CN118292136A - Modified meta-aramid fiber capable of improving light fastness and preparation method thereof - Google Patents
Modified meta-aramid fiber capable of improving light fastness and preparation method thereof Download PDFInfo
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- CN118292136A CN118292136A CN202410718130.2A CN202410718130A CN118292136A CN 118292136 A CN118292136 A CN 118292136A CN 202410718130 A CN202410718130 A CN 202410718130A CN 118292136 A CN118292136 A CN 118292136A
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000004760 aramid Substances 0.000 claims abstract description 144
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 143
- 239000011550 stock solution Substances 0.000 claims abstract description 131
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 69
- 239000002250 absorbent Substances 0.000 claims abstract description 59
- 230000002745 absorbent Effects 0.000 claims abstract description 59
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 41
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 21
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 14
- 238000009987 spinning Methods 0.000 claims abstract description 14
- 230000004224 protection Effects 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 46
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 230000035484 reaction time Effects 0.000 claims description 19
- 238000009998 heat setting Methods 0.000 claims description 18
- 230000001112 coagulating effect Effects 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 239000004952 Polyamide Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 229920002647 polyamide Polymers 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 5
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 4
- 229940111759 benzophenone-2 Drugs 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- -1 octyltriazinone Chemical compound 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YIMHRDBSVCPJOV-UHFFFAOYSA-N n'-(2-ethoxyphenyl)-n-(2-ethylphenyl)oxamide Chemical compound CCOC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1CC YIMHRDBSVCPJOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 19
- 230000003472 neutralizing effect Effects 0.000 abstract description 15
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 59
- 239000000835 fiber Substances 0.000 description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 33
- 238000003756 stirring Methods 0.000 description 29
- 238000009210 therapy by ultrasound Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 230000032683 aging Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004753 textile 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
- BIXKJKMPXGUOCP-UHFFFAOYSA-N C(CCCCCCC)C=1C(NN=NC=1)=O Chemical compound C(CCCCCCC)C=1C(NN=NC=1)=O BIXKJKMPXGUOCP-UHFFFAOYSA-N 0.000 description 2
- 238000012666 chain growth polycondensation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
- D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Polyamides (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to a modified meta-aramid fiber for improving light fastness and a preparation method thereof, wherein under the protection of inert gas, in a solvent, isophthaloyl dichloride reacts with hyperbranched polymer and inorganic ultraviolet absorbent to obtain a polymer liquid mixture; under the polymerization condition, slowly adding the polymerization liquid mixture into m-phenylenediamine in batches for reaction, and after the reaction is finished, carrying out neutralization treatment to remove inorganic acid generated by the reaction; adding isophthaloyl dichloride and an organic ultraviolet absorbent for reaction, and adding a neutralizing agent for neutralization after the reaction is finished to obtain a modified aramid stock solution; and then obtaining the modified meta-aramid fiber through a spinning process. The modified meta-aramid fiber has the advantages that the light fastness, the mechanical property and the thermal stability of the meta-aramid fiber are improved on the basis of keeping the high-strength and high-modulus characteristics of the aramid fiber.
Description
Technical Field
The invention relates to a modified meta-aramid fiber for improving light fastness and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
Meta-aramid fiber is one of the outstanding high performance fibers because of its high strength, high modulus, light weight, heat resistance, impact resistance, wear resistance, excellent acid and alkali resistance, and the like, and because of these excellent properties, meta-aramid fiber is widely used in the fields of aerospace and fire-fighting wear, and protective clothing, racing wear, heat-resistant clothing, gloves, sportswear, and the like worn under antistatic working conditions. Besides, the textile is also suitable for household textiles such as filter bags, carpets, curtains, floor coverings and the like.
The meta-aramid fiber is also called as poly m-phenylene isophthalamide fiber, is a rigid macromolecule with amide groups and benzene rings connected, regular molecular chain arrangement is saw-tooth, however, the meta-aramid fiber is a light-sensitive organic fiber, a large number of chromophores (amide groups and benzene rings) contained in the molecular chain are easy to absorb ultraviolet radiation to cause the fracture of amide bonds, so that the oxidative degradation of the polymer chains is accelerated, the regular structure of the meta-aramid fiber is damaged, the mechanical property of the fiber is damaged, and because intermolecular hydrogen bonds exist between the amide groups, the structure is compact, the crystallinity is very high, and functional additives are difficult to enter the fiber, so that a proper anti-ultraviolet aging agent is selected, an effective anti-ultraviolet modification method is designed, the light fastness of the fiber is improved, the service life of the fiber is prolonged, and the meta-aramid fiber is one of hot spots for modification research.
At present, the modification method of meta-aramid fiber for resisting ultraviolet aging mainly comprises the steps of directly coating an ultraviolet-resistant absorbent or shielding agent coating on the surface of the fiber, and adding the ultraviolet-resistant absorbent into spinning solution to prepare the fiber with high light fastness. For research on ultraviolet aging resistance of meta-aramid fiber, the ultraviolet resistance of the modified fiber is ensured, and the influence of the modification process on the comprehensive performance of the fiber is considered. The surface coating of the fiber has high crystallinity of meta-aramid fiber surface and no active group, and needs to perform physical or chemical treatment on the fiber, so that the production line process is increased, the process is long in time consumption, the energy consumption is increased, the cost is increased, and the method is not friendly to the environment, for example, the method is used in Chinese patent application CN104911896A, CN106592216A, CN116377708A, CN114753154A, the method is easy to damage the mechanical property of the fiber, the problem of the bonding fastness of the surface coating and the fiber is not solved well, and the problem of the light fastness of the fabric is reduced in the repeated washing process of the fabric, so that the problem cannot be solved fundamentally. The ultraviolet-resistant absorbent is added into the spinning stock solution to achieve the effect of improving the light fastness of the fibers, the simple physical mixing does not react with the stock solution groups, the dispersion effect of the functional auxiliary agent in the stock solution is poor, the agglomeration phenomenon is easily formed in the fibers, the filter and the spinneret plate are blocked, the phenomena of fiber yarn breakage and yarn breakage are frequently generated, and the spinning progress and the fiber mechanical property are affected.
Therefore, how to improve the light fastness of meta-aramid fiber and further optimize the preparation process of the aramid fiber on the basis of maintaining the high-strength and high-modulus characteristics of the aramid fiber is a problem to be solved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a modified meta-aramid fiber for improving the light fastness and a preparation method thereof, and the light fastness, the mechanical property and the thermal stability of the meta-aramid fiber are improved on the basis of keeping the high-strength high-modulus characteristic of the aramid fiber.
The technical scheme for solving the technical problems is as follows: a preparation method of modified meta-aramid fiber for improving light fastness, which comprises the following steps:
S1, under the protection of inert gas, in a solvent, reacting isophthaloyl dichloride with a hyperbranched polymer and an inorganic ultraviolet absorbent to obtain a polymerization liquid mixture;
S2, slowly adding the polymerization liquid mixture into m-phenylenediamine in batches under the polymerization condition for reaction, and after the reaction is finished, carrying out neutralization treatment to remove inorganic acid generated by the reaction;
s3, adding isophthaloyl dichloride and an organic ultraviolet absorbent into the system in the step S2 to react, and adding a neutralizer to neutralize after the reaction is finished to obtain a modified aramid stock solution;
S4, the modified meta-aramid fiber is obtained by the spinning process of the modified aramid stock solution.
Further, the hyperbranched polymer is at least one of hydroxyl-terminated aliphatic hyperbranched polyester, carboxyl-terminated aromatic hyperbranched polyester, amino-terminated hyperbranched polyamide, hydroxyl-terminated hyperbranched polyamide, carboxyl-terminated hyperbranched polyamide, hydroxyl-terminated aromatic hyperbranched polymer and carboxyl-terminated aliphatic hyperbranched polymer.
