CN1070880C - Method for preparing polyarylene sulfide with high molecular and high toughness - Google Patents

Method for preparing polyarylene sulfide with high molecular and high toughness Download PDF

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CN1070880C
CN1070880C CN95111471A CN95111471A CN1070880C CN 1070880 C CN1070880 C CN 1070880C CN 95111471 A CN95111471 A CN 95111471A CN 95111471 A CN95111471 A CN 95111471A CN 1070880 C CN1070880 C CN 1070880C
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reaction
sulphur
many halogenated
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aromatic compounds
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CN1143652A (en
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严永刚
余洪仪
陈永荣
伍齐贤
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Sichuan Union University
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Abstract

The present invention relates to a preparation method for ductile aromatic polythioether with high molecular weight, and sulfur, proper power supply bodies and multiple halogenating aromatic compounds react in polar aprotic solvent. The main component of a used polycomponent composite catalyst or a reaction auxiliary agent is composed of inorganic salts of LiF, etc., organic acid salts and lactone or lactam. S/[H] is form 0.1 to 6, the mol ratio of the sulfur to the halogenating aromatic compounds is from 1:0.5 to 2; the mol ratio of the sulfur to the catalyst is from 1:0.03 to 1. the reaction has two steps of the reaction of 1 to 6 hours at the temperature of 120 DEGC to 240DEGC and the reaction of 1 to 6 hours at the temperature of 160 DEGC to 320 DEGC. the conversion rate of the sulfur reaches more than 95%; the present invention has the advantages of white product, little discoloration, high thermal stability and good toughness.

Description

The preparation method of high molecular toughness poly arylidene thio-ester
The invention belongs to the preparation method of high-molecular linear poly arylidene thio-ester.
Poly arylidene thio-ester, as polyphenylene sulfide (PPS), polyphenylene sulfide ketone (PPSK), PPSS (PPSF) because have that high temperature resistant, resistance to chemical attack, electrical property are good, radiation hardness, difficult combustion, characteristics such as physical strength height, dimensional stabilizing, as coating, plastics, structured material, binding agent, fiber and film, can be widely used in automobile, aerospace, petrochemical complex, light industry and machinery, electronics, food and engineering aspect.In modern industry was produced, poly arylidene thio-ester was mainly used sodium sulphite (Na 2S) or sulphur and aromatic compound prepared in reaction, as Phillips company with sodium sulphite and santochlor (DCB) at rare gas element (as N 2) in polar solvent (NMP) compressive reaction prepare polyphenylene sulfide (PPS) (U.S.P3,354,129[1967]).Because this method requires sodium sulphite and aromatics to produce polymkeric substance in the normal pressure one-step reaction.Its Sodium sulphate anhydrous, 99min is impure more, and is bigger to the reaction influence.Macallum proposed melting polymerization (Ma callum AD, J, org, chem, 1948:13,154 in 1948; U.S.P.2513188, U.S.P.2538941), its product is the similar starlike structure of high branching, and not really stable, and reaction mechanism is comparatively complicated, and practical value is little.United States Patent (USP) (U.S.P3878176) be reported in the polar solvent with sulphur and yellow soda ash be raw material add be pressed into polyphenylene sulfide (PPS), its transformation efficiency is low, reaction process is emitted CO 2, influence polyreaction.Kawakami Yukichika's report (the clear 58-47026 of JP, 1983) of Japan Wu Yu company is produced polyphenylene sulfide (PPS) with sodium formiate, sulphur and santochlor compressive reaction in NMP.But the report of any performances such as product-free fusing point, viscosity.
At the deficiencies in the prior art part, the invention provides a kind of new preparation method of linear high molecular weight poly arylidene thio-ester, be intended to improve the transformation efficiency of sulphur, thermostability, intensity and the toughness of product, enlarge its application in materials such as engineering plastics, fiber and film.
The objective of the invention is to realize by following proposal.
The present invention with sulphur and suitably power supply body and many halogenated aromatic compounds polar aprotic solvent (such as, HMPA, NMP etc.) in, utilization composite catalyst or reaction promoter, by two elementary reactions, the high son amount of preparation line style poly arylidene thio-ester.Its reaction formula is:
Figure C9511147100051
In the reaction formula:
X=F, Cl, Br or I,
R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8=H, CH 3, (CH 2) m-CH 3, CN ,-NR 2,-OH, COOM ,-SOH 3,-OR ,-SR ,-CON (R) 2,-N (R)-COR ' etc.
