CN104744698A - Method for synthesizing linear high molecular weight polyphenylene sulfide - Google Patents
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Abstract
The invention discloses a method for synthesizing linear high molecular weight polyphenylene sulfide and belongs to the technical field of chemical material. The method comprises the following steps: by taking sodium sulphide and dichloro diphenyl as raw materials, synthesizing the linear high molecular weight polyphenylene sulfide (PPP) resin through a solution polycondensation method and a secondary polymerization process in a compound solvent and a cosolvent system. The method is simple in process and convenient to operate; the product has a high molecular weight linear structure; in the whole polymerization process, the molecular weight is controllable. Compared with the prior art, the method has the advantages of good solvent system dissolving property, low salt content and easy separation. The monomer reactivity of the linear polymerization reaction is high and the chain extension is easy to process. The dosage of the alkali metal or the alkaline earth chloride is few and the metal ion can be easily washed. The linear high molecular weight polyphenylene sulfide does not have irritant or carcinogenic property and is environmentally friendly to operate.
Description
Technical field
The invention belongs to chemical material technical field, be specifically related to a kind of with sodium sulphite and santochlor for raw material, under alkali lye, double solvents and adjuvant system, utilize solution polycondensation and after polymerization technique synthesizing linear high molecular weight polyphenylene sulfide (PPS) resin methods.
Background technology
Polyphenylene sulfide (PPS) is a kind of special engineering plastics of excellent combination property, there is excellent high temperature resistant, corrosion-resistant, radiation hardness, fire-retardant, balanced physical and mechanical properties and the feature such as fabulous dimensional stability and excellent electrical property, be widely used as structural macromolecular material, by filling, modifiedly can be used as special engineering plastics.Meanwhile, also can be made into various functional film, coating and matrix material, succeed in fields such as electronic apparatus, aerospace, Automobile Transportations application.
At present, the method of synthesis polyphenylene sulfide (PPS) is a lot, as halogen thiophenol salt from polycondensation, to the melt polymerization of halogen hexichol and sulphur, the electrophilic reaction of sulphur and benzene, alkali metalsulphide and the solution polycondensation (sodium sulfide method) to two halobenzenes, the solution polycondensation (sulfur solution route) of sulphur and santochlor, diphenyl disulfide polymerization under Lewis acid effect etc.Sodium sulfide method and sulfur solution route is mainly at present for industrial.
Sodium sulfide method in polar solvent, obtains polyphenylene sulfide with santochlor and Sodium sulphate anhydrous, 99min by condensation reaction.Conventional polar solvent mainly contains N-Methyl pyrrolidone, pyridine, HMPA etc., in industrial production-as adopt N-Methyl pyrrolidone and HMPA etc.This method advantage is that raw material is easy to get, good product quality, and yield is high, and shortcoming is that technical process is long, and feed purification difficulty is large, the sodium ion containing trace in polyphenylene sulfide, and product has straight chain type, half cross-linking type and cross-linking type, and wet fastness, electrical resistance and formability are not good.
Sulfur solution route is within the scope of 175 ~ 250 DEG C, and with HMPA or N-Methyl pyrrolidone for solvent, santochlor and sulphur polycondensation occur at ambient pressure and generates polyphenylene sulfide, and reaction yield is more than 85%.The easy accurate feed proportioning of this method, quality product is better, but technical difficulty is comparatively large, and in industrial production, sulphur is not easily purified, and the abraum salt amount of by-product is large, not easily industrialization.
Patent CN104045828A reports with moisture sodium sulphite, santochlor, phase solvent, solvent, auxiliary agent in the production formula of interior polyphenylene sulfide and method.CN102329426A to disclose with sodium sulphite and santochlor as raw material, under METHYLPYRROLIDONE solvent, is synthesized the technique of low halogen polyphenylene sulfide in autoclave by polycondensation.Patent CN101717510A discloses and many water cure sodium, lithium chloride and solvent N-methyl pyrilidone is mixed, polyphenylene sulfide is obtained by reacting with santochlor after component distillation dehydration, by filtering flash distillation two-section type recycling design, xylene solution crystallisation by cooling reclaims the production technique of lithium chloride.Also have patent CN1539863A refer to and adopt sulphur and p-dichlorobenzene to obtain the polyphenylene sulfide of high molecular at screw reactor generation melt polycondensation reaction, without the need to separated from solvent, and production cost and energy consumption reduce greatly.
