CN103087317B - Manufacturing method of high-molecular-weight polyphenylene sulfide sulfone - Google Patents
Manufacturing method of high-molecular-weight polyphenylene sulfide sulfone Download PDFInfo
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Abstract
The invention discloses a manufacturing method of high-molecular-weight polyphenylene sulfide sulfone. The method comprises the steps that: 1, pre-polymerization material treatment is carried out, wherein an alkali metal hydroxide, a sulfur-containing compound, and N-methylpyrrolidone are mixed according to a molar ratio of 0.1-0.3:1:3-5; and high-temperature dehydration is carried out, such that a mixture with organic alkali metal salt content no lower than 0.03mol/Smol is obtained; 2, polymerization is carried out, wherein the water content of the mixture is regulated to 5-10mol/Smol; 0.98-1.04mol/Smol of dihalo sulfone is added into the mixture; the temperature is increased to 90-120 DEG C, and is maintained for 0.5-3h; the temperature is increased to 175-190 DEG C, and is maintained for 3-5h, such that a polymer is obtained; and 3, shaping and recovery are carried out. The method provided by the invention has the advantages that: with the method, polyphenylene sulfide sulfone with high molecular weight and good thermal stability can be obtained; the reaction is more stable, side reaction is less, polymerization efficiency is increased, and cost is reduced.
Description
Technical field
The present invention relates to the manufacture method of thermoplastics, be specifically related to the manufacture method of high molecular weight polyphenylene sulfide sulfone.
Background technology
PPSS is a kind of thermoplastic special engineering plastic of non-crystalline type, has good thermostability, mechanical property and electric insulating quality, by rapid Design and can be molded as required section bar, can be used for multiple field such as automobile, aerospace.
PPSS also dissolves in special solvent, makes it be suitable for preparation coating and film.
The synthetic method of usually known PPSS be disclose in the United States Patent (USP) of " US4102875 " at publication number by Phillips oil company, is specially and sodium sulphite and dichloro diphenyl sulfone are synthesized PPSS being greater than contact reacts in the organic solvent of 200 DEG C.The shortcoming of the method is, the PPSS molecular weight obtained is low, poor heat stability.
Be in the United States Patent (USP) of " US4301274 " at publication number, disclose the synthetic method of another kind of PPSS, namely use alkaline carbonate as catalyzer, and the phase adds a certain amount of dihalo-sulfobenzide synthesis PPSS in addition after the reaction.The method can improve the melt-flow plasticity of PPSS, but does not contribute for the raising of molecular weight product and thermostability.
Be in the United States Patent (USP) of " US5331069 " at publication number, disclose utilize zinc compound in organic solvent p-poly-phenyl thioether sulfone carry out the method for reprocessing, the method is for improving the thermostability of PPSS, there is certain effect, but process line is long, process is complicated, and cost is high.
In addition, also have a kind of synthetic method of disclosed PPSS, it is in usual building-up process, adds Third monomer and utilizes composite catalyst to synthesize the PPSS of high molecular.This method, owing to introducing Third monomer and various other materials, is brought comparatively burden to the recovery in later stage, is unfavorable for industrialization.
Summary of the invention
It is high that namely object of the present invention is to overcome existing PPSS manufacturing process cost, and process is complicated, cannot obtain that molecular weight is high, the deficiency of the PPSS of Heat stability is good, provides a kind of manufacture method of high molecular weight polyphenylene sulfide sulfone.
Object of the present invention is achieved through the following technical solutions:
The manufacture method of high molecular weight polyphenylene sulfide sulfone, comprises the steps:
A. material process before polymerization: by alkali metal hydroxide, sulfocompound, N-Methyl pyrrolidone according to high temperature dehydration after the ratio mixing of mol ratio 0.1 ~ 0.3:1:3 ~ 5, obtain the mixture that organic alkali metal salts contg is not less than 0.03mol/Smol.Wherein alkali metal hydroxide and sulfocompound are all mixed by the mode of solution, and the mass concentration of alkali hydroxide soln is between 10% ~ 50%, and the mass concentration of sulfocompound solution is between 48% ~ 60%.
The content of organic alkali metal salt is measured in the following manner: get mixture, and acid adding adjustment PH is 4, filters.Getting filtered liquid utilizes high performance liquid chromatography to analyze content, obtains measuring result.The method is this area customary means, is not described in detail herein.