Z=-CO-,-SO 2-,-SO-,-CON (R) ,-C (R) 2-,-O-,-SiRR ' etc.
m=0~6。
[H] provided by reducing substances for the reductibility reactive hydrogen atom maybe can provide the reducing substances of electronics, comprising:
(1)MOOCCOOM(M=H、Li、Na、K、Bb)。
(2) RCHO (R=H, alkyl) or poly aldehyde;
(3) R-NH 2, X (R=H, OH, NH 2Or C 3H 5-NH-; X=H 2O, F, Cl, Br, I, SO 4, NO 3), HN=HN, HOCN=NCOH or HOOCN=NCOOH;
(4) HNx (x=1,2,3; M=H, Li, Na, Rb, Cs, Be, Mg, Ca, Sr, Ba, Al, N, B, P, Ga, In, Ta); NaBH 4, KBH 4Or LalH 4
In the synthetic method provided by the invention, the ratio of hydrogenous material and sulphur, different and different with the material of candidate, but all be quantitative reaction, S/[H] be 0.1~6 to be 0.3~3.0 o'clock best results.In the inventive method, organic polar solvent comprises amine, lactan, sulfone and similar compounds, commonly used has: hexamethylphosphoramide (HMPA), N-N-methyl-2-2-pyrrolidone N-(NMP), N, N-vinyl pyrrolidone, hexanolactam, tetramethyl-urea, dimethyl sulfoxide (DMSO), tetramethylene sulfone etc. are material similarly.
In the synthetic method provided by the invention, used aromatic compound is phenyl polyhalide, naphthalene polyhalide, many halogenated quinolines, many halos anthracene, many halos connection (three) benzene, many halogenated diphenyl ether, many halogenated diphenyls ketone, many halogenated diphenyls sulfone, many halogenated diphenyls methane, many halogenated diphenyls silane, many halogenated diphenyls phosphine fat, many halogenated diphenyls acid amides, many halogenated diphenyls imide, many halogenated pyrroles, many halos furans, many halogenated thiophenes etc.Modal have: santochlor, Meta Dichlorobenzene, orthodichlorobenzene, 4,4 '-two chloro benzophenones, 4,4 '-dichloro diphenyl sulfone, 4,4 '-dichloro diphenyl methane, 4,4 '-dichloro-diphenyl ether, paradibromobenzene, m-dibromobenzene, adjacent dibromobenzene, 4,4 '-dibromobenzene.
Synthetic method provided by the invention can obtain more high molecular weight polymers with active polyfunctional group aromatic compound as the 3rd monomer or linking agent.Mainly comprise aromatic amine, nitroaromatic, as 1,4-dichlorphenamide bulk powder, 1,3-dichlorphenamide bulk powder, p-Chlorobenzoic acid amide, m-chloro aniline, Ortho-Chloro aniline, phenylenediamine (adjacent,, to), 1,4 dichloronitrobenzenes, 1,3-dichloronitrobenzene, dinitrobenzene, 4,4 '-diaminodiphenylsulfone(DDS) or 4,4 '-diaminodiphenyl oxide; Phenols, as 1,4-chlorophenesic acid or 2,4 dichloro phenol; Many halogenated aromatic compounds, as 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1 or Perchlorobenzene etc.
In the method for the present invention, the mol ratio of halogenated aromatic compound and sulphur is (0.5~2): 1, be preferably in (0.9~1): in 1 scope; The consumption of polar solvent can change in a big way, and every mole of sulphur needs 50~5000ml, and when consumption was 200~1000ml, effect was better; The consumption of the 3rd monomer or linking agent is generally 0.05%~3%mol of sulphur, and in the time of between this 0.4%~0.8%mol, effect is better.
In the method for the present invention, adopt polycomponent composite catalyst or reaction promoter, main component is the material of following composition:
(1): MXm (m=1,2,3, M=Li, Na, K, Be, Mg, Ca, Ba, Cu or Zn; X=F, Cl, Br, I, CO 3, SO 4, PO 4Or NO;
(2): organic acid salt: Y-(CH 2) mCOOH (M), (Y=H ,-OH ,-SH or-NH 2(RR ') etc., m=(0~12), R-C 6H 4(CH 2) nCOOM, R-C 6H 4SO 3M, substituted furan hydrochlorate or substituted pyridines hydrochlorate, (M is with (1));
(3): lactone or lactan, as hexanolactam.
