CN105384929A - Aromatic polyamide polymer capable of being melted - Google Patents
Aromatic polyamide polymer capable of being melted Download PDFInfo
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- CN105384929A CN105384929A CN201510915957.3A CN201510915957A CN105384929A CN 105384929 A CN105384929 A CN 105384929A CN 201510915957 A CN201510915957 A CN 201510915957A CN 105384929 A CN105384929 A CN 105384929A
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- chloride
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- aromatic polyamide
- polyamide polymer
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- 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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- Polymers & Plastics (AREA)
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Abstract
The invention discloses an aromatic polyamide polymer capable of being melted. The polymer is characterized by being represented by a structural formula (in the description). In the structural formula, the R1 represents a single unit comprising straight chain, branch chain, ring, or benzene ring or represents a combination of straight chain, branch chain, ring, and benzene ring. The viscosity of the polymer is 200 to 800 P, the melting temperature is 345 to 385 DEG C, and the decomposition temperature is higher than 400 DEG C. The invention also discloses a preparation method of the polymer. The provided aromatic polyamide polymer is prepared by introducing a novel compound with a diacyl chloride structure into aramid fiber to change the molecular structure, so that the polymer will not be directly carbonized at a high temperature, and has a certain melting point, at the same time, the excellent characteristics of aramid fiber are maximally preserved, the provided polymer has greater advantages in the engineering plastic application field, at the same time, the cost of the polymer is low, and the industrial production of the polymer can be realized easily.
Description
Technical field
The present invention relates to a kind of macromolecular material, be specifically related to a kind of melting aromatic polyamide polymer.
Background technology
Material prepared by aromatic polyamide polymer has excellent characteristic, makes it be developed in multiple field and apply.The application of its fiber art that what current development was the most ripe is, its aramid fiber prepared is described as one of large high performance fibre material in the world today three, has the good characteristic such as high temperature resistant, inherent flame retardant, electrical isolation, radioprotective, resistance to chemical attack; Being widely used in army and police's safety protective clothing, high-temperature environmental-protection filter material, industrial safety protective clothing, high-end electrical apparatus insulation material, aircraft and the bullet train time field such as stressed member, fabrics for industrial use, is the important foundation material involved the interests of the state and the people.
In addition, mould material prepared by aromatic polyamide polymer also has suitable prospect, develops very rapid.On Vehicles Collected from Market, most reverse osmosis membrane and part nanofiltration membrane all have employed such material; Japan Supreme Being people is studied (see patent: WO2006123811) in lithium battery diaphragm field in aromatic polyamide polymer application, and existing many companies have lithium electric thin novel product prepared by aromatic polyamide polymer at present.
Although aromatic polyamide has excellent characteristic, cannot directly apply in engineering plastics field, reason is that aromatic polyamide polymer material fusing point is higher than carbonization temperature, cannot carry out melt-processed preparation.For obtaining the performance of aromatic polyamide polymer material excellence, Chinese scholars has carried out large quantity research around aromatic polyamide melting polymer material.
US Patent No. 4278779 and US5621067 have studied different diamines and the acyl chloride reactions such as xylylene amine respectively, add with the diamines comparing different ratios and affect the resistance toheat of aromatic polyamide, two Patents all do not relate to the relevant melting characteristic of product.
Cai Ming medium in 2002 " petrochemical complex " 31 volume the 6th phase " syntheses and properties of chloride substituent poly(isophthaloyl metaphenylene diamine) " with 2,5-dichloro p-phthaloyl chloride is as Third monomer, by itself and m-phthaloyl chloride, mphenylenediamine at N, cryogenic solution copolycondensation reaction is carried out in N-N,N-DIMETHYLACETAMIDE, synthesize chloride substituent poly(isophthaloyl metaphenylene diamine) resin, its heat decomposition temperature (weightless 5%) is 395 DEG C, occurs without fusing point.
Xie Xinyu etc. " synthon " 4 volumes the 19th phase in 2005 " synthesis of Ursol D modification meta-aromatic polyamide and Thermal Properties " with the Ursol D of 5%-15% be Third monomer and mphenylenediamine, m-phthaloyl chloride is at N, cryogenic solution copolycondensation reaction is carried out in N-N,N-DIMETHYLACETAMIDE, synthesize the PPDA/PMIA modified copolymer of different ratios, heat decomposition temperature more than 375 DEG C, occurs without fusing point.
The semi-aromatic nylon of Kuraray company exploitation is (see Japanese Patent: No.2001-169159; Chinese patent: 02126383.3 and 200410075135.0), has started to start to popularize in field of plastic products at present.But the main raw material that semiaromatic polyamide composition adopts is di-carboxylic acid and diamine, and final product fusing point is lower, and fusing point, at 308 DEG C, only can be applied at generic engineering plastics arts.
Current high temperature classification special engineering plastics price is general very expensive, and for polyether-ether-ketone (Tm is about 334-384 DEG C), price is about 49-62 ten thousand yuan/ton.Therefore, developing low-cost has the aromatic polyamide polymer of melting performance, to meet the application demand of aramid fiber in engineering plastics field, significant.
Summary of the invention
The present invention is directed to existing aromatic polyamide cannot high-temperature fusion, in the present situation of engineering plastics field application, can not provide a kind of aromatic polyamide polymer with high-temperature fusion characteristic, and this polymeric polymerization process for preparing.
Melting aromatic polyamide polymer provided by the invention, is characterized in that this polymer structure general formula is as follows:
Wherein, R
1derive from a kind of novel diacid chloride structural compounds.R
1in contained carbon atom number too much unsuitable, usually require 2≤R
1(C)≤15, otherwise can impact reactive behavior, cause whole reaction to carry out or polymer viscosity cannot reach particular requirement.
R involved in above-mentioned formula
1the general structure of novel diacid chloride structural compounds of originating is as follows:
in formula, acid chloride groups is respectively at the two ends of molecular chain, R
1can represent is containing straight-chain, branched, ring-type or the single structure containing phenyl ring, also can be the mutual unitized construction of straight chain, side chain, loop chain and phenyl ring.Corresponding novel diacid chloride structural compounds includes but not limited to following compound:
Adipoyl Chloride, sebacoyl chloride, azelaoyl dichloro, suberoyl chlorine, glutaryl chlorine, fumaryl chloride, hexafluoro glutaryl chlorine, decyl two acyl dichloro, 2-methyl cyclopropane-1, 1-diacid chloride, 2, 2, 3-trimethylammonium succinyl dichloro, cyclopropane-1, 2-dichloro compound, 2-fourth malonyl chloride, Adipoyl Chloride-D8, 2, 3, 5, 6-tetrachloro-p-phenylene dimethyl chloride, nitrogen benzide-4, 4'-bis-dicarbonyl chloride, 2, 6-pyridine dimethyl chloride, 2, 2-is oxidized diethyl acyl chlorides, [2, 2 '-dipyridyl]-6, 6 '-dicarboxylic acid, 4, 4'-diacid chloride phenyl ether, 2, 2-phenyl disulfide formyl chloride, 1, 4-phenylene two acrylate chloride, 4, 4 '-xenyl Acetyl Chloride 98Min., 2-(3-fluoropropyl) malonyl chloride.
Above-mentioned melting aromatic polyamide polymer viscosity is 200-800P, and melt temperature is 345-385 DEG C, decomposition temperature > 400 DEG C.
The preparation method of the new aromatic polyamide polymer of melting characteristic provided by the invention, is characterized in that the material choice of the method, processing step and condition, specific as follows:
(1) phenylenediamine 15-50 part of the parts by weight by material is added 100-200 part polar solvent stirring and dissolving, then add novel diacid chloride structural compounds 3-6 part reaction 0.2-0.8h at 20-55 DEG C;
(2) lower the temperature, add phthalyl chloride 10-40 part reaction 0.8-2h at 10-25 DEG C;
(3) then control temperature adds novel diacid chloride structural compounds 2-4 part reaction 0.2-0.6h at 35-75 DEG C.The melting aromatic polyamide polymer that viscosity is 200-800P can be obtained.
The phenylenediamine related in aforesaid method can be selected from mphenylenediamine, Ursol D and O-Phenylene Diamine, wherein preferred mphenylenediamine and Ursol D.
The phthalyl chloride related in aforesaid method, can be selected from phthalyl chloride, m-phthaloyl chloride and p-phthaloyl chloride, wherein preferred m-phthaloyl chloride and p-phthaloyl chloride.
The polar solvent related in aforesaid method can be selected from dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone, but consider in actual production that N,N-DIMETHYLACETAMIDE is compared with dimethyl formamide, its thermostability, stability to hydrolysis are high, corrodibility and toxicity little, the present invention preferentially selects N,N-DIMETHYLACETAMIDE and N-Methyl pyrrolidone.
Melting aromatic polyamide polymer material involved in the present invention has following advantage:
(1) the melting aromatic polyamide polymer that the present invention relates to, being on the basis of original aramid fiber, by introducing novel diacid chloride structural compounds, modification having been carried out to molecular structure, change the performance of its original high temperature direct carbonization, make it have certain fusing point.What this mode was greatly possible remains the original multiple excellent properties of aramid fiber, and makes melting aromatic polyamide polymer have larger advantage in engineering plastics Application Areas.
(2) the melting aromatic polyamide polymer melt temperature that the present invention relates to can reach 345-385 DEG C, has good heat resistance, can play greater advantages, and have splendid low-cost advantage, be easy to realize suitability for industrialized production in special engineering plastics field.
Embodiment
For further illustrating the present invention, being below specific embodiment mode, but should not regarding limitation of the present invention as.In embodiment and comparative example, all characteristics, measure all by the following method.
1. limiting viscosity [η]
Adopt the kinetic viscosity of BROOKFIELDDV-II+Pro test polymer solution, select No. 4 rotors, result is finally converted into the viscosity of (25 DEG C) at mark condition temperature and characterizes.
2. thermal characteristics
Adopt METTLERTOLEDOSTAR
esystem, DSC822e differential scanning calorimeter are carried out test to polymer thermal characteristics and are characterized, heating rate: 20K/min.
Embodiment 1
Mphenylenediamine 18 parts by amount of substance part is added 100 parts of N,N-DIMETHYLACETAMIDE stirring and dissolving, then adds cyclopropane-1,2-dichloro compound 3 parts reaction 0.4h at 29 DEG C.Cooling, adds m-phthaloyl chloride 13 parts reaction 1.8h at 17 DEG C.Heat up, and control temperature adds cyclopropane-1,2-dichloro compound 2 parts reaction 0.5h at 70 DEG C.After having reacted, obtaining viscosity is 410P(25 DEG C) melting aromatic polyamide polymer.
To the polymer film obtained, washing, oven dry, adopt DSC822e differential scanning calorimeter to carry out thermal performance test to polymer baked film afterwards, fusing point is 368 DEG C.
Embodiment 2
Ursol D 35 parts by amount of substance part is added 150 parts of N-Methyl pyrrolidone stirring and dissolving, then adds 2-(3-fluoropropyl at 45 DEG C) malonyl chloride 6 parts reaction 0.7h.Cooling, adds m-phthaloyl chloride 27 parts reaction 2h at 22 DEG C.Then control temperature adds 2-(3-fluoropropyl at 65 DEG C) malonyl chloride structural compounds 2 parts reaction 0.4h.After having reacted, obtaining viscosity is 324P(25 DEG C) melting aromatic polyamide polymer.
To the polymer film obtained, washing, oven dry, adopt DSC822e differential scanning calorimeter to carry out thermal performance test to polymer baked film afterwards, fusing point is 365 DEG C.
The above embodiment is only that the preferred embodiment of the present invention is described; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (3)
1. a melting aromatic polyamide polymer, is characterized in that this polymer structure general formula is as follows:
Wherein, R
1derive from the novel diacid chloride structural compounds that a kind of general structure is following:
In formula, acid chloride groups respectively at the two ends of molecular chain, R
1representative is containing straight-chain, branched, ring-type or containing the single structure of phenyl ring and the structure of combination mutually thereof, contained carbon atom number is between 2-5.
2. a kind of melting aromatic polyamide polymer according to claim 1, it is characterized in that: described novel diacid chloride structural compounds comprises: Adipoyl Chloride, sebacoyl chloride, azelaoyl dichloro, suberoyl chlorine, glutaryl chlorine, fumaryl chloride, hexafluoro glutaryl chlorine, decyl two acyl dichloro, 2-methyl cyclopropane-1, 1-diacid chloride, 2, 2, 3-trimethylammonium succinyl dichloro, cyclopropane-1, 2-dichloro compound, 2-fourth malonyl chloride, Adipoyl Chloride-D8, 2, 3, 5, 6-tetrachloro-p-phenylene dimethyl chloride, nitrogen benzide-4, 4'-bis-dicarbonyl chloride, 2, 6-pyridine dimethyl chloride, 2, 2-is oxidized diethyl acyl chlorides, [2, 2 '-dipyridyl]-6, 6 '-dicarboxylic acid, 4, 4'-diacid chloride phenyl ether, 2, 2-phenyl disulfide formyl chloride, 1, 4-phenylene two acrylate chloride, 4, 4 '-xenyl Acetyl Chloride 98Min., 2-(3-fluoropropyl) malonyl chloride.
