN-UHFFFAOYSA-N 2-chloro-4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1Cl LOCWBQIWHWIRGN-UHFFFAOYSA-N 0.000 claims description 8
- 150000004982 aromatic amines Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- MUHLVSZIVTURCZ-UHFFFAOYSA-N 2-amino-3-bromo-5-nitrobenzonitrile Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1C#N MUHLVSZIVTURCZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- YMZIFDLWYUSZCC-UHFFFAOYSA-N 2,6-dibromo-4-nitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1Br YMZIFDLWYUSZCC-UHFFFAOYSA-N 0.000 claims description 6
- KWMDHCLJYMVBNS-UHFFFAOYSA-N 2-bromo-4,6-dinitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1[N+]([O-])=O KWMDHCLJYMVBNS-UHFFFAOYSA-N 0.000 claims description 6
- CGPPWNTVTNCHDO-UHFFFAOYSA-N 2-bromo-4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1Br CGPPWNTVTNCHDO-UHFFFAOYSA-N 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- BIXZHMJUSMUDOQ-UHFFFAOYSA-N dichloran Chemical compound NC1=C(Cl)C=C([N+]([O-])=O)C=C1Cl BIXZHMJUSMUDOQ-UHFFFAOYSA-N 0.000 claims description 6
- IPMNLGOBXWTQRV-UHFFFAOYSA-N 4-aminobenzene-1,3-dicarbonitrile Chemical compound NC1=CC=C(C#N)C=C1C#N IPMNLGOBXWTQRV-UHFFFAOYSA-N 0.000 claims description 5
- 230000001112 coagulating effect Effects 0.000 claims description 5
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 claims description 5
- IOGXOCVLYRDXLW-UHFFFAOYSA-N tert-butyl nitrite Chemical compound CC(C)(C)ON=O IOGXOCVLYRDXLW-UHFFFAOYSA-N 0.000 claims description 5
- 239000012414 tert-butyl nitrite Substances 0.000 claims description 5
- 230000015271 coagulation Effects 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 22
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 238000000638 solvent extraction Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000004760 aramid Substances 0.000 description 22
- 229920003235 aromatic polyamide Polymers 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- IIBLBHFIGGRWLR-UHFFFAOYSA-N 2-chloro-1-(diazonioamino)-4-nitrobenzene Chemical class ClC1=C(N[N+]#N)C=CC(=C1)[N+](=O)[O-] IIBLBHFIGGRWLR-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000008149 soap solution Substances 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 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 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- OFHIINHZXMHVGF-UHFFFAOYSA-N 1,3-dibromo-2-(diazonioamino)-5-nitrobenzene Chemical group [O-][N+](=O)C1=CC(Br)=C(N[N+]#N)C(Br)=C1 OFHIINHZXMHVGF-UHFFFAOYSA-N 0.000 description 1
- UJFWHVRVHMVUBJ-UHFFFAOYSA-N 1,3-dichloro-2-(diazonioamino)-5-nitrobenzene Chemical group [O-][N+](=O)C1=CC(Cl)=C(N[N+]#N)C(Cl)=C1 UJFWHVRVHMVUBJ-UHFFFAOYSA-N 0.000 description 1
- SMPWMWAUBBVQHF-UHFFFAOYSA-N 1-(diazonioamino)-2,4-dinitrobenzene Chemical group [N+](=O)([O-])C1=C(N[N+]#N)C=CC(=C1)[N+](=O)[O-] SMPWMWAUBBVQHF-UHFFFAOYSA-N 0.000 description 1
- LKMAYECHGYYAHT-UHFFFAOYSA-N 1-bromo-2-(diazonioamino)-3,5-dinitrobenzene Chemical group [N+](=O)([O-])C1=C(N[N+]#N)C(=CC(=C1)[N+](=O)[O-])Br LKMAYECHGYYAHT-UHFFFAOYSA-N 0.000 description 1
- RIXGKWZUWZDYSR-UHFFFAOYSA-N C1=CC(=C(C=C1[N+](=O)[O-])Br)N[N+]#N Chemical group C1=CC(=C(C=C1[N+](=O)[O-])Br)N[N+]#N RIXGKWZUWZDYSR-UHFFFAOYSA-N 0.000 description 1
- NIYOSJLVVCQRLE-UHFFFAOYSA-N N#CC(C=C(C=C1Br)[N+]([O-])=O)=C1N[N+]#N Chemical group N#CC(C=C(C=C1Br)[N+]([O-])=O)=C1N[N+]#N NIYOSJLVVCQRLE-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Artificial Filaments (AREA)
Abstract
