CN103087317A - 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, can and be molded as needed section bar by rapid Design, can be used for a plurality of fields such as automobile, aerospace.
PPSS also dissolves in special solvent, makes it be suitable for preparing coating and film.
The synthetic method of the PPSS usually be by the Phillips oil company at publication number for open in the United States Patent (USP) of " US4102875 ", be specially sodium sulphite and dichloro diphenyl sulfone contact reacts in greater than the organic solvent of 200 ℃ synthesized PPSS.The shortcoming of the method is, the PPSS molecular weight that obtains 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 add in addition a certain amount of dihalo-sulfobenzide to synthesize PPSS in the reaction later stage.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 the zinc compound method that p-poly-phenyl thioether sulfone is processed again in organic solvent of utilizing, the method is for the thermostability that improves PPSS, has certain effect, but the technique circuit is long, and process is complicated, and cost is high.
In addition, also have a kind of synthetic method of disclosed PPSS, it adds the 3rd monomer and utilizes the PPSS of composite catalyst synthetic macromolecule amount in the building-up process of common use.This method brings than burden for the recovery in later stage owing to having introduced the 3rd monomer and various other materials, is unfavorable for industrialization.
Summary of the invention
It is high that purpose of the present invention namely is to overcome existing PPSS manufacturing process cost, and process is complicated, can't obtain that molecular weight is high, the deficiency of the PPSS of Heat stability is good, and a kind of manufacture method of high molecular weight polyphenylene sulfide sulfone is provided.
Purpose 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. before polymerization, material is processed: high temperature dehydration after alkali metal hydroxide, sulfocompound, N-Methyl pyrrolidone are mixed according to the ratio of mol ratio 0.1 ~ 0.3:1:3 ~ 5 obtains the mixture that the organic alkali metal salts contg is not less than 0.03mol/Smol.Wherein alkali metal hydroxide and sulfocompound are all to mix 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, it is 4 that acid adding is adjusted PH, filters.Get filtered liquid and utilize high performance liquid chromatography that content is analyzed, obtain measuring result.The method is this area customary means, is not described in detail herein.
B. polymerization: the water content of mixture is adjusted to 5 ~ 10mol/Smol, adds dihalo-sulfobenzide 0.98 ~ 1.04mol/Smol in mixture, then be warmed up to 90 ~ 120 ℃, insulation 0.5 ~ 3h, then be warmed up to 175 ~ 190 ℃, insulation 3 ~ 5h obtains polymkeric substance.This step adopts the two-part mode to heat up, and has guaranteed that reaction has higher transformation efficiency to the dihalo-sulfobenzide in the fs, can improve the molecular weight of PPSS.Water content to mixture is regulated, and can improve the controllability of reaction, makes reaction more stable, reduces side reaction, improves productive rate.
The water content of mixture is measured by the following method: utilize gas-chromatography, select the DB-17 capillary column, hydrogen flame detector, under 220 ℃ of conditions of column temperature to steps A in the dehydration liquid of mixture analyze, thereby calculate the water content of mixture.The method is this area customary means, is not described in detail herein.
C. moulding is reclaimed: add forming agent in polymkeric substance, and after filtration, obtain finished product after drying.
Need to prove, unit " mol/Smol " the relative 1mol sulphur of expression comprises a certain amount of other material.
Alkali metal hydroxide is at least a in lithium hydroxide, potassium hydroxide or sodium hydroxide.
Sulfocompound is at least a in Sodium sulfhydrate, potassium sulphide or sodium sulphite.
Organic alkali metal salt is at least a in N-methylamino Sodium propanecarboxylate, N-methylamino potassium butyrate or N-methylamino butyric acid lithium; Above-mentioned three kinds of organic metal salts play catalyzer, are used for promoting the PPSS formed product.
Preferably, described dihalo-sulfobenzide is at least a in 4,4-difluorodiphenyl sulfone, DDS or 4,4-dibromo sulfobenzide.The dihalo-sulfobenzide is for making the main raw material of PPSS.
Preferably, described forming agent is at least a 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 ℃ with the speed of 1 ℃/min.Heat up by this speed and can further improve the molecular weight of PPSS.
