CN1143652A - 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 PDFInfo
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- CN1143652A CN1143652A CN95111471A CN95111471A CN1143652A CN 1143652 A CN1143652 A CN 1143652A CN 95111471 A CN95111471 A CN 95111471A CN 95111471 A CN95111471 A CN 95111471A CN 1143652 A CN1143652 A CN 1143652A
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Abstract
A process for preparing tough high-molecular polyaryl thioether features the reaction of sulfur with proper electric donor and polyhaloaromatic compound in polar non-protonic solvent under the catalysis of multi-element compound catalyst or reaction assistant whose main components are inorganic salt (such as LiF), organic acid salt and lactone or lactam. Said reaction is divided into two stages, that is, at 120-240 deg.C for 1-6 hr and at 160-320 deg.C for 1-6 hr. The S/[H] is 0.1-6; sulfur: haloaromatic compound (mol)=1:(0.5-2); and sulfur: catalyst (mol)=1:(0.03-1). The product features high transform rate of sulfur up to 95%, low decolouring, high toughness and thermal stability.
Description
The invention belongs to the preparation method of high-molecular linear poly arylidene thio-ester.
Poly arylidene thio-ester, as polyphenylene sulfide (PP8), 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, oil foundry, 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) in rare gas element (as N2) in polar solvent (NMP) compressive reaction prepare polyphenylene sulfide (PPS) (U.S.P3,354,129[1967]).Because this method requires sodium sulphite purity height, dehydration thoroughly, reaction process is comparatively complicated.Domestic mainly the reaction in normal pressure one-step with Sodium sulphate anhydrous, 99min and aromatics produced polymkeric substance.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.It is that raw material adds and is pressed into polyphenylene sulfide (PPS) that United States Patent (USP) (U.S.P.3878176) is reported in the polar solvent with sulphur and yellow soda ash, and its transformation efficiency is low, and reaction process is emitted CO
2, influence polyreaction.Kawakami Yukichika's report (the clear 58-47026 of JP, 1983) of Wu Yu company of Japan 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, the thermostability of product, intensity and toughness 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:
In the reaction formula:
X＝F、Cl、Br、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 ,-COM (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), poly aldehyde;
(3)?R-NH
2，X(R＝H、OH、NH
2、C
8H
5-NH-；X＝H
2O、F、Cl、Br、I、SO
4、NO
3)、HN＝NH、HOCN＝NCOH、HOOCN＝NCOOH；
(4)MH
x(x＝l、2、3；M＝H、Li、Na、K、Rb、Cs、Be、Mg、Ca、Sr、Ba、Al、N、B、P、Ga、In、Ta)；NaBH
4、KBH
4、LiAlH
4；
In the synthetic method provided by the invention, the ratio of hydrogenous material and sulphur, different and different with the material of selecting, but all be quantitative reaction, S/[H] be 0.1～6, be 0.3～3.0 o'clock best results.In the method for the present invention, 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-dimethylacetamide, N, dinethylformamide, N-ethyl hexanolactam, 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 alkali, 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, to two fluorobenzene, m-difluorobenzene, 1,2-Difluorobenzene, 4,4 '-difluoro benzophenone, 4,4 '-difluorodiphenyl sulfone, 4,4 '-difluoro-diphenylmethane, 4,4 '-difluorodiphenyl ether, paradibromobenzene, m-dibromobenzene, adjacent dibromobenzene, 4,4 '-bromine hexichol.
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.Comprise that mainly fragrance is by, 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), 4,4 '-diaminodiphenyl oxide; Phenols, as 1,4-chlorophenesic acid, 2,4 dichloro phenol; Many halogenated aromatic compounds, as 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1, Perchlorobenzene etc.
In the method for the present invention, (0.5～2) that the mol ratio of halogenated aromatic compound and sulphur is: 1, be preferably in this (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)：MX
m(m＝1、2、3，M＝Li、Na、K、Be、Mg、Ca、Ba、Cu、Zn；X＝F、Cl、Br、I、CO
3、SO
4、PO
4、NO；
(2): organic acid salt: Y-(CH
2)
mCOOH (M), (Y=H ,-OH ,-SH ,-NH
2(RR ') etc., m=3～12), R-C
6H
4(CH
2)
nCOOM, R-CaH
4SO
3M, substituted furan hydrochlorate, 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, subordinate phase is reacted 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:
In the reactor of 1L, add 580mL HMPA, 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 230 ℃, 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 and dissolved viscosity: 1500Pa.
Embodiment 2:
Operation replaces lithium formate with embodiment 1 with trioxymethylene.It the results are shown in table 1.