The invention discloses a method for preparing colored meta-aramid fiber by adopting a reactive stock solution coloring technology, which comprises the following steps: s1, preparing a weak alkaline aromatic amine diazonium salt solid; s2, dissolving diazonium salt in N, N-dimethylacetamide, and uniformly stirring to prepare diazonium salt solution; s3, adding the diazonium salt solution obtained in the step S2 into the spinning solution of meta-aramid fiber, and stirring and reacting at room temperature; s4, carrying out wet spinning on the spinning solution in the step S3; and S5, washing, drying, heat treatment, crimping and cutting the fiber obtained in the step S4, and finally spinning to obtain the colored meta-aramid fiber. The fiber forming in the spinning process is facilitated, so that the physical and mechanical properties of the spun fiber are basically maintained; the fiber has excellent color fastness and organic solvent extraction resistance; meanwhile, the preparation method is simple, the operation is simple and convenient, the problems of waste acid and the like are avoided, and the method is environment-friendly.
Description
Technical Field
The invention relates to the technical field of aramid fibers and a preparation method thereof, in particular to a method for preparing colored meta-aramid fibers by adopting a reactive stock solution coloring technology.
Background
Meta-aramid is fiber formed by spinning poly-m-phenylene isophthalamide, and has the characteristics of excellent dimensional stability, high temperature resistance, corrosion resistance, flame retardance and the like. However, meta-aramid is difficult to dye because of the very compact structure and the difficulty of dye molecules penetrating into the fiber. The commercial colored aramid fiber is usually obtained by adopting a pre-spinning stock solution coloring method (refer to CN101514495A; CN 100422401C), namely, a dyeing pigment and related auxiliary agents are added into the spinning solution, or a color master batch is added into the spinning solution, so that the spinning solution obtains color, and then the spinning is carried out to obtain a colored product. However, this process has the problem that the added dye pigments are often present in the form of particles or aggregates in the fibers, which not only affect the fiber formation during spinning, but also have a negative effect on the physical and mechanical properties of the fibers.
Meanwhile, patent (CN 114836997 a) discloses a coupling color development method for meta-aramid fiber, namely, m-phenylenediamine on meta-aramid fiber macromolecules is used as a coupling reaction site, and a weak alkaline aromatic amine diazonium salt is used for coupling reaction, so that azo color bodies are formed on the aramid fiber macromolecules in situ, and the aramid fiber is developed. However, the main disadvantages of this method are: the meta-aramid fiber can be well developed after being pretreated by adopting an organic solvent such as dimethyl sulfoxide and the like, and the physical and mechanical properties of the meta-aramid fiber are seriously reduced after the development due to the effect of the dimethyl sulfoxide.
Therefore, there is a need for a method for preparing colored meta-aramid fibers that ensures convenient fiber formation, while not affecting the physical and mechanical properties of the fibers as much as possible.
Disclosure of Invention
In order to solve certain or some technical problems existing in the prior art, the application aims to provide a method for preparing colored meta-aramid fiber by adopting a reactive stock solution coloring technology, which is beneficial to fiber forming in the spinning process and enables the physical and mechanical properties of the fiber after spinning to be basically maintained; the fiber has excellent color fastness and organic solvent extraction resistance; meanwhile, the preparation method is simple, the operation is simple and convenient, the problems of waste acid and the like are avoided, and the method is environment-friendly.