The consumption of polycomponent composite catalyst or reaction promoter is approximately 3%~100%mol of sulphur, and effect is best in 10%~30%mol scope.
Method provided by the invention is divided into two step of reaction, and the fs is reflected between 120 ℃-240 ℃ carries out, when temperature during at 160 ℃~180 ℃, effect is better, second stage reacts between 160 ℃~320 ℃, and when temperature was 200 ℃~280 ℃, effect was best.Fs evenly forms oligopolymer, and subordinate phase improves molecular weight, and two stages are to the contribution difference of polyreaction.Fs reaction needed 1~6 hour, subordinate phase needs 1~6 hour, and reaction always needs 2~12 hours, and when the time was 4~8 hours, effect was best.
Method provided by the invention, the transformation efficiency of sulphur is up to more than 95%, side reaction is few, adopts compound multicomponent catalyst or reaction promoter, utilization two-stage reaction process, obtain the linear macromolecule weight polymers, product is a white, the thermostability height, and processing back colour-change is less, toughness, intensity all improve a lot, and can satisfy engineering, electronics, automobile and other purposes.
Embodiment 1: add 580ml HMPA in the reactor of 1L, 86gNaOH (2.15mol), 15.8gHCOOLi (0.29mol), be warming up to 140 ℃, add sulphur 30.9g (0.96mol), be heated to 175 ℃, add santochlor 148g (0.997mol), 180 ℃ of reactions 2.75 hours, the fs reaction was finished; Be warming up to 223 ℃, add lithium chloride 12.8g (0.22mol) reaction 3 hours, be cooled to 140 ℃, slowly add deionized water, filter, washing, in 120 ℃ of dryings 12 hours, white products 92g, productive rate: 87.8%, fusing point Tm=292 ℃, 303 ℃ melt viscosity: 15000Pa.
Embodiment 2:
Operation replaces lithium formate with embodiment 1 with trioxymethylene.It the results are shown in table 1.
Implement 3:
Operation replaces lithium chloride with embodiment 1 with the amino n-caproic acid of 6-.It the results are shown in table 1.
Embodiment 4:
In the reactor of 1L, add 580Ml HMPA, 86gNaOH (2.15mol), 10.5gNH 2OH (0.33mol) is warming up to 140 ℃, adds sulphur 30.9g (0.66mol), is heated to 175 ℃, adds santochlor 140g (0.967mol), and 180 ℃ of reactions 2.75 hours, the fs reaction was finished; Be warming up to 280 ℃, add the amino n-caproic acid 30g of 6-(0.22mol) reaction 3 hours, be cooled to 140 ℃, slowly add deionized water, filter, washing, in 120 ℃ of dryings 12 hours, white products 92g, productive rate: 87.8%, fusing point Tm=292 ℃, 303 ℃ melt viscosity: 1500Pa.
Embodiment 5:
In the reactor of 250ml, add 98Ml HMPA, 3.2gNH 2OH, 17.8gNaOH is warming up to 120 ℃, adds sulphur 6.47g, be warming up to 175 ℃, add santochlor 29.7g, 180 ℃ of reactions 3 hours, add chloro lithium 2.7g, pressurization is warming up to 250 ℃, reacts 3 hours, be cooled to room temperature, slowly add deionized water, filter, washing, in 120 ℃ of dryings 12 hours, white products 19.2g, productive rate: 89%, fusing point Tm=290 ℃, 303 ℃ melt viscosity: 2000Pa.
Embodiment 6:
Operation is with embodiment 5, with NaBH 4Replace lithium formate.It the results are shown in table 1.
Embodiment 7:
Operation replaces lithium formate with embodiment 1 with the terephthalic acid lithium.It the results are shown in table 1.
Embodiment 8:
In the reactor of 1L, add 580Ml HMPA, 86gNaOH (2.15mol), 15.8gHOOLi (0.29mol) is warming up to 140 ℃, add sulphur 30.9g (0.96mol), be heated to 175 ℃, add 4,4 ' dichloro diphenyl sulfone 290g (1.009mol), finish in 180 ℃ of reactions, 2.75 hour fs reaction, be warming up to 230 ℃, add chloro lithium 12.8g (0.22mol) reaction 3 hours, be cooled to 140 ℃, slowly add deionized water, filter, washing was in 120 ℃ of dryings 12 hours, get white products 239g, productive rate: 96.7%, fusing point: Tm=278 ℃, 30 ℃=0.47.