Further, the inorganic ultraviolet absorbent is at least one of titanium dioxide and zinc oxide, and the particle size of the inorganic ultraviolet absorbent is 30-2000 nm.
Further, the organic ultraviolet absorber is at least one of benzophenone-2, 2-hydroxy-4-methoxybenzophenone, 2', 4' -tetrahydroxybenzophenone, 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, 2' -methylenebis (4-tert-octyl-6-benzotriazole phenol), 4-dimethylaminobenzoic acid, octyltriazinone, N- (2-ethoxyphenyl) -N ' - (2-ethylphenyl) -ethanediamide.
The organic ultraviolet absorbent can react with hyperbranched polymers with a large number of active groups, and can be grafted on polymer molecular chains of the modified aramid stock solution through the polycondensation reaction of the hyperbranched polymers with m-phenylenediamine and isophthaloyl dichloride, so that the compatibility and the dispersibility of the ultraviolet absorbent and the aramid stock solution are fundamentally improved.
Further, the total amount of the intermediate phthaloyl chloride in the step S1 and the intermediate phthaloyl chloride in the step S3 is calculated according to 100%, and the dosage of the intermediate phthaloyl chloride in the step S1 is 93% -96%; the consumption of the intermediate phthaloyl chloride in the step S3 is 4% -7%;
In the preparation method, the ratio of the total molar quantity of the m-phenylenediamine to the m-phthaloyl chloride is 1:0.99-1.05;
The dosage of the hyperbranched polymer is 0.1-5% of the mass of the modified aramid stock solution; the dosage of the inorganic ultraviolet absorber is 0.3-3% of the mass of the modified aramid stock solution; the dosage of the organic ultraviolet absorber is 0.1-6% of the mass of the modified aramid stock solution.
Further, the reaction temperature in the step S1 is 30-65 ℃ and the reaction time is 2-4 hours; the reaction temperature in the step S2 is-15-25 ℃, and the reaction time is 1-2 hours; the reaction temperature in the step S2 is 30-50 ℃ and the reaction time is 1-2 h.
Further, the solid content of the modified aramid stock solution is 4% -23%, the viscosity is 300-900 Pa.s, the pH value is 7-8, and the molecular weight distribution of the modified aramid stock solution clock polymer is Mw/Mn=1-1.5.
In step S4, after the modified aramid stock solution is sprayed out through a spinning cap, the modified meta-aramid fiber is obtained through coagulation bath, stretching bath stretching, hot water bath stretching, heat setting, oiling and drying.
Further, the number of holes of the spinning cap is 1000-40000, and the aperture is 0.03-0.13mm;
the temperature of the coagulating bath is 25-50 ℃, and the concentration of the N, N-dimethylacetamide aqueous solution in the coagulating bath is 55-65%;
the temperature of the stretching bath is 25-50 ℃, and the concentration of the N, N-dimethylacetamide aqueous solution in the stretching bath is 45-60%;
the temperature of the hot water bath is 60-75 ℃;
The heat setting temperature is 300-400 ℃, and the heat setting time is 2-5 min; the oiling concentration is 0.1% -2%; the drying temperature is 100-180 ℃.
The invention discloses a modified meta-aramid fiber for improving light fastness, which is prepared according to the preparation method.
The beneficial effects of the invention are as follows:
According to the preparation method of the modified meta-aramid fiber, on the basis of preparing an aramid polymer, the prepared modified meta-aramid fiber is prepared by combining an organic ultraviolet absorber and an inorganic ultraviolet absorber in a matched mode, and on the basis of keeping the high-strength high-modulus characteristic of the aramid fiber, the light fastness, the mechanical property and the thermal stability of the meta-aramid fiber are effectively improved.
According to the preparation method, the hyperbranched polymer, the m-phenylenediamine and the isophthaloyl dichloride are used for preparing the modified aramid stock solution, a large number of active end groups of the hyperbranched polymer can react with the isophthaloyl dichloride and simultaneously can effectively adsorb the inorganic ultraviolet absorbent, the hyperbranched polymer has a three-dimensional structure and a larger space structure, electrostatic repulsion exists between the hyperbranched polymers, and the agglomeration behavior of the inorganic ultraviolet absorbent can be slowed down after the adsorption; the organic ultraviolet absorbent can react with active groups of the hyperbranched polymer, and the hyperbranched polymer, m-phenylenediamine and m-phthaloyl chloride continue to undergo chain growth polycondensation reaction, so that the organic ultraviolet absorbent is grafted on an aramid stock solution molecular chain, the compatibility and the dispersibility of the ultraviolet absorbent and the aramid stock solution are fundamentally improved, and the mechanical property of the aramid fiber is ensured.
The mechanism of the modified aramid stock solution provided by the invention is different from that of the traditional method that the light fastness of the meta-aramid fiber is improved by means of an inorganic ultraviolet screening agent, and the method disclosed by the invention keeps the molecular structural integrity of the aramid fiber polymer, so that the inherent characteristics of high strength, high modulus, intrinsic flame retardance, high temperature resistance, low dielectric property and the like of the meta-aramid fiber are reserved, meanwhile, the light fastness of the meta-aramid fiber can be effectively improved, the operation is simple, the reaction condition is mild, the used reagents are low-toxic or nontoxic substances, the safety is high, and the method has good environmental protection significance.
Drawings
FIG. 1 is a scanning electron microscope image of a cross section of a modified meta-aramid fiber prepared in example 2.
Fig. 2 is a scanning electron microscope image of a cross section of the meta-aramid fiber prepared in comparative example 1.
Detailed Description
The following describes the present invention in detail. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
A preparation method of modified meta-aramid fiber for improving light fastness, which comprises the following steps:
S1, under the protection of inert gas, in a solvent, reacting isophthaloyl dichloride with a hyperbranched polymer and an inorganic ultraviolet absorbent to obtain a polymerization liquid mixture;
S2, slowly adding the polymerization liquid mixture into m-phenylenediamine in batches under the polymerization condition for reaction, and after the reaction is finished, carrying out neutralization treatment to remove inorganic acid generated by the reaction;
s3, adding isophthaloyl dichloride and an organic ultraviolet absorbent into the system in the step S2 to react, and adding a neutralizer to neutralize after the reaction is finished to obtain a modified aramid stock solution;
S4, the modified meta-aramid fiber is obtained by the spinning process of the modified aramid stock solution.
Specifically, the hyperbranched polymer is at least one of hydroxyl-terminated aliphatic hyperbranched polyester, carboxyl-terminated aromatic hyperbranched polyester, amino-terminated hyperbranched polyamide, hydroxyl-terminated hyperbranched polyamide, carboxyl-terminated hyperbranched polyamide, hydroxyl-terminated aromatic hyperbranched polymer and carboxyl-terminated aliphatic hyperbranched polymer.
Specifically, the inorganic ultraviolet absorbent is at least one of titanium dioxide and zinc oxide, and the particle size of the inorganic ultraviolet absorbent is 30-2000 nm.
Specifically, the organic ultraviolet absorbent is at least one of benzophenone-2, 2-hydroxy-4-methoxybenzophenone, 2', 4' -tetrahydroxybenzophenone, 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, 2' -methylenebis (4-tert-octyl-6-benzotriazole phenol), 4-dimethylaminobenzoic acid, octyl triazinone, N- (2-ethoxyphenyl) -N ' - (2-ethylphenyl) -glyoxalic acid diamide.
Specifically, the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
Specifically, the total amount of the intermediate phthaloyl chloride in the step S1 and the intermediate phthaloyl chloride in the step S3 is calculated according to 100%, and the dosage of the intermediate phthaloyl chloride in the step S1 is 93% -96%; the consumption of the intermediate phthaloyl chloride in the step S3 is 4% -7%;
In the preparation method, the ratio of the total molar quantity of the m-phenylenediamine to the m-phthaloyl chloride is 1:0.99-1.05;
The dosage of the hyperbranched polymer is 0.1-5% of the mass of the modified aramid stock solution; the dosage of the inorganic ultraviolet absorber is 0.3-3% of the mass of the modified aramid stock solution; the dosage of the organic ultraviolet absorber is 0.1-6% of the mass of the modified aramid stock solution.