B. be polymerized: the water content of mixture is adjusted to 5 ~ 10mol/Smol, adds dihalo-sulfobenzide 0.98 ~ 1.04mol/Smol, be then warmed up to 90 ~ 120 DEG C in mixture, insulation 0.5 ~ 3h, then be warmed up to 175 ~ 190 DEG C, insulation 3 ~ 5h, obtains polymkeric substance.This step adopts two-part mode to heat up, and ensure that reaction has higher transformation efficiency to dihalo-sulfobenzide in the first stage, can improve the molecular weight of PPSS.The water content of mixture is regulated, the controllability of reaction can be improved, make reaction more stable, reduce side reaction, improve productive rate.
The water content of mixture is measured by the following method: utilize gas-chromatography, selects DB-17 capillary column, hydrogen flame detector, under column temperature 220 DEG C of conditions to steps A in the dehydration liquid of mixture analyze, thus calculate the water content of mixture.The method is this area customary means, is not described in detail herein.
C. shaping recovery: add forming agent in polymkeric substance, and after filtration, obtain finished product after drying.
It should be noted that, unit " mol/Smol " represents that relative 1mol sulphur comprises other material a certain amount of.
Alkali metal hydroxide is at least one in lithium hydroxide, potassium hydroxide or sodium hydroxide.
Sulfocompound is at least one in Sodium sulfhydrate, potassium sulphide or sodium sulphite.
Organic alkali metal salt is at least one in N-methylaminobutyric sodium, N-methylaminobutyric potassium or N-methylaminobutyric lithium; Above-mentioned three kinds of organic metal salts play catalyzer, for promoting PPSS formed product.
Preferably, described dihalo-sulfobenzide is at least one in 4,4-difluorodiphenyl sulfone, DDS or 4,4-dibromo sulfobenzide.Dihalo-sulfobenzide is the main raw material manufacturing PPSS.
Preferably, described forming agent is at least one in N-Methyl pyrrolidone, acetone or water.
Preferably, in described steps A, dewatering time is 1h.
Preferably, in described step B, after insulation 0.5 ~ 3h, be warmed up to 175 ~ 190 DEG C with the speed of 1 DEG C/min.Heated up by this speed and can improve the molecular weight of PPSS further.
Preferably, described forming agent is the mixture of 50% mass fraction acetone and 50% mass fraction water.
Preferably, in described step C, in polymkeric substance, add forming agent by high-pressure pump, filter after being cooled to room temperature, filter cake 75 ~ 85 DEG C of water are cleaned, then filter cake is obtained finished product with after Vacuumdrier drying 4.5 ~ 5.5h at 80 DEG C.
Preferably, in described step B, by adding the water content of deionized water adjustment mixture.
The invention also discloses a kind of high molecular weight polyphenylene sulfide sulfone utilizing aforesaid method to manufacture, the molecular formula of described high molecular weight polyphenylene sulfide sulfone is:
.
Advantage of the present invention and beneficial effect are:
1. before polymerization in material treatment step, add a certain amount of alkali metal hydroxide, at high temperature alkali metal hydroxide and N-Methyl pyrrolidone are obtained by reacting the organic alkali metal salt that can play katalysis, without the need to extra catalyst, reduce recovery difficult, improve polymerization efficiency, reduce cost, be conducive to industrialization;
2. in polymerization procedure, regulate the water content of mixture, and adopt two-part mode to heat up, the controllability of reaction can be made to improve, and react more stable, side reaction is few, improves polymerization efficiency, improves the molecular weight of PPSS product;
3. the present invention effectively can improve the molecular weight of PPSS product (melt mass flow rate speed is lower, molecular weight is higher), make the MFR(melt mass flow rate of PPSS product) <30g/10min, improve thermostability and the thermotolerance of PPSS product.
Embodiment
In order to make those skilled in the art understand the present invention better, below in conjunction with in the embodiment of the present invention, clear, complete description is carried out to the technical scheme in the embodiment of the present invention.Apparent, embodiment described below is only the part in the embodiment of the present invention, instead of all.Based on the embodiment that the present invention records, other all embodiment that those skilled in the art obtain when not paying creative work, all in the scope of protection of the invention.