Embodiment 9:
Together, wherein 4,4 ' two chloro benzophenones replace 4,4 ' dichloro diphenyl sulfone on operation and the embodiment 8, and it the results are shown in table 1.
Embodiment 10:
Operate identically with embodiment 1, wherein dibromobenzene replaces dichlorobenzene, and it the results are shown in table 1.
Embodiment 11:
Operate identically with embodiment 5, wherein, replace NMP with HMPA, it the results are shown in table 1.
Embodiment 12:
Add 580ml HMPA:86gNaOH (2.15mol) in the reactor of 1L, 61gHCOONa (0.99mol) is warming up to 140 ℃, add sulphur 30.9g (0.96mol), be heated to 175 ℃ and add santochlor 148g (0.997mol), be warming up to 230 ℃, reacted 3 hours, and be cooled to 140 ℃, slowly add deionized water, filter, washing was in 120 ℃ of dryings 12 hours, get white products 88.6g, productive rate: 82%, fusing point: Tm=272 ℃, 303 ℃ melt viscosity: 100Pa.
Embodiment 13:
In the reactor of 1L, add 580ml HMPA:86gNaOH (2.15mol), be warming up to 140 ℃, add sulphur 30.9g (0.96mol), be heated to 175 ℃ and add santochlor 148g (0.997mol), be warming up to 230 ℃, reacted 6 hours, be cooled to 140 ℃, slowly add deionized water, filter, washing, in 120 ℃ of dryings 12 hours, white products 54.6g, productive rate: 50%, fusing point: Tm=256 ℃, 303 ℃ melt viscosity: can not measure.
Embodiment 14:
Operate identically, wherein, replace NaOH with KOH with embodiment 1.Its as a result Comparative Examples in table 2.
Embodiment 15:
Operate identically, wherein, replace NaOH with KOH with embodiment 13.Its as a result Comparative Examples in table 2.
Embodiment 16:
Product of the present invention and oneself have technical products to compare (listing in table 3) about the effect of mechanical property
The reaction of table 1 embodiment 1-embodiment 11 and comparison sheet as a result thereof
The embodiment project 1 2 3 4 5 6 7 8 9 10 11
Sulphur (mol.) 0.96 0.96 0.96 0.96 0.20 0.96 0.9 0.96 0.96 0.96 0.20
Santochlor (mol..) hydrogenous material (mol..) 0.997 HCOOLi 0.29 0.997 trioxymethylene 0.25 0.997 HCOOLi 0.29 0.997 NH 2OH 0.33 0.21 NH 2OH 0.11 0.997 NaBH 4 0.33 0.21 NH 2OH 0.11 1.009 HCOOLi 0.29 0.999 HCOOLi 0.29 1.009 HCOOLi 0.29 0.21 HCOOLi 0.11
Oxyhydroxide (mol..) NaOH 2.15 NaOH 2.15 NaOH 2.15 NaOH 2.15 NaOH 0.41 NaOH 2.15 NaOH 0.41 NaOH 2.15 NaOH 2.15 NaOH 2.15 NaOH 0.41
Solvent (ml) 580 580 580 580 580 580 98 580 98 580 95
Time fs (h) temperature (℃) 2.75 80 2.8 182 2.9 179 2.6 175 3 180 2.8 175 2.6 185 2.75 180 2.75 180 2.75 180 3 180
Subordinate phase time (h) temperature (℃) 3 230 2.5 226 3.5 232 3 230 3 250 3.5 245 3.6 255 3 230 3 230 3 230 3 250
Catalyzer (mol.) LiCl 0.22 With 1 0.12 LiCl 0.21 6 hexosamines 0.12 With 1 0.03 With 1 0.03 With 1 0.03 With 1 0.22 LiCl 0.22 With 1 0.22 With 4 0.03
Polymkeric substance proterties productive rate (%) 87.8 89 90 92 93 91 91.5 96.7 95 93 94.5
State (color) White White White White White White White White White Yellow White
Fusing point (℃) 292 291 292 290 289 290 291 278 291 353 291.5
Viscosity (303 ℃, Pa) 1500 700 1400 1580 2000 1600 1874 - 1489 - 1276
Table 2 embodiment 12-15 reaction and comparison sheet as a result thereof
The embodiment project 12 13 14 15
Sulphur (mol.) 0.96 0.96 0.96 0.96