In order to solve the above-mentioned existing technical problem, this application adopts following technical scheme to realize:
a method for preparing colored meta-aramid fiber by adopting reactive stock solution coloring technology is characterized in that: the method comprises the following steps:
s1, preparing a weak alkaline aromatic amine diazonium salt solid: adding weakly basic arylamine and 1, 5-naphthalene disulfonic acid into ethyl acetate, heating to 40-60 ℃, stirring at constant temperature until the mixture is clarified, cooling to 20-25 ℃, slowly adding tert-butyl nitrite, cooling to 0-5 ℃, continuously stirring for 30-120 min until the reaction is finished, performing reduced pressure suction filtration on the reaction solution, and washing with ethyl acetate, ethanol and diethyl ether for multiple times in sequence to finally prepare diazonium salt solid;
s2, dissolving diazonium salt in N, N-dimethylacetamide, and uniformly stirring to prepare diazonium salt solution;
s3, adding the diazonium salt solution obtained in the step S2 into the spinning solution of meta-aramid fiber, and stirring and reacting at room temperature;
s4, carrying out wet spinning on the spinning solution in the step S3;
and S5, washing, drying, heat treatment, crimping and cutting the fiber obtained in the step S4, and finally spinning to obtain the colored meta-aramid fiber.
Preferably, the ratio of the weakly basic aromatic amine, the 1, 5-naphthalene disulfonic acid, the ethyl acetate and the tert-butyl nitrite in the step S1 is 1:1:10:1.5.
Preferably, the weakly basic aromatic amine in the step S1 includes 2-chloro-4-nitroaniline, 2, 4-dinitroaniline, 2, 4-dicyanoaniline, 2, 6-dichloro-4-nitroaniline, 2, 6-dibromo-4-nitroaniline, 2-bromo-4-nitro-6-cyanoaniline, 2-bromo-4, 6-dinitroaniline, 2-bromo-4-nitroaniline, and the like.
Preferably, the concentration of the diazonium salt solution in the step S2 is 10-30 g/L.
Preferably, the spinning solution in the step S3 is an N, N-dimethylacetamide solution containing poly (m-phenylene isophthalamide) and calcium chloride; the concentration of the poly (m-phenylene isophthalamide) is 5-25wt%; the concentration of the calcium chloride is 4-8wt%.
Preferably, the reaction time in the step S3 is 30 to 60 minutes.
Preferably, the wet spinning in the step S4 is to defoam the spinning mixture and extrude the spinning mixture through a spinneret hole, form a nascent fiber in a coagulating bath, and then draft the nascent fiber in a hot water bath containing N, N-dimethylacetamide by 2-5 times to make the nascent fiber have certain physical and mechanical properties.
Preferably, the spinning pressure in the step S4 is 0.2-0.5 MPa; the spinning temperature is 40-50 ℃; the coagulation bath composition was N, N-dimethylacetamide/water=40/60; the temperature of the coagulating bath is 20-40 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the conventional stock solution coloring technology of meta-aramid, the invention uses meta-phenylenediamine units in meta-aramid macromolecules as coupling components, and diazonium salt solution is added into spinning solution, and diazonium salt and meta-phenylenediamine units in meta-aramid macromolecules undergo coupling reaction, so that colored meta-aramid is finally spun. The azo color bodies are formed in situ, namely the color bodies and meta-aramid macromolecules are integrated, so that the fiber forming in the spinning process is facilitated, and the physical and mechanical properties of the spun fiber are better;
2. compared with meta-aramid fibers obtained by conventional stock solution coloring, the colored meta-aramid fibers obtained by the invention have higher color fastness and better organic solvent extraction resistance;
3. compared with the patent (CN 114836997A), the invention directly develops color of meta-aramid before spinning, and does not need to pretreat the spun fiber by using an organic solvent, so that the mechanical property of the obtained colored meta-aramid is greatly improved;
4. compared with the patent (CN 114836997A), the method disclosed by the invention has the advantages that the solid diazonium salt is added into the spinning solution for reaction after being dissolved by the spinning solvent, the operation is simpler and more convenient, the problems of waste acid and the like are avoided, and the method is more environment-friendly.
Drawings
FIG. 1 is a flow chart of the colored meta-aramid prepared by reactive liquid coloring technique according to the present invention;
FIG. 2 is a chart of the mechanism of coloring meta-aramid reactive stock solution.
Detailed Description
The present application will be further described with reference to the drawings and detailed description, which should be understood that, on the premise of no conflict, the following embodiments or technical features may be arbitrarily combined to form new embodiments.
