CN103642030A - Industrial synthesis method of poly(aromatic ether sulfone) resin with high solid content - Google Patents
Industrial synthesis method of poly(aromatic ether sulfone) resin with high solid content Download PDFInfo
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Abstract
The invention discloses an industrial synthesis method of a poly(aromatic ether sulfone) resin with a high solid content. The synthesis method comprises the following steps: taking 4,4'-dichlorodiphenyl sulfone and 4,4'-biphenol or 4,4'-dihydroxyl diphenyl sulfone as the reaction monomers, sulfolane as the solvent, and sodium carbonate as the salt forming agent, adding the solvent into a reactor filled with nitrogen gas, then stirring, heating to a temperature of 60 to 80 DEG C, orderly adding the reaction monomers, fully dissolving the monomers, adding the salt forming agent into the reactor, then adding a water separating agent, keeping on stirring, heating to a temperature of 200 to 210 DEG C, carrying out salt forming reactions for 1 to 2 hours; completely evaporating the water separating agent after the salt forming reactions, then transporting the salt forming reaction products to a polymerization reactor to carry out reactions; wherein the solid content of the system in the salt forming phase is 20% to 25%, and the solid content of the system in the polymerization phase is 35% to 45%; cooling the polymerization sticky liquid after the polymerization reactions, grinding into powder, filtering, then boiling and washing with deionized water to remove the solvent and byproduct namely the salt, and finally drying so as to obtain the target product. The synthesis technology can reduce the using amount of solvent sulfolane, shortens the polymerization time, and increases the output.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of Industrialized synthesis method of high solids content polyaryl ether sulphone resin.
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 ° of 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 the production technique that employing sulfobenzide is solvent, for example European patent document EP2008067700 and american documentation literature US20100310804A1, and adopt the production technique that tetramethylene sulfone is solvent, see Chinese patent literature CN85105138A, CN1765953A, CN1844196A, CN101704951A, CN101735459A.The content of the resin that two kinds of explained hereafter relate in solvent in 20 ~ 35% scopes, preferably 25 ~ 30%, more preferably 25% left and right.Produce one ton of polyaryl ether sulphone resin and need to add 3 tons of tetramethylene sulfone.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, thereby make the rate of recovery of tetramethylene sulfone in whole technical process only in 80% left and right, that is to say that 1 ton of polyether sulphone of every production will lose 600.00KG tetramethylene sulfone.
If directly improve the solid content of polymerization system, if design system solid content is in 30 ~ 40% scopes, we find that speed of response is not accelerated along with the increase of concentration in tetramethylene sulfone system, increase speed of response along with concentration declines on the contrary, when solid content is 30 ~ 35% time, speed of response is dropped by nearly half.This may be due to the speed of response of system, to be controlled by the concentration (DDS) of 4,4 ￠-dichloro diphenyl sulfone, when DDS concentration surpasses certain value, polymer molecular chain is had to unzipping, thereby causes speed of response to reduce; Also having a kind of reason is to form low-molecular-weight performed polymer at salt-forming stage, the number of performed polymer molecular chain and the concentration of monomer are directly related, increase pre-polymerization scale of construction increase along with monomer concentration, monomer concentration step-down after performed polymer is increased to a certain degree in system, cause later stage polymerization velocity to weaken, occur the too high speed of response of solid content slack-off phenomenon on the contrary.Therefore, directly improve system solid content and also have certain defect.Chinese patent literature CN1268526A discloses and a kind ofly in system, has added viscosity-controlling agent silicoorganic compound can improve the way of solid content to 40 ~ 45%, but need to additionally add organosilicon to increase post-processing difficulty, and its polymerization cycle is also longer.
Summary of the invention
The object of the invention is to overcome the defect of above-mentioned prior art, a kind of consumption that can greatly reduce solvent sulfolane is provided, can shorten again the Industrialized synthesis method of the polyaryl ether sulphone resin of polymerization time, raising production capacity.