To dihydrobenzene (mol.) 0.997 0.997 0.99 0.997
Hydrogenous material (mol.) NaOOCH 0.69 --- NaOOCH 0.69
Oxyhydroxide (mol.) NaOH 2.15 NaOH 2.15 KOH 2.15 KOH 2.15
Solvent (mol.) 580 580 580 580
Reaction time (h) temperature (℃) catalyzer (mol.) 3 230 --- 4.5 226 --- 3.5 232 --- 5 230 ---
The polymkeric substance proterties, the molten point of productive rate (%) state (℃) viscosity (303 ℃, Pa) 82 canescence 272 100 50 canescence 256--- 73 canescence 270 78 49 canescence 262---
Table 3. mechanical property relatively
Property PPS-1 PPS-2 PPS-3 Ryton-1 PPS-1110
Tensile strength(Mpa) Tensile modulus(Gpa) Tensile yiekd(%) Tensile strength(KJ/m 2) 82.8 1.04 12.0 67.4 74.4 0.96 8.0 27.9 89.6 1.14 17.0 33.4 66 -- 1.6 6 48.1 -- 8.0 7.6
Annotate: PPS-1110 is Sichuan special engineering plastics factory product in 1992.

Claims (15)

1, a kind of preparation is the method for unitary linear macromolecule weight polymers with logical formula I,
Figure C9511147100021
It is characterized in that this method is: many halogenated aromatic compounds that will lead to formula II
With sulphur, the reaction of power supply body and caustic soda, reaction with amine, lactan, sulfone or sulfone similar compound be organic polar solvent, be catalyzer with inorganic salt (MXm), organic acid salt, lactone or lactan, X, R, Z, m in the logical formula II are respectively:
X is: F, Cl, Br or I, R 1, R 2, R 3, R 4, R 5, R 6, R 7, R 8For: H, CH 3, (CH 2) m-CH 3-CN ,-NH 2,-OH ,-COOH ,-SOH 3,-OR ,-SR ,-CON (R) 2-or-N (R)-COR,
Z is :-CO-,-SO 2-,-SO-,-CON (R)-,-C (R) 2-,-C (R) 2-,-O-or-SiRR '-
M is: 0~6,
The quantitative reaction ratio of power supply body and sulphur is S/[H in the reaction]=0.1: 6.
2, according to the method for claim 1, the body that it is characterized in that powering comprises:
(1), (M is MOOCCOOM: H, Li, Na, K or R b),
(2), RCHO (R is H, alkyl) or poly aldehyde,
(3), R-NH 2, (R is X: H, OH, NH 2, C 8H 5-NH-, X are H 2O, F, Cl, Br, I, SO 4, NO 3), NH=HN, HOCH=NCOH or HOOCN=NCOOH,
(4), MHx (x for, 1,2,3, M is: H, Li, Na, K, Rb, Cm, Be, Mg, Ca, Sr, Ba, Al, N, B, P, Ga, In, Ta), NmBH 4, KBH or LiAlH 4,
The power supply body is S/[H with the optimum amount ratio of sulphur]=0.3: 3.0.
3, according to the method for claim 1, it is characterized in that many halogenated aromatic compounds are: phenyl polyhalide, many halogenated quinolines, many halos anthracene, many halos terphenyl, many halogenated diphenyl ether, many halogenated diphenyls ketone, many halogenated diphenyls sulfone, many halogenated diphenyls methane, phenyl polyhalide silane, many halogenated diphenyls phosphatide, many halogenated diphenyls acid amides, many halogenated diphenyls imide, many halogenated pyrroles, many halos furans or many halogenated thiophenes, the amount ratio of many halogenated aromatic compounds and sulphur are mol ratio (0.5~2): 1.
4, according to the method for claim 1, it is characterized in that reaction is the 3rd monomer or crosslinked body with active more function group aromatic compound, comprise aromatic amine, nitroaromatic, phenols or many halogenated aromatic compounds, the 3rd monomer or dosage of crosslinking agent are 0.05%~3%mol of sulphur.