Preferably, described forming agent is the mixture of 50% mass fraction acetone and 50% mass fraction water.
Preferably, in described step C, add forming agent by high-pressure pump in polymkeric substance, filter after being cooled to room temperature, filter cake is cleaned with 75 ~ 85 ℃ of water, then filter cake is being obtained finished product after with Vacuumdrier drying 4.5 ~ 5.5h under 80 ℃.
Preferably, in described step B, adjust the water content of mixture by adding deionized water.
The invention also discloses a kind of high molecular weight polyphenylene sulfide sulfone that utilizes aforesaid method to make, 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 the material treatment step, add a certain amount of alkali metal hydroxide, at high temperature alkali metal hydroxide and N-Methyl pyrrolidone reaction obtains rising the organic alkali metal salt of katalysis, need not extra catalyst, reduced recovery difficult, improve polymerization efficiency, reduced cost, be conducive to industrialization;
2. in polymerization procedure, the water content of mixture is regulated, and adopt the two-part mode to heat up, the controllability of reaction is improved, react more stable, side reaction is few, has improved polymerization efficiency, has improved the molecular weight of PPSS product;
3. the present invention can effectively 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, improved thermostability and the thermotolerance of PPSS product.
Embodiment
In order to make those skilled in the art understand better the present invention, below in conjunction with in the embodiment of the present invention, the technical scheme in the embodiment of the present invention being carried out clear, complete description.Apparent, embodiment described below is only the part in the embodiment of the present invention, rather than all.Based on the embodiment of the present invention record, those skilled in the art are not in the situation that pay other all embodiment that creative work obtains, 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 is processed before polymerization: to 15L with stirring, the aqueous sodium hydroxide solution 128g that adds mass concentration 50% in the reactor of dewatering unit, N-Methyl pyrrolidone 3168g, mass concentration is 48% Sodium sulfhydrate aqueous solution 933g(alkali metal hydroxide, sulfocompound, the mol ratio of N-Methyl pyrrolidone is 0.2:1:4), open reactor, with the rotating speed of the 200rpm/min rear off-response device that stirs, pass into high temperature nitrogen in reactor, make the inside reactor temperature rapidly increase to 170 ℃, and dewatered 1 hour at this temperature, deviate from the mixture 305g of N-Methyl pyrrolidone and water, water-content 271g wherein.Get the mixture sample, it is 4 that acid adding is adjusted PH, filters, and gets filtered liquid and utilizes high performance liquid chromatography that content is analyzed, and detecting and drawing N-methylamino Sodium propanecarboxylate content is 0.05mol/Smol.
B. polymerization: add deionized water 737g in mixture, utilize gas-chromatography, select the DB-17 capillary column, hydrogen flame detector, under 220 ℃ of conditions of column temperature, the mixture that enters deionized water is analyzed, the water content that calculates mixture is 7.6mol/Smol, then adds 2296g 4, the 4-dichloro diphenyl sulfone, be rapidly heated 110 ℃, insulation 45min, then the speed with 1 ℃/min is warmed up to 185 ℃, insulation 4h obtains polymkeric substance.
C. moulding is reclaimed: utilize high-pressure pump to add the mixture 1520g that contains 50% mass fraction acetone and 50% mass fraction water in polymkeric substance, impel formed product, then be cooled to room temperature, moulding product is filtered, filter cake cleans 8 times with the hot water of 80 ℃, filter cake is placed in dry 5 hours of the vacuum drying oven of 120 ℃, 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, be 60% sodium sulphite (sodium hydroxide and sodium sulphite are identical in quality) except the Sodium sulfhydrate aqueous solution that adds sulfur compound by mass concentration 48% changes mass concentration into, all the other raw materials, add-on and operational path are identical, obtain 1805g, canescence, evengranular polyphenylene sulfide sulphone resin, its melt mass flow rate MFR=18g/10min.
Embodiment 3:
The present embodiment is compared with embodiment 1, except adding DDS to change 4 of homogenous quantities into, outside 4-dibromo sulfobenzide, all the other raw materials, add-on and operational path are identical, 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, except adding forming agent to change into the 3960g N-Methyl pyrrolidone, all the other raw materials, add-on and operational path are identical, obtain 1780g, pure white, evengranular polyphenylene sulfide sulphone resin, its melt mass flow rate MFR=8g/10min.