Specifically, the reaction temperature in the step S1 is 30-65 ℃ and the reaction time is 2-4 hours; the reaction temperature in the step S2 is-15-25 ℃, and the reaction time is 1-2 hours; the reaction temperature in the step S2 is 30-50 ℃ and the reaction time is 1-2 h.
Specifically, the solid content of the modified aramid stock solution is 4% -23%, the viscosity is 300-900 Pa.s, the pH value is 7-8, and the molecular weight distribution of the polymer in the modified aramid stock solution is Mw/Mn=1-1.5.
Specifically, in step S4, after the modified aramid stock solution is sprayed out through a spinning nozzle, the modified meta-aramid fiber is obtained through coagulation bath, stretching bath stretching, hot water bath stretching, heat setting, oiling and drying in sequence.
Specifically, the number of holes of the spinning cap is 1000-40000, and the aperture is 0.03-0.13mm;
the temperature of the coagulating bath is 25-50 ℃, and the concentration of the N, N-dimethylacetamide aqueous solution in the coagulating bath is 55-65%;
the temperature of the stretching bath is 25-50 ℃, and the concentration of the N, N-dimethylacetamide aqueous solution in the stretching bath is 45-60%;
the temperature of the hot water bath is 60-75 ℃;
The heat setting temperature is 300-400 ℃, and the heat setting time is 2-5 min; the oiling concentration is 0.1% -2%; the drying temperature is 100-180 ℃.
Example 1
A preparation method of modified meta-aramid fiber for improving light fastness comprises the following steps:
(1) Preparation of the polymerization liquid mixture:
the hydroxyl-terminated aliphatic hyperbranched polyester (the addition amount is 0.1% of the mass of the theoretical aramid polymer stock solution; the market manufacturer and model are the chemical company of Wuhan hyperbranched resin, hyPer H and 10) and titanium dioxide with the particle size of 2000nm (the addition amount is 3% of the mass of the theoretical aramid polymer stock solution) are both dissolved in N, N-dimethylacetamide and are subjected to ultrasonic treatment for 90min to prepare a solution with the mass concentration of 15%; under the protection of dry N 2, adding the prepared solution into isophthaloyl dichloride (the mass ratio of the solution to the isophthaloyl dichloride is 1:19), carrying out ultrasonic treatment for 10min, controlling the polymerization temperature to 65 ℃, stirring at the speed of 1000r/min, and reacting for 2h to obtain a polymerization liquid mixture.
(2) Pre-condensing the aramid polymer stock solution:
Under the polymerization condition, m-phenylenediamine is dissolved in N, N-dimethylacetamide to prepare a solution with the mass concentration of 15%, after ultrasonic treatment is carried out for 10min, a polymerization solution mixture is slowly added into the solution in batches for reaction, stirring is carried out at the rotating speed of 500r/min, the temperature is controlled to be minus 15 ℃, the reaction time is 2h, a neutralizing agent calcium oxide is added after the reaction is finished to neutralize inorganic acid in the polymerization solution, and salts generated by neutralization are removed by filtration.
(3) Preparing a modified aramid stock solution:
Adding isophthaloyl dichloride into the system in the step (2), gradually and slowly dripping an organic ultraviolet absorbent of 2-hydroxy-4-methoxyl benzophenone (the addition amount is 6% of the mass of the theoretical aramid polymer stock solution), stirring at a rotating speed of 1000r/min, controlling the temperature at 50 ℃ for 2 hours, and adding a neutralizer after the reaction is finished to neutralize inorganic acid generated in the polymerization process to obtain a modified aramid polymer stock solution;
The total amount of the intermediate phthaloyl chloride in the step (1) and the intermediate phthaloyl chloride in the step (3) is calculated as 100%, and the dosage of the intermediate phthaloyl chloride in the step (1) is 97%; the dosage of the intermediate phthaloyl chloride in the step (3) is 3%; the ratio of the total molar amounts of m-phenylenediamine (in step (2)) and m-phthaloyl chloride (steps (1) and (3)) was 1:1.05;
The mass concentration of the aramid polymer in the modified aramid stock solution is 23%, the viscosity is 900Pa.s, the pH value is 7, and the molecular weight distribution of the aramid polymer is Mw/Mn=1.
(4) And (3) forming modified meta-aramid fiber:
after defoaming the modified aramid stock solution obtained in the step (3), introducing the defoamed modified aramid stock solution into a coagulating bath consisting of N, N-dimethylacetamide and water through a 1000-hole spinneret plate with the aperture of 0.13mm, wherein the concentration of the N, N-dimethylacetamide is 55%, the bath temperature is 50 ℃, and then introducing the defoamed modified aramid stock solution into a stretching bath with the concentration of the N, N-dimethylacetamide of 45% for stretching, wherein the stretching ratio is 1:1.5, the bath temperature is 50 ℃, then the fiber is put into hot water bath with the temperature of 75 ℃ for 1.2 times of drafting, and is oiled after heat setting for 5min at 400 ℃, the oiling concentration is 2%, the drying temperature is 180 ℃, and finally the modified meta-aramid fiber is obtained after curling and cutting.
Example 2
A preparation method of modified meta-aramid fiber for improving light fastness comprises the following steps:
(1) Preparation of the polymerization liquid mixture:
Carboxyl-terminated aromatic hyperbranched polyester (the addition amount is 3% of the mass of the theoretical modified aramid stock solution; the market manufacturer and model are the chemical Co., ltd.; hyPer C) and titanium dioxide with the particle size of 30nm (the addition amount is 3% of the theoretical modified aramid stock solution) are both dissolved in N, N-dimethylformamide, and the solution with the mass concentration of 15% is prepared by ultrasonic treatment for 90 min; under the protection of dry N 2, adding the prepared solution into isophthaloyl dichloride (the mass ratio of the solution to the isophthaloyl dichloride is 1:19), carrying out ultrasonic treatment for 10min, controlling the polymerization temperature to be 30 ℃, stirring at the speed of 1000r/min, and reacting for 4h to obtain a polymerization liquid mixture.
(2) Pre-condensing the aramid polymer stock solution:
Under the polymerization condition, m-phenylenediamine is dissolved in N, N-dimethylformamide to prepare a solution with the mass concentration of 15%, after ultrasonic treatment is carried out for 10min, the solution is slowly added into a polymerization solution mixture in batches for reaction, the reaction is carried out at the rotating speed of 500r/min, the temperature is controlled to be 0 ℃, the reaction time is 1.5h, a neutralizing agent sodium carbonate is added after the reaction is finished to neutralize inorganic acid in the polymerization solution, and salts generated by neutralization are filtered and removed.
(3) Preparing a modified aramid stock solution:
Adding isophthaloyl dichloride into the system in the step (2), gradually and slowly dripping 2,2', 4' -tetrahydroxybenzophenone organic ultraviolet absorbent (the addition amount is 0.1% of the mass of the theoretical modified aramid stock solution), stirring at a stirring speed of 1000r/min, controlling the temperature to be 30 ℃ for reaction for 1h, and adding a neutralizer to neutralize inorganic acid generated in the polymerization process after the reaction is finished to obtain the modified aramid stock solution;
The total amount of the intermediate phthaloyl chloride in the step (1) and the intermediate phthaloyl chloride in the step (3) is calculated as 100%, and the dosage of the intermediate phthaloyl chloride in the step (1) is 96%; the dosage of the intermediate phthaloyl chloride in the step (3) is 4%; the ratio of the total molar amounts of m-phenylenediamine (in step (2)) and m-phthaloyl chloride (steps (1) and (3)) was 1:1, a step of;
the mass concentration of the aramid polymer in the modified aramid stock solution is 16%, the viscosity is 600Pa.s, the pH value is 7.5, and the molecular weight distribution of the aramid polymer is Mw/Mn=1.25.