The invention and the manner in which it is carried out are further described below in connection with examples. These examples are only intended to further illustrate the invention and are not intended to limit the protection of the invention. The raw materials or reagents described in the present invention are commercially available unless otherwise specified. Solid diazonium salts can be prepared from the corresponding aromatic primary amine compounds using methods conventional in the art, as described in reference (Jinjing. Preparation of stable diazonium salts of weakly basic aromatic amines and their use in azo disperse dye synthesis [ d. university of company, university, 2019.). The dope may be prepared by methods conventional in the art, and reference may be made to the document (CN 107815741 a).
As shown in fig. 1 and 2, a method for preparing colored meta-aramid fiber by reactive liquid-batch coloring technology comprises the following steps:
s1, preparing a weak alkaline aromatic amine diazonium salt solid: adding weakly basic arylamine and 1, 5-naphthalene disulfonic acid into ethyl acetate, heating to 40-60 ℃, stirring at constant temperature until the mixture is clarified, cooling to 20-25 ℃, slowly adding tert-butyl nitrite, cooling to 0-5 ℃, continuously stirring for 30-120 min until the reaction is finished, performing reduced pressure suction filtration on the reaction solution, and washing with ethyl acetate, ethanol and diethyl ether for multiple times in sequence to finally prepare diazonium salt solid; the weakly basic aromatic amine comprises 2-chloro-4-nitroaniline, 2, 4-dinitroaniline, 2, 4-dicyanoaniline, 2, 6-dichloro-4-nitroaniline, 2, 6-dibromo-4-nitroaniline, 2-bromo-4-nitro-6-cyanoaniline, 2-bromo-4, 6-dinitroaniline, 2-bromo-4-nitroaniline, and the like;
preparation of weakly basic aromatic amine diazonium salt solid 1: preparation of solid diazonium salts of 2-chloro-4-nitroaniline:
10mmol (1.76 g, 98.0%) of 2-chloro-4-nitroaniline and 10mmol (2.93 g, 98.5%) of 1, 5-naphthalenedisulfonic acid were added to 100mL of ethyl acetate, heated at 50℃and stirred for 10min, cooled to 20℃and 15mmol (1.57 g, 98.5%) of tert-butyl nitrite were slowly added under stirring. Cooling to 0-5 deg.c and stirring for 30min. After the reaction is finished, the reaction solution is subjected to vacuum filtration, and is washed with 300mL of ethyl acetate, 100mL of ethanol and 50mL of diethyl ether for multiple times in sequence, so that the diazonium salt solid of 2-chloro-4-nitroaniline is finally prepared.
Preparation of weakly basic aromatic amine diazonium salt solid 2: preparation of solid diazonium salts of 2-bromo-4-nitroaniline:
2-bromo-4-nitroaniline is replaced by 2-bromo-4-nitroaniline, and other diazonium salt solids such as those used to prepare the weakly basic aromatic amine diazonium salt solid 1, are prepared.
Preparation of weakly basic aromatic amine diazonium salt solid 3: preparation of solid diazonium salts of 2, 4-dinitroaniline:
2-chloro-4-nitroaniline is replaced by 2, 4-dinitroaniline, and after the addition is finished, the system is continuously stirred at 0-5 ℃ for 120min, and other products such as the preparation of alkalescent aromatic amine diazonium salt solid 1 are prepared to obtain the diazonium salt solid of 2, 4-dinitroaniline.
Preparation of weakly basic aromatic amine diazonium salt solid 4: preparation of solid diazonium salts of 2, 4-dicyanoaniline:
2, 4-dinitroaniline is replaced by 2, 4-dicyanoaniline, and other diazonium salt solids such as weak basic aromatic amine diazonium salt solids 3 are prepared to obtain 2, 4-dicyanoaniline diazonium salt solids.
Preparation of weakly basic aromatic amine diazonium salt solid 5: preparation of solid diazonium salts of 2, 6-dichloro-4-nitroaniline:
2, 4-dinitroaniline is replaced by 2, 6-dichloro-4-nitroaniline, and other diazonium salt solids such as weak alkaline aromatic amine diazonium salt solids 3 are prepared to obtain 2, 6-dichloro-4-nitroaniline.