Embodiment 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 58mL 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 (0.22mol.) of 6-, reacted 3 hours, be cooled to 140 ℃, slowly add deionized water, filter, washing was in 120 ℃ of dryings 12 hours, get white products 92g, productive rate: 87.8%, fusing point: Tm=292 ℃, 303 ℃ melting viscosity: 1500Pa.
Embodiment 5:
In the autoclave of 250mL, add 98mL NMP, 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 synthesis under normal pressure 3 hours, add the amino n-caproic acid 2.7g of 6-, 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 ℃ melting viscosity: 2000Pa.
Embodiment 6:
Operation is with embodiment 1, with NaBH
4Replace lithium formate.It the results are shown in table 1.
Embodiment 7:
Operation replaces lithium formate with embodiment 5 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.) 15.8gHCOOLi (0.29mol.), be warming up to 140 ℃, add sulphur 30.9g (0.96mol.), be heated to 175 ℃ and add 4,4 ' dichloro diphenyl sulfone 290g (1.009mol.) finishes in 180 ℃ of reactions, 2.75 hour fs reaction, is warming up to 230 ℃, add chloro lithium 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 239g, productive rate: 96.7%, fusing point: Tm=278 ℃, η 30 ℃=0.47.
Embodiment 9:
Together, wherein with 4,4 '-difluoro benzophenone replaces 4 on operation and the embodiment 8,4 '-difluorodiphenyl sulfone, and it the results are shown in table 1.
Embodiment 10:
Operate identically with embodiment 1, wherein, replace dichlorobenzene with dibromobenzene, 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:
In the reactor of 1L, add 580mL HMPA, 86gNaOH (2.15mol.), 61gHCOONa (0.99mol.), 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 3 hours, be cooled to 140 ℃, slowly add deionized water, filter, washing, in 120 ℃ of dryings 12 hours, white products 88.6g, productive rate: 82%, fusing point: Tm=272 ℃, 303 ℃ melting viscosity: 100Pa.
Embodiment 13:
Add 580mL HMPA in the reactor of 1L, 86gNaOH (2.15mol.) is warming up to 140 ℃, add sulphur 30.9g (0.96mol.), be heated to 175 ℃ of addings, be warming up to 230 ℃ chlorobenzene 148g (0.997mol.), reacted 6 hours, and be cooled to 140 ℃, slowly add deionized water, filtration washing, in 120 ℃ of dryings 12 hours, white products 54.6g, productive rate: 50%, fusing point: Tm=256 ℃, 303 ℃ melting viscosity: can not measure.
Embodiment 14:
Operate identically, wherein, replace NaoH with KOH with embodiment 12.Table 2 is listed in base result contrast.
Embodiment 15:
Operate identically, wherein, replace NaoH with KOH with embodiment 13.Table 2 is listed in its result's contrast.
Embodiment 16:
Product of the present invention and prior art product 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 40.33 | ?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 | ?98 | 580 | ?98 | ?580 | ?580 | ?580 | ?95 |
| Time fs (h) temperature (℃) | 2.75 180 | 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 4 0.03 | With 1 0.03 | With 1 0.30 | 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 | ?94.3 |
| 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) 1800 | 1500 | 700 | ?1400 | ??1580 | ?2000 | 1800 | ??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 |
| Santochlor (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?yield(％) Impact?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 ?73.4 | ??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 general formula (I),
It is characterized in that this method is:
Many halogenated aromatic compounds with general formula (II)
With sulphur, the reaction of power supply body and caustic soda, reaction with amine, lactan, sulfone, sulfone similar compound be organic polar solvent, be catalyzer with inorganic salt (MXm), organic acid salt, lactone, lactan, X, R, Z, m in the general 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 ,-NR
2,-OH ,-COOH ,-SOH
3,-OR ,-SR ,-CON (R)
2,-N (R)-COR,
Z is :-CO-,-SO
2-,-SO-,-CON (R)-,-C (R)
2-,-C (R)
2-,-O-,-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, R
b),
(2), RCHO (R is: H, alkyl), poly aldehyde,
(3), R-NH
2, (R is X: H, OH, NH
2, C
3H
5-NH-, X is: H
2O, F, Cl, Br, I, SO
4, NO
3), HN=HN, HOCN=NCOH, HOOCN=NCOOH,
(4), MH
x(x is, 1,2,3, M is: H, Li, Na, K, Rb, Ca, Be, Mg, Ca, Sr, Ba, Al, N, B, P, Ga, In, Ta), N
aBH
4, KBH
4, 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 are feared, many halos terphenyl, many halogenated diphenyl ether, many halogenated diphenyls ketone, many halogenated diphenyls sulfone, many halogenated diphenyls methane, many halogenated diphenyls silane, many halogenated diphenyls phosphatide, many halogenated diphenyls acid amides, many halogenated diphenyls imide, many halogenated pyrroles, many halos furans, many halogenated thiophenes, and the amount ratio of many halogenated aromatic compounds and sulphur is 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, 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 polar solvent is hexamethylphosphoramide (HMPA), N-N-methyl-2-2-pyrrolidone N-(NMP), N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N-ethyl hexanolactam, N, N-vinyl pyrrolidone, caprolactam, tetramethyl-, dimethyl sulfoxide (DMSO), tetramethylene sulfone, organic polar solvent consumption are every mole of sulphur of 50～500ml/.