Summary of the invention
The object of this invention is to provide a kind of with sodium sulphite and p-dichlorobenzene for raw material, under alkali lye, double solvents and adjuvant system, through the method for pre-polymerization, polycondensation, linear condensation synthesizing linear macromolecular weight poly benzene thioether resin.The method process control is stablized, and operating environment is good, especially the polymerisate after polycondensation is carried out secondary hardening polyreaction again after desalination purification, achieves the second lift of polyphenylene sulfide polymer molecular weight.
Technical scheme of the present invention is as follows: with sodium sulphite and santochlor for raw material, under alkali lye, double solvents and adjuvant system, utilize the method for solution polycondensation synthesizing linear macromolecular weight poly benzene thioether resin.
The present invention is the method for synthesizing linear macromolecular weight poly benzene thioether resin, it is characterized in that carrying out according to following step:
(1) in the autoclave that mechanical stirring, water coolant, charging opening and pneumatic outlet are housed, sodium sulphite, santochlor, alkali lye, solvent and auxiliary agent is added successively; electrified regulation heats up under nitrogen protection; prepolymerization reaction 1 ~ 4h is carried out at 160 ~ 200 DEG C; when temperature rises to 220 DEG C; stop heating; reaction heat is utilized to make reactor temperature continue to rise; open water coolant with the good reactor temperature of regulation and control simultaneously; temperature 240 ~ 280 DEG C; under pressure 1 ~ 1.5MPa condition, carry out polycondensation 1 ~ 3h.
(2) after reactor cooling, pressure release, reaction slurry is through overcooling; filter; filter cake is through pickling; deionized water wash; the polyphenylene sulfide polymer obtained and sodium sulphite, santochlor, solvent, auxiliary agent are joined in above-mentioned autoclave successively; under nitrogen protection; in 260 ~ 300 DEG C; under pressure 1 ~ 1.5MPa condition, carry out linear condensation reaction 1 ~ 3h, after the cooling of question response still, pressure release, reaction slurry is through overcooling; filter; filter cake through pickling, deionized water wash, then dry polyphenylene sulfide (PPS) resin.Melt viscosity can reach more than 500Pas, and product weight yield reaches more than 96%, and weight-average molecular weight (Mw) is 55000 ~ 60000 after measured, and molecular weight distributing index can reach 2 ~ 3.
Wherein in step (1), sodium sulphite is the sodium sulphite or the Sodium sulphate anhydrous, 99min that contain crystal water.Wherein sodium sulphite: santochlor mol ratio is (1.02 ~ 1.05): 1, sodium sulphite in step (2): santochlor mol ratio is 1:1.
Wherein in step (1), alkali lye is one or more in sodium hydroxide, calcium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate; Wherein alkali lye: santochlor mol ratio is (1 ~ 1.3): 1.
Wherein in step (1) and (2), solvent is composite solvent system, namely in N-Methyl pyrrolidone, N,N-dimethylacetamide, pyridine, HMPA, DMI or N-methylmorpholine any two kinds; Wherein solvent in step (1): santochlor mol ratio is (5 ~ 10): 1, solvent in step (2): santochlor mol ratio is (3 ~ 6): 1.
Wherein step (1) and (2) middle auxiliary agent are the muriate of basic metal or alkaline-earth metal, the mixture of one or more namely in lithium chloride, calcium chloride, aluminum chloride, Repone K, sodium-chlor, magnesium chloride; Wherein step (1) auxiliary agent: santochlor mol ratio is (0.005 ~ 0.01): 1, wherein step (2) auxiliary agent: santochlor mol ratio is (0.001 ~ 0.004): 1.