Preparation of weakly basic aromatic amine diazonium salt solid 6: preparation of solid diazonium salts of 2, 6-dibromo-4-nitroaniline:
2, 4-dinitroaniline is replaced by 2, 6-dibromo-4-nitroaniline, and other diazonium salt solids such as weak alkaline aromatic amine diazonium salt solids 3 are prepared to obtain 2, 6-dibromo-4-nitroaniline.
Preparation of weakly basic aromatic amine diazonium salt solid 7: preparation of solid diazonium salts of 2-bromo-4-nitro-6-cyanoaniline:
2-bromo-4-nitro-6-cyanoaniline is prepared by replacing 2, 4-dinitroaniline with 2-bromo-4-nitro-6-cyanoaniline, and otherwise preparing the diazonium salt solid of 2-bromo-4-nitro-6-cyanoaniline as the basic aromatic amine diazonium salt solid 3.
Preparation of weakly basic aromatic amine diazonium salt solid 8: preparation of solid diazonium salts of 2-bromo-4, 6-dinitroaniline:
2, 4-dinitroaniline is replaced by 2-bromo-4, 6-dinitroaniline, and other diazonium salt solids such as weak basic aromatic amine diazonium salt solids 3 are prepared to obtain 2-bromo-4, 6-dinitroaniline.
S2, dissolving diazonium salt in N, N-dimethylacetamide, and uniformly stirring to prepare diazonium salt solution, wherein the concentration of the diazonium salt solution is 10-30 g/L;
s3, adding the diazonium salt solution obtained in the step S2 into a spinning solution of meta-aramid fiber, stirring at room temperature, and reacting for 30-60 min, wherein the spinning solution is an N, N-dimethylacetamide solution containing poly-m-phenylene isophthalamide and calcium chloride; the concentration of the poly (m-phenylene isophthalamide) is 5-25wt%; the concentration of the calcium chloride is 4-8wt%;
s4, carrying out wet spinning on the spinning solution in the step S3; the wet spinning is to defoam the spinning mixed solution and extrude the spinning mixed solution through a spinneret hole, form a nascent fiber in a coagulating bath, and then draft the nascent fiber in a hot water bath containing N, N-dimethylacetamide for 2-5 times so as to lead the nascent fiber to have certain physical and mechanical properties; the spinning pressure is 0.2-0.5 MPa; the spinning temperature is 40-50 ℃; the coagulation bath composition was N, N-dimethylacetamide/water=40/60; the temperature of the coagulating bath is 20-40 ℃;
and S5, washing, drying, heat treatment, crimping and cutting the fiber obtained in the step S4, and finally spinning to obtain the colored meta-aramid fiber.
Example 1:
20L of a solution of 2-chloro-4-nitroaniline diazonium salt in N, N-dimethylacetamide at a concentration of 15g/L was added to a spinning solution (48.5 kg) of polymetaphenylene isophthalamide at a concentration of 20wt%, and stirred and reacted at 20℃for 60 minutes. After the reaction is finished, carrying out wet spinning on the spinning solution, and finally carrying out water washing, drying, heat treatment, crimping and cutting off on the spun fibers. The meta-aramid fiber with the linear density of 1.80dtex is prepared.
Example 2:
the 2-chloro-4-nitroaniline diazonium salt of example 1 was replaced with a 2-bromo-4-nitroaniline diazonium salt, and the other steps were as described in example 1. The meta-aramid fiber with the linear density of 1.80dtex is prepared.
Example 3:
the 2-chloro-4-nitroaniline diazonium salt of example 1 was replaced with a 2, 4-dinitroaniline diazonium salt, and the other steps were as described in example 1. The meta-aramid fiber with the linear density of 1.80dtex is prepared.
Example 4:
the 2-chloro-4-nitroaniline diazonium salt of example 1 was replaced with a 2, 4-dicyanoaniline diazonium salt, and the other steps were as described in example 1. The meta-aramid fiber with the linear density of 1.80dtex is prepared.
Example 5:
the 2-chloro-4-nitroaniline diazonium salt of example 1 was replaced with a 2, 6-dichloro-4-nitroaniline diazonium salt, and the other steps were as described in example 1. The meta-aramid fiber with the linear density of 1.80dtex is prepared.