Embodiment 5:
A. material is processed before polymerization: to 15L with stirring, the aqueous sodium hydroxide solution 128g that adds mass concentration 50% 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, with the rotating speed of the 200rpm/min rear off-response device that stirs, pass into high temperature nitrogen in reactor, make the inside reactor temperature rapidly increase to 170 ℃, and dewatered 1 hour at this temperature, deviate from the mixture 401g of N-Methyl pyrrolidone and water, water-content 322g wherein.Get the mixture sample, it is 4 that acid adding is adjusted PH, filters, and gets filtered liquid and utilizes high performance liquid chromatography that content is analyzed, and detecting and drawing N-methylamino Sodium propanecarboxylate content is 0.06mol/Smol.
B. polymerization: add deionized water 816g in mixture, utilize gas-chromatography, select the DB-17 capillary column, hydrogen flame detector, under 220 ℃ of conditions of column temperature, the mixture that enters deionized water is analyzed, the water content that calculates mixture is 7.8mol/Smol, then adds 2296g 4, the 4-dichloro diphenyl sulfone, be rapidly heated 110 ℃, insulation 45min, then the speed with 1 ℃/min is warmed up to 185 ℃, insulation 4h obtains polymkeric substance.
C. moulding is reclaimed: utilize high-pressure pump to add the mixture 1520g that contains 50% mass fraction acetone and 50% mass fraction water in polymkeric substance, impel formed product, then be cooled to room temperature, moulding product is filtered, filter cake cleans 8 times with the hot water of 80 ℃, filter cake is placed in dry 5 hours of the vacuum drying oven of 120 ℃, 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 64g with mass concentration 50% changes 50% aqueous sodium hydroxide solution 128g into, the mol ratio of adding N-Methyl pyrrolidone 3960g(alkali metal hydroxide, sulfocompound, N-Methyl pyrrolidone is 0.1:1:5) outside, all the other raw materials, add-on and operational path are identical, 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 64g of mass concentration 50% being changed into the aqueous sodium hydroxide solution 192g of mass concentration 50%, the mol ratio that adds N-Methyl pyrrolidone 1376g(alkali metal hydroxide, sulfocompound, N-Methyl pyrrolidone is 0.3:1:3) outside, all the other raw materials, add-on and operational path are identical, 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 in step B, first paragraph being heated up 90 ℃, insulation 0.5h, heat up again 175 ℃, outside insulation 3h, all the other raw materials, add-on and operational path are identical, 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 in step B, first paragraph being heated up 120 ℃, insulation 3h, heat up again 90 ℃, outside insulation 3h, all the other raw materials, add-on and operational path are identical, 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, except adding aqueous sodium hydroxide solution to change into lithium hydroxide aqueous solution (aqueous sodium hydroxide solution is identical with quality and the mass concentration of lithium hydroxide aqueous solution) in steps A, all the other raw materials, add-on and operational path are identical, 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, except adding aqueous sodium hydroxide solution to change into potassium hydroxide aqueous solution (aqueous sodium hydroxide solution is identical with quality and the mass concentration of potassium hydroxide aqueous solution) in steps A, all the other raw materials, add-on and operational path are identical, 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 will add 4 in step C, the 4-dichloro diphenyl sulfone changes 4 of homogenous quantities into, outside 4-difluorodiphenyl sulfone, all the other raw materials, add-on and operational path are identical, obtain 1812g white, evengranular polyphenylene sulfide sulphone resin, its melt mass flow rate MFR=27g/10min.
Embodiment 13:
The present embodiment is the Comparative Examples of embodiment 1.
The manufacture method of high molecular weight polyphenylene sulfide sulfone comprises the steps:
A. before polymerization, material is processed: add N-Methyl pyrrolidone 3168g in the reactor of 15L with stirring, rectifier unit, mass concentration is 48% Sodium sulfhydrate aqueous solution 933g, open reactor, with the rotating speed of the 200rpm/min rear off-response device that stirs, pass into high temperature nitrogen in reactor, make the inside reactor temperature rapidly increase to 170 ℃, and dewatered 1 hour at this temperature, deviate from the mixture 320g of N-Methyl pyrrolidone and water, wherein water-content 276g.Get the mixture sample, it is 4 that acid adding is adjusted PH, filters, and gets filtered liquid and utilizes high performance liquid chromatography that content is analyzed, and detecting and drawing N-methylamino Sodium propanecarboxylate content is 0.