5, according to the method for claim 1, it is characterized in that organic utmost point solvent is hexamethylphosphoramide (HMPA), N-N-methyl-2-2-pyrrolidone N-(NMP), N, N-N,N-DIMETHYLACETAMIDE, N, N-dimethylformamide, N-ethyl hexanolactam, N, N-vinyl pyrrolidone, hexanolactam, tetramethyl-urea, dimethyl sulfoxide (DMSO) or tetramethylene sulfone, organic polar solvent consumption are every mole of sulphur of 50~500ml/.
6,, it is characterized in that the many groups composite catalyst or the reaction promoter that react employing are according to the method for claim 1:
1), MX m, wherein, m=1,2 or 3,
M=Li, Na, K, Be, Mg, Ca, Ba, Cu or Zn,
X=F, Cl, Br, I, CO 3, SO 4, PO 4Or NO 3,
2), organic acid salt, Y-(CH 2) MCOOH (M), R-C 8H 4(CH 2) nCOOM, R-C 8M 4SO 3M, substituted furan hydrochlorate or substituted pyridines hydrochlorate,
Wherein, m=3,4,5,6,7,8,9,10,11 or 12,
Y=H、-OH、-SH、-NH 2
M=Li, Na, K, Be, Mg, Ca, Ba, Cu or Zn,
3), lactone or lactan,
The consumption of catalyzer or reaction promoter is 3%~100%mol of sulphur.
7, according to the method for claim 1, Ji Tezheng is that reaction divides two stages to carry out 120 ℃~240 ℃ of fs temperature of reaction, 1~6 hour reaction times, 160 ℃~320 ℃ of subordinate phase temperature of reaction, 1~6 hour reaction times.
8, according to any one method in claim 1 and 3, it is characterized in that the many halogenated aromatic compounds that react commonly used are to hexichol chlorine, Meta Dichlorobenzene, orthodichlorobenzene, 4,4-two chloro benzophenones, 4,4 '-dichloro diphenyl sulfone, 4,4 '-dichloro diphenyl methane, 4,4 '-dichloro-diphenyl ether, to two fluorobenzene, m-difluorobenzene, 1,2-Difluorobenzene, 4,4 '-difluorodiphenyl ether, paradibromobenzene, m-dibromobenzene, adjacent dibromobenzene or 4,4 '-bromine hexichol, many halogenated aromatic compounds are mol ratio (0.9~1.1) with the optimum amount ratio of sulphur: 1.
9, according to any one method in claim 1 and 4, it is characterized in that having 1 as the aromatic amine or the nitroaromatic of the 3rd monomer and linking agent, 4-dichlorphenamide bulk powder, 1,3-dichlorphenamide bulk powder, p-Chlorobenzoic acid amide, m-chloro aniline, Ortho-Chloro aniline, phenylenediamine (adjacent,, to), 1,4-dichloronitrobenzene, 1,3-dichloronitrobenzene, dinitrobenzene, 4,4 '-Vdolac or 4,4 '-dichloride base phenyl ether.
10,, it is characterized in that phenols as the 3rd monomer and linking agent has 1,4-chlorophenesic acid or 2,4 dichloro phenol according to any one method in claim 1 and 4.
11, according to any one method in claim 1 and 4, it is characterized in that having 1,2 as many halogenated aromatic compounds of the 3rd monomer and linking agent, 4-trichlorobenzene, 1,3,5-trichlorobenzene, 1 or Perchlorobenzene.
12, according to any one method in claim 1 and 5, the consumption that it is characterized in that organic solvent is every mole of sulphur of 200~1000ml/.
13, according to any one method in claim 1 and 6, it is characterized in that the lactan in the catalysts is a hexanolactam, the consumption of catalyzer or reaction promoter is 10%~30mol of sulphur.
14, according to the method for claim 7, the temperature of reaction that it is characterized in that the fs is 160~180 ℃, and the reaction times is 24 hours, and the temperature of reaction of subordinate phase reaction is~200~280 ℃, and the reaction times is 2~4 hours.
15, according to claim 1, the method for any one in 4,9 and 11, the consumption that it is characterized in that the 3rd monomer or linking agent is 0.2%~0.8% of a sulphur.
CN95111471A 1995-08-21 1995-08-21 Method for preparing polyarylene sulfide with high molecular and high toughness Expired - Fee Related CN1070880C (en)

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JPS62252430A (en) * 1986-04-24 1987-11-04 Dainippon Ink & Chem Inc Production of polyphenylene sulfide
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