Example 6:
the 2-chloro-4-nitroaniline diazonium salt of example 1 was replaced with a 2, 6-dibromo-4-nitroaniline diazonium salt, and the other steps were as described in example 1. The meta-aramid fiber with the linear density of 1.80dtex is prepared.
Example 7:
the 2-chloro-4-nitroaniline diazonium salt of example 1 was replaced with a 2-bromo-4-nitro-6-cyanoaniline diazonium salt, and the other steps were as described in example 1. The meta-aramid fiber with the linear density of 1.80dtex is prepared.
Example 8:
the 2-chloro-4-nitroaniline diazonium salt of example 1 was replaced with a 2-bromo-4, 6-dinitroaniline diazonium salt, and the other steps were as described in example 1. The meta-aramid fiber with the linear density of 1.80dtex is prepared.
Comparative example 1:
under the condition that no diazonium salt is added, the meta-aramid spinning solution is directly subjected to wet spinning, and the spun fiber is subjected to water washing, drying, heat treatment, crimping and cutting to obtain the meta-aramid fiber with the linear density of 1.80 dtex.
Comparative example 2:
the prepared diazonium salt is acted on the meta-aramid fiber prepared in comparative example 1 according to patent CN114836997A by taking 2-chloro-4-nitroaniline as a raw material to prepare colored meta-aramid fiber.
Comparative example 3:
the high temperature resistant pigment red 254 is selected as a colorant, and meta-aramid fiber with the linear density of 1.82dtex is prepared according to the patent CN 100422401C.
The invention describes the colors of meta-aramid fibers prepared in examples 1 to 8 and comparative examples 1 to 3, and the tensile properties of the fibers were tested, the test equipment was an Instron universal material tester, and Table 1 shows the test results:
TABLE 1
The meta-aramid fiber without any treatment showed pale yellow color (comparative example 1), and the meta-aramid fibers prepared in examples 1 to 8 were brownish red or tan, and the breaking strength and breaking elongation of the colored fiber were only slightly reduced compared to comparative example 1. The colored meta-aramid fiber prepared in comparative example 2 has significantly reduced tensile properties due to the dimethyl sulfoxide. The red meta-aramid fiber produced in comparative example 3 had uneven dispersion of the colorant or had aggregated, and thus the tensile properties of the fiber were inferior to those of examples 1 to 8.
The present invention conducted soaping and N, N-dimethylformamide stripping experiments on meta-aramid fibers prepared in examples 1 to 8 and comparative example 3, and described the color of soap solution and stripping solution after soaping and stripping. The soaping method comprises the following steps: weighing a certain amount of soap flakes and sodium carbonate, adding into deionized water, stirring and dissolving to prepare soap solution with soap flakes concentration of 5g/L and sodium carbonate concentration of 2g/L, placing 0.5g of aramid fiber into 25mL of soap solution, sealing and vibrating for 45min at 60 ℃. After returning to room temperature, the fibers were removed and the color of the soap was observed. The stripping method comprises the following steps: 0.5g of aramid fiber is placed in 25mLN, N-dimethylformamide, and is oscillated for 60min at 120 ℃, after the room temperature is restored, the fiber is taken out, and the color of the stripping liquid is observed. Table 2 shows the test results:
TABLE 2
The soap solutions of the meta-aramid fibers prepared in examples 1 to 8 and comparative example 3 are colorless after being subjected to soaping; the stripping solutions of the meta-aramid fibers prepared in examples 1 to 8 were almost colorless, but the stripping solution of the aramid fiber prepared in comparative example 3 showed pale red.
Thus, as can be seen from tables 1 and 2, the physical and mechanical properties of the colored meta-aramid fiber prepared by the present invention are substantially maintained, and the colored meta-aramid fiber has excellent color fastness and organic solvent extraction resistance; meanwhile, the preparation method is simple, the operation is simple and convenient, the problems of waste acid and the like are avoided, and the method is environment-friendly.
The above embodiments are only preferred embodiments of the present application, and the scope of the present application is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present application are intended to be within the scope of the present application.
