CN105330863A - Method for adding chain extender to middle piece to synthesize high-strength polyether sulphone resin - Google Patents
Method for adding chain extender to middle piece to synthesize high-strength polyether sulphone resin Download PDFInfo
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Abstract
The invention discloses a method for adding a chain extender to a middle piece to synthesize high-strength polyether sulphone resin. The method comprises the steps that 4,4'-dichlorodiphenyl sulfone and 4,4'-dihydroxybiphenyl or 4,4'-dihydroxy diphenyl sulfone are used as reaction monomers, in a reaction kettle under nitrogen protection, solvent is added, then stirring begins to be carried out, the temperature rises to 60 DEG C-80 DEG C, the reaction monomers are added sequentially, after dissolving, a salt-forming agent is added, then a water separating agent is added, stirring continues to be carried out, the temperature rises to 200 DEG C-210 DEG C, and the salt forming reaction is carried out for 1-2 h; then the temperature rises to 220 DEG C-240 DEG C, the constant-temperature polymerization reaction is carried out for 1-2 h, then the chain extender is added, the reaction continues to be carried out for 40 min to obtain high-strength polyether sulphone resin viscous liquid, and the viscous liquid is cooled, then smashed, filtered and dried in a vacuum mode. The synthesis process is simple, production efficiency is high, and the synthesized novel enhancing type polyether sulphone resin has higher mechanical strength and lower melt viscosity, and is easier to process and form, and higher in heat stability.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of method of adding chainextender industrialization synthesizing high-strength polyaryl ether sulphone resin in stage casing.
Background technology
Polyether sulphone is a kind of high performance engineering plastics, comprise polyethersulfone (PES) and biphenyl polyether sulfone (PPSU), all there is very high second-order transition temperature (~ 220 DEG C), because they have thermotolerance, hot water resistance, creep resistance, dimensional stability, shock-resistance, chemical proofing, the excellent over-all properties such as nontoxic, fire-retardant, thus for a long time electronics, electrical equipment, machinery, automobile, medical apparatus, food-processing and not the field such as stickness paint be widely used.
Industrial important polyether sulphone has employing sulfobenzide and tetramethylene sulfone to be the production technique of solvent, as European patent document EP2008067700, american documentation literature US20100310804A1, Chinese patent literature CN85105138A, CN1765953A, CN1844196A, CN101704951A, CN101735459A.The resin that two kinds of explained hereafter relate to content in a solvent in 20 ~ 35% scopes, preferably 25 ~ 30%, more preferably about 25%.There is following defect in these two kinds of techniques: under (1) identical device condition, the production capacity of polyether sulphone is low; (2) due to tetramethylene sulfone unstable at high temperature, thus make the rate of recovery loss of whole technical process sulfolan larger; (3) in the polymerization-filling later stage, rate of polymerization weakens, the more difficult growth of molecular weight; (4) the polyether sulphone molecular weight distribution produced is uneven, and melt viscosity is difficult to control, and product performance are unstable, make it apply and are restricted.
The speed of response of polymerization system affects larger by system concentration, we find that speed of response declines along with the increase speed of response of concentration in Sulfolane System, and when solid content is 30 ~ 35% time, speed of response is dropped by nearly half, therefore, also there is certain defect in direct raising system solid content.Chinese patent literature CN1268526A discloses and a kind ofly in system, adds the way that viscosity-controlling agent silicoorganic compound can improve solid content to 40 ~ 45%, but needs additionally to add organosilicon and increase post-processing difficulty, and its polymerization cycle is also longer.
Polymer performance mainly affects by molecular chain structure, carries out the research direction that novel polysulfones Molecular Structure Design and study on the modification are polysulfone material in recent years.At present, the most frequently used method carries out auxiliary agent blending and modifying, but polysulfones itself is more responsive to auxiliary agent, carries the high performance work-ing life that simultaneously can reduce plastics itself.Chinese patent literature CN102532899A discloses and a kind ofly in polyethersulfone, adds titanium dioxide and glass fibre utilizes the physical method of mechanical blending to improve its comprehensive mechanical performance such as adhesiveproperties, consistency, but titanium dioxide and glass fibre all can produce certain impact to the light transmission of resin and the shock strength of resin obviously be declined.Chinese patent literature CN102532899A discloses main chain and contains organo silicone polyether sulphone resin of line style and cage modle and preparation method thereof, by introducing polyethersulfone hydrophobic performance and the specific inductivity of the raising of functional molecular structure on polyethersulfone main chain, but the polyethersulfone transmittance that this method is synthesized is not high, is mainly limited to coating and field of microelectronic devices.
Summary of the invention
The object of the invention is to the defect overcoming above-mentioned prior art, provide a kind of synthesis technique simple, production efficiency is high, the novel tree-like polyaryl ether sulphone resin Industrialized synthesis method that performance is more excellent.
A kind of method of adding chainextender industrialization synthesizing high-strength polyaryl ether sulphone resin in stage casing of the present invention, comprises the following steps:
(1) polyreaction
With 4,4 '-dichloro diphenyl sulfone (two chlorine monomer) and 4,4 '-'-biphenyl diphenol or 4,4 '-dihydroxy diphenylsulphone (biphenol monomer) is reaction monomers, is solvent with tetramethylene sulfone, take sodium carbonate as salt forming agent;
In the reactor of nitrogen filled protection, start stirring after adding sulfolane solvent and be warming up to 60 DEG C ~ 80 DEG C, add reaction monomers in turn, after monomer all dissolves, then add salt forming agent in system, the consumption of salt forming agent is 4,4 '-'-biphenyl diphenol or 4, the 1.05-1.2 of 4 '-dihydroxy diphenylsulphone molar weight doubly, adds a point aqua subsequently, continue stirring and be warming up to 200 DEG C ~ 210 DEG C, salt-forming reaction 1 ~ 2 hour; 220 DEG C ~ 240 DEG C are warming up to again after salt-forming reaction completes, constant temperature polyreaction 1 ~ 2 hour, a certain amount of chainextender is added again in system, chainextender consumption is 4,0.2 ~ 10.0% of 4 '-dichloro diphenyl sulfone molar weight, continue reaction about 40 minutes, obtain high strength polyaryl ether sulphone resin mucus;
Wherein, being 20% ~ 25% at the solid content of salt-forming reaction stage system, is 35 ~ 45% at the solid content of polymerization stage system;
Described 4,4 '-'-biphenyl diphenol or 4, the molar weight of 4 '-dihydroxy diphenylsulphone comparatively 4,4 '-dichloro diphenyl sulfone excessive 0.1% ~ 2%, or, 4, the molar weight of 4 '-dichloro diphenyl sulfone comparatively 4,4 '-'-biphenyl diphenol or 4,4 '-dihydroxy diphenylsulphone excessive 0.1% ~ 2%;
(2) aftertreatment
Polymerization mucus is ground into powder after water cooling, removes desolventizing and by-product salt with deionized water boiling washing again after filtration, then namely obtain polyaryl ether sulphone resin after drying.
The present invention is in 200 ~ 210 DEG C at salt-forming stage system temperature, completes prepolymerisation stage simultaneously, namely forms low-molecular-weight performed polymer at salt-forming stage, the number of performed polymer molecular chain and the concentration residing for monomer directly related.Along with the increase pre-polymerization scale of construction of monomer concentration increases, when performed polymer is increased to the monomer concentration step-down to a certain degree in system, later stage polymerization velocity is caused to weaken, there is the phenomenon that the too high speed of response of solid content is slack-off on the contrary, therefore, the present invention is preferred, controls to be 20% ~ 25% at salt-forming reaction stage system solid content, control to be 35 ~ 45% at polymerization stage system solid content, thus ensure the concentration of polymerization stage monomer.Polymerization stage high solids content is conducive to polyreaction, greatly can reduce the consumption of crucial solvent sulfolane, reduces energy consumption, cost-saving.
Preferably, be 38 ~ 42% at the solid content of polymerization stage system, more preferably solid content is 39 ~ 41%.
Of the present invention point of aqua comprises toluene, dimethylbenzene, trimethylbenzene, durene, ethylbenzene, diethylbenzene or the mixture of one or more partially in diethylbenzene.Preferably 160 DEG C of < boiling points <200 DEG C and density are less than hypotoxicity organic point of aqua of water, are specially the mixture of one or more in toluene, dimethylbenzene, sym-trimethylbenzene, hemimellitol, a trimethylbenzene, diethylbenzene, partially diethylbenzene or durene.Adopt high boiling point of aqua, reaction heat-up rate is obviously the heat-up rate of point aqua faster than employing lower boiling dimethylbenzene, 1 ~ 2 hour reaction time single batch can be shortened in the industrial production, reduce production energy consumption, reduce material local temperature thus obtain the polyaryl ether sulphone resin of better color and luster.
The molar weight of biphenol monomer of the present invention and two chlorine monomer controls in the scope of 1.001 ~ 1.2:1, when 4,4 '-'-biphenyl diphenol or 4, the molar weight (biphenol monomer) of 4 '-dihydroxy diphenylsulphone is compared with 4, during 4 '-dichloro diphenyl sulfone (two chlorine monomer) excessive 0.1% ~ 2%, produce the resin obtained and be mainly applicable to common plastomer.
When the molar weight comparatively 4 of 4,4 '-dichloro diphenyl sulfone, 4 '-'-biphenyl diphenol or 4,4 '-dihydroxy diphenylsulphone excessive 0.1% ~ 2% time, produce the resin obtained and be mainly applicable to coating.
Chainextender of the present invention is the mixture of one or more in dichloro substitution compound or trichlorine substitution compound or tetrachloro substitution compound, and its structural formula is as follows:
Wherein M is carbon, silicon or titanium; R
1, R
2, R
3for hydrogen, chlorine, alkyl, alkoxyl group, alicyclic radical, aryl or chloro alkyl, have at least in one containing chlorine element.
Described chainextender R
1, R
2, R
3in atomic number of alkyl carbon be 1 ~ 18, alkoxyl group carbonatoms is 1 ~ 18, alicyclic radical carbonatoms is 5 ~ 20, and aryl carbon atoms is 6 ~ 15, and chloro atomic number of alkyl carbon is 1 ~ 17.
The now preferred R of chainextender
1, R
2, R
3can be methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, isobutyl-, methoxyl group, oxyethyl group, isopropoxy, cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, phenmethyl, Phenylmethoxy, chloromethyl or Chloroethyl etc.
The present invention compared with prior art, has following beneficial effect:
1) the present invention is by being controlled to the solid content of salt phase and polymerization stage, greatly can reduce the consumption of crucial solvent sulfolane, improves production capacity nearly 1/3rd.In 40% solid content, often producing 1 ton of polyaryl ether sulphone resin only needs, with tetramethylene sulfone 1.5 tons, by the rate of recovery of tetramethylene sulfone 80%, directly to lose 300KG tetramethylene sulfone less, greatly saved cost compared with 25% solid content technique;
2) the present invention adopts high boiling point of aqua energy Reaction time shorten, improves production capacity;
3) salt forming agent of the present invention adopts the Na that is produced from China's Mainland
2cO
3, save purchase cost; In addition excessive Na
2cO
3be present in powder form in system, hydrolyzed alkaline is obviously than KOH, NaOH and K
2cO
3system is low, weak to the toxic side effect of system, and adopts domestic Na
2cO
3the polyether sulphone product of explained hereafter and use import Na
2cO
3the product produced for salt forming agent is distinguished without color and luster.
4) reach Quick high polymers molecular weight object by chain extension mode, Reaction time shorten, simplifies synthesis technique;
5) the present invention carries out chain extension by introducing polynary chlorine substitution compound, and the novel tree-like polyaryl ether sulphone resin of synthesis, has higher mechanical strength, lower melt viscosity, is easier to machine-shaping and the more high performance of thermostability.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the concrete embodiment of the present invention, but embodiments of the present invention are by the restriction of following embodiment.
Embodiment 1
In the 300L stainless steel cauldron that logical nitrogen tube and condensation water trap and high-efficiency stirrer are housed, start stirring after first adding 85.00KG tetramethylene sulfone and be warming up to 80 DEG C, add 36.0KG4 in turn, 4 '-dichloro diphenyl sulfone, 23.0KG4, 4 '-'-biphenyl diphenol, after monomer all dissolves, in system, 15.0KG sodium carbonate is added again when being warming up to 110 DEG C, add 65.0 liters of durenes subsequently, 200 DEG C are warming up under continuing stirring, salt-forming reaction starts, the water generated in system and durene azeotropic, start have water coolant to drip in prolong, layering in water trap, become after clarification until upper strata durene from muddiness, continue backflow 20 minutes more complete to ensure salt-forming reaction, salt-forming stage 1.2 hours, the system solid content in salt-forming reaction stage is 26%, steam whole durene after salify completes, then be warming up to 232 DEG C, constant temperature added 50.04g phenyl-trichloro-silicane after 1.0 ~ 2.0 hours, and continue reaction and within 30 minutes, obtain setting viscosity polymeric mucus, the system solid content of polymerization stage is 36%, to be polymerized mucus directly to pulverize after film forming cooling on Stainless Steel Band water cooler, then the powder after filtering is added new deionized water and boils 1 hour, 8 ~ 10 times so repeatedly, in water, chloride ion content is till below 5ppm.By filter after polymkeric substance vacuum-drying to moisture weight content lower than 0.5%, obtain polyphenylene ether sulfone (PPSU) virgin resin.
Gained PPSU resin melting index M I=20.0g/10min (365.0 DEG C, 5KG).
Embodiment 2
With embodiment 1, except tetramethylene sulfone consumption is 70.0KG, 64.0 liters of sym-trimethylbenzene, constant temperature added 40.04g titanium tetrachloride after 1. ~ 2.0 hours, continued reaction and within 35 minutes, obtained setting viscosity polymeric mucus, the system solid content of polymerization stage is 42%, and other conditions are identical.
Gained PPSU resin melting index M I=28.5g/10min (365.0 DEG C, 5KG).
Embodiment 3
With embodiment 1, except tetramethylene sulfone consumption be 65.0KG, between 60.0 liters except trimethylbenzene, constant temperature added 60.04g dimethyldichlorosilane(DMCS) after 1.0 ~ 2.0 hours, continued reaction and within 40 minutes, obtained setting viscosity polymeric mucus, the system solid content of polymerization stage is 38%, and other conditions are identical.
Gained PPSU resin melting index M I=23.8g/10min (365.0 DEG C, 5KG).
Embodiment 4
In the 300L stainless steel cauldron that logical nitrogen tube and condensation water trap and high-efficiency stirrer are housed, start stirring after first adding 73.00KG tetramethylene sulfone and be warming up to 80 DEG C, add 32.00KG4 in turn, 4 '-dichloro diphenyl sulfone, 26.80KG4, 4 '-dihydroxy diphenylsulphone, after monomer all dissolves, in system, 13.50KG sodium carbonate is added again when being warming up to 100 DEG C, add 60 liters of durenes subsequently, 200 DEG C are warming up under continuing stirring, salt-forming reaction starts, the water generated in system and durene azeotropic, start have water coolant to drip in prolong, layering in water trap, treating to become clarification from muddiness by upper strata durene, to continue backflow 20 minutes more complete to ensure salt-forming reaction, salt-forming stage about 1 hour, the system solid content in salt-forming reaction stage is 27%, steam whole durene after salify completes, then be warming up to 230 DEG C, constant temperature adds 50.04g phenyl trichloromethane after 1.0 ~ 2.0 hours, and continue reaction and within 35 minutes, obtain setting viscosity polymeric mucus, the system solid content of polymerization stage is 42%, to be polymerized mucus directly to pulverize after film forming cooling on Stainless Steel Band water cooler, then the powder after filtering is added new deionized water and boils 1 hour, 8 ~ 10 times so repeatedly, in water, chloride ion content is till below 5ppm.By filter after polymkeric substance vacuum-drying to moisture weight content lower than 0.5%, obtain polyethersulfone (PES) virgin resin.
Gained PES resin melting index M I=26.5g/10min (365.0 DEG C, 5KG).
Embodiment 5
With embodiment 4, except tetramethylene sulfone consumption is 70.0KG, 64.0 liters of hemimellitols, constant temperature added 40.05g ethyl trichlorosilane after 1.5 ~ 2.0 hours, continued reaction and within 36 minutes, obtained setting viscosity polymeric mucus, the system solid content of polymerization stage is 39%, and other conditions are identical.
Gained PES resin melting index M I=25.0g/10min (365.0 DEG C, 5KG).
Embodiment 6
With embodiment 4, except tetramethylene sulfone consumption is 80.0KG, 56.0 liters of durenes, constant temperature added 40.05g phenyl-trichloro-silicane after 1.5 ~ 2.0 hours, continued reaction and within 45 minutes, obtained setting viscosity polymeric mucus, the system solid content of polymerization stage is 41%, and other conditions are identical.
Gained PES resin melting index M I=30.0g/10min (365.0 DEG C, 5KG).
Claims (9)
1. add a method for chainextender industrialization synthesizing high-strength polyaryl ether sulphone resin in stage casing, it is characterized in that, comprise the following steps:
(1) polyreaction
With 4,4 '-dichloro diphenyl sulfone and 4,4 '-'-biphenyl diphenol (or 4,4 '-dihydroxy diphenylsulphone) be reaction monomers, being solvent with tetramethylene sulfone, take sodium carbonate as salt forming agent;
In the reactor of nitrogen filled protection, start stirring after adding sulfolane solvent and be warming up to 60 DEG C ~ 80 DEG C, add reaction monomers in turn, after monomer all dissolves, then add salt forming agent in system, the consumption of salt forming agent is 4,4 '-'-biphenyl diphenol or 4, the 1.05-1.2 of 4 '-dihydroxy diphenylsulphone molar weight doubly, adds a point aqua subsequently, continue stirring and be warming up to 200 DEG C ~ 210 DEG C, salt-forming reaction 1 ~ 2 hour; Be warming up to 220 DEG C ~ 240 DEG C after salt-forming reaction completes again, constant temperature polyreaction 1 ~ 2 hour, then add chainextender in system, continue reaction 40 minutes, obtain high strength polyaryl ether sulphone resin mucus;
Wherein, being 20% ~ 25% at the solid content of salt-forming reaction stage system, is 35 ~ 45% at the solid content of polymerization stage system;
Described 4,4 '-'-biphenyl diphenol or 4, the molar weight of 4 '-dihydroxy diphenylsulphone comparatively 4,4 '-dichloro diphenyl sulfone excessive 0.1% ~ 2%, or, 4, the molar weight of 4 '-dichloro diphenyl sulfone comparatively 4,4 '-'-biphenyl diphenol or 4,4 '-dihydroxy diphenylsulphone excessive 0.1% ~ 2%;
(2) aftertreatment
Polymerization mucus is ground into powder after water cooling, removes desolventizing and by-product salt with deionized water boiling washing again after filtration, more namely obtain polyaryl ether sulphone resin after drying.
2. a kind of method of adding chainextender industrialization synthesizing high-strength polyaryl ether sulphone resin in stage casing according to claim 1, it is characterized in that, described point of aqua comprises toluene, dimethylbenzene, sym-trimethylbenzene, hemimellitol, a trimethylbenzene, durene, ethylbenzene, diethylbenzene or the mixture of one or more partially in diethylbenzene.
3. a kind of method of adding chainextender industrialization synthesizing high-strength polyaryl ether sulphone resin in stage casing according to claim 2, it is characterized in that, described point of aqua is 160 DEG C of < boiling points <200 DEG C and density is less than hypotoxicity organic point of aqua of water, is specially the mixture of one or more in sym-trimethylbenzene, hemimellitol, a trimethylbenzene, diethylbenzene, partially diethylbenzene or durene.
4. a kind of method of adding chainextender industrialization synthesizing high-strength polyaryl ether sulphone resin in stage casing according to claim 1, it is characterized in that, be 38 ~ 42% at the solid content of polymerization stage system.
5. a kind of method of adding chainextender industrialization synthesizing high-strength polyaryl ether sulphone resin in stage casing according to claim 4, it is characterized in that, be 39 ~ 41% at the solid content of polymerization stage system.
6. a kind of method of adding chainextender industrialization synthesizing high-strength polyaryl ether sulphone resin in stage casing according to claim 1, it is characterized in that, described salt forming agent is domestic sodium carbonate.
7. a kind of method of adding chainextender industrialization synthesizing high-strength polyaryl ether sulphone resin in stage casing according to claim 1, it is characterized in that, described chainextender consumption is 4,0.2 ~ 10.0% of 4 '-dichloro diphenyl sulfone molar weight.
8. a kind of method of adding chainextender industrialization synthesizing high-strength polyaryl ether sulphone resin in stage casing according to claim 1, it is characterized in that, described chainextender is the mixture of one or more in dichloro substitution compound or trichlorine substitution compound or tetrachloro substitution compound, and its structural formula is as follows:
Wherein M is carbon, silicon or titanium; R
1, R
2, R
3for hydrogen, chlorine, alkyl, alkoxyl group, alicyclic radical, aryl or chloro alkyl, have at least in one containing chlorine element.
9. a kind of method of adding chainextender industrialization synthesizing high-strength polyaryl ether sulphone resin in stage casing according to claim 8, is characterized in that, described chainextender R
1, R
2, R
3in atomic number of alkyl carbon be 1 ~ 18, alkoxyl group carbonatoms is 1 ~ 18, alicyclic radical carbonatoms is 5 ~ 20, and aryl carbon atoms is 6 ~ 15, and chloro atomic number of alkyl carbon is 1 ~ 17.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111621013A (en) * | 2020-05-14 | 2020-09-04 | 万华化学集团股份有限公司 | Preparation method of polyether sulfone resin |
| CN113881045A (en) * | 2021-12-07 | 2022-01-04 | 富海(东营)新材料科技有限公司 | Synthetic method for stably improving impact strength of polyether sulfone |
| CN114891218A (en) * | 2022-03-28 | 2022-08-12 | 桂林理工大学 | High-performance polyether sulfone resin and preparation method and application thereof |
| CN116003796A (en) * | 2023-03-23 | 2023-04-25 | 东营华联石油化工厂有限公司 | Method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073720A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Method for synthesizing low-color high-purity fiber-grade polyphenylene sulfide resin |
| CN103642030A (en) * | 2013-11-27 | 2014-03-19 | 江门市优巨新材料有限公司 | Industrial synthesis method of poly(aromatic ether sulfone) resin with high solid content |
| CN104271639A (en) * | 2012-05-11 | 2015-01-07 | 埃姆斯专利股份公司 | Method for the production of polysulfones, and polysulfones |
-
2015
- 2015-11-30 CN CN201510869403.4A patent/CN105330863B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073720A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Method for synthesizing low-color high-purity fiber-grade polyphenylene sulfide resin |
| CN104271639A (en) * | 2012-05-11 | 2015-01-07 | 埃姆斯专利股份公司 | Method for the production of polysulfones, and polysulfones |
| CN103642030A (en) * | 2013-11-27 | 2014-03-19 | 江门市优巨新材料有限公司 | Industrial synthesis method of poly(aromatic ether sulfone) resin with high solid content |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111621013A (en) * | 2020-05-14 | 2020-09-04 | 万华化学集团股份有限公司 | Preparation method of polyether sulfone resin |
| CN113881045A (en) * | 2021-12-07 | 2022-01-04 | 富海(东营)新材料科技有限公司 | Synthetic method for stably improving impact strength of polyether sulfone |
| CN114891218A (en) * | 2022-03-28 | 2022-08-12 | 桂林理工大学 | High-performance polyether sulfone resin and preparation method and application thereof |
| CN116003796A (en) * | 2023-03-23 | 2023-04-25 | 东营华联石油化工厂有限公司 | Method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination |
| CN116003796B (en) * | 2023-03-23 | 2023-07-28 | 东营华联石油化工厂有限公司 | Method for preparing polysulfone resin by nucleophilic polycondensation-anionic ring-opening polymerization combination |
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Effective date of registration: 20180110 Address after: 529040 Guangdong province Jiangmen City Road No. 291 dragon Jianghai District 1 buildings, 3 buildings Co-patentee after: GUANGDONG YOUJU ADVANCED MATERIAL RESEARCH CO., LTD. Patentee after: JIANGMEN YOUJU NEW MATERIALS CO., LTD. Address before: 529040 Guangdong province Jiangmen City Road No. 291, building 1, Jianghai District Dragon first floor Patentee before: GUANGDONG YOUJU ADVANCED MATERIAL RESEARCH CO., LTD. |
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Address after: 529040 Guangdong province Jiangmen City Road No. 291 dragon Jianghai District 1 buildings, 3 buildings Patentee after: Guangdong Youju advanced new material Co., Ltd Patentee after: GUANGDONG YOUJU ADVANCED MATERIAL RESEARCH Co.,Ltd. Address before: 529040 Guangdong province Jiangmen City Road No. 291 dragon Jianghai District 1 buildings, 3 buildings Patentee before: JIANGMEN YOUJU NEW MATERIALS Co.,Ltd. Patentee before: GUANGDONG YOUJU ADVANCED MATERIAL RESEARCH Co.,Ltd. |