The prepolymerization reaction temperature of wherein carrying out in step (1) is 160 ~ 200 DEG C, reaction times 1 ~ 4h; Wherein temperature is preferably 170 ~ 185 DEG C, and the time is preferably 2 ~ 3h.
The polycondensation temperature of wherein carrying out in step (1) is 240 ~ 280 DEG C, pressure 1 ~ 1.5MPa, reaction times 1 ~ 3h; Wherein temperature is preferably 250 ~ 260 DEG C, pressure 1.2 ~ 1.3MPa, time 1.5 ~ 2h.
The linear condensation temperature of reaction of wherein carrying out in step (2) is 260 ~ 300 DEG C, pressure 1 ~ 1.5MPa, reaction times 1 ~ 3h; Wherein temperature is preferably 265 ~ 280 DEG C, pressure 1.2 ~ 1.3MPa, time 1.5 ~ 2h.
Wherein cooling temperature is 100 ~ 120 DEG C in step (2), pickling washing 1 ~ 3 time, deionized water wash 1 ~ 3 time, and acid wherein used is one or both of hydrochloric acid or sulfuric acid.
The invention provides the strengthening polymerization process of simple, the easy to operate solution polymerization process synthesis polyphenylene sulfide of a kind of process, product has the linear structure of higher molecular weight, and whole polymerization process, molecular weight is controlled, compared with prior art advantage is remarkable: 1. the solubility property of solvent system is good, salts contg is low, is separated easily.2. linear polymerization reaction monomers activity is high, is easy to chain extension.3. the muriatic consumption of basic metal or alkaline-earth metal is few, is easy to wash metal ion.4. to human body nonirritant and carinogenicity, operating environment is friendly.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of solution polycondensation synthesizing linear macromolecular weight poly benzene thioether resin of the present invention.
Fig. 2 is the autoclave structural representation that the present invention uses; 1-magnetic driver device; 2-tensimeter; 3-thermopair; 4-safety valve; 5-shaft joint; Stir shaft under 6-; 7-agitator; 8-an electric heating element and holding furnace cylinder; 9-cooling water outlet; 10-cooling water intake; 11-breather valve.
Embodiment
Present invention process schema as shown in Figure 1.
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
Embodiment 1
Mechanical stirring is being housed, water coolant, 1.02mol sodium sulphite is added successively in the autoclave of charging opening and pneumatic outlet, 1mol santochlor, 1mol sodium hydroxide, 5mol solvent (N-Methyl pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE) and 0.005mol lithium chloride, electrified regulation heats up under nitrogen protection, prepolymerization reaction 1h is carried out at 160 DEG C, when temperature rises to 220 DEG C, stop heating, reaction heat is utilized to make reactor temperature continue to rise, open water coolant with the good reactor temperature of regulation and control simultaneously, temperature 240 DEG C, under pressure 1MPa condition, terminate after carrying out polycondensation 1h.Reactor is lowered the temperature, after release, reaction slurry is through being cooled to 100 DEG C, filter, filter cake is through salt acid elution 1 time, deionized water wash 1 time, by the polyphenylene sulfide polymer that obtains and 1mol sodium sulphite, 1mol santochlor, 3mol solvent (N-Methyl pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE) and 0.001mol lithium chloride join in above-mentioned autoclave successively, under nitrogen protection, in 260 DEG C, under pressure 1MPa condition, carry out linear condensation reaction 1h, question response still is lowered the temperature, after release, reaction slurry is through being cooled to 100 DEG C, filter, filter cake is through salt acid elution 1 time, deionized water wash 1 time, then dry polyphenylene sulfide (PPS) resin.Melt viscosity can reach 516Pas, and product weight yield reaches 96%, and weight-average molecular weight (Mw) is 55865 after measured, molecular weight distributing index 2.25.
Embodiment 2
Mechanical stirring is being housed, water coolant, 1.02mol sodium sulphite is added successively in the autoclave of charging opening and pneumatic outlet, 1mol santochlor, 1.1mol potassium hydroxide, 6mol solvent (N-Methyl pyrrolidone, HMPA) and 0.006mol calcium chloride, electrified regulation heats up under nitrogen protection, prepolymerization reaction 1.5h is carried out at 170 DEG C, when temperature rises to 220 DEG C, stop heating, reaction heat is utilized to make reactor temperature continue to rise, open water coolant with the good reactor temperature of regulation and control simultaneously, temperature 250 DEG C, under pressure 1.2MPa condition, terminate after carrying out polycondensation 1.5h.Reactor is lowered the temperature, after release, reaction slurry is through being cooled to 105 DEG C, filter, filter cake is through salt acid elution 2 times, deionized water wash 1 time, by the polyphenylene sulfide polymer that obtains and 1mol sodium sulphite, 1mol santochlor, 4mol solvent (N-Methyl pyrrolidone, HMPA) and 0.002mol calcium chloride join in above-mentioned autoclave successively, under nitrogen protection, in 265 DEG C, under pressure 1.2MPa condition, carry out linear condensation reaction 1.5h, question response still is lowered the temperature, after pressure release, reaction slurry is through being cooled to 105 DEG C, filter, filter cake is through salt acid elution 2 times, deionized water wash 1 time, then dry polyphenylene sulfide (PPS) resin.Melt viscosity can reach 554Pas, and product weight yield reaches 97%, and molecular weight (Mw) is 56754 after measured, molecular weight distributing index 2.20.
Embodiment 3
Mechanical stirring is being housed, water coolant, 1.03mol sodium sulphite is added successively in the autoclave of charging opening and pneumatic outlet, 1mol santochlor, 1.2mol calcium hydroxide, 7mol solvent (N-Methyl pyrrolidone, pyridine) and 0.006mol Repone K, electrified regulation heats up under nitrogen protection, prepolymerization reaction 2h is carried out at 180 DEG C, when temperature rises to 220 DEG C, stop heating, reaction heat is utilized to make reactor temperature continue to rise, open water coolant with the good reactor temperature of regulation and control simultaneously, temperature 260 DEG C, under pressure 1.3MPa condition, terminate after carrying out polycondensation 2h.Reactor is lowered the temperature, after release, reaction slurry is through being cooled to 110 DEG C, filter, filter cake is through salt acid elution 2 times, deionized water wash 2 times, by the polyphenylene sulfide polymer that obtains and 1mol sodium sulphite, 1mol santochlor, 5mol solvent (N-Methyl pyrrolidone, pyridine) and 0.003mol Repone K join in above-mentioned autoclave successively, under nitrogen protection, in 270 DEG C, under pressure 1.3MPa condition, carry out linear condensation reaction 2h, question response still is lowered the temperature, after pressure release, reaction slurry is through being cooled to 110 DEG C, filter, filter cake is through salt acid elution 2 times, deionized water wash 2 times, then dry polyphenylene sulfide (PPS) resin.Melt viscosity can reach 586Pas, and product weight yield reaches 98%, and weight-average molecular weight (Mw) is 59543 after measured, molecular weight distributing index 2.05.
Embodiment 4
Mechanical stirring is being housed, water coolant, 1.04mol Sodium sulphate anhydrous, 99min is added successively in the autoclave of charging opening and pneumatic outlet, 1mol santochlor, 1.2mol sodium carbonate, 8mol solvent (N-Methyl pyrrolidone, 1, 3-dimethyl-2-imidazolinone) and 0.007mol aluminum chloride, electrified regulation heats up under nitrogen protection, prepolymerization reaction 2.5h is carried out at 190 DEG C, when temperature rises to 220 DEG C, stop heating, reaction heat is utilized to make reactor temperature continue to rise, open water coolant with the good reactor temperature of regulation and control simultaneously, temperature 270 DEG C, under pressure 1.4MPa condition, terminate after carrying out polycondensation 2.5h.Reactor is lowered the temperature, after release, reaction slurry is through being cooled to 115 DEG C, filter, filter cake is through sulfuric acid scrubbing 2 times, deionized water wash 3 times, by the polyphenylene sulfide polymer that obtains and 1mol sodium sulphite, 1mol santochlor, 5mol solvent (N-Methyl pyrrolidone, 1, 3-dimethyl-2-imidazolinone) and 0.003mol aluminum chloride join in above-mentioned autoclave successively, under nitrogen protection, in 280 DEG C, under pressure 1.3MPa condition, carry out linear condensation reaction 2.5h, question response still is lowered the temperature, after pressure release, reaction slurry is through being cooled to 115 DEG C, filter, filter cake is through salt acid elution 2 times, deionized water wash 3 times, then dry polyphenylene sulfide (PPS) resin.Melt viscosity can reach 573Pas, and product weight yield reaches 97%, and weight-average molecular weight (Mw) is 58142 after measured, molecular weight distributing index 2.18.
Embodiment 5
Mechanical stirring is being housed, water coolant, 10.5mol Sodium sulphate anhydrous, 99min is added successively in the autoclave of charging opening and pneumatic outlet, 10mol santochlor, 13mol sodium carbonate, 90mol solvent (N-Methyl pyrrolidone, N-methylmorpholine) and 0.08mol sodium-chlor, electrified regulation heats up under nitrogen protection, prepolymerization reaction 2.5h is carried out at 190 DEG C, when temperature rises to 220 DEG C, stop heating, reaction heat is utilized to make reactor temperature continue to rise, open water coolant with the good reactor temperature of regulation and control simultaneously, temperature 270 DEG C, under pressure 1.4MPa condition, terminate after carrying out polycondensation 3h.Reactor is lowered the temperature, after release, reaction slurry is through being cooled to 120 DEG C, filter, filter cake is through sulfuric acid scrubbing 3 times, deionized water wash 3 times, by the polyphenylene sulfide polymer that obtains and 10mol sodium sulphite, 10mol santochlor, 50mol solvent (N-Methyl pyrrolidone, N-methylmorpholine) and 0.03mol sodium-chlor join in above-mentioned autoclave successively, under nitrogen protection, in 290 DEG C, under pressure 1.4MPa condition, carry out linear condensation reaction 3h, question response still is lowered the temperature, after pressure release, reaction slurry is through being cooled to 120 DEG C, filter, filter cake is through salt acid elution 3 times, deionized water wash 3 times, then dry polyphenylene sulfide (PPS) resin.Melt viscosity can reach 565Pas, and product weight yield reaches 97%, and weight-average molecular weight (Mw) is 58003 after measured, molecular weight distributing index 2.20.
Embodiment 6
Mechanical stirring is being housed, water coolant, 105mol Sodium sulphate anhydrous, 99min is added successively in the autoclave of charging opening and pneumatic outlet, 100mol santochlor, 130mol sodium bicarbonate, 1000mol solvent (N-Methyl pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE) and 1mol magnesium chloride, electrified regulation heats up under nitrogen protection, prepolymerization reaction 3h is carried out at 200 DEG C, when temperature rises to 220 DEG C, stop heating, reaction heat is utilized to make reactor temperature continue to rise, open water coolant with the good reactor temperature of regulation and control simultaneously, temperature 280 DEG C, under pressure 1.5MPa condition, terminate after carrying out polycondensation 3h.Reactor is lowered the temperature, after release, reaction slurry is through being cooled to 120 DEG C, filter, filter cake is through sulfuric acid scrubbing 3 times, deionized water wash 3 times, by the polyphenylene sulfide polymer that obtains and 100mol sodium sulphite, 100mol santochlor, 600mol solvent (N-Methyl pyrrolidone, N, N-N,N-DIMETHYLACETAMIDE) and 0.4mol magnesium chloride join in above-mentioned autoclave successively, under nitrogen protection, in 300 DEG C, under pressure 1.5MPa condition, carry out linear condensation reaction 3h, question response still is lowered the temperature, after pressure release, reaction slurry is through being cooled to 120 DEG C, filter, filter cake is through salt acid elution 3 times, deionized water wash 3 times, then dry polyphenylene sulfide (PPS) resin.Melt viscosity can reach 570Pas, and product weight yield reaches 97%, and weight-average molecular weight (Mw) is 58143 after measured, molecular weight distributing index 2.18.
Claims (9)
1. a synthetic method for linear high molecular weight polyphenylene sulfide, is characterized in that carrying out according to following step:
(1) in the autoclave that mechanical stirring, water coolant, charging opening and pneumatic outlet are housed, sodium sulphite, santochlor, alkali lye, solvent and auxiliary agent is added successively, electrified regulation heats up under nitrogen protection, prepolymerization reaction 1 ~ 4h is carried out at 160 ~ 200 DEG C, when temperature rises to 220 DEG C, stop heating, reaction heat is utilized to make reactor temperature continue to rise, open water coolant with the good reactor temperature of regulation and control simultaneously, temperature 240 ~ 280 DEG C, under pressure 1 ~ 1.5MPa condition, carry out polycondensation 1 ~ 3h;
(2) after reactor cooling, pressure release, reaction slurry is through overcooling, filter, filter cake is through pickling, deionized water wash, the polyphenylene sulfide polymer obtained and sodium sulphite, santochlor, solvent, auxiliary agent are joined in above-mentioned autoclave successively, under nitrogen protection, in 260 ~ 300 DEG C, under pressure 1 ~ 1.5MPa condition, carry out linear condensation reaction 1 ~ 3h, after the cooling of question response still, pressure release, reaction slurry is through overcooling, filter, filter cake through pickling, deionized water wash, then dry polyphenylene sulfide (PPS) resin; Melt viscosity can reach more than 500Pas, and product weight yield reaches more than 96%, after measured weight-average molecular weight (M
w) be 55000 ~ 60000, molecular weight distributing index can reach 2 ~ 3.
2. the synthetic method of a kind of linear high molecular weight polyphenylene sulfide according to claim 1, is characterized in that wherein the middle sodium sulphite of step (1) is the sodium sulphite or the Sodium sulphate anhydrous, 99min that contain crystal water; Wherein sodium sulphite: santochlor mol ratio is (1.02 ~ 1.05): 1, sodium sulphite in step (2): santochlor mol ratio is 1:1.
3. the synthetic method of a kind of linear high molecular weight polyphenylene sulfide according to claim 1, is characterized in that alkali lye in wherein step (1) is one or more in sodium hydroxide, calcium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate; Wherein alkali lye: santochlor mol ratio is (1 ~ 1.3): 1.
4. the synthetic method of a kind of linear high molecular weight polyphenylene sulfide according to claim 1, it is characterized in that wherein step (1) and (2) middle solvent are composite solvent system, i.e. N-Methyl pyrrolidone, N, in N-N,N-DIMETHYLACETAMIDE, pyridine, HMPA, DMI or N-methylmorpholine any two kinds; Wherein solvent in step (1): santochlor mol ratio is (5 ~ 10): 1, solvent in step (2): santochlor mol ratio is (3 ~ 6): 1.
5. the synthetic method of a kind of linear high molecular weight polyphenylene sulfide according to claim 1, it is characterized in that wherein step (1) and (2) middle auxiliary agent are the muriate of basic metal or alkaline-earth metal, the mixture of one or more namely in lithium chloride, calcium chloride, aluminum chloride, Repone K, sodium-chlor, magnesium chloride; Wherein step (1) auxiliary agent: santochlor mol ratio is (0.005 ~ 0.01): 1, wherein step (2) auxiliary agent: santochlor mol ratio is (0.001 ~ 0.004): 1.
6. the synthetic method of a kind of linear high molecular weight polyphenylene sulfide according to claim 1, is characterized in that the prepolymerization reaction temperature of carrying out in wherein step (1) is 160 ~ 200 DEG C, reaction times 1 ~ 4h; Wherein temperature is preferably 170 ~ 185 DEG C, and the time is preferably 2 ~ 3h.
7. the synthetic method of a kind of linear high molecular weight polyphenylene sulfide according to claim 1, is characterized in that the polycondensation temperature of carrying out in wherein step (1) is 240 ~ 280 DEG C, pressure 1 ~ 1.5MPa, reaction times 1 ~ 3h; Wherein temperature is preferably 250 ~ 260 DEG C, pressure 1.2 ~ 1.3MPa, time 1.5 ~ 2h.
8. the synthetic method of a kind of linear high molecular weight polyphenylene sulfide according to claim 1, is characterized in that the linear condensation temperature of reaction of carrying out in wherein step (2) is 260 ~ 300 DEG C, pressure 1 ~ 1.5MPa, reaction times 1 ~ 3h; Wherein temperature is preferably 265 ~ 280 DEG C, pressure 1.2 ~ 1.3MPa, time 1.5 ~ 2h.
9. the synthetic method of a kind of linear high molecular weight polyphenylene sulfide according to claim 1, it is characterized in that wherein the middle cooling temperature of step (2) is 100 ~ 120 DEG C, pickling washing 1 ~ 3 time, deionized water wash 1 ~ 3 time, acid wherein used is one or both of hydrochloric acid or sulfuric acid.
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| CN106893102A (en) * | 2017-03-10 | 2017-06-27 | 四川中科兴业高新材料有限公司 | A kind of method that synthesis mother liquid prepares polyphenylene sulfide |
| CN107936250A (en) * | 2017-11-29 | 2018-04-20 | 中国石油化工股份有限公司 | A kind of method of polyphenylene sulfide oligomer recycling |
| CN108164702A (en) * | 2017-12-27 | 2018-06-15 | 浙江新和成股份有限公司 | A kind of preparation method of polyphenylene sulfide and the polyphenylene sulfide being prepared by it |
| CN108752586A (en) * | 2018-07-04 | 2018-11-06 | 西北师范大学 | A kind of preparation method of colored fascicular texture polyphenylene sulfide |
| CN109608638A (en) * | 2018-11-19 | 2019-04-12 | 太原理工大学 | A kind of synthetic method of linear polyphenylthioether of high molecular weight |
| CN109776798A (en) * | 2018-12-18 | 2019-05-21 | 浙江新和成特种材料有限公司 | Macromolecular weight poly benzene thioether resin and its preparation method and application |
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| CN105713199B (en) * | 2016-01-19 | 2018-01-30 | 成都汇莹新材料有限公司 | A kind of high-purity polyphenylene sulfide resin production process |
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| CN106893102A (en) * | 2017-03-10 | 2017-06-27 | 四川中科兴业高新材料有限公司 | A kind of method that synthesis mother liquid prepares polyphenylene sulfide |
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| CN107936250B (en) * | 2017-11-29 | 2020-06-16 | 中国石油化工股份有限公司 | Method for recycling polyphenylene sulfide oligomer |
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| WO2020125048A1 (en) * | 2018-12-18 | 2020-06-25 | 浙江新和成股份有限公司 | High-molecular-weight polyphenylene sulfide resin and preparation method and use thereof |
| CN109776798B (en) * | 2018-12-18 | 2020-08-25 | 浙江新和成特种材料有限公司 | High molecular weight polyphenylene sulfide resin and preparation method and application thereof |
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| JP2021510749A (en) * | 2018-12-18 | 2021-04-30 | 浙江新和成股▲分▼有限公司Ｚｈｅｊｉａｎｇ Ｎｈｕ Ｃｏ．，Ｌｔｄ． | High molecular weight polyphenylene sulfide resin and its manufacturing method and use |
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| JP7194189B2 (en) | 2018-12-18 | 2022-12-21 | 浙江新和成股▲分▼有限公司 | High molecular weight polyphenylene sulfide resin and its production method and use |
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