Claims (7)
1. A method for preparing colored meta-aramid fiber by adopting reactive stock solution coloring technology is characterized in that: the method comprises the following steps:
s1, preparing a weak alkaline aromatic amine diazonium salt solid: adding weakly basic arylamine and 1, 5-naphthalene disulfonic acid into ethyl acetate, heating to 40-60 ℃, stirring at constant temperature until the mixture is clarified, cooling to 20-25 ℃, slowly adding tert-butyl nitrite, cooling to 0-5 ℃, continuously stirring for 30-120 min until the reaction is finished, performing reduced pressure suction filtration on the reaction solution, and washing with ethyl acetate, ethanol and diethyl ether for multiple times in sequence to finally prepare diazonium salt solid;
s2, dissolving diazonium salt in N, N-dimethylacetamide, and uniformly stirring to prepare diazonium salt solution;
s3, adding the diazonium salt solution obtained in the step S2 into the spinning solution of meta-aramid fiber, and stirring and reacting at room temperature;
s4, carrying out wet spinning on the spinning solution in the step S3;
and S5, washing, drying, heat treatment, crimping and cutting the fiber obtained in the step S4, and finally spinning to obtain the colored meta-aramid fiber.
2. The method for preparing colored meta-aramid fiber by reactive liquid coloring technology according to claim 1, wherein the method comprises the following steps: the weakly basic aromatic amine in the step S1 comprises 2-chloro-4-nitroaniline, 2, 4-dinitroaniline, 2, 4-dicyanoaniline, 2, 6-dichloro-4-nitroaniline, 2, 6-dibromo-4-nitroaniline, 2-bromo-4-nitro-6-cyanoaniline, 2-bromo-4, 6-dinitroaniline and 2-bromo-4-nitroaniline.
3. The method for preparing colored meta-aramid fiber by reactive liquid coloring technology according to claim 1, wherein the method comprises the following steps: the concentration of the diazonium salt solution in the step S2 is 10-30 g/L.
4. The method for preparing colored meta-aramid fiber by reactive liquid coloring technology according to claim 1, wherein the method comprises the following steps: the spinning solution in the step S3 is an N, N-dimethylacetamide solution containing poly (m-phenylene isophthalamide) and calcium chloride; the concentration of the poly (m-phenylene isophthalamide) is 5-25 wt%; the concentration of the calcium chloride is 4-8wt%.
5. The method for preparing colored meta-aramid fiber by reactive liquid coloring technique according to claim 4, wherein: the reaction time in the step S3 is 30-60 min.
6. The method for preparing colored meta-aramid fiber by reactive liquid coloring technology according to claim 1, wherein the method comprises the following steps: the wet spinning in the step S4 is to defoam the spinning mixed solution and extrude the spinning mixed solution through a spinneret hole, form a nascent fiber in a coagulating bath, and then draft the nascent fiber in a hot water bath containing N, N-dimethylacetamide for 2-4 times to enable the nascent fiber to have certain physical and mechanical properties.
7. The method for preparing colored meta-aramid fiber by reactive liquid coloring technique according to claim 6, wherein: the spinning pressure in the step S4 is 0.2-0.5 MPa; the spinning temperature is 40-50 ℃; the coagulation bath composition was N, N-dimethylacetamide/water=40/60; the coagulation bath temperature is 20-40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211565819.3A CN115976677B (en) | 2022-12-07 | 2022-12-07 | Method for preparing colored meta-aramid fiber by adopting reactive stock solution coloring technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211565819.3A CN115976677B (en) | 2022-12-07 | 2022-12-07 | Method for preparing colored meta-aramid fiber by adopting reactive stock solution coloring technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115976677A CN115976677A (en) | 2023-04-18 |
| CN115976677B true CN115976677B (en) | 2023-12-22 |
Family