3. a kind of melting aromatic polyamide polymer according to claim 1, it is characterized in that: melting aromatic polyamide polymer viscosity is 200-800P, melt temperature is 345-385 DEG C, decomposition temperature > 400 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106690620A (en) * | 2016-12-07 | 2017-05-24 | 青岛亿和海丽安防科技有限公司 | Children comprehensive emergency helmet |
| CN106832263A (en) * | 2017-02-15 | 2017-06-13 | 烟台泰和新材料股份有限公司 | A kind of high-melting-point ternary aromatic polyamides condensate and the method that fibrid is prepared using it |
| CN110343242A (en) * | 2019-07-04 | 2019-10-18 | 岭南师范学院 | Photochromic hyperbranched azopolyamide of one kind and preparation method thereof |
| KR20200096092A (en) * | 2019-02-01 | 2020-08-11 | 주식회사 엘지화학 | Polyamide resin, and polymer film, resin laminate using the same |
| KR20200112742A (en) * | 2019-03-20 | 2020-10-05 | 주식회사 엘지화학 | Polyamide copolymers and polyamide film comprising the same |
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| CA806740A (en) * | 1969-02-18 | F. Holub Fred | Aromatic n-arylamide polymers | |
| US4169932A (en) * | 1976-07-26 | 1979-10-02 | Petrukhin Vyacheslav S | Method of producing poly-p-phenyleneterephthalamide or its copolymers |
| CN1844195A (en) * | 2006-05-15 | 2006-10-11 | 上海市合成树脂研究所 | Method for preparing aryl amide copolymer |
| CN101724149A (en) * | 2008-10-13 | 2010-06-09 | 比亚迪股份有限公司 | Polyamide and preparation method thereof |
| CN101798384A (en) * | 2010-03-17 | 2010-08-11 | 上海大学 | Poly[1,4-diiminophenyl-4-(difluoromethyl-carbonyl)benzoyl-1,4-diiminophenyl p-dibenzoyl] and synthetic method thereof |
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Patent Citations (5)
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| CA806740A (en) * | 1969-02-18 | F. Holub Fred | Aromatic n-arylamide polymers | |
| US4169932A (en) * | 1976-07-26 | 1979-10-02 | Petrukhin Vyacheslav S | Method of producing poly-p-phenyleneterephthalamide or its copolymers |
| CN1844195A (en) * | 2006-05-15 | 2006-10-11 | 上海市合成树脂研究所 | Method for preparing aryl amide copolymer |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106690620A (en) * | 2016-12-07 | 2017-05-24 | 青岛亿和海丽安防科技有限公司 | Children comprehensive emergency helmet |
| CN106832263A (en) * | 2017-02-15 | 2017-06-13 | 烟台泰和新材料股份有限公司 | A kind of high-melting-point ternary aromatic polyamides condensate and the method that fibrid is prepared using it |
| KR20200096092A (en) * | 2019-02-01 | 2020-08-11 | 주식회사 엘지화학 | Polyamide resin, and polymer film, resin laminate using the same |
| KR102423808B1 (en) | 2019-02-01 | 2022-07-21 | 주식회사 엘지화학 | Polyamide resin, and polymer film, resin laminate using the same |
| KR20200112742A (en) * | 2019-03-20 | 2020-10-05 | 주식회사 엘지화학 | Polyamide copolymers and polyamide film comprising the same |
| KR102308712B1 (en) * | 2019-03-20 | 2021-10-05 | 주식회사 엘지화학 | Polyamide copolymers and polyamide film comprising the same |
| CN110343242A (en) * | 2019-07-04 | 2019-10-18 | 岭南师范学院 | Photochromic hyperbranched azopolyamide of one kind and preparation method thereof |
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Application publication date: 20160309 |