B. polymerization: add deionized water 732g in mixture, then add the 2296g DDS, be rapidly heated 110 ℃, insulation 45min, then the speed with 1 ℃/min is warmed up to 185 ℃, and insulation 4h obtains polymkeric substance.
C. moulding is reclaimed: utilize high-pressure pump to add the mixture 1520g that contains 50% mass fraction acetone and 50% mass fraction water in polymkeric substance, impel formed product, then be cooled to room temperature, open the reactor inspection, the material pulp does not have the product of moulding to generate.
The present embodiment does not add sodium hydroxide than embodiment 1, and all the other are substantially identical with embodiment 1.Can find out, owing to not adding sodium hydroxide, can't generate the organic alkali metal salt of katalysis, and then can't obtain the product of moulding.
Embodiment 14:
The present embodiment is the Comparative Examples of embodiment 1.
The manufacture method of high molecular weight polyphenylene sulfide sulfone comprises the steps:
A. material is processed before polymerization: to 15L with stirring, the aqueous sodium hydroxide solution 128g that adds mass concentration 50% in the reactor of rectifier unit, N-Methyl pyrrolidone 3168g, mass concentration is 48% Sodium sulfhydrate aqueous solution 933g(alkali metal hydroxide, sulfocompound, the mol ratio of N-Methyl pyrrolidone is 0.2:1:4), open reactor, with the rotating speed of the 200rpm/min rear off-response device that stirs, pass into high temperature nitrogen in reactor, make the inside reactor temperature rapidly increase to 170 ℃, and dewatered 1 hour at this temperature, deviate from the mixture 305g of N-Methyl pyrrolidone and water, water-content 271g wherein.Get the mixture sample, it is 4 that acid adding is adjusted PH, filters, and gets filtered liquid and utilizes high performance liquid chromatography that content is analyzed, and detecting and drawing N-methylamino Sodium propanecarboxylate content is 0.05mol/Smol.
B. polymerization: add deionized water 737g in mixture, utilize gas-chromatography, select the DB-17 capillary column, hydrogen flame detector is analyzed the mixture that enters deionized water under 220 ℃ of conditions of column temperature, the water content that calculates mixture is 7.6mol/Smol, then add the 2296g DDS, be warmed up to 185 ℃ with the speed of 1 ℃/min, insulation 4h obtains polymkeric substance.
C. moulding is reclaimed: utilize high-pressure pump to add the mixture 1520g that contains 50% mass fraction acetone and 50% mass fraction water in polymkeric substance, impel formed product, then be cooled to room temperature, moulding product is filtered, filter cake cleans 8 times with the hot water of 80 ℃, filter cake is placed in dry 5 hours of the vacuum drying oven of 120 ℃, obtains 1782g white, evengranular PPSS finished product, its melt mass flow rate MFR=162g/10min.
The present embodiment does not adopt the two-part mode to heat up than embodiment 1, causes the 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 is processed before polymerization: to 15L with stirring, the aqueous sodium hydroxide solution 128g that adds mass concentration 50% in the reactor of rectifier unit, N-Methyl pyrrolidone 3168g, mass concentration is 48% Sodium sulfhydrate aqueous solution 933g(alkali metal hydroxide, sulfocompound, the mol ratio of N-Methyl pyrrolidone is 0.2:1:4), open reactor, with the rotating speed of the 200rpm/min rear off-response device that stirs, pass into high temperature nitrogen in reactor, make the inside reactor temperature rapidly increase to 170 ℃, and dewatered 1 hour at this temperature, deviate from the mixture 305g of N-Methyl pyrrolidone and water, water-content 271g wherein.Get the mixture sample, it is 4 that acid adding is adjusted PH, filters, and gets filtered liquid and utilizes high performance liquid chromatography that content is analyzed, and detecting and drawing N-methylamino Sodium propanecarboxylate content is 0.05mol/Smol.