Embodiment 1:
The manufacture method of high molecular weight polyphenylene sulfide sulfone, comprises the steps:
A. material process before polymerization: to 15L with stirring, the aqueous sodium hydroxide solution 128g of mass concentration 50% is added in the reactor of dewatering unit, N-Methyl pyrrolidone 3168g, mass concentration is the Sodium sulfhydrate aqueous solution 933g(alkali metal hydroxide of 48%, sulfocompound, the mol ratio of N-Methyl pyrrolidone is 0.2:1:4), open reactor, off-response device after stirring with the rotating speed of 200rpm/min, high temperature nitrogen is passed in reactor, inside reactor temperature is made to rapidly increase to 170 DEG C, and dewater 1 hour at this temperature, deviate from the mixture 305g of N-Methyl pyrrolidone and water, wherein water-content 271g.Get mixture sample, acid adding adjustment PH is 4, filters, gets filtered liquid and utilize high performance liquid chromatography to analyze content, detect and show that N-methylaminobutyric sodium content is 0.05mol/Smol.
B. be polymerized: in mixture, add deionized water 737g, utilize gas-chromatography, select DB-17 capillary column, hydrogen flame detector, analyze the mixture entering deionized water under column temperature 220 DEG C of conditions, the water content calculating mixture is 7.6mol/Smol, then adds 2296g 4,4-dichloro diphenyl sulfone, be rapidly heated 110 DEG C, insulation 45min, is then warmed up to 185 DEG C with the speed of 1 DEG C/min, insulation 4h, obtains polymkeric substance.
C. shaping recovery: utilize high-pressure pump to add mixture 1520g containing 50% mass fraction acetone and 50% mass fraction water in polymkeric substance, impel formed product, then room temperature is cooled to, moulding product is filtered, the filter cake hot water of 80 DEG C cleans 8 times, filter cake is placed in dry 5 hours of the vacuum drying oven of 120 DEG C, obtains 1845g white, evengranular PPSS finished product, its melt mass flow rate MFR=15g/10min.
Embodiment 2:
The present embodiment is compared with embodiment 1, except add the Sodium sulfhydrate aqueous solution of sulfur compound by mass concentration 48% change into mass concentration be 60% sodium sulphite except (sodium hydroxide and sodium sulphite identical in quality), all the other raw materials, add-on are identical with operational path, obtain 1805g, canescence, evengranular polyphenylene sulfide sulphone resin, its melt mass flow rate MFR=18g/10min.
Embodiment 3:
The present embodiment compared with embodiment 1, except add that DDS changes homogenous quantities into 4, outside 4-dibromo sulfobenzide, all the other raw materials, add-on are identical with operational path, obtain 1888g white, evengranular polyphenylene sulfide sulphone resin, its melt mass flow rate MFR=26g/10min.
Embodiment 4:
The present embodiment is compared with embodiment 1, change into except 3960g N-Methyl pyrrolidone except adding forming agent, all the other raw materials, add-on are identical with operational path, obtain 1780g, pure white, evengranular polyphenylene sulfide sulphone resin, its melt mass flow rate MFR=8g/10min.
Embodiment 5:
A. material process before polymerization: to 15L with stirring, the aqueous sodium hydroxide solution 128g of mass concentration 50% is added in the reactor of rectifier unit, N-Methyl pyrrolidone 3168g, anhydrous potassium sulphide 882g(alkali metal hydroxide, sulfocompound, the mol ratio of N-Methyl pyrrolidone is 0.2:1:4), deionized water 450g, open reactor, off-response device after stirring with the rotating speed of 200rpm/min, high temperature nitrogen is passed in reactor, inside reactor temperature is made to rapidly increase to 170 DEG C, and dewater 1 hour at this temperature, deviate from the mixture 401g of N-Methyl pyrrolidone and water, wherein water-content 322g.Get mixture sample, acid adding adjustment PH is 4, filters, gets filtered liquid and utilize high performance liquid chromatography to analyze content, detect and show that N-methylaminobutyric sodium content is 0.06mol/Smol.
B. be polymerized: in mixture, add deionized water 816g, utilize gas-chromatography, select DB-17 capillary column, hydrogen flame detector, analyze the mixture entering deionized water under column temperature 220 DEG C of conditions, the water content calculating mixture is 7.8mol/Smol, then adds 2296g 4,4-dichloro diphenyl sulfone, be rapidly heated 110 DEG C, insulation 45min, is then warmed up to 185 DEG C with the speed of 1 DEG C/min, insulation 4h, obtains polymkeric substance.
C. shaping recovery: utilize high-pressure pump to add mixture 1520g containing 50% mass fraction acetone and 50% mass fraction water in polymkeric substance, impel formed product, then room temperature is cooled to, moulding product is filtered, the filter cake hot water of 80 DEG C cleans 8 times, filter cake is placed in dry 5 hours of the vacuum drying oven of 120 DEG C, obtains 1845g white, evengranular PPSS finished product, its melt mass flow rate MFR=11g/10min.
The aqueous sodium hydroxide solution 128g of embodiment 6:50%, N-Methyl pyrrolidone 3168g
The present embodiment is compared with embodiment 1, except the aqueous sodium hydroxide solution 128g aqueous sodium hydroxide solution 64g of mass concentration 50% being changed into 50%, the mol ratio of interpolation N-Methyl pyrrolidone 3960g(alkali metal hydroxide, sulfocompound, N-Methyl pyrrolidone is 0.1:1:5) outside, all the other raw materials, add-on are identical with operational path, obtain 1788g, pure white, evengranular polyphenylene sulfide sulphone resin, its melt mass flow rate MFR=20g/10min.
Embodiment 7:
The present embodiment is compared with embodiment 1, except the aqueous sodium hydroxide solution 192g aqueous sodium hydroxide solution 64g of mass concentration 50% being changed into mass concentration 50%, add N-Methyl pyrrolidone 1376g(alkali metal hydroxide, sulfocompound, N-Methyl pyrrolidone mol ratio be 0.3:1:3) outside, all the other raw materials, add-on are identical with operational path, obtain 1775g, pure white, evengranular polyphenylene sulfide sulphone resin, its melt mass flow rate MFR=26g/10min.
Embodiment 8:
The present embodiment is compared with embodiment 1, except first paragraph being heated up 90 DEG C in stepb, insulation 0.5h, heat up 175 DEG C again, outside insulation 3h, all the other raw materials, add-on are identical with operational path, obtain 1856g white, evengranular PPSS finished product, its melt mass flow rate MFR=21g/10min.
Embodiment 9:
The present embodiment is compared with embodiment 1, except first paragraph being heated up 120 DEG C in stepb, insulation 3h, heat up 90 DEG C again, outside insulation 3h, all the other raw materials, add-on are identical with operational path, obtain 1856g white, evengranular PPSS finished product, its melt mass flow rate MFR=8g/10min.
Embodiment 10:
The present embodiment is compared with embodiment 1, change into except lithium hydroxide aqueous solution (aqueous sodium hydroxide solution is identical with mass concentration with the quality of lithium hydroxide aqueous solution) except aqueous sodium hydroxide solution will be added in step, all the other raw materials, add-on are identical with operational path, obtain 1832g white, evengranular polyphenylene sulfide sulphone resin, its melt mass flow rate MFR=24g/10min.
Embodiment 11
The present embodiment is compared with embodiment 1, change into except potassium hydroxide aqueous solution (aqueous sodium hydroxide solution is identical with mass concentration with the quality of potassium hydroxide aqueous solution) except aqueous sodium hydroxide solution will be added in step, all the other raw materials, add-on are identical with operational path, obtain 1832g white, evengranular polyphenylene sulfide sulphone resin, its melt mass flow rate MFR=30g/10min.
Embodiment 12:
The present embodiment is compared with embodiment 1, except adding 4 in step C, 4-dichloro diphenyl sulfone changes 4 of homogenous quantities into, outside 4-difluorodiphenyl sulfone, all the other raw materials, add-on are identical with operational path, obtain 1812g white, evengranular polyphenylene sulfide sulphone resin, its melt mass flow rate MFR=27g/10min.
Embodiment 13:
The present embodiment is the comparative example of embodiment 1.
The manufacture method of high molecular weight polyphenylene sulfide sulfone, comprises the steps:
A. material process before polymerization: to 15L with stirring, add N-Methyl pyrrolidone 3168g in the reactor of rectifier unit, mass concentration is the Sodium sulfhydrate aqueous solution 933g of 48%, open reactor, off-response device after stirring with the rotating speed of 200rpm/min, in reactor, pass into high temperature nitrogen, make inside reactor temperature rapidly increase to 170 DEG C, and dewater 1 hour at this temperature, deviate from the mixture 320g of N-Methyl pyrrolidone and water, wherein water-content 276g.Get mixture sample, acid adding adjustment PH is 4, filters, gets filtered liquid and utilize high performance liquid chromatography to analyze content, detect and show that N-methylaminobutyric sodium content is 0.
B. be polymerized: in mixture, add deionized water 732g, then add 2296g DDS, be rapidly heated 110 DEG C, insulation 45min, is then warmed up to 185 DEG C with the speed of 1 DEG C/min, and insulation 4h, obtains polymkeric substance.
C. shaping recovery: utilize high-pressure pump to add mixture 1520g containing 50% mass fraction acetone and 50% mass fraction water in polymkeric substance, impel formed product, be then cooled to room temperature, open reactor inspection, material pulp, does not have shaping product to generate.
The present embodiment, compared to embodiment 1, does not add sodium hydroxide, and all the other are substantially identical with embodiment 1.Can find out, owing to not adding sodium hydroxide, the organic alkali metal salt of katalysis cannot have been generated, and then shaping product cannot be obtained.
Embodiment 14:
The present embodiment is the comparative example of embodiment 1.
The manufacture method of high molecular weight polyphenylene sulfide sulfone, comprises the steps:
A. material process before polymerization: to 15L with stirring, the aqueous sodium hydroxide solution 128g of mass concentration 50% is added in the reactor of rectifier unit, N-Methyl pyrrolidone 3168g, mass concentration is the Sodium sulfhydrate aqueous solution 933g(alkali metal hydroxide of 48%, sulfocompound, the mol ratio of N-Methyl pyrrolidone is 0.2:1:4), open reactor, off-response device after stirring with the rotating speed of 200rpm/min, high temperature nitrogen is passed in reactor, inside reactor temperature is made to rapidly increase to 170 DEG C, and dewater 1 hour at this temperature, deviate from the mixture 305g of N-Methyl pyrrolidone and water, wherein water-content 271g.Get mixture sample, acid adding adjustment PH is 4, filters, gets filtered liquid and utilize high performance liquid chromatography to analyze content, detect and show that N-methylaminobutyric sodium content is 0.05mol/Smol.
B. be polymerized: in mixture, add deionized water 737g, utilize gas-chromatography, select DB-17 capillary column, hydrogen flame detector, under column temperature 220 DEG C of conditions, the mixture entering deionized water is analyzed, the water content calculating mixture is 7.6mol/Smol, then add 2296g DDS, be warmed up to 185 DEG C with the speed of 1 DEG C/min, insulation 4h, obtains polymkeric substance.
C. shaping recovery: utilize high-pressure pump to add mixture 1520g containing 50% mass fraction acetone and 50% mass fraction water in polymkeric substance, impel formed product, then room temperature is cooled to, moulding product is filtered, the filter cake hot water of 80 DEG C cleans 8 times, filter cake is placed in dry 5 hours of the vacuum drying oven of 120 DEG C, obtains 1782g white, evengranular PPSS finished product, its melt mass flow rate MFR=162g/10min.
The present embodiment, compared to embodiment 1, does not adopt two-part mode to heat up, and causes product percent polymerization low, and its molecular weight is also far below embodiment 1.
Embodiment 15:
The present embodiment is the comparative example of embodiment 1.
The manufacture method of high molecular weight polyphenylene sulfide sulfone, comprises the steps:
A. material process before polymerization: to 15L with stirring, the aqueous sodium hydroxide solution 128g of mass concentration 50% is added in the reactor of rectifier unit, N-Methyl pyrrolidone 3168g, mass concentration is the Sodium sulfhydrate aqueous solution 933g(alkali metal hydroxide of 48%, sulfocompound, the mol ratio of N-Methyl pyrrolidone is 0.2:1:4), open reactor, off-response device after stirring with the rotating speed of 200rpm/min, high temperature nitrogen is passed in reactor, inside reactor temperature is made to rapidly increase to 170 DEG C, and dewater 1 hour at this temperature, deviate from the mixture 305g of N-Methyl pyrrolidone and water, wherein water-content 271g.Get mixture sample, acid adding adjustment PH is 4, filters, gets filtered liquid and utilize high performance liquid chromatography to analyze content, detect and show that N-methylaminobutyric sodium content is 0.05mol/Smol.
B. be polymerized: add 2296g DDS, be rapidly heated 110 DEG C, insulation 45min, is then warmed up to 185 DEG C with the speed of 1 DEG C/min, and insulation 4h, obtains polymkeric substance.
C. shaping recovery: utilize high-pressure pump to add mixture 1520g containing 50% mass fraction acetone and 50% mass fraction water in polymkeric substance, impel formed product, then room temperature is cooled to, open reactor inspection, reactor wall lumps in a large number, and there is unreacted sulfide centre, a small amount of fine particle in bottom, after super-dry, the melt mass flow rate MFR=123g/10min of finished product.
The present embodiment is compared to embodiment 1, and do not add deionized water and regulate water content, cause controllability low, reaction is unstable, and side reaction is many, greatly reduces polymerization efficiency, and the finished product molecular weight obtained is far below embodiment 1.
Embodiment 16:
Utilize a kind of high molecular weight polyphenylene sulfide sulfone that the method described in above-mentioned any one embodiment manufactures, the molecular formula of described high molecular weight polyphenylene sulfide sulfone is:
.
Claims (8)
1. the manufacture method of high molecular weight polyphenylene sulfide sulfone, is characterized in that, comprises the steps:
A. material process before polymerization: by alkali metal hydroxide, sulfocompound, N-Methyl pyrrolidone according to high temperature dehydration after the ratio mixing of mol ratio 0.1 ~ 0.3:1:3 ~ 5, obtain the mixture that organic alkali metal salts contg is not less than 0.03mol/Smol;
B. be polymerized: the water content of mixture is adjusted to 5 ~ 10mol/Smol, adds dihalo-sulfobenzide 0.98 ~ 1.04mol/Smol, be then warmed up to 90 ~ 120 DEG C in mixture, insulation 0.5 ~ 3h, then be warmed up to 175 ~ 190 DEG C, insulation 3 ~ 5h, obtains polymkeric substance;
C. shaping recovery: add forming agent in polymkeric substance, and after filtration, obtain finished product after drying;
Alkali metal hydroxide is at least one in lithium hydroxide, potassium hydroxide or sodium hydroxide;
Sulfocompound is at least one in Sodium sulfhydrate, potassium sulphide or sodium sulphite;
Organic alkali metal salt is at least one in N-methylaminobutyric sodium, N-methylaminobutyric potassium or N-methylaminobutyric lithium.
2. the manufacture method of high molecular weight polyphenylene sulfide sulfone according to claim 1, is characterized in that: described dihalo-sulfobenzide is at least one in 4,4-difluorodiphenyl sulfone, DDS or 4,4-dibromo sulfobenzide.
3. the manufacture method of high molecular weight polyphenylene sulfide sulfone according to claim 1, is characterized in that: described forming agent is at least one in N-Methyl pyrrolidone, acetone or water.
4. the manufacture method of high molecular weight polyphenylene sulfide sulfone according to claim 1, is characterized in that: in described steps A, dewatering time is 1h.
5. the manufacture method of high molecular weight polyphenylene sulfide sulfone according to claim 1, is characterized in that: in described step B, after insulation 0.5 ~ 3h, is warmed up to 175 ~ 190 DEG C with the speed of 1 DEG C/min.
6. the manufacture method of high molecular weight polyphenylene sulfide sulfone according to claim 3, is characterized in that: described forming agent is the mixture of 50% mass fraction acetone and 50% mass fraction water.
7. the manufacture method of the high molecular weight polyphenylene sulfide sulfone according to claim 1 or 6, it is characterized in that: in described step C, in polymkeric substance, forming agent is added by high-pressure pump, filter after being cooled to room temperature, cleaning filter cake, then obtains finished product with after Vacuumdrier drying 4.5 ~ 5.5h by filter cake at 80 DEG C.
8. the manufacture method of high molecular weight polyphenylene sulfide sulfone according to claim 1, is characterized in that: in described step B, by adding the water content of deionized water adjustment mixture.
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| CN104292462A (en) * | 2014-09-17 | 2015-01-21 | 黄孟良 | Polyphenylene sulfide/polyphenylene sulfide sulphone copolymer and preparation method thereof |
| CN106750302B (en) * | 2017-01-13 | 2019-01-08 | 四川中科兴业高新材料有限公司 | A kind of preparation method of heat-resisting, corrosion resistant high molecular weight poly arylidene thio-ester sulfone |
| CN106832283B (en) * | 2017-03-10 | 2019-03-05 | 四川中科兴业高新材料有限公司 | A method of preparing polyaryl thioether sulfone |
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| JP2002293938A (en) * | 2001-03-30 | 2002-10-09 | Petroleum Energy Center | Method for continuous production of polyarylene sulfide |
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