6,, it is characterized in that the polycomponent composite catalyst or the reaction promoter that react employing are according to the method for claim 1:
1), MX
m, wherein, m=1,2,3,
M＝Li、Na、K、Be、Mg、Ca、Ba、Cu、Zn，
X＝F、Cl、Br、I、CO
3、SO
4、PO
4、NO
3，
2), organic acid salt, Y-(CH
2) mCOOH (M), R-C
5H
4(CH
2)
nCOOM, R-C
3M
4SO
3M, substituted furan hydrochlorate, substituted pyridines hydrochlorate,
Wherein, m=3,4,5,6,7,8,9,10,11,12,
Y＝H、-OH、-SH、-NH
2，
M＝Li、Na、K、Be、Mg、Ca、Ba、Cu、Zn，
3), lactone, 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 claim 1,3 method, 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 '-difluoro benzophenone, 4,4 '-difluorodiphenyl sulfone, 4,4 '-difluoro-diphenylmethane, 4,4 '-difluorodiphenyl ether, paradibromobenzene, m-dibromobenzene, adjacent dibromobenzene, 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 claim 1,4 method, it is characterized in that as the aromatic amine of the 3rd monomer and linking agent or nitroaromatic have 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-dichloro nitre an aromatic plant metioned in ancient books benzene, 1,3-dichloronitrobenzene, dinitrobenzene, 4,4 '-diamino an aromatic plant metioned in ancient books sulfobenzide, 4,4 '-diaminodiphenyl oxide.
10,, it is characterized in that phenols as the 3rd monomer and linking agent has 1,4-chlorophenesic acid, 2,4-chlorophenesic acid according to claim 1,4 method.
11,, it is characterized in that many halogenated aromatic compounds as the 3rd monomer and linking agent have 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,2,3-trichlorobenzene, Perchlorobenzene according to claim 1,4 method.
12, according to claim 1,5 method, the optimum amount that it is characterized in that organic polar solvent is every mole of sulphur of 200～1000ml/.
13, according to claim 1,6 method, it is characterized in that the lactan in the catalysts is a hexanolactam, the optimum amount of catalyzer or reaction promoter is 10%～30%mol of sulphur.
14, according to claim 1,7 method, it is characterized in that the fs optimal reaction temperature of reaction is 160 °～180 ℃, optimum reacting time is 2～4 hours, and the optimal reaction temperature of subordinate phase reaction is 200 °～280 ℃, and optimum reacting time is 2～4 hours.
15, according to claim 1,4,9,10,11 method, the optimum amount that it is characterized in that the 3rd monomer or linking agent is 0.2%～0.8% of a sulphur.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111471A CN1070880C (en) | 1995-08-21 | 1995-08-21 | Method for preparing polyarylene sulfide with high molecular and high toughness |
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|---|---|---|---|
| CN95111471A CN1070880C (en) | 1995-08-21 | 1995-08-21 | Method for preparing polyarylene sulfide with high molecular and high toughness |
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| CN1070880C CN1070880C (en) | 2001-09-12 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326911C (en) * | 2002-12-27 | 2007-07-18 | 株式会社吴羽 | Process for producing and method of cleaning polyarylene sulfide, and method of purifying organic solvent used for cleaning |
| CN1331917C (en) * | 2003-04-25 | 2007-08-15 | 四川省华拓科技有限责任公司 | Tchnical method of fusing sulfur for synthesizing resin of polyphenylene sulfide |
| CN102502521A (en) * | 2011-11-02 | 2012-06-20 | 陕西科技大学 | Preparation method for sulfur micro-emulsion |
| CN102702529A (en) * | 2012-06-01 | 2012-10-03 | 四川大学 | Color-changing aromatic thioether compound and preparation method thereof |
| CN103965475A (en) * | 2014-04-29 | 2014-08-06 | 成都大诺工程技术咨询有限公司 | High-toughness polyphenylene sulfide and preparation method thereof |
| CN104629053A (en) * | 2013-11-12 | 2015-05-20 | 江苏扬农化工集团有限公司 | Preparation method of polyphenylene sulfide |
| CN108948355A (en) * | 2018-07-26 | 2018-12-07 | 四川中科兴业高新材料有限公司 | A method of polyphenylene sulfide is prepared using benzene and sulphur as raw material |
| CN108976421A (en) * | 2018-07-26 | 2018-12-11 | 四川中科兴业高新材料有限公司 | A kind of preparation method of film-grade PPS resin |
| CN109705346A (en) * | 2018-12-29 | 2019-05-03 | 重庆晟淦新材料科技有限公司 | Polyphenylene sulfide and the preparation method and application thereof without lithium chloride and additive |
| CN114213659A (en) * | 2021-12-27 | 2022-03-22 | 中鼎凯瑞科技成都有限公司 | Heat-resistant silicon-containing polyarylene sulfide and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5869227A (en) * | 1981-10-20 | 1983-04-25 | Kureha Chem Ind Co Ltd | Production of aromatic sulfide polymer |
| JPH072846B2 (en) * | 1986-04-24 | 1995-01-18 | 大日本インキ化学工業株式会社 | Method for producing polyphenylene sulfide |
| US4859762A (en) * | 1988-06-28 | 1989-08-22 | Eastman Kodak Company | Process for the preparation of copoly(arylene sulfide) |
| DE3927657A1 (en) * | 1989-08-22 | 1991-02-28 | Bayer Ag | HEXAHYDROTRIAZINTRION-CONTAINING POLYARYL SULFIDES AND METHOD FOR THE PRODUCTION THEREOF |
| US5239050A (en) * | 1991-05-13 | 1993-08-24 | Phillips Petroleum Company | Process for preparing arylene sulfide polymer with addition of aqueous alkali metal carboxylate prior to termination of polymerization |
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1995
- 1995-08-21 CN CN95111471A patent/CN1070880C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326911C (en) * | 2002-12-27 | 2007-07-18 | 株式会社吴羽 | Process for producing and method of cleaning polyarylene sulfide, and method of purifying organic solvent used for cleaning |
| CN1331917C (en) * | 2003-04-25 | 2007-08-15 | 四川省华拓科技有限责任公司 | Tchnical method of fusing sulfur for synthesizing resin of polyphenylene sulfide |
| CN102502521A (en) * | 2011-11-02 | 2012-06-20 | 陕西科技大学 | Preparation method for sulfur micro-emulsion |
| CN102702529A (en) * | 2012-06-01 | 2012-10-03 | 四川大学 | Color-changing aromatic thioether compound and preparation method thereof |
| CN102702529B (en) * | 2012-06-01 | 2014-01-08 | 四川大学 | Color-changing aromatic thioether compound and preparation method thereof |
| CN104629053A (en) * | 2013-11-12 | 2015-05-20 | 江苏扬农化工集团有限公司 | Preparation method of polyphenylene sulfide |
| CN103965475A (en) * | 2014-04-29 | 2014-08-06 | 成都大诺工程技术咨询有限公司 | High-toughness polyphenylene sulfide and preparation method thereof |
| CN103965475B (en) * | 2014-04-29 | 2016-03-30 | 四川中科兴业高新材料有限公司 | A kind of high toughness polyphenyl thioether and preparation method thereof |
| CN108948355A (en) * | 2018-07-26 | 2018-12-07 | 四川中科兴业高新材料有限公司 | A method of polyphenylene sulfide is prepared using benzene and sulphur as raw material |
| CN108976421A (en) * | 2018-07-26 | 2018-12-11 | 四川中科兴业高新材料有限公司 | A kind of preparation method of film-grade PPS resin |
| CN109705346A (en) * | 2018-12-29 | 2019-05-03 | 重庆晟淦新材料科技有限公司 | Polyphenylene sulfide and the preparation method and application thereof without lithium chloride and additive |
| CN114213659A (en) * | 2021-12-27 | 2022-03-22 | 中鼎凯瑞科技成都有限公司 | Heat-resistant silicon-containing polyarylene sulfide and preparation method thereof |
| CN114213659B (en) * | 2021-12-27 | 2024-03-26 | 中鼎凯瑞科技成都有限公司 | Heat-resistant silicon-containing polyarylene sulfide and preparation method thereof |
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