The Industrialized synthesis method of the polyaryl ether sulphone resin of a kind of high solids content of the present invention, comprises the following steps:
(1) polyreaction
With 4,4 '-dichloro diphenyl sulfone and 4,4 '-'-biphenyl diphenol or 4,4 '-dihydroxy diphenylsulphone is reaction monomers, take tetramethylene sulfone as solvent, take sodium carbonate as salt forming agent;
In the reactor of nitrogen filled protection, add to start to stir after sulfolane solvent and be warming up to 60 ℃ ~ 80 ℃, add in turn reaction monomers, 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 minute aqua subsequently, continue to stir and be warming up to 200 ℃ ~ 210 ℃, salt-forming reaction 1 ~ 2 hour; After completing, salt-forming reaction steams all minute aquas, be warming up to again 220 ℃ ~ 240 ℃, proceed to and be full of nitrogen and be warming up in the reactor of 220 ℃ ~ 240 ℃, beginning is stirred with the stirring velocity of 50 ~ 70 turn/min, constant temperature strengthened stirring velocity to 70 ~ 90 after 0.5 ~ 1.0 hour turn/min, continue constant temperature and within 0.5 ~ 1.0 hour, arrive setting viscosity, obtain polymerization mucus;
Wherein, at the solid content of salt-forming reaction stage system, be 20% ~ 25%, at the solid content of polymerization stage system, be 35 ~ 45%;
Described 4,4 '-'-biphenyl diphenol or 4, the molar weight of 4 '-dihydroxy diphenylsulphone is compared with 4,4 '-dichloro diphenyl sulfone excessive 0.1% ~ 2%
Or, 4, the molar weight of 4 '-dichloro diphenyl sulfone is compared with 4,4 '-'-biphenyl diphenol or 4,4 '-dihydroxy diphenylsulphone excessive 0.1% ~ 2%;
(2) aftertreatment
Polymerization mucus is ground into powder after water cooling, after filtration, with deionized water boiling washing, removes desolventizing and by-product salt again, after being then dried, obtain polyaryl ether sulphone resin.
Its reaction formula is as follows:
The present invention in 200 ~ 210 ° of C, completes prepolymerisation stage at salt-forming stage system temperature simultaneously, at salt-forming stage, forms low-molecular-weight performed polymer, and number and the residing concentration of monomer of performed polymer molecular chain are directly related.Increase pre-polymerization scale of construction increase along with monomer concentration, monomer concentration step-down after performed polymer is increased to a certain degree in system, cause later stage polymerization velocity to weaken, there is the too high speed of response of solid content slack-off phenomenon on the contrary, therefore, the present invention is preferred, and at salt-forming reaction stage system solid content, controlling is 20% ~ 25%, at polymerization stage system solid content, controlling is 35 ~ 45%, thereby guarantees the concentration of polymerization stage monomer.Polymerization stage high solids content is conducive to polyreaction, can greatly reduce the consumption of crucial solvent sulfolane, reduces energy consumption, cost-saving.
Preferably, at the solid content of polymerization stage system, be 38 ~ 42%, more preferably solid content is 39 ~ 41%.
Of the present invention minute aqua comprises toluene, dimethylbenzene, trimethylbenzene, durene, ethylbenzene, diethylbenzene or the mixture of one or more in diethylbenzene partially.Preferably 200 ° of C of 160 ° of C< boiling point < and density are less than the organic minute aqua of hypotoxicity of water, are specially toluene, dimethylbenzene, sym-trimethylbenzene, hemimellitol, a trimethylbenzene, diethylbenzene, the mixture of one or more in diethylbenzene or durene partially.Adopt high boiling minute aqua, reaction heat-up rate is obviously faster than the heat-up rate that adopts lower boiling dimethylbenzene for minute aqua, in industrial production, can shorten 1 ~ 2 hour single batch of reaction time, reduce production energy consumption, thereby reduce the polyaryl ether sulphone resin that material local temperature obtains better color and luster.
The molar weight of biphenol monomer of the present invention and two chlorine monomers is controlled in the scope of 1.001 ~ 1.2:1, when 4,4 '-'-biphenyl diphenol or 4, the molar weight of 4 '-dihydroxy diphenylsulphone (biphenol monomer) is compared with 4, during 4 '-dichloro diphenyl sulfone (two chlorine monomer) excessive 0.1% ~ 2%, produce the resin obtaining and be mainly applicable to common plastomer.
When 4, the molar weight of 4 '-dichloro diphenyl sulfone is compared with 4, and 4 '-'-biphenyl diphenol or 4, during 4 '-dihydroxy diphenylsulphone excessive 0.1% ~ 2%, is produced the resin obtaining and is mainly applicable to coating.
The present invention compared with prior art, has following beneficial effect:
1) the present invention, by being controlled to the solid content of salt phase and polymerization stage, can greatly reduce the consumption of crucial solvent sulfolane,
Improve production capacity nearly 1/3rd.In 40% solid content, 1 ton of polyaryl ether sulphone resin of every production only needs, with 1.5 tons of tetramethylene sulfone, by the rate of recovery of tetramethylene sulfone 80%, to compare and directly lose less 300KG tetramethylene sulfone with 25% solid content technique, has greatly saved cost;
2) pattern of process using of the present invention two stills series connection, after salify completes, proceeds to polymeric kettle after steaming whole minute aquas again,
Can realize production capacity maximizes;
3) the present invention adopts high boiling minute aqua energy Reaction time shorten, improves production capacity;
4) salt forming agent of the present invention adopts the Na that produce China's Mainland
2cO
3, save purchase cost; In addition excessive Na
2cO
3with powder type, be present in system, hydrolysis alkalescence is obviously than KOH, NaOH and K
2cO
3system is low, a little less than the toxic side effect of system, and adopts domestic Na
2cO
3the polyether sulphone product of explained hereafter and use import Na
2cO
3for the product that salt forming agent is produced is distinguished without color and luster.
Embodiment
Below by embodiment, further illustrate the present invention, following examples are the concrete embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
Embodiment 1
In 300 liters of stainless steel cauldrons of logical nitrogen tube and condensation water trap and high-efficiency stirrer are housed, first add to start to stir after 75.00 KG tetramethylene sulfone and be warming up to 80 ℃, add in turn 35.0 KG 4, 4 '-dichloro diphenyl sulfone, 22.50 KG 4, 4 '-'-biphenyl diphenol, after monomer all dissolves, when being warming up to 100 ℃, in system, add 14.0 KG sodium carbonate again, add subsequently 60.0 liters of durenes, under continuing to stir, be warming up to 200 ℃, salt-forming reaction starts, the water generating in system and durene azeotropic, in prolong, starting has water coolant to drip, layering in water trap, until upper strata durene after muddiness becomes clarification, continue to reflux again 20 minutes complete to guarantee salt-forming reaction, salt-forming stage 1 hour, the system solid content in salt-forming reaction stage is 25%, after completing, salify steams whole durenes, be warming up to again 230 ℃, squeeze into and utilize in advance purity nitrogen to replace and to be warming up in 200 liters of stainless steel cauldrons of 230 ℃, the stirring velocity that beginning turns with per minute 60 stirs, constant temperature strengthens stirring velocity to per minute 80 and turns after 1.0 hours, continue constant temperature and within 0.5 ~ 1.0 hour, arrive setting viscosity, obtain polymerization mucus, the system solid content of polymerization stage is 35%, by the directly cooling rear pulverizing of film forming on Stainless Steel Band water cooler of polymerization mucus, then add new deionized water to boil 1 hour in the powder after filtering, 8 ~ 10 times so repeatedly, until in water chloride ion content below 5ppm.By the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain polyphenylene ether sulfone (PPSU) virgin resin.
Gained PPSU resin melting index M I=26.0 g/10min (365.0 ℃, 5KG, 5 minutes).
Embodiment 2
With embodiment 1, except tetramethylene sulfone consumption is 70.0 KG, 64.0 liters of sym-trimethylbenzene, the system solid content of polymerization stage is 45%, and other conditions are identical.
Gained PPSU resin melting index M I=26.3 g/10min (365.0 ℃, 5KG, 5 minutes).
Embodiment 3
With embodiment 1, except tetramethylene sulfone consumption is between 80.0 KG, 56.0 liters trimethylbenzene, the system solid content of polymerization stage is 38%, and other conditions are identical.
Gained PPSU resin melting index M I=25.8 g/10min (365.0 ℃, 5KG, 5 minutes).
Embodiment 4
In 300 liters of stainless steel cauldrons of logical nitrogen tube and condensation water trap and high-efficiency stirrer are housed, first add to start to stir after 75.00 KG tetramethylene sulfone and be warming up to 80 ℃, add in turn 31.00 KG 4, 4 '-dichloro diphenyl sulfone, 26.00 KG 4, 4 '-dihydroxy diphenylsulphone, after monomer all dissolves, when being warming up to 100 ℃, in system, add 12.50 KG sodium carbonate again, add subsequently 60 liters of durenes, under continuing to stir, be warming up to 200 ℃, salt-forming reaction starts, the water generating in system and durene azeotropic, in prolong, starting has water coolant to drip, layering in water trap, treat upper strata durene from muddiness become clarification continue again to reflux 20 minutes complete to guarantee salt-forming reaction, salt-forming stage approximately 1 hour, the system solid content in salt-forming reaction stage is 25%, after completing, salify steams whole durenes, be warming up to again 230 ℃, squeeze into and utilize in advance purity nitrogen to replace and to be warming up in 200 liters of stainless steel cauldrons of 240 ℃, the stirring velocity that beginning turns with per minute 60 stirs, constant temperature strengthens stirring velocity to per minute 80 and turns after 1.0 hours, continue constant temperature and to setting viscosity, obtain polymerization mucus in 0.5 ~ 1.5 hour, the system solid content of polymerization stage is 42%, by the directly cooling rear pulverizing of film forming on Stainless Steel Band water cooler of polymerization mucus, then add new deionized water to boil 1 hour in the powder after filtering, 8 ~ 10 times so repeatedly, until in water chloride ion content below 5ppm.By the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain polyethersulfone (PES) virgin resin.
Gained PES resin melting index M I=23.5 g/10min (365.0 ℃, 5KG, 5 minutes).
Embodiment 5
With embodiment 5, except tetramethylene sulfone consumption is 70.0 KG, 64.0 liters of hemimellitols, the system solid content of polymerization stage is 39%, and other conditions are identical.
Gained PES resin melting index M I=23.0 g/10min (365.0 ℃, 5KG, 5 minutes).
Embodiment 6
With embodiment 5, except tetramethylene sulfone consumption is 80.0 KG, 56.0 liters of durenes, the system solid content of polymerization stage is 41%, and other conditions are identical.
Gained PES resin melting index M I=24.0 g/10min (365.0 ℃, 5KG, 5 minutes).
Comparative example 1
In 300 liters of stainless steel cauldrons of logical nitrogen tube and condensation water trap and high-efficiency stirrer are housed, first add to start to stir after 130.00KG tetramethylene sulfone and be warming up to 80 ℃, add in turn 35.0 KG 4, 4 '-dichloro diphenyl sulfone, 22.50 KG 4, 4 '-'-biphenyl diphenol, after monomer all dissolves, when being warming up to 100 ℃, in system, add 14.0 KG sodium carbonate again, add subsequently 62.0 liters of dimethylbenzene, under continuing to stir, be warming up to 200 ℃, salt-forming reaction starts, system solid content is 20%, the water generating in system and dimethylbenzene azeotropic, in prolong, starting has water coolant to drip, layering in water trap, treat upper strata dimethylbenzene from muddiness become clarification continue again to reflux 20 minutes complete to guarantee salt-forming reaction, salt-forming stage 2 hours, after salt-forming reaction completes, be warming up to 240 ℃, constant temperature guarantees that polyreaction is complete, obtains polymerization mucus for 3.5 hours again, by the directly cooling rear pulverizing of film forming on Stainless Steel Band water cooler of polymerization mucus, then add new deionized water to boil 1 hour in the powder after filtering, 8 ~ 10 times so repeatedly, until in water chloride ion content below 5ppm.By the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain polyphenylene ether sulfone (PPSU) virgin resin.
Gained PPSU resin melting index M I=26.0 g/10min (365.0 ℃, 5KG, 5 minutes).
Comparative example 2
In 300 liters of stainless steel cauldrons of logical nitrogen tube and condensation water trap and high-efficiency stirrer are housed, first add to start to stir after 130.00 KG tetramethylene sulfone and be warming up to 80 ℃, add in turn 31.00 KG 4, 4 '-dichloro diphenyl sulfone, 26.00 KG 4, 4 '-dihydroxy diphenylsulphone, after monomer all dissolves, when being warming up to 100 ℃, in system, add 12.50 KG sodium carbonate again, add subsequently 62 liters of dimethylbenzene, under continuing to stir, be warming up to 200 ℃, salt-forming reaction starts, system solid content is 25%, the water generating in system and dimethylbenzene azeotropic, in prolong, starting has water coolant to drip, layering in water trap, treat upper strata dimethylbenzene from muddiness become clarification continue again to reflux 20 minutes complete to guarantee salt-forming reaction, salt-forming stage approximately 2.5 hours, after salify completes, be warming up to 240 ℃, constant temperature guarantees that polyreaction is complete, obtains polymerization mucus for 3 hours again, by the directly cooling rear pulverizing of film forming on Stainless Steel Band water cooler of polymerization mucus, then add new deionized water to boil 1 hour in the powder after filtering, 8 ~ 10 times so repeatedly, until in water chloride ion content below 5ppm.By the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain polyethersulfone (PES) virgin resin.
Gained PES resin melting index M I=23.5 g/10min (365.0 ℃, 5KG, 5 minutes).
Comparative example 3
In 300 liters of stainless steel cauldrons of logical nitrogen tube and condensation water trap and high-efficiency stirrer are housed, first add to start to stir after 75.00 KG tetramethylene sulfone and be warming up to 80 ℃, add in turn 31.00 KG 4, 4 '-dichloro diphenyl sulfone, 26.00 KG 4, 4 '-dihydroxy diphenylsulphone, after monomer all dissolves, when being warming up to 100 ℃, in system, add 12.50 KG sodium carbonate again, add subsequently 60 liters of durenes, under continuing to stir, be warming up to 200 ℃, salt-forming reaction starts, system solid content is 35%, the water generating in system and durene azeotropic, in prolong, starting has water coolant to drip, layering in water trap, treat upper strata durene from muddiness become clarification continue again to reflux 20 minutes complete to guarantee salt-forming reaction, salt-forming stage approximately 1.5 hours, after salify completes, be warming up to 240 ℃, constant temperature guarantees that polyreaction is complete, obtains polymerization mucus for 3 hours again, by the directly cooling rear pulverizing of film forming on Stainless Steel Band water cooler of polymerization mucus, then add new deionized water to boil 1 hour in the powder after filtering, 8 ~ 10 times so repeatedly, until in water chloride ion content below 5ppm.By the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain polyethersulfone (PES) virgin resin.
Gained PES resin melting index M I=23.5 g/10min (365.0 ℃, 5KG, 5 minutes).
Embodiment 1-6 and comparative example 1-3 comparative analysis result is as shown in table 1:
Table 1 embodiment 1 ~ 6 and comparative example 1 ~ 3 comparing result (wt%)
By the above results, can be found out, in comparative example 1 and comparative example 2, the solid content of system is 25%, content is lower, and a minute aqua is selected lower boiling dimethylbenzene, and embodiment 1-6 is by being controlled to respectively the solid content of salt phase and polymerization stage, greatly reduced the consumption of tetramethylene sulfone, select high boiling minute aqua, can Reaction time shorten 1-2 hour in industrial production, greatly improved production capacity, reduce energy consumption, cost-saving.
In comparative example 3, be directly the solid content of system to be brought up to 35%, result shows, its speed of response, along with the increase of concentration can decline, extends reaction time.
Claims (6)
1. an Industrialized synthesis method for high solids content polyaryl ether sulphone resin, is characterized in that, comprises the following steps:
(1) polyreaction
With 4,4 '-dichloro diphenyl sulfone and 4,4 '-'-biphenyl diphenol or 4,4 '-dihydroxy diphenylsulphone is reaction monomers, take tetramethylene sulfone as solvent, take sodium carbonate as salt forming agent;
In the reactor of nitrogen filled protection, add to start to stir after sulfolane solvent and be warming up to 60 ℃ ~ 80 ℃, add in turn reaction monomers, 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 minute aqua subsequently, continue to stir and be warming up to 200 ℃ ~ 210 ℃, salt-forming reaction 1 ~ 2 hour; After completing, salt-forming reaction steams all minute aquas, be warming up to again 