(4) And (3) forming modified meta-aramid fiber:
After defoaming the modified aramid stock solution obtained in the step (3), introducing the modified aramid stock solution into a coagulating bath consisting of N, N-dimethylacetamide and water through a 40000-hole spinneret plate with the aperture of 0.03mm, wherein the concentration of the N, N-dimethylacetamide is 65%, the bath temperature is 25 ℃, and then introducing the modified aramid stock solution into a stretching bath with the concentration of the N, N-dimethylacetamide of 60% for stretching, wherein the stretching ratio is 1:1.5, the bath temperature is 25 ℃, then the fiber is put into a hot water bath with the temperature of 60 ℃ for 1.2 times of drafting, and is oiled after heat setting with the temperature of 300 ℃ for 2min, the oiling concentration is 0.1%, the drying temperature is 100 ℃, and finally the modified meta-aramid fiber is obtained after curling and cutting. The scanning electron microscope image of the cross section of the modified meta-aramid fiber is shown in fig. 1, and it can be seen from fig. 1 that each functional auxiliary agent (hyperbranched polymer, organic ultraviolet absorbent and inorganic ultraviolet absorbent) is uniformly dispersed in the fiber, a large number of active end groups of the carboxyl-terminated aromatic hyperbranched polyester form effective chemical combination with meta-aramid stock solution and the 2', 4' -tetrahydroxybenzophenone organic ultraviolet absorbent, and the carboxyl-terminated aromatic hyperbranched polyester can enable the inorganic ultraviolet absorbent to be dispersed in a porous three-dimensional structure, so that agglomeration caused by mutual collision among particles is avoided, and the stability of the inorganic ultraviolet absorbent is improved.
Example 3
A preparation method of modified meta-aramid fiber for improving light fastness comprises the following steps:
(1) Preparation of the polymerization liquid mixture:
Dissolving amino-terminated hyperbranched polyamide (the addition amount is 5% of the mass of the theoretical aramid polymer stock solution; the market manufacturer and model are the chemical Co., ltd.; hyPer N) and zinc oxide with the particle size of 30nm (the addition amount is 0.3% of the mass of the theoretical aramid polymer stock solution) in N-methylpyrrolidone, and carrying out ultrasonic treatment for 90min to prepare a solution with the mass concentration of 15%; under the protection of dry N 2, adding the prepared solution into isophthaloyl dichloride (the mass ratio of the solution to the isophthaloyl dichloride is 1:19), carrying out ultrasonic treatment for 10min, controlling the polymerization temperature to be 50 ℃, stirring at the speed of 1000r/min, and reacting for 3h to obtain a polymerization liquid mixture.
(2) Pre-condensing the aramid polymer stock solution:
Under the polymerization condition, m-phenylenediamine is dissolved in N-methylpyrrolidone to prepare a solution with the mass concentration of 15%, after ultrasonic treatment is carried out for 10min, a polymerization solution mixture is slowly added into the solution in batches for reaction, the reaction is carried out under the condition of 500r/min while stirring, the reaction is carried out at the temperature of 25 ℃ for 1h, a neutralizing agent calcium hydroxide is added after the reaction is finished to neutralize inorganic acid in the polymerization solution, and salts generated by neutralization are removed by filtration.
(3) Preparing a modified aramid stock solution:
Adding isophthaloyl dichloride into the system in the step (2), gradually and slowly dripping 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorinated benzotriazole organic ultraviolet absorbent (the addition amount is 0.5% of the mass of the theoretical aramid polymer stock solution), stirring at a stirring speed of 1000r/min, controlling the temperature to be 50 ℃ and the reaction time to be 1.5h, and adding a neutralizing agent to neutralize inorganic acid generated in the polymerization process after the reaction is finished to obtain modified aramid stock solution;
The total amount of the intermediate phthaloyl chloride in the step (1) and the intermediate phthaloyl chloride in the step (3) is calculated as 100%, and the dosage of the intermediate phthaloyl chloride in the step (1) is 95%; the dosage of the intermediate phthaloyl chloride in the step (3) is 5%; the ratio of the total molar amounts of m-phenylenediamine (in step (2)) and m-phthaloyl chloride (steps (1) and (3)) was 1:0.99;
The mass concentration of the aramid polymer in the modified aramid stock solution is 4%, the viscosity is 300Pa.s, the pH value is 8, and the molecular weight distribution Mw/Mn of the aramid polymer is=1.5.
(4) And (3) forming modified meta-aramid fiber:
After defoaming the modified aramid stock solution obtained in the step (3), introducing the modified aramid stock solution into a coagulating bath consisting of N, N-dimethylacetamide and water through a 10000-hole spinneret plate with the aperture of 0.1mm, wherein the concentration of the N, N-dimethylacetamide is 65%, the bath temperature is 25 ℃, and then introducing the modified aramid stock solution into a stretching bath with the concentration of the N, N-dimethylacetamide of 60% for stretching, wherein the stretching ratio is 1:1.5, the bath temperature is 25 ℃, then the fiber is put into a hot water bath with the temperature of 60 ℃ for 1.2 times of drafting, and is oiled after heat setting for 4min at 400 ℃, the oiling concentration is 1%, the drying temperature is 150 ℃, and finally the modified meta-aramid fiber is obtained after curling and cutting.
Example 4
A preparation method of modified meta-aramid fiber for improving light fastness comprises the following steps:
(1) Preparation of the polymerization liquid mixture:
Dissolving hydroxyl-terminated aromatic hyperbranched polymer (the addition amount is 2% of the mass of the theoretical aramid polymer stock solution; the market manufacturer and model are chemical Co., ltd.; hyPer H) and titanium dioxide with the particle size of 1000nm (the addition amount is 2% of the mass of the theoretical aramid polymer stock solution) in dimethyl sulfoxide, and carrying out ultrasonic treatment for 90min to prepare a solution with the mass concentration of 15%; under the protection of dry N 2, adding the prepared solution into isophthaloyl dichloride (the mass ratio of the solution to the isophthaloyl dichloride is 1:19), carrying out ultrasonic treatment for 10min, controlling the polymerization temperature to be 50 ℃, stirring at the speed of 1000r/min, and reacting for 3h to obtain a polymerization liquid mixture.
(2) Pre-condensing the aramid polymer stock solution:
Under the polymerization condition, m-phenylenediamine is dissolved in dimethyl sulfoxide to prepare a solution with the mass ratio of 13%, after ultrasonic treatment is carried out for 10min, a polymerization liquid mixture is slowly added into the solution in batches for reaction, the temperature is controlled to be 20 ℃ while stirring is carried out at the rotating speed of 500r/min, the reaction time is 2h, a neutralizing agent sodium hydroxide is added after the reaction is finished to neutralize inorganic acid in the polymerization liquid, and salts generated by neutralization are removed through filtration.
(3) Preparing a modified aramid stock solution:
adding isophthaloyl dichloride into the system in the step (2), gradually and slowly dripping octyl triazinone organic ultraviolet absorber (the addition amount is 0.1% of the mass of the theoretical aramid polymer stock solution), stirring at 1000r/min, controlling the temperature at 50 ℃, reacting for 1h, and adding a neutralizing agent to neutralize inorganic acid generated in the polymerization process after the reaction is finished to obtain a modified aramid stock solution;
the total amount of the intermediate phthaloyl chloride in the step (1) and the intermediate phthaloyl chloride in the step (3) is calculated as 100%, and the dosage of the intermediate phthaloyl chloride in the step (1) is 94%; the dosage of the intermediate phthaloyl chloride in the step (3) is 6%; the ratio of the total molar amounts of m-phenylenediamine (in step (2)) and m-phthaloyl chloride (steps (1) and (3)) was 1:1, a step of;
The mass concentration of the aramid polymer in the modified aramid stock solution is 18%, the viscosity is 900Pa.s, the pH value is 7, and the molecular weight distribution Mw/Mn=1 of the aramid polymer.
(4) And (3) forming modified meta-aramid fiber:
after defoaming the modified aramid stock solution obtained in the step (3), introducing the modified aramid stock solution into a coagulating bath consisting of N, N-dimethylacetamide and water through a 20000 hole spinneret plate with the aperture of 0.06mm, wherein the concentration of the N, N-dimethylacetamide is 65%, the bath temperature is 25 ℃, and then introducing the modified aramid stock solution into a stretching bath with the concentration of the N, N-dimethylacetamide of 60% for stretching, wherein the stretching ratio is 1:1.5, the bath temperature is 25 ℃, then the fiber is put into a hot water bath with the temperature of 60 ℃ for 1.2 times of drafting, and is oiled after heat setting for 4min at 300 ℃, the oiling concentration is 1%, the drying temperature is 180 ℃, and finally the modified meta-aramid fiber is obtained after curling and cutting.
Example 5
A preparation method of modified meta-aramid fiber for improving light fastness comprises the following steps:
(1) Preparation of the polymerization liquid mixture:
The preparation method comprises the steps of dissolving hydroxyl-terminated hyperbranched polyamide (the addition amount is 0.5% of the mass of the theoretical aramid polymer stock solution respectively; the manufacturers and the models of the hydroxyl-terminated hyperbranched polyamide are WU-arm hyperbranched resin science and technology Co., hyPer HPN202,202) and titanium dioxide with the particle size of 60nm and zinc oxide with the particle size of 60nm (the addition amount is 0.3% of the mass of the theoretical aramid polymer stock solution respectively) in N, N-dimethylacetamide, and carrying out ultrasonic treatment for 90min to prepare a solution with the mass concentration of 15%; under the protection of dry N 2, adding the prepared solution into isophthaloyl dichloride (the mass ratio of the solution to the isophthaloyl dichloride is 1:19), carrying out ultrasonic treatment for 10min, controlling the polymerization temperature to be 50 ℃, stirring at the speed of 1000r/min, and reacting for 3h to obtain a polymerization liquid mixture.
(2) Pre-condensing the aramid polymer stock solution:
Under the polymerization condition, m-phenylenediamine is dissolved in N, N-dimethylacetamide to prepare a solution with the mass concentration of 15%, after ultrasonic treatment is carried out for 10min, a polymerization solution mixture is slowly added into the solution in batches for reaction, the temperature is controlled at 20 ℃ while stirring is carried out at the speed of 500r/min, the reaction time is 2h, a neutralizing agent sodium carbonate is added after the reaction is finished to neutralize inorganic acid in the polymerization solution, and salts generated by neutralization are removed by filtration.
(3) Preparing a modified aramid stock solution:
Adding m-phthaloyl chloride into the system in the step (2), gradually and slowly dripping 2,2' -methylenebis (4-tert-octyl-6-benzotriazole phenol) and 4-dimethylaminobenzoic acid organic ultraviolet absorbent (the addition amounts are 0.1% of the mass of the theoretical aramid polymer stock solution respectively), stirring at a stirring speed of 1000r/min, controlling the temperature at 50 ℃ and the reaction time at 1.5h, and adding a neutralizing agent to neutralize inorganic acid generated in the polymerization process after the reaction is finished to obtain a modified aramid stock solution;
The total amount of the intermediate phthaloyl chloride in the step (1) and the intermediate phthaloyl chloride in the step (3) is calculated as 100%, and the dosage of the intermediate phthaloyl chloride in the step (1) is 94%; the dosage of the intermediate phthaloyl chloride in the step (3) is 6%; the ratio of the total molar amounts of m-phenylenediamine (in step (2)) and m-phthaloyl chloride (steps (1) and (3)) was 1:0.99;
the mass concentration of the aramid polymer in the modified aramid stock solution is 18%, the viscosity is 800Pa.s, the pH value is 7, and the molecular weight distribution Mw/Mn of the aramid polymer is=1.1.
(4) And (3) forming modified meta-aramid fiber:
after defoaming the modified aramid stock solution obtained in the step (3), introducing the modified aramid stock solution into a coagulating bath consisting of N, N-dimethylacetamide and water through a 3000-hole spinneret plate with the aperture of 0.1mm, wherein the concentration of the N, N-dimethylacetamide is 65%, the bath temperature is 25 ℃, and then introducing the modified aramid stock solution into a stretching bath with the concentration of the N, N-dimethylacetamide of 60% for stretching, wherein the stretching ratio is 1:1.5, the bath temperature is 25 ℃, then the fiber is put into a hot water bath with the temperature of 60 ℃ for 1.2 times of drafting, and is oiled after heat setting for 4min at 300 ℃, the oiling concentration is 0.8%, the drying temperature is 180 ℃, and finally the modified meta-aramid fiber is obtained after curling and cutting.
Comparative example 1
Meta-aramid fiber was prepared by the same method as in example 2 except that: the hyperbranched polymer, the inorganic ultraviolet absorbent and the organic ultraviolet absorbent are not added, and the specific preparation process is as follows:
a preparation method of modified meta-aramid fiber for improving light fastness comprises the following steps:
(1) The isophthaloyl dichloride is dissolved in N, N-dimethylformamide, the ultrasonic treatment is carried out for 10min, and then the polymerization temperature is controlled to be 30 ℃ to obtain a uniform isophthaloyl dichloride solution.
(2) Pre-condensing the aramid polymer stock solution:
under the polymerization condition, m-phenylenediamine is dissolved in N, N-dimethylformamide to prepare a solution with the mass concentration of 15%, after ultrasonic treatment is carried out for 10min, the solution is slowly added into the m-phthaloyl chloride solution in the step (1) in batches for reaction, stirring is carried out at the rotating speed of 500r/min, the temperature is controlled to be 0 ℃, the reaction time is 1.5h, a neutralizing agent sodium carbonate is added after the reaction is finished to neutralize inorganic acid in the polymerization solution, and salts generated by neutralization are removed by filtration.
(3) Preparing an aramid fiber stock solution:
Adding isophthaloyl dichloride into the system in the step (2), stirring at a stirring speed of 1000r/min, controlling the temperature to be 30 ℃ for reaction for 1h, and adding a neutralizing agent to neutralize inorganic acid generated in the polymerization process after the reaction is finished to obtain an aramid stock solution;
The total amount of the intermediate phthaloyl chloride in the step (1) and the intermediate phthaloyl chloride in the step (3) is calculated as 100%, and the dosage of the intermediate phthaloyl chloride in the step (1) is 96%; the dosage of the intermediate phthaloyl chloride in the step (3) is 4%; the ratio of the total molar amounts of m-phenylenediamine (in step (2)) and m-phthaloyl chloride (steps (1) and (3)) was 1:1, a step of;
the mass concentration of the aramid polymer in the modified aramid stock solution is 16%, the viscosity is 590Pa.s, the pH value is 7.5, and the molecular weight distribution of the aramid polymer is Mw/Mn=1.
(4) And (3) forming modified meta-aramid fiber:
After defoaming the aramid stock solution obtained in the step (3), introducing the aramid stock solution into a coagulating bath consisting of N, N-dimethylacetamide and water through a 40000-hole spinneret plate with the aperture of 0.03mm, wherein the concentration of the N, N-dimethylacetamide is 65%, the bath temperature is 25 ℃, and then introducing the aramid stock solution into a stretching bath with the concentration of the N, N-dimethylacetamide of 60% for stretching, wherein the stretching ratio is 1:1.5, the bath temperature is 25 ℃, then the fiber is put into a hot water bath with the temperature of 60 ℃ for 1.2 times of drafting, and is oiled after heat setting for 2 minutes at 300 ℃, the oiling concentration is 0.1%, the drying temperature is 100 ℃, and finally the meta-aramid fiber is obtained after curling and cutting. The scanning electron microscope diagram of the meta-aramid fiber cross section is shown in fig. 2, and can be seen from the comparison of fig. 2 and fig. 1: the meta-aramid fiber of figure 2 has a smoother cross section, no agglomeration or cavitation, and no reactive auxiliary agent in the fiber.
Meta-aramid fiber, also called poly-m-phenylene isophthalamide fiber, is a rigid macromolecule with amide groups and benzene rings connected, orderly arranged molecular chains, whereas meta-aramid fiber is a light-sensitive organic fiber, a large number of chromophores (amide groups and benzene rings) contained in the molecular chains are easy to absorb ultraviolet radiation to cause amide bond fracture, accelerate oxidative degradation of the macromolecular chains, destroy the regular structure of meta-aramid fiber, damage the mechanical properties of fiber, and because intermolecular hydrogen bonds exist between the amide groups, the structure is compact, the crystallinity is very high, functional additives are difficult to enter the fiber, so that a proper anti-ultraviolet aging agent is selected, an effective anti-ultraviolet modification method is designed, the light fastness of fiber is improved, the service life of fiber is prolonged, and the meta-aramid fiber is one of hot spots for modification research
Comparative example 2
Meta-aramid fiber was prepared by the same method as in example 2 except that: no hyperbranched polymer was added.
Experiments show that the organic ultraviolet absorber cannot be effectively grafted in the meta-aramid stock solution molecular chain due to the fact that the hyperbranched polymer does not act as a bridge, and the inorganic ultraviolet absorber cannot be dispersed in a porous three-dimensional structure, so that the organic ultraviolet absorber and the inorganic ultraviolet absorber are seriously aggregated, and the modified aramid stock solution cannot be spun.
Comparative example 3
Meta-aramid fiber was prepared by the same method as in example 2 except that: the required isophthaloyl dichloride in the whole preparation process is used in the step (1), and the isophthaloyl dichloride is not added in the step (3), and the specific process is as follows:
(1) Preparation of the polymerization liquid mixture:
Carboxyl-terminated aromatic hyperbranched polyester (the addition amount is 3% of the mass of the theoretical modified aramid stock solution; the market manufacturer and model are the chemical Co., ltd.; hyPer C) and titanium dioxide with the particle size of 30nm (the addition amount is 3% of the theoretical modified aramid stock solution) are both dissolved in N, N-dimethylformamide, and the solution with the mass concentration of 15% is prepared by ultrasonic treatment for 90 min; under the protection of dry N 2, adding the prepared solution into isophthaloyl dichloride (the mass ratio of the solution to the isophthaloyl dichloride is 1:19), carrying out ultrasonic treatment for 10min, controlling the polymerization temperature to be 30 ℃, stirring at the speed of 1000r/min, and reacting for 4h to obtain a polymerization liquid mixture.
(2) Pre-condensing the aramid polymer stock solution:
under the polymerization condition, m-phenylenediamine is dissolved in N, N-dimethylformamide to prepare a solution with the mass concentration of 15%, after ultrasonic treatment is carried out for 10min, the solution is slowly added into a polymerization solution mixture in batches for reaction, the reaction is carried out at the rotating speed of 500r/min, the temperature is controlled to be 0 ℃, the reaction time is 1.5h, a neutralizing agent sodium carbonate is added after the reaction is finished to neutralize inorganic acid in the polymerization solution, and salts generated by neutralization are filtered and removed. The ratio of m-phenylenediamine (in step (2)) to m-phthaloyl chloride molar amount (in step (1)) was 1:1.
(3) Preparing a modified aramid stock solution:
Gradually and slowly dripping 2,2', 4' -tetrahydroxybenzophenone organic ultraviolet absorbent (the addition amount is 0.1% of the mass of the theoretical modified aramid stock solution) into the system in the step (2), stirring at a stirring speed of 1000r/min, controlling the temperature to be 30 ℃ for reaction, and obtaining the modified aramid stock solution after the reaction is finished for 1 h;
The mass concentration of the aramid polymer in the modified aramid stock solution is 16%, the viscosity is 580Pa.s, the pH value is 7.5, and the molecular weight distribution of the aramid polymer is Mw/Mn=1.25.
(4) And (3) forming modified meta-aramid fiber:
After defoaming the modified aramid stock solution obtained in the step (3), introducing the modified aramid stock solution into a coagulating bath consisting of N, N-dimethylacetamide and water through a 40000-hole spinneret plate with the aperture of 0.03mm, wherein the concentration of the N, N-dimethylacetamide is 65%, the bath temperature is 25 ℃, and then introducing the modified aramid stock solution into a stretching bath with the concentration of the N, N-dimethylacetamide of 60% for stretching, wherein the stretching ratio is 1:1.5, the bath temperature is 25 ℃, then the fiber is put into a hot water bath with the temperature of 60 ℃ for 1.2 times of drafting, and is oiled after heat setting with the temperature of 300 ℃ for 2min, the oiling concentration is 0.1%, the drying temperature is 100 ℃, and finally the modified meta-aramid fiber is obtained after curling and cutting.
Comparative example 4
Meta-aramid fiber was prepared by the same method as in example 2 except that: the step (1) and the step (2) are carried out simultaneously, and the specific process is as follows:
(1) Preparation of a polymerization solution mixture and pre-polycondensation of an aramid polymer stock solution:
Carboxyl-terminated aromatic hyperbranched polyester (the addition amount is 3% of the mass of the theoretical modified aramid stock solution; the market manufacturer and model are the chemical Co., ltd.; hyPer C) and titanium dioxide with the particle size of 30nm (the addition amount is 3% of the theoretical modified aramid stock solution) are both dissolved in N, N-dimethylformamide, and the solution with the mass concentration of 15% is prepared by ultrasonic treatment for 90 min;
M-phenylenediamine is dissolved in N, N-dimethylformamide to prepare a solution with the mass concentration of 15%, and the solution is subjected to ultrasonic treatment for 10min to be uniform;
Under the protection of dry N 2, slowly adding the two solutions into isophthaloyl dichloride, carrying out ultrasonic treatment for 10min, controlling the polymerization temperature to be 30 ℃, stirring at a speed of 1000r/min, reacting for 4h, adding a neutralizing agent sodium carbonate to neutralize inorganic acid in the polymerization solution after the reaction is finished, and filtering to remove salt generated by neutralization.
(2) Preparing a modified aramid stock solution:
Adding isophthaloyl dichloride into the system in the step (1), gradually and slowly dripping 2,2', 4' -tetrahydroxybenzophenone organic ultraviolet absorbent (the addition amount is 0.1% of the mass of the theoretical modified aramid stock solution), stirring at a stirring speed of 1000r/min, controlling the temperature to be 30 ℃ for reaction for 1h, and adding a neutralizer to neutralize inorganic acid generated in the polymerization process after the reaction is finished to obtain the modified aramid stock solution;
The total amount of the intermediate phthaloyl chloride in the step (1) and the intermediate phthaloyl chloride in the step (2) is calculated as 100%, and the dosage of the intermediate phthaloyl chloride in the step (1) is 96%; the dosage of the intermediate phthaloyl chloride in the step (2) is 4%; the ratio of the total molar amounts of m-phenylenediamine (in step (2)) and m-phthaloyl chloride (steps (1) and (2)) was 1:1, a step of;
the mass concentration of the aramid polymer in the modified aramid stock solution is 16%, the viscosity is 620Pa.s, the pH value is 7.5, and the molecular weight distribution of the aramid polymer is Mw/Mn=1.15.
(3) And (3) forming modified meta-aramid fiber:
After defoaming the modified aramid stock solution obtained in the step (2), introducing the modified aramid stock solution into a coagulating bath consisting of N, N-dimethylacetamide and water through a 40000-hole spinneret plate with the aperture of 0.03mm, wherein the concentration of the N, N-dimethylacetamide is 65%, the bath temperature is 25 ℃, and then introducing the modified aramid stock solution into a stretching bath with the concentration of the N, N-dimethylacetamide of 60% for stretching, wherein the stretching ratio is 1:1.5, the bath temperature is 25 ℃, then the fiber is put into a hot water bath with the temperature of 60 ℃ for 1.2 times of drafting, and is oiled after heat setting with the temperature of 300 ℃ for 2min, the oiling concentration is 0.1%, the drying temperature is 100 ℃, and finally the modified meta-aramid fiber is obtained after curling and cutting.
Comparative example 5
Meta-aramid fiber was prepared by the same method as in example 2 except that: the reaction temperature in step (1) was 20 ℃ (lower than the temperature conditions defined in the present invention), and the other conditions were exactly the same as in example 2.
Comparative example 6
Meta-aramid fiber was prepared by the same method as in example 2 except that: the whole preparation process does not use inorganic ultraviolet absorbent in the step (1), and the inorganic ultraviolet absorbent is added in the step (3), and the specific process is as follows:
(1) Preparation of the polymerization liquid mixture:
Carboxyl-terminated aromatic hyperbranched polyester (the addition amount is 3% of the mass of theoretical modified aramid stock solution; the market manufacturer and model are HyPer C% of Wuhan hyperbranched resin technology Co., ltd.) is dissolved in N, N-dimethylformamide, and is subjected to ultrasonic treatment for 90min to prepare a solution with the mass concentration of 7.5%; under the protection of dry N 2, adding the prepared solution into isophthaloyl dichloride (the mass ratio of the solution to the isophthaloyl dichloride is 1:19), carrying out ultrasonic treatment for 10min, controlling the polymerization temperature to be 30 ℃, stirring at the speed of 1000r/min, and reacting for 4h to obtain a polymerization liquid mixture.
(2) Pre-condensing the aramid polymer stock solution:
Under the polymerization condition, m-phenylenediamine is dissolved in N, N-dimethylformamide to prepare a solution with the mass concentration of 15%, after ultrasonic treatment is carried out for 10min, the solution is slowly added into a polymerization solution mixture in batches for reaction, the reaction is carried out at the rotating speed of 500r/min, the temperature is controlled to be 0 ℃, the reaction time is 1.5h, a neutralizing agent sodium carbonate is added after the reaction is finished to neutralize inorganic acid in the polymerization solution, and salts generated by neutralization are filtered and removed.
(3) Preparing a modified aramid stock solution:
Adding isophthaloyl dichloride into the system in the step (2), gradually and slowly dripping 2,2', 4' -tetrahydroxybenzophenone organic ultraviolet absorbent (the addition amount is 0.1% of the mass of the theoretical modified aramid stock solution) and titanium dioxide with the particle size of 30nm (the addition amount is 3% of the theoretical modified aramid stock solution), stirring at the stirring speed of 1000r/min, controlling the temperature to be 30 ℃ for reaction, controlling the reaction time to be 1h, and adding a neutralizing agent to neutralize inorganic acid generated in the polymerization process after the reaction is finished to obtain the modified aramid stock solution;
The total amount of the intermediate phthaloyl chloride in the step (1) and the intermediate phthaloyl chloride in the step (3) is calculated as 100%, and the dosage of the intermediate phthaloyl chloride in the step (1) is 96%; the dosage of the intermediate phthaloyl chloride in the step (3) is 4%; the ratio of the total molar amounts of m-phenylenediamine (in step (2)) and m-phthaloyl chloride (steps (1) and (3)) was 1:1, a step of;
the mass concentration of the aramid polymer in the modified aramid stock solution is 16%, the viscosity is 600Pa.s, the pH value is 7.5, and the molecular weight distribution of the aramid polymer is Mw/Mn=1.25.
(4) And (3) forming modified meta-aramid fiber:
After defoaming the modified aramid stock solution obtained in the step (3), introducing the modified aramid stock solution into a coagulating bath consisting of N, N-dimethylacetamide and water through a 40000-hole spinneret plate with the aperture of 0.03mm, wherein the concentration of the N, N-dimethylacetamide is 65%, the bath temperature is 25 ℃, and then introducing the modified aramid stock solution into a stretching bath with the concentration of the N, N-dimethylacetamide of 60% for stretching, wherein the stretching ratio is 1:1.5, the bath temperature is 25 ℃, then the fiber is put into a hot water bath with the temperature of 60 ℃ for 1.2 times of drafting, and is oiled after heat setting with the temperature of 300 ℃ for 2min, the oiling concentration is 0.1%, the drying temperature is 100 ℃, and finally the modified meta-aramid fiber is obtained after curling and cutting.
The meta-aramid fibers prepared in the above examples and comparative examples were subjected to performance testing, and the specific related testing method was as follows: GB/T8427-2019 (textile color fastness to artificial light fastness to xenon arc); GB/T19975-2005 (tensile Property test method for high-strength fiber filaments). The specific test results are shown in Table 1 below.
TABLE 1 aramid fiber performance parameters
From the data in Table 1 above, it can be seen that: the modified meta-aramid fiber prepared by the preparation method provided by the invention has the advantages that the light fastness, mechanical property and thermal stability of the meta-aramid fiber are effectively improved on the basis of keeping the high-strength and high-modulus characteristics of the aramid fiber. According to the preparation method, the hyperbranched polymer, the m-phenylenediamine and the isophthaloyl dichloride are used for preparing the modified aramid stock solution, a large number of active end groups of the hyperbranched polymer can react with the isophthaloyl dichloride and simultaneously can effectively adsorb the inorganic ultraviolet absorbent, the hyperbranched polymer has a three-dimensional structure and a larger space structure, electrostatic repulsion exists between the hyperbranched polymers, and the agglomeration behavior of the inorganic ultraviolet absorbent can be slowed down after the adsorption; the organic ultraviolet absorbent can react with active groups of the hyperbranched polymer, and the hyperbranched polymer, m-phenylenediamine and m-phthaloyl chloride continue to undergo chain growth polycondensation reaction, so that the organic ultraviolet absorbent is grafted on an aramid stock solution molecular chain, the compatibility and the dispersibility of the ultraviolet absorbent and the aramid stock solution are fundamentally improved, and the mechanical property of the aramid fiber is ensured.
From the comparison of comparative example 1 and example 2, it can be seen that: as no functional auxiliary agent is added, the inside of the aramid fiber is smooth and flat, no agglomeration and void phenomenon exist, and the mechanical property of the aramid fiber is slightly better than that of the embodiment 2, but the light fastness of the aramid fiber is poor in light fastness due to the fact that no ultraviolet absorbent is added.
From the comparison of comparative example 2 and example 2, it can be seen that: if the hyperbranched polymer is not added, the organic ultraviolet absorbent cannot be effectively grafted in the meta-aramid stock solution molecular chain without the bridge function of the hyperbranched polymer, and the inorganic ultraviolet absorbent cannot be dispersed in a porous three-dimensional structure, so that the agglomeration phenomenon of the organic/inorganic ultraviolet absorbent is serious, and the modified aramid stock solution cannot realize spinning.
From the comparison of comparative example 3 and example 2, it can be seen that: if the intermediate phthaloyl chloride is not used in batches in the whole preparation process, the intermediate phthaloyl chloride and the m-phenylenediamine completely react in the step (2) to form a stable high-molecular polymer, and the organic ultraviolet absorbent in the step (3) cannot further react with the aramid polymer stock solution, so that the organic ultraviolet absorbent is accumulated in the fiber, and the mechanical property and the light fastness grade of the fiber are affected.
From the comparison of comparative example 4 and example 2, it can be seen that: if the two reactions in the step (1) and the step (2) are carried out simultaneously, the hyperbranched polymer can react with the m-phthaloyl chloride and the m-phenylenediamine simultaneously, the product is uncontrollable, the polymerization between the m-phthaloyl chloride and the m-phenylenediamine is affected, the incomplete reaction can be possibly caused, the molding of the modified meta-aramid fiber is affected to a certain extent, and the mechanical property is reduced.
From the comparison of comparative example 5 and example 2, it can be seen that: if the reaction temperature in the step (1) is lower than the temperature defined by the invention, the isophthaloyl dichloride and the hyperbranched polymer do not carry out polymerization reaction, the organic ultraviolet absorbent cannot be effectively grafted on the molecular chain of the aramid stock solution, and the hyperbranched polymer, the organic ultraviolet absorbent and the inorganic ultraviolet absorbent are all accumulated in the fiber, so that the mechanical property and the light fastness grade of the fiber are seriously affected.
From the comparison of comparative example 6 and example 2, it can be seen that: if the inorganic ultraviolet absorbent is not used in the step (1), and the inorganic ultraviolet absorbent is added in the step (3), insufficient combination of the inorganic ultraviolet absorbent and the hyperbranched polymer is easily caused, the agglomeration phenomenon of the inorganic ultraviolet absorbent is obviously improved, and the mechanical properties of the fiber are affected.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of the modified meta-aramid fiber for improving the light fastness is characterized by comprising the following steps of:
S1, under the protection of inert gas, in a solvent, reacting isophthaloyl dichloride with a hyperbranched polymer and an inorganic ultraviolet absorbent to obtain a polymerization liquid mixture;
S2, slowly adding the polymerization liquid mixture into m-phenylenediamine in batches under the polymerization condition for reaction, and after the reaction is finished, carrying out neutralization treatment to remove inorganic acid generated by the reaction;
s3, adding isophthaloyl dichloride and an organic ultraviolet absorbent into the system in the step S2 to react, and adding a neutralizer to neutralize after the reaction is finished to obtain a modified aramid stock solution;
S4, the modified meta-aramid fiber is obtained by the spinning process of the modified aramid stock solution.
2. The method for preparing the modified meta-aramid fiber with improved light fastness according to claim 1, wherein the hyperbranched polymer is at least one of hydroxyl-terminated aliphatic hyperbranched polyester, carboxyl-terminated aromatic hyperbranched polyester, amino-terminated hyperbranched polyamide, hydroxyl-terminated hyperbranched polyamide, carboxyl-terminated hyperbranched polyamide, hydroxyl-terminated aromatic hyperbranched polymer and carboxyl-terminated aliphatic hyperbranched polymer.
3. The method for preparing the modified meta-aramid fiber with improved light fastness according to claim 1, wherein the inorganic ultraviolet absorbent is at least one of titanium dioxide and zinc oxide, and the particle size of the inorganic ultraviolet absorbent is 30-2000 nm.
4. The method for preparing a modified meta-aramid fiber with improved light fastness according to claim 1, wherein the organic ultraviolet absorber is at least one of benzophenone-2, 2-hydroxy-4-methoxybenzophenone, 2', 4' -tetrahydroxybenzophenone, 2- (2 ' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, 2' -methylenebis (4-tert-octyl-6-benzotriazole phenol), 4-dimethylaminobenzoic acid, octyltriazinone, N- (2-ethoxyphenyl) -N ' - (2-ethylphenyl) -ethanediamide.
5. The preparation method of the modified meta-aramid fiber with improved light fastness according to claim 1, wherein the total amount of the intermediate phthaloyl chloride in the step S1 and the intermediate phthaloyl chloride in the step S3 is calculated according to 100%, and the dosage of the intermediate phthaloyl chloride in the step S1 is 93% -96%; the consumption of the intermediate phthaloyl chloride in the step S3 is 4% -7%;
In the preparation method, the ratio of the total molar quantity of the m-phenylenediamine to the m-phthaloyl chloride is 1:0.99-1.05;
The dosage of the hyperbranched polymer is 0.1-5% of the mass of the modified aramid stock solution; the dosage of the inorganic ultraviolet absorber is 0.3-3% of the mass of the modified aramid stock solution; the dosage of the organic ultraviolet absorber is 0.1-6% of the mass of the modified aramid stock solution.
6. The method for preparing the modified meta-aramid fiber with improved light fastness according to claim 1, wherein the reaction temperature in the step S1 is 30-65 ℃ and the reaction time is 2-4 hours; the reaction temperature in the step S2 is-15-25 ℃, and the reaction time is 1-2 hours; the reaction temperature in the step S2 is 30-50 ℃ and the reaction time is 1-2 h.
7. The preparation method of the modified meta-aramid fiber with improved light fastness according to claim 1, wherein the solid content of the modified aramid fiber stock solution is 4% -23%, the viscosity is 300-900 pa.s, the pH value is 7-8, and the molecular weight distribution of the polymer in the modified aramid fiber stock solution is Mw/Mn=1-1.5.
8. The method for preparing the modified meta-aramid fiber with improved light fastness according to claim 1, wherein in the step S4, after the modified aramid fiber stock solution is sprayed out through a spinning cap, the modified meta-aramid fiber is obtained through coagulation bath, stretching bath stretching, hot water bath stretching, heat setting, oiling and drying.
9. The method for preparing the modified meta-aramid fiber with improved light fastness according to claim 8, wherein the number of holes of the spinning cap is 1000-40000, and the aperture is 0.03-0.13mm;
the temperature of the coagulating bath is 25-50 ℃, and the concentration of the N, N-dimethylacetamide aqueous solution in the coagulating bath is 55-65%;
the temperature of the stretching bath is 25-50 ℃, and the concentration of the N, N-dimethylacetamide aqueous solution in the stretching bath is 45-60%;
the temperature of the hot water bath is 60-75 ℃;
The heat setting temperature is 300-400 ℃, and the heat setting time is 2-5 min; the oiling concentration is 0.1% -2%; the drying temperature is 100-180 ℃.
10. A modified meta-aramid fiber having improved light fastness, wherein the modified meta-aramid fiber is prepared according to the preparation method of any one of claims 1 to 9.
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| CN1354767A (en) * | 1999-05-05 | 2002-06-19 | 罗迪亚尼尔公司 | Hyperbranched copolyamide, composition based on said hyperbranched copolyamide, and method for obtaining same |
| JP2009052150A (en) * | 2007-08-23 | 2009-03-12 | Toray Ind Inc | Fiber |
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| CN117248292A (en) * | 2023-09-26 | 2023-12-19 | 株洲时代新材料科技股份有限公司 | Preparation method of coloring meta-aramid fiber |
| CN117363007A (en) * | 2023-12-08 | 2024-01-09 | 烟台泰和新材高分子新材料研究院有限公司 | Modified aramid stock solution and preparation method and application thereof |
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| CN1354767A (en) * | 1999-05-05 | 2002-06-19 | 罗迪亚尼尔公司 | Hyperbranched copolyamide, composition based on said hyperbranched copolyamide, and method for obtaining same |
| JP2009052150A (en) * | 2007-08-23 | 2009-03-12 | Toray Ind Inc | Fiber |
| CN109438697A (en) * | 2018-09-27 | 2019-03-08 | 株洲时代新材料科技股份有限公司 | A kind of preparation method of aromatic amides |
| CN117248292A (en) * | 2023-09-26 | 2023-12-19 | 株洲时代新材料科技股份有限公司 | Preparation method of coloring meta-aramid fiber |
| CN117363007A (en) * | 2023-12-08 | 2024-01-09 | 烟台泰和新材高分子新材料研究院有限公司 | Modified aramid stock solution and preparation method and application thereof |
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