B. polymerization: add the 2296g DDS, be rapidly heated 110 ℃, insulation 45min, then the speed with 1 ℃/min is warmed up to 185 ℃, and insulation 4h obtains polymkeric substance.
C. moulding is reclaimed: utilize high-pressure pump to add the mixture 1520g that contains 50% mass fraction acetone and 50% mass fraction water in polymkeric substance, impel formed product, then be cooled to room temperature, open the reactor inspection, lump in a large number on reactor wall, there is unreacted sulfide the 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 does not add deionized water to regulate water content than embodiment 1, causes controllability low, reacts unstable, and side reaction is many, greatly reduces polymerization efficiency, and the finished product molecular weight that obtains is far below embodiment 1.
Embodiment 16:
A kind of high molecular weight polyphenylene sulfide sulfone that utilizes the described method of above-mentioned any one embodiment to make, 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. before polymerization, material is processed: high temperature dehydration after alkali metal hydroxide, sulfocompound, N-Methyl pyrrolidone are mixed according to the ratio of mol ratio 0.1 ~ 0.3:1:3 ~ 5 obtains the mixture that the organic alkali metal salts contg is not less than 0.03mol/Smol;
B. polymerization: the water content of mixture is adjusted to 5 ~ 10mol/Smol, adds dihalo-sulfobenzide 0.98 ~ 1.04mol/Smol in mixture, then be warmed up to 90 ~ 120 ℃, insulation 0.5 ~ 3h, then be warmed up to 175 ~ 190 ℃, insulation 3 ~ 5h obtains polymkeric substance;
C. moulding is reclaimed: add forming agent in polymkeric substance, and after filtration, obtain finished product after drying;
Alkali metal hydroxide is at least a in lithium hydroxide, potassium hydroxide or sodium hydroxide;
Sulfocompound is at least a in Sodium sulfhydrate, potassium sulphide or sodium sulphite;
Organic alkali metal salt is at least a in N-methylamino Sodium propanecarboxylate, N-methylamino potassium butyrate or N-methylamino butyric acid 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 a 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 a in N-Methyl pyrrolidone, acetone or water.
4. the manufacture method of high molecular weight polyphenylene sulfide sulfone according to claim 1, it 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, be warmed up to 175 ~ 190 ℃ with the speed of 1 ℃/min.
6. the manufacture method of high molecular weight polyphenylene sulfide sulfone according to claim 3, it 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 according to claim 1 or 6 described high molecular weight polyphenylene sulfide sulfones, it is characterized in that: in described step C, add forming agent by high-pressure pump in polymkeric substance, filter after being cooled to room temperature, clean filter cake, then filter cake is being obtained finished product after with Vacuumdrier drying 4.5 ~ 5.5h under 80 ℃
The manufacture method of high molecular weight polyphenylene sulfide sulfone according to claim 1 is characterized in that: in described step B, adjust the water content of mixture by adding deionized water.
8. high molecular weight polyphenylene sulfide sulfone, it is characterized in that: the molecular formula of described high molecular weight polyphenylene sulfide sulfone is:
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| CN103709405A (en) * | 2013-12-16 | 2014-04-09 | 四川大学 | High-purity autocatalytic polyarylene sulfide and preparation method thereof |
| CN103709405B (en) * | 2013-12-16 | 2015-11-18 | 四川大学 | A kind of High-purity autocatalytic polyarylene sulfide and preparation method thereof |
| CN104292462A (en) * | 2014-09-17 | 2015-01-21 | 黄孟良 | Polyphenylene sulfide/polyphenylene sulfide sulphone copolymer and preparation method thereof |
| CN106750302A (en) * | 2017-01-13 | 2017-05-31 | 四川中科兴业高新材料有限公司 | A kind of preparation method of heat resistance, corrosion resistant HMW poly arylidene thio-ester sulfone |
| 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 |
| CN106832283A (en) * | 2017-03-10 | 2017-06-13 | 四川中科兴业高新材料有限公司 | A kind of new method for preparing polyaryl thioether 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 |
| CN107501553A (en) * | 2017-09-30 | 2017-12-22 | 四川金和成科技有限公司 | A kind of preparation method of the polyphenylene sulfide of no catalyst |
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