ID=85960359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211565819.3A Active CN115976677B (en) | 2022-12-07 | 2022-12-07 | Method for preparing colored meta-aramid fiber by adopting reactive stock solution coloring technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115976677B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116623309B (en) * | 2023-07-21 | 2023-10-03 | 江苏新视界先进功能纤维创新中心有限公司 | Polymer coloring method, spinning color paste, spinning solution and colored fiber |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847475A (en) * | 2006-04-13 | 2006-10-18 | 烟台氨纶股份有限公司 | Spun dyeing meta-aramid short fiber and its preparation process |
| CN104746366A (en) * | 2015-03-31 | 2015-07-01 | 东华大学 | Method for preparing colored meta-aramid |
| CN109183179A (en) * | 2018-09-19 | 2019-01-11 | 超美斯新材料（淮安）有限公司 | A kind of preparation method of meta-aramid colored fibre |
| CN114836997A (en) * | 2022-06-16 | 2022-08-02 | 浙江理工大学 | In-situ coupling color development method of meta-aramid and obtained color development aramid |
| CN114989088A (en) * | 2022-06-16 | 2022-09-02 | 浙江理工大学 | Meta-aramid fiber color development method and used treating agent |
-
2022
- 2022-12-07 CN CN202211565819.3A patent/CN115976677B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1847475A (en) * | 2006-04-13 | 2006-10-18 | 烟台氨纶股份有限公司 | Spun dyeing meta-aramid short fiber and its preparation process |
| CN104746366A (en) * | 2015-03-31 | 2015-07-01 | 东华大学 | Method for preparing colored meta-aramid |
| CN109183179A (en) * | 2018-09-19 | 2019-01-11 | 超美斯新材料（淮安）有限公司 | A kind of preparation method of meta-aramid colored fibre |
| CN114836997A (en) * | 2022-06-16 | 2022-08-02 | 浙江理工大学 | In-situ coupling color development method of meta-aramid and obtained color development aramid |
| CN114989088A (en) * | 2022-06-16 | 2022-09-02 | 浙江理工大学 | Meta-aramid fiber color development method and used treating agent |
Non-Patent Citations (1)
| Title |
|---|
| 江华 ; 蔡金芳 ; 崔志华 ; 陈维国 ; 孙岩峰 ; .芳胺重氮盐对蚕丝偶合染色的构效关系研究.丝绸.2019,(第06期),1-5. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115976677A (en) | 2023-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100422401C (en) | Spun dyeing meta-aramid short fiber and its preparation process | |
| CN115976677B (en) | Method for preparing colored meta-aramid fiber by adopting reactive stock solution coloring technology | |
| CN103668523B (en) | The manufacture method of dry acrylic fiber fiber | |
| CN101962819A (en) | Ultrawhite ultrahigh-molecular weight ultrahigh-modulus polyethylene fibers and preparation process thereof | |
| JPH08109514A (en) | Rayon modified with polymeric amine compound | |
| WO2010035834A1 (en) | Easily dyeable meta-form wholly aromatic polyamide fiber | |
| KR20150006850A (en) | Method for producing moulded articles | |
| CN112095168B (en) | Colored ultrahigh molecular weight polyethylene fiber and preparation method thereof | |
| CN107814928B (en) | Modified polyisophthaloyl metaphenylene diamine easy to dye by cationic dye and preparation method and application thereof | |
| JPH07300719A (en) | Amine-substituted cellulose synthetic fiber | |
| PT1951820E (en) | Liquid direct dye formulations | |
| CN111100478B (en) | Preparation method and application of blue dye with three active groups | |
| JP2009120976A (en) | Easily dyeable meta-type wholly aromatic polyamide fiber | |
| CN1079121C (en) | Preparation of spinnable isotropic cellulose solution | |
| US4474696A (en) | Reactive disazo dyestuffs containing triazines | |
| CN113355764B (en) | Method for preparing colored meta-aramid fiber by one-step method | |
| JPH0881827A (en) | Easily dyeable meta-aromatic polyamide fiber | |
| NO127452B (en) | ||
| JP2002146028A (en) | Modified lignosulfonate and application | |
| CN102516795A (en) | Preparation method of blue dye | |
| CN110387144A (en) | Blue dyestuff of a kind of dispersion and application thereof | |
| CN1844507A (en) | Technology for producing coloured chitosan fiber by reaction kettle process | |
| JP2020117831A (en) | Easily-dyeable meta-type wholly aromatic polyamide fiber, and method for producing the same | |
| JPS60133064A (en) | Disazo compound and dyeing process using the same | |
| KR100291887B1 (en) | Disazo reactive yellow dyestuff, preparing method thereof and composition containing the same |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |