CN114606598A - Heterocyclic meta-aramid fiber and preparation method thereof - Google Patents
Heterocyclic meta-aramid fiber and preparation method thereof Download PDFInfo
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- CN114606598A CN114606598A CN202210403620.4A CN202210403620A CN114606598A CN 114606598 A CN114606598 A CN 114606598A CN 202210403620 A CN202210403620 A CN 202210403620A CN 114606598 A CN114606598 A CN 114606598A
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- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 131
- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 61
- 238000009987 spinning Methods 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 42
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims abstract description 40
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 39
- 238000009998 heat setting Methods 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 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 29
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 238000011033 desalting Methods 0.000 claims abstract description 17
- 230000009477 glass transition Effects 0.000 claims abstract description 15
- 238000001891 gel spinning Methods 0.000 claims abstract description 14
- 238000005096 rolling process Methods 0.000 claims abstract description 14
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims abstract description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920003235 aromatic polyamide Polymers 0.000 claims description 93
- 238000000034 method Methods 0.000 claims description 93
- 239000004760 aramid Substances 0.000 claims description 90
- 239000000243 solution Substances 0.000 claims description 69
- 229920000642 polymer Polymers 0.000 claims description 62
- 230000008569 process Effects 0.000 claims description 41
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical group C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 claims description 37
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 20
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 20
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 16
- 238000007711 solidification Methods 0.000 claims description 13
- 230000008023 solidification Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 230000015271 coagulation Effects 0.000 claims description 8
- 238000005345 coagulation Methods 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 239000002798 polar solvent Substances 0.000 claims description 8
- 239000006184 cosolvent Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 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
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 15
- 230000036632 reaction speed Effects 0.000 abstract description 6
- 229940113088 dimethylacetamide Drugs 0.000 description 13
- 239000000835 fiber Substances 0.000 description 11
- 230000001112 coagulating effect Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 238000000703 high-speed centrifugation Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000011160 research Methods 0.000 description 5
- 125000001246 bromo group Chemical group Br* 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229960002816 potassium chloride Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- PGXWDLGWMQIXDT-UHFFFAOYSA-N methylsulfinylmethane;hydrate Chemical compound O.CS(C)=O PGXWDLGWMQIXDT-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 iodo radical Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RAYLUPYCGGKXQO-UHFFFAOYSA-N n,n-dimethylacetamide;hydrate Chemical compound O.CN(C)C(C)=O RAYLUPYCGGKXQO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Images
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyamides (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a heterocyclic meta-aramid fiber with a general formula A and a preparation method thereof, wherein m and n are positive integers, the ratio of m to n is less than or equal to 1, and R is1、R2Respectively hydrogen radical, fluorine radical, chlorine radical, bromine radical and iodine radical. The preparation method comprises the steps of adding m-phenylenediamine, a third imidazolyl monomer and 4-pyrrolidinyl pyridine into a composite solvent in an inert atmosphere; adding m-phthaloyl chloride, and reacting at 40-70 ℃; adjusting pH, desalting, defoaming, carrying out dry-wet spinning, solidifying, washing, spinning, drying, hot stretching, heat setting and rolling to obtain the m-aramid fiber containing the bis-imidazolyl heterocycle. The glass transition temperature of the heterocyclic meta-aramid fiber is 320-380 ℃, and the loss temperature of 5% thermal mass is 370-470 ℃; breaking strength25-40 cN/dtex, elastic modulus 800-1500 cN/dtex, elongation at break 2.0-8.0%, fast reaction speed and high efficiency.
Description
Technical Field
The invention belongs to the field of aromatic polyamide and a synthetic method thereof, and relates to heterocyclic meta-aramid and a preparation method thereof.
Background
The heterocyclic aramid fiber is high-strength, high-modulus and high-temperature-resistant high-performance organic fiber, and is obtained by introducing a heterocyclic third monomer for copolymerization on the basis of the aramid fiber. The heterocyclic aramid fiber has excellent performances of high strength and high modulus, flame retardance, heat resistance, chemical corrosion resistance and the like, and is widely applied to the fields of aerospace, electronics, electricity, military protection and the like. The heterocyclic polyaramids can be classified into five-membered heterocyclic polyaramids and six-membered heterocyclic polyaramids according to the difference of heterocycles in the molecular main chain. The foreign heterocyclic aramid fiber representative product is mainly the APMOC of Russia®. The domestic heterocyclic aramid fiber is sold as aramid fiber III, the introduced third monomer is 5 (6) -amido-2- (4-aminophenyl) benzimidazole, and the main research and production units are as follows: zhonglan Chenguang chemical research design institute, Guangdong colourful GmbH, inner Mongolia synthetic chemical research institute, and Sichuan glow science and technology Inc. Due to the excellent mechanical property and thermal property of the heterocyclic aramid fiber, the heterocyclic aramid fiber is widely applied to the fields of military industry/aviation and the like.
Currently, the research on meta-heterocyclic aramid fiber is relatively lacked, and the preparation methods thereof mainly comprise three methods: (1) low-temperature solution polymerization; (2) emulsion polymerization; (3) interfacial polymerization. The method mainly used at present is a low-temperature solution polymerization method, and compared with the other two methods, the method has the advantages of small solvent consumption, high reaction efficiency, simple and convenient operation, economic production mode, low energy consumption and the like. The third monomer type mainly takes benzimidazole as a basic unit, and is not easy to be oxidized due to high amino stability and relatively low activity; the flexibility is enhanced, the crystal structure of the fiber forming process is prevented from being generated too early, and finally the unique fiber forming processing mechanism of the high-strength mode fiber is formed by the thermotropic liquid crystal behavior. Therefore, the formed heterocyclic meta-aramid has good orientation, high mechanical property, more stable color and higher temperature resistance.
In patent CN201910892704.7, aromatic diamine a and aromatic diamine B are dissolved in an amide polar solvent, and the mixed solution is cooled by freezing and then mixed with molten isophthaloyl dichloride at low temperature to react to obtain a meta-heterocyclic aramid solution; adopting a wet spinning process to obtain heterocyclic aramid 1313 fibers; however, the process of the heterocyclic aramid fiber is complex, and the mechanical property of the obtained meta-heterocyclic aramid fiber is not obviously improved compared with that of the traditional high-performance fiber. Some uses isophthaloyl dichloride and 2- (4-aminophenyl) -5-aminobenzimidazole as raw materials, uses N, N-dimethylacetamide as a solvent, introduces an imidazole structure into a main chain of a polyaramide molecule through low-temperature solution polycondensation, and then obtains a fiber filament through dry-wet spinning.
From the above analysis, the research on the heterocyclic meta-aramid is less at present, and various heterocyclic meta-aramid and the preparation method thereof have various disadvantages while introducing different third monomers, although the advantages are provided. For example, the use of benzimidazolyl as the third monomer basic unit for polymerization spinning can result in high energy consumption, high operation and treatment difficulty and the like, and the use of triazine heterocycles as the third monomer basic unit for polymerization spinning can result in low mechanical properties and low temperature resistance of the synthesized heterocyclic meta-aramid. The invention adopts a third imidazolyl monomer to perform low-temperature solution polymerization reaction with isophthaloyl chloride and m-phenylenediamine, creatively solves the problems of complicated operation, low raw material utilization rate, low reaction efficiency, low reaction speed and the like, is a preparation method of the heterocyclic meta-aramid with high efficiency, high reaction speed and simple and convenient operation, and the obtained heterocyclic meta-aramid has high mechanical property, good thermal property and durability.
Disclosure of Invention
The invention aims to solve the technical problems that the mechanical property, the thermal property and the durability of the conventional heterocyclic meta-aramid are difficult to be improved at the same time, the operation is complicated, the raw material utilization rate is low, the reaction efficiency is low, the reaction speed is low and the like in the prior art, and provides the heterocyclic meta-aramid and the preparation method thereof, which can not only expand the category of the conventional heterocyclic meta-aramid, but also endow the heterocyclic meta-aramid with high mechanical property, good thermal property and durability, and thus can be applied to the field of textile production of the heterocyclic meta-aramid. The invention solves the problems of the heterocyclic meta-aramid in the polymerization spinning production, such as complex operation, low utilization rate of raw materials, low reaction efficiency, low reaction speed and the like, and the obtained heterocyclic meta-aramid has excellent properties, abundant varieties and popularization value.
The invention aims to provide heterocyclic meta-aramid and a preparation method thereof, and particularly provides heterocyclic meta-aramid with high chemical performance, good thermal performance and durability and a preparation method thereof.
According to the preparation method of the heterocyclic meta-aramid, the chemical structure, the mechanical property and the thermal property of the heterocyclic meta-aramid are optimized and improved.
Crystallinity, molecular structure effects: due to the introduction of a part of heterocyclic structure, the structural regularity is reduced to a certain extent, so that the crystallinity is reduced, and the higher the content of the heterocyclic structure is, the more obvious the crystallinity is reduced. In the block polymer heterocyclic aramid fiber, a hydrogen bond is formed by amino and carbonyl groups of a block where a large-volume bis-imidazolyl third monomer is located, so that the crystal face distance is enlarged.
The elongation at break of the fiber increases with increasing proportion of the bisimidazole structure segments. This is mainly because the crystallinity gradually decreases with increasing content of the heterocyclic segment, and the larger the proportion of amorphous portion in the stretching process, the more easily the segment moves, macroscopically showing an increase in elongation at break; the double imidazole structure causes the distance between chains to be increased, the possibility of regular and compact arrangement required by crystallization is damaged, and an amorphous structure is formed in the spinning forming process. The introduction of the heterocyclic structure influences intermolecular force and molecular packing density, and finally influences the crystallinity and interplanar spacing of the fiber.
Mechanical properties: the improvement has two reasons, namely, the double imidazole structure is added, so that the solubility of the double imidazole structure is improved, higher relative molecular mass can be obtained during low-temperature polycondensation, and a polymer is not precipitated; on the other hand, although the introduction of the heterocyclic structure reduces the regularity of the molecular structure and intermolecular forces, the heterocyclic structure cannot be an ordered three-dimensional structure, and molecules can obtain the maximum orientation along the axial direction during subsequent spinning stretching and heat treatment, so that the tensile strength and the tensile modulus are improved.
Thermal properties: 1. thermogravimetric analysis-the initial thermal decomposition temperature tends to decrease gradually as the heterocyclic structure content increases. The method mainly corresponds to the crystallinity of several fibers, the higher the crystallinity, the more stable the aggregation structure, the less the content of amido bond in an amorphous area, and the lower the probability of molecular chain breakage, because the thermal decomposition of the aramid fiber is firstly started from the amido bond breakage. 2. Dynamic thermomechanical analysis-the glass transition temperature decreases with increasing proportion of heterocyclic segments. This is because the structure regularity and rigidity of the bisimidazolyl group are small, so that the molecular chain moves more easily, and the glass transition temperature is lowered. 3. Thermal oxidation stability analysis, namely the existence of a heterocyclic structure, is favorable for improving the thermal oxygen stability. This is mainly because the heterocyclic aramid has a higher crystallinity and a more stable aggregate structure. The aggregation structure of the fiber can be rearranged at high temperature, and the entanglement and lap joint of the molecular chain ends of the heterocyclic aramid fiber are more perfect, so that the weak links among the molecular chains are less, the tensile strength can not be reduced quickly, and the macro expression shows that the heterocyclic aramid fiber has better thermo-oxidative aging resistance.
By adjusting the monomer ratio, the content of the heterocyclic structure can be adjusted, so that the properties of the final fiber such as strength, modulus and the like can be adjusted. As a preferred technical scheme:
the heterocyclic meta-aramid fiber and the preparation method thereof have the advantages that the glass transition temperature of the heterocyclic meta-aramid fiber is 320-380 ℃, and the 5% thermal mass loss temperature is 370-470 ℃; the breaking strength is 25-40 cN/dtex, the elastic modulus is 800-1500 cN/dtex, and the elongation at break is 2.0-8.0%.
The invention provides a heterocyclic meta-aramid fiber and a preparation method thereof, wherein m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine are added into a composite solvent consisting of an aprotic polar solvent and a cosolvent; adding m-phthaloyl chloride, reacting and adjusting the pH value; and centrifuging to remove salt, defoaming, spinning by a dry-wet method, and carrying out solidification, washing, spinning, drying, hot stretching, heat setting and rolling to obtain the bis-imidazolyl heterocyclic meta-aramid.
The heterocyclic meta-aramid fiber and the preparation method thereof comprise the following steps:
the method comprises the following steps: under the protection of inert gas, adding an aprotic polar solvent and a cosolvent into a reaction kettle, starting stirring and forming a composite solvent;
step two: under the condition of low temperature, m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine are added into the composite solvent until the m-phenylenediamine, the third monomer with bis-imidazolyl and the 4-pyrrolidinyl pyridine are completely dissolved;
step three: adding m-phthaloyl chloride into the solution, and reacting at a certain reaction temperature;
step four: and adding alkali for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure.
Step five: and desalting the polymer solution, then filling the polymer solution into a reaction tank for defoaming, then carrying out dry-wet spinning, and carrying out solidification, washing, spinning, drying, hot stretching, heat setting and rolling to obtain the heterocyclic meta-aramid fiber containing the bisimidazole structure.
The reaction mechanism of the heterocyclic meta-aramid polymer is that isophthaloyl dichloride forms acyl free radicals under the action of a catalyst 4-pyrrolidinyl pyridine, then the free radicals and a metaphenylene diamine and a third monomer of a bis-imidazolyl group are subjected to free radical addition, and hydrogen chloride micromolecules are removed, so that the heterocyclic meta-aramid polymer of the bis-imidazolyl group is formed.
As a preferred technical scheme:
in the method, in the first step, the inert gas is one of nitrogen, helium and argon; the aprotic polar solvent is one of dimethylformamide, dimethylacetamide and dimethyl sulfoxide; the cosolvent is one of lithium chloride, potassium chloride and calcium chloride.
The method comprises the step two, wherein the low-temperature condition is-5 to-10 ℃, and the chemical structure of the third bisimidazolyl monomer is
. Wherein R is1Is hydrogen radical, fluorine radical, chlorine radical, bromine radical, iodine radical, R2Hydrogen radical, fluorine radical, chlorine radical, bromine radical and iodine radical.
The method comprises the third step, wherein the reaction temperature is 40-60 ℃, and the reaction time is 30-90 min.
In the fourth step of the method, the alkali is lithium hydroxide, potassium hydroxide or calcium hydroxide, and the solid content of the heterocyclic meta-aramid polymer solution containing the bisimidazole structure is (15-30) wt%.
The method comprises the following steps of one to four, wherein the molar ratio of the aprotic polar solvent to the cosolvent to the m-phenylenediamine to the third bis-imidazolyl monomer to the 4-pyrrolidinylpyridine to the m-phthaloyl chloride to the alkali is (50-200): 5-20): 0.5-1.5): 1: (0.01-0.1): 1.8-2.8): 10-30.
In the fifth step, the desalting method is high-speed centrifugal desalting, and the centrifugal speed is 10000-20000 r/min; the defoaming method is vacuum defoaming, and the vacuum degree is 0.08-0.12 kPa; the coagulation process parameters are that the temperature of a coagulation bath is 20-30 ℃, the concentration of the coagulation bath is 45-60%, and a solvent used by the coagulation bath is one of a dimethylformamide aqueous solution, a dimethylacetamide aqueous solution and a dimethylsulfoxide aqueous solution; the washing technological parameters are that the washing bath condition is 70-90 ℃, and the solvent used by the washing bath is pure water; the height of the air bath is 15 +/-3 mm; the spinning technological parameters are that the rotating speed of a metering pump is 5-8 r/min, the spinning speed is 5-10 m/min, and the specification of a spinneret plate is phi 0.08 mm multiplied by 100 holes; the drying method is hot roller contact drying, the drying temperature is 120-200 ℃, and the drying time is 120-180 min; the hot stretching process parameter is 290-310 ℃ of hot stretching temperature; the heat setting process parameter is 270-320 ℃, and the time is 60-120 s.
Has the advantages that:
(1) the heterocyclic meta-aramid fiber is a meta-aramid fiber material formed by ternary polymerization by introducing a bis-imidazolyl third monomer to a main chain of the meta-aramid fiber, and has high mechanical strength, high temperature resistance and durability;
(2) according to the preparation method of the heterocyclic meta-aramid, a low-temperature solution polymerization method is adopted in the preparation process, and a novel catalyst 4-pyrrolidinylpyridine is added in the reaction, so that the reaction speed is higher, and the efficiency is higher;
(3) the preparation method of the heterocyclic meta-aramid effectively expands the range of the conventional heterocyclic meta-aramid, is simple and is suitable for application and popularization.
Drawings
FIG. 1 is a flow chart of a preparation method of heterocyclic meta-aramid of the invention.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The invention relates to heterocyclic meta-aramid which has a molecular structure general formula as follows:
wherein m and n are positive integers, the ratio of m to n is 0.1, and R1Is hydrogen radical, R2Is a hydrogen radical.
The preparation method of the heterocyclic meta-aramid fiber has a process flow schematic diagram as shown in figure 1, and specifically comprises the following steps:
(1) preparing a heterocyclic meta-aramid polymer containing a bisimidazole structure:
(1.1) under the protection of nitrogen, adding dimethylformamide and lithium chloride into a reaction kettle, starting stirring and forming a composite solvent;
(1.2) -5 ℃, adding m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine into the composite solvent until the m-phenylenediamine, the third monomer with bis-imidazolyl and the 4-pyrrolidinyl pyridine are completely dissolved; said bis-imidazolyl third monomer junctionStructure is as
；
(1.3) adding isophthaloyl dichloride into the solution, and reacting at 40 ℃ for 30 min;
and (1.4) adding lithium hydroxide for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure.
Wherein the molar ratio of dimethylformamide, lithium chloride, m-phenylenediamine, a third diimidazole monomer, 4-pyrrolidinylpyridine, isophthaloyl dichloride and lithium hydroxide is 50:5:0.5:1:0.01:1.8: 10; the solid content of the heterocyclic meta-aramid polymer solution containing the bisimidazole structure is 15 wt%.
(2) The spinning method comprises the following steps:
and (2) desalting the polymer solution through high-speed centrifugation at the centrifugal speed of 10000r/min, then filling the polymer solution into a reaction tank for vacuum deaeration, controlling the vacuum degree to be 0.08kPa, then performing dry-wet spinning, and performing processes such as solidification, washing, spinning, drying, hot stretching, heat setting, rolling and the like to obtain the meta-aramid fiber containing the bis-imidazolyl heterocycle. The main process parameters are as follows: the coagulating bath is dimethylformamide water solution with the temperature of 20 ℃ and the concentration of 45 percent; the water washing is pure water washing at 70 ℃, and the height of an air bath is 12 mm; the rotating speed of a metering pump is 5r/min, the spinning speed is 5m/min, and the specification of a spinneret plate is phi 0.08 mm multiplied by 100 holes; the drying method is hot roller contact drying at 120 deg.C for 120 min; the hot stretching temperature is 290 ℃; the heat setting temperature is 270 ℃ and the heat setting time is 60 s.
Through tests, the glass transition temperature of the heterocyclic meta-aramid prepared by the method of the embodiment is 320 ℃, and the 5% thermal mass loss temperature is 370 ℃; the breaking strength was 25cN/dtex, the modulus of elasticity was 800cN/dtex, and the elongation at break was 2.0%.
Example 2
The invention relates to heterocyclic meta-aramid which has a molecular structure general formula as follows:
wherein m and n are positive integers, the ratio of m to n is 0.2, and R1Is hydrogen radical, R2Is a fluorine group.
The preparation method of the heterocyclic meta-aramid fiber has a process flow schematic diagram as shown in figure 1, and specifically comprises the following steps:
(1) preparing a heterocyclic meta-aramid polymer containing a bisimidazole structure:
(1.1) under the protection of argon, adding dimethylacetamide and potassium chloride into a reaction kettle, starting stirring and forming a composite solvent;
at the temperature of (1.2) -6 ℃, m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine are added into the composite solvent until the m-phenylenediamine, the third monomer with bis-imidazolyl and the 4-pyrrolidinyl pyridine are completely dissolved; the structural formula of the third bis-imidazolyl monomer is shown in the specification
；
(1.3) adding isophthaloyl dichloride into the solution, and reacting at 41 ℃ for 35 min;
and (1.4) adding potassium hydroxide for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure.
Wherein the molar ratio of dimethylacetamide, potassium chloride, m-phenylenediamine, a third imidazolyl monomer, 4-pyrrolidinylpyridine, isophthaloyl dichloride and potassium hydroxide is 65:7:0.6:1:0.02:1.9: 12; the solid content of the heterocyclic meta-aramid polymer solution containing the bisimidazole structure is 17 wt%.
(2) The spinning method comprises the following steps:
and (2) desalting the polymer solution through high-speed centrifugation at the centrifugal speed of 11000 r/min, then filling the polymer solution into a reaction tank for vacuum deaeration, controlling the vacuum degree to be 0.08kPa, then carrying out dry-wet spinning, and carrying out processes such as solidification, washing, spinning, drying, hot stretching, heat setting, rolling and the like to obtain the meta-aramid containing the bis-imidazolyl heterocycle. The main process parameters are as follows: the coagulating bath is a dimethylacetamide aqueous solution with the temperature of 21 ℃ and the concentration of 46 percent; the water washing is pure water washing at 73 ℃, and the height of an air bath is 13 mm; the rotating speed of a metering pump is 5r/min, the spinning speed is 5m/min, and the specification of a spinneret plate is phi 0.08 mm multiplied by 100 holes; the drying method is hot roller contact drying at 130 deg.C for 125 min; the hot stretching temperature is 293 ℃; the heat setting temperature was 275 ℃ and the heat setting time was 65 seconds.
Through tests, the glass transition temperature of the heterocyclic meta-aramid prepared by the method of the embodiment is 330 ℃, and the 5% thermal mass loss temperature is 380 ℃; the breaking strength was 28cN/dtex, the modulus of elasticity was 850cN/dtex, and the elongation at break was 2.5%.
Example 3
The invention relates to heterocyclic meta-aramid which has a molecular structural general formula as follows:
wherein m and n are positive integers, the ratio of m to n is 0.3, and R1Is hydrogen radical, R2Is a chlorine group.
The preparation method of the heterocyclic meta-aramid fiber has a process flow schematic diagram as shown in figure 1, and specifically comprises the following steps:
(1) preparing a heterocyclic meta-aramid polymer containing a bisimidazole structure:
(1.1) under the protection of helium, adding dimethylformamide and lithium chloride into a reaction kettle, starting stirring and forming a composite solvent;
(1.2) adding m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine into the composite solvent at the temperature of between 7 and 1 ℃ until the m-phenylenediamine and the third monomer with bis-imidazolyl are completely dissolved; the structural formula of the third bis-imidazolyl monomer is shown in the specification
；
(1.3) adding isophthaloyl dichloride into the solution, and reacting at 43 ℃ for 40 min;
and (1.4) adding lithium hydroxide for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure.
Wherein the molar ratio of dimethylformamide to lithium chloride to m-phenylenediamine to a third imidazolyl monomer to 4-pyrrolidinylpyridine to isophthaloyl dichloride to lithium hydroxide is 75:8:0.7:1:0.03:2.0: 15; the solid content of the heterocyclic meta-aramid polymer solution containing the bisimidazole structure is 19 wt%.
(2) The spinning method comprises the following steps:
and (2) desalting the polymer solution through high-speed centrifugation at 12000 r/min, then filling the polymer solution into a reaction tank for vacuum deaeration, controlling the vacuum degree to be 0.09kPa, then carrying out dry-wet spinning, and carrying out processes such as solidification, washing, spinning, drying, hot stretching, heat setting, rolling and the like to obtain the meta-aramid fiber containing the bis-imidazolyl heterocycle. The main process parameters are as follows: the coagulating bath is dimethylformamide water solution with the temperature of 22 ℃ and the concentration of 48 percent; the water washing is pure water washing at 75 ℃, and the height of an air bath is 13 mm; the rotating speed of a metering pump is 6 r/min, the spinning speed is 6 m/min, and the specification of a spinneret plate is phi 0.08 mm multiplied by 100 holes; the drying method is hot roller contact drying at 135 deg.C for 130 min; the hot stretching temperature is 295 ℃; the heat setting temperature is 280 ℃ and the heat setting time is 70 s.
Through tests, the glass transition temperature of the heterocyclic meta-aramid prepared by the method of the embodiment is 338 ℃, and the 5% thermal mass loss temperature is 395 ℃; the breaking strength was 30cN/dtex, the modulus of elasticity was 900cN/dtex, and the elongation at break was 3.0%.
Example 4
The invention relates to heterocyclic meta-aramid which has a molecular structural general formula as follows:
wherein m and n are positive integers, the ratio of m to n is 0.4, and R1Is hydrogen radical, R2Is a bromo group.
The preparation method of the heterocyclic meta-aramid fiber has a process flow schematic diagram as shown in figure 1, and specifically comprises the following steps:
(1) preparing a heterocyclic meta-aramid polymer containing a bisimidazole structure:
(1.1) under the protection of nitrogen, adding dimethyl sulfoxide and calcium chloride into a reaction kettle, and starting stirring to form a composite solvent;
at 1.2-8 deg.C in the above-mentioned composite solventAdding m-phenylenediamine, a third imidazolyl monomer and 4-pyrrolidinyl pyridine until the m-phenylenediamine, the third imidazolyl monomer and the 4-pyrrolidinyl pyridine are completely dissolved; the structural formula of the third bis-imidazolyl monomer is shown in the specification
；
(1.3) adding isophthaloyl dichloride into the solution, and reacting for 45min at 45 ℃;
and (1.4) adding calcium hydroxide for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure.
Wherein the molar ratio of dimethyl sulfoxide to calcium chloride to m-phenylenediamine to a third imidazolyl monomer to 4-pyrrolidinylpyridine to isophthaloyl dichloride to calcium hydroxide is 90:10:0.8:1:0.04:2.1: 17; the solid content of the heterocyclic meta-aramid polymer solution containing the bisimidazole structure is 21 wt%.
(2) The spinning method comprises the following steps:
and (2) desalting the polymer solution by high-speed centrifugation at 13000 r/min, then placing the polymer solution into a reaction tank for vacuum deaeration, controlling the vacuum degree to be 0.09kPa, then carrying out dry-wet spinning, and carrying out processes such as solidification, washing, spinning, drying, hot stretching, heat setting, rolling and the like to obtain the meta-aramid fiber containing the bis-imidazolyl heterocycle. The main process parameters are as follows: the coagulating bath is dimethyl sulfoxide water solution with the temperature of 23 ℃ and the concentration of 50%; the water washing is pure water washing at 78 ℃, and the height of an air bath is 14 mm; the rotating speed of a metering pump is 6 r/min, the spinning speed is 7 m/min, and the specification of a spinneret plate is phi 0.08 mm multiplied by 100 holes; the drying method is hot roller contact drying at 140 deg.C for 140 min; the hot stretching temperature is 298 ℃; the heat setting temperature is 285 ℃, and the heat setting time is 75 s.
Through tests, the glass transition temperature of the heterocyclic meta-aramid prepared by the method of the embodiment is 345 ℃, and the 5% thermal mass loss temperature is 410 ℃; the breaking strength was 32cN/dtex, the modulus of elasticity was 950cN/dtex, and the elongation at break was 4.0%.
Example 5
The invention relates to heterocyclic meta-aramid which has a molecular structure general formula as follows:
wherein m and n are positive integers, the ratio of m to n is 0.5, and R1Is hydrogen radical, R2Is an iodine radical.
The preparation method of the heterocyclic meta-aramid fiber has a process flow schematic diagram as shown in figure 1, and specifically comprises the following steps:
(1) preparing a heterocyclic meta-aramid polymer containing a bisimidazole structure:
(1.1) under the protection of argon, adding dimethylacetamide and potassium chloride into a reaction kettle, starting stirring and forming a composite solvent;
(1.2) adding m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine into the composite solvent at the temperature of between 9 and 9 ℃ until the m-phenylenediamine, the third monomer with bis-imidazolyl and the 4-pyrrolidinyl pyridine are completely dissolved; the structural formula of the third diimidazole group monomer is shown in the specification
；
(1.3) adding isophthaloyl dichloride into the solution, and reacting for 50min at 48 ℃;
and (1.4) adding lithium hydroxide for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure.
Wherein the molar ratio of dimethylacetamide, potassium chloride, m-phenylenediamine, a third imidazolyl monomer, 4-pyrrolidinylpyridine, isophthaloyl dichloride and lithium hydroxide is 100:12:0.9:1:0.05:2.2: 20; the solid content of the heterocyclic meta-aramid polymer solution containing the bisimidazole structure is 23 wt%.
(2) The spinning method comprises the following steps:
and (2) desalting the polymer solution through high-speed centrifugation at 14000 r/min, then placing the polymer solution into a reaction tank for vacuum deaeration, controlling the vacuum degree to be 0.10kPa, then carrying out dry-wet spinning, and carrying out processes such as solidification, washing, spinning, drying, hot stretching, heat setting, rolling and the like to obtain the meta-aramid fiber containing the bis-imidazolyl heterocycle. The main process parameters are as follows: the coagulating bath is a dimethylacetamide aqueous solution with the temperature of 24 ℃ and the concentration of 52 percent; the water washing is pure water washing at 80 ℃, and the height of an air bath is 15 mm; the rotating speed of a metering pump is 6 r/min, the spinning speed is 7 m/min, and the specification of a spinneret plate is phi 0.08 mm multiplied by 100 holes; the drying method is hot roller contact drying at 150 deg.C for 150 min; the hot stretching temperature is 298 ℃; the heat setting temperature was 290 ℃ and the heat setting time was 80 seconds.
Through tests, the glass transition temperature of the heterocyclic meta-aramid prepared by the method of the embodiment is 350 ℃, and the 5% thermal mass loss temperature is 420 ℃; the breaking strength was 33cN/dtex, the modulus of elasticity was 1000cN/dtex, and the elongation at break was 4.5%.
Example 6
The invention relates to heterocyclic meta-aramid which has a molecular structure general formula as follows:
wherein m and n are positive integers, the ratio of m to n is 0.6, and R1Is fluoro radical, R2Is a hydrogen radical.
The preparation method of the heterocyclic meta-aramid fiber has a process flow schematic diagram as shown in figure 1, and specifically comprises the following steps:
(1) preparing a heterocyclic meta-aramid polymer containing a bisimidazole structure:
(1.1) under the protection of argon, adding dimethylformamide and lithium chloride into a reaction kettle, starting stirring and forming a composite solvent;
(1.2) -10 ℃, adding m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine into the composite solvent until the m-phenylenediamine, the third monomer with bis-imidazolyl and the 4-pyrrolidinyl pyridine are completely dissolved; the structural formula of the third bis-imidazolyl monomer is shown in the specification
；
(1.3) adding isophthaloyl dichloride into the solution, and reacting for 60min at 50 ℃;
and (1.4) adding lithium hydroxide for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure.
Wherein the molar ratio of dimethylformamide, lithium chloride, m-phenylenediamine, a third diimidazole monomer, 4-pyrrolidinylpyridine, isophthaloyl dichloride and lithium hydroxide is 120:14:1.0:1:0.06:2.3: 22; the solid content of the heterocyclic meta-aramid polymer solution containing the bisimidazole structure is 24 wt%.
(2) The spinning method comprises the following steps:
and (2) desalting the polymer solution through high-speed centrifugation at the centrifugal speed of 15000 r/min, then filling the polymer solution into a reaction tank for vacuum deaeration, controlling the vacuum degree to be 0.10kPa, then carrying out dry-wet spinning, and carrying out processes such as solidification, washing, spinning, drying, hot stretching, heat setting, rolling and the like to obtain the meta-aramid fiber containing the bis-imidazolyl heterocycle. The main process parameters are as follows: the coagulating bath is dimethylformamide water solution with the temperature of 24 ℃ and the concentration of 54 percent; the water washing is pure water washing at 82 ℃, and the height of an air bath is 15 mm; the rotating speed of a metering pump is 7r/min, the spinning speed is 8m/min, and the specification of a spinneret plate is phi 0.08 mm multiplied by 100 holes; the drying method is hot roller contact drying at 160 deg.C for 160 min; the hot stretching temperature is 300 ℃; the heat setting temperature is 300 ℃ and the heat setting time is 85 s.
Through tests, the glass transition temperature of the heterocyclic meta-aramid prepared by the method of the embodiment is 360 ℃, and the 5% thermal mass loss temperature is 430 ℃; the breaking strength is 35cN/dtex, the elastic modulus is 1100cN/dtex, and the elongation at break is 5.0%.
Example 7
The invention relates to heterocyclic meta-aramid which has a molecular structure general formula as follows:
wherein m and n are positive integers, the ratio of m to n is 0.7, and R1Is chloro, R2Is a chlorine group.
The preparation method of the heterocyclic meta-aramid fiber has a process flow schematic diagram as shown in figure 1, and specifically comprises the following steps:
(1) preparing a heterocyclic meta-aramid polymer containing a bisimidazole structure:
(1.1) under the protection of nitrogen, adding dimethylacetamide and potassium chloride into a reaction kettle, starting stirring and forming a composite solvent;
at the temperature of (1.2) -6 ℃, m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine are added into the composite solvent until the m-phenylenediamine, the third monomer with bis-imidazolyl and the 4-pyrrolidinyl pyridine are completely dissolved; the structural formula of the third bis-imidazolyl monomer is shown in the specification
；
(1.3) adding isophthaloyl dichloride into the solution, and reacting at 53 ℃ for 70 min;
and (1.4) adding potassium hydroxide for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure.
Wherein the molar ratio of dimethylacetamide, potassium chloride, m-phenylenediamine, a third imidazolyl monomer, 4-pyrrolidinylpyridine, isophthaloyl dichloride and potassium hydroxide is 140:15:1.1:1:0.07:2.4: 24; the solid content of the heterocyclic meta-aramid polymer solution containing the bisimidazole structure is 25 wt%.
(2) The spinning method comprises the following steps:
and (2) desalting the polymer solution by high-speed centrifugation at 16000 r/min, then placing the polymer solution into a reaction tank for vacuum deaeration, controlling the vacuum degree to be 0.11kPa, then carrying out dry-wet spinning, and carrying out processes such as solidification, washing, spinning, drying, hot stretching, heat setting, rolling and the like to obtain the meta-aramid containing the bis-imidazolyl heterocycle. The main process parameters are as follows: the coagulating bath is a dimethylacetamide aqueous solution with the temperature of 26 ℃ and the concentration of 55 percent; the water washing is carried out by pure water washing at 84 ℃, and the height of an air bath is 16 mm; the rotating speed of a metering pump is 7r/min, the spinning speed is 8m/min, and the specification of a spinneret plate is phi 0.08 mm multiplied by 100 holes; the drying method is hot roller contact drying at 170 deg.C for 165 min; the hot stretching temperature is 304 ℃; the heat setting temperature is 310 ℃ and the heat setting time is 90 s.
Through tests, the glass transition temperature of the heterocyclic meta-aramid prepared by the method of the embodiment is 365 ℃, and the 5% thermal mass loss temperature is 440 ℃; the breaking strength was 36cN/dtex, the modulus of elasticity was 1150cN/dtex, and the elongation at break was 6.0%.
Example 8
The invention relates to heterocyclic meta-aramid which has a molecular structural general formula as follows:
wherein m and n are positive integers, the ratio of m to n is 0.8, and R1Is chloro, R2Is a bromo group.
The preparation method of the heterocyclic meta-aramid fiber has a process flow schematic diagram as shown in figure 1, and specifically comprises the following steps:
(1) preparing a heterocyclic meta-aramid polymer containing a bisimidazole structure:
(1.1) under the protection of helium, adding dimethyl sulfoxide and calcium chloride into a reaction kettle, and starting stirring to form a composite solvent;
(1.2) -8 ℃, adding m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine into the composite solvent until the m-phenylenediamine, the third monomer with bis-imidazolyl and the 4-pyrrolidinyl pyridine are completely dissolved; the structural formula of the third diimidazole group monomer is shown in the specification
；
(1.3) adding isophthaloyl dichloride into the solution, and reacting for 80min at 55 ℃;
and (1.4) adding calcium hydroxide for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure.
Wherein the molar ratio of dimethyl sulfoxide, calcium chloride, m-phenylenediamine, a third imidazolyl monomer, 4-pyrrolidinylpyridine, isophthaloyl dichloride and calcium hydroxide is 160:16:1.2:1:0.08:2.6: 26; the solid content of the heterocyclic meta-aramid polymer solution containing the bisimidazole structure is 27 wt%.
(2) The spinning method comprises the following steps:
and (2) desalting the polymer solution by high-speed centrifugation at the centrifugal speed of 17000 r/min, then filling the polymer solution into a reaction tank for vacuum deaeration, controlling the vacuum degree to be 0.11kPa, then carrying out dry-wet spinning, and carrying out processes such as solidification, washing, spinning, drying, hot stretching, heat setting, rolling and the like to obtain the meta-aramid containing bis-imidazolyl heterocycle. The main process parameters are as follows: the coagulating bath is dimethyl sulfoxide water solution with the temperature of 27 ℃ and the concentration of 56 percent; the water washing is pure water washing at 86 ℃, and the height of an air bath is 16 mm; the rotating speed of a metering pump is 7r/min, the spinning speed is 9 m/min, and the specification of a spinneret plate is phi 0.08 mm multiplied by 100 holes; the drying method is hot roller contact drying at 180 deg.C for 170 min; the hot stretching temperature is 306 ℃; the heat setting temperature was 310 ℃ and the heat setting time was 100 seconds.
Through tests, the glass transition temperature of the heterocyclic meta-aramid prepared by the method of the embodiment is 370 ℃, and the 5% thermal mass loss temperature is 450 ℃; the breaking strength was 37cN/dtex, the modulus of elasticity was 1250cN/dtex, and the elongation at break was 6.5%.
Example 9
The invention relates to heterocyclic meta-aramid which has a molecular structural general formula as follows:
wherein m and n are positive integers, the ratio of m to n is 0.9, and R1Is bromo, R2Is a bromo group.
The preparation method of the heterocyclic meta-aramid fiber has a process flow schematic diagram as shown in figure 1, and specifically comprises the following steps:
(1) preparing a heterocyclic meta-aramid polymer containing a bisimidazole structure:
(1.1) under the protection of nitrogen, adding dimethylformamide and lithium chloride into a reaction kettle, starting stirring and forming a composite solvent;
(1.2) adding m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine into the composite solvent at the temperature of between 9 and 9 ℃ until the m-phenylenediamine, the third monomer with bis-imidazolyl and the 4-pyrrolidinyl pyridine are completely dissolved; the structural formula of the third bis-imidazolyl monomer is shown in the specification
；
(1.3) adding isophthaloyl dichloride into the solution, and reacting for 85min at 58 ℃;
and (1.4) adding lithium hydroxide for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure.
Wherein the molar ratio of dimethylformamide, lithium chloride, m-phenylenediamine, a third bis-imidazolyl monomer, 4-pyrrolidinylpyridine, isophthaloyl dichloride and lithium hydroxide is 180:17:1.4:1:0.09:2.7: 28; the solid content of the heterocyclic meta-aramid polymer solution containing the bisimidazole structure is 29 wt%.
(2) The spinning method comprises the following steps:
and (2) desalting the polymer solution by high-speed centrifugation at 19000 r/min, then placing the polymer solution into a reaction tank for vacuum deaeration, controlling the vacuum degree to be 0.12 kPa, then carrying out dry-wet spinning, and carrying out processes such as solidification, washing, spinning, drying, hot stretching, heat setting, rolling and the like to obtain the meta-aramid fiber containing the bis-imidazolyl heterocycle. The main process parameters are as follows: the coagulating bath is dimethylformamide water solution with the temperature of 29 ℃ and the concentration of 59 percent; the water washing is pure water washing at 88 ℃, and the height of an air bath is 17 mm; the rotating speed of a metering pump is 8 r/min, the spinning speed is 10 m/min, and the specification of a spinneret plate is phi 0.08 mm multiplied by 100 holes; the drying method is hot roller contact drying at 190 deg.C for 175 min; the hot stretching temperature is 308 ℃; the heat setting temperature is 315 ℃ and the heat setting time is 110 s.
Through tests, the glass transition temperature of the heterocyclic meta-aramid prepared by the method of the embodiment is 375 ℃, and the 5% thermal mass loss temperature is 460 ℃; the breaking strength was 39cN/dtex, the modulus of elasticity was 1400cN/dtex, and the elongation at break was 7.0%.
Example 10
The invention relates to heterocyclic meta-aramid which has a molecular structural general formula as follows:
wherein m and n are positive integers, the ratio of m to n is 1, and R1Is an iodo radical, R2Is an iodine radical.
The preparation method of the heterocyclic meta-aramid fiber has a process flow schematic diagram as shown in figure 1, and specifically comprises the following steps:
(1) preparing a heterocyclic meta-aramid polymer containing a bisimidazole structure:
(1.1) under the protection of helium, adding dimethylacetamide and potassium chloride into a reaction kettle, and stirring to form a composite solvent;
(1.2) -10 ℃, adding m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine into the composite solvent until the m-phenylenediamine, the third monomer with bis-imidazolyl and the 4-pyrrolidinyl pyridine are completely dissolved; the structural formula of the third bis-imidazolyl monomer is shown in the specification
；
(1.3) adding isophthaloyl dichloride into the solution, and reacting for 90min at 60 ℃;
and (1.4) adding potassium hydroxide for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure.
Wherein the molar ratio of dimethylacetamide, potassium chloride, m-phenylenediamine, a third imidazolyl monomer, 4-pyrrolidinylpyridine, isophthaloyl dichloride and potassium hydroxide is 200:20:1.5:1:0.1:2.8: 30; the solid content of the heterocyclic meta-aramid polymer solution containing the bisimidazole structure is 30 wt%.
(2) The spinning method comprises the following steps:
and (2) desalting the polymer solution through high-speed centrifugation at the centrifugation speed of 20000 r/min, then filling the polymer solution into a reaction tank for vacuum deaeration, controlling the vacuum degree to be 0.12 kPa, then carrying out dry-wet spinning, and carrying out processes such as solidification, washing, spinning, drying, hot stretching, heat setting, rolling and the like to obtain the meta-aramid fiber containing the bis-imidazolyl heterocycle. The main process parameters are as follows: the coagulating bath is a 60% dimethyl acetamide water solution with the temperature of 30 ℃; the water washing is pure water washing at 90 ℃, and the height of an air bath is 18 mm; the rotating speed of a metering pump is 8 r/min, the spinning speed is 10 m/min, and the specification of a spinneret plate is phi 0.08 mm multiplied by 100 holes; the drying method is hot roller contact drying at 200 deg.C for 180 min; the hot stretching temperature is 310 ℃; the heat setting temperature is 320 ℃, and the heat setting time is 120 s.
Through tests, the glass transition temperature of the heterocyclic meta-aramid prepared by the method of the embodiment is 380 ℃, and the 5% thermal mass loss temperature is 470 ℃; the breaking strength was 40cN/dtex, the modulus of elasticity was 1500cN/dtex, and the elongation at break was 8.0%.
Claims (16)
1. The heterocyclic meta-aramid is characterized in that the molecular structural general formula of the heterocyclic meta-aramid is shown as the following formula (A):
wherein m and n are positive integers, the ratio of m to n is less than or equal to 1, R1Is hydrogen radical, fluorine radical, chlorine radical, bromine radical, iodine radical, R2Hydrogen radical, fluorine radical, chlorine radical, bromine radical and iodine radical.
2. The heterocyclic meta-aramid fiber of claim 1, wherein the glass transition temperature of the heterocyclic meta-aramid fiber is 320-380 ℃ and the 5% thermal mass loss temperature is 370-470 ℃; the breaking strength is 25-40 cN/dtex, the elastic modulus is 800-1500 cN/dtex, and the elongation at break is 2.0-8.0%.
3. A preparation method of heterocyclic meta-aramid comprises the following steps:
the method comprises the following steps: under the protection of inert gas, adding an aprotic polar solvent and a cosolvent into a reaction kettle, starting stirring and forming a composite solvent;
step two: under the condition of low temperature, m-phenylenediamine, a third monomer with bis-imidazolyl and 4-pyrrolidinyl pyridine are added into the composite solvent until the m-phenylenediamine, the third monomer with bis-imidazolyl and the 4-pyrrolidinyl pyridine are completely dissolved;
step three: adding m-phthaloyl chloride into the solution, and reacting at a certain reaction temperature;
step four: adding alkali for neutralization to obtain a heterocyclic meta-aramid polymer solution containing a bisimidazole structure;
step five: and desalting the polymer solution, then filling the polymer solution into a reaction tank for defoaming, then carrying out dry-wet spinning, and carrying out solidification, washing, spinning, drying, hot stretching, heat setting and rolling to obtain the heterocyclic meta-aramid fiber containing the bisimidazole structure.
4. The method according to claim 3, wherein in the first step, the inert gas is one of nitrogen, helium and argon; the aprotic polar solvent is one of dimethylformamide, dimethylacetamide and dimethyl sulfoxide; the cosolvent is one of lithium chloride, potassium chloride and calcium chloride.
5. The method according to claim 3, wherein in the second step, the low temperature condition is-5 to-10 ℃, and the chemical structure of the third bisimidazolyl monomer is
(ii) a Wherein R is1Is hydrogen radical, fluorine radical, chlorine radical, bromine radical, iodine radical, R2Hydrogen radical, fluorine radical, chlorine radical, bromine radical and iodine radical.
6. The method according to claim 3, wherein in the third step, the reaction temperature is 40-60 ℃, and the reaction time is 30-90 min.
7. The method as claimed in claim 3, wherein in the fourth step, the alkali is lithium hydroxide, potassium hydroxide or calcium hydroxide, and the solid content of the heterocyclic meta-aramid polymer solution containing a bis-imidazole structure is (15-30) wt%.
8. The method of claim 3, wherein the molar ratio of the aprotic polar solvent, the cosolvent, the m-phenylenediamine, the third bis-imidazolyl monomer, the 4-pyrrolidinylpyridine, the isophthaloyl dichloride, and the base in the first to fourth steps is (50-200): 5-20): 0.5-1.5): 1, (0.01-0.1): 1.8-2.8): 10-30.
9. The method according to claim 3, wherein in the fifth step, the desalting method is high-speed centrifugal desalting, and the centrifugal speed is 10000-20000 r/min.
10. The method according to claim 3, wherein in the fifth step, the defoaming method is vacuum defoaming, and the vacuum degree is 0.08-0.12 kPa.
11. The method according to claim 3, wherein in the fifth step, the coagulation process parameter is that the coagulation bath temperature is 20-30 ℃, the coagulation bath concentration is 45% -60%, and the solvent used in the coagulation bath is one of a dimethylformamide aqueous solution, a dimethylacetamide aqueous solution and a dimethylsulfoxide aqueous solution.
12. The method according to claim 3, wherein in the fifth step, the washing process parameters are that the washing bath condition is 70-90 ℃, and the solvent used in the washing bath is pure water; the height of the air bath is 15 +/-3 mm.
13. The method of claim 3, wherein in the fifth step, the spinning process parameters are that the rotating speed of a metering pump is 5 to 8 r/min, the spinning speed is 5 to 10 m/min, and the specification of a spinneret plate is phi 0.08 mm x 100 holes.
14. The method according to claim 3, wherein in the fifth step, the drying method is hot roller contact drying, the drying temperature is 120-200 ℃, and the drying time is 120-180 min.
15. The method according to claim 3, wherein in the fifth step, the hot stretching process parameter is a hot stretching temperature of 290-310 ℃.
16. The method according to claim 3, wherein in the fifth step, the heat setting process parameter is 270-320 ℃ and the time is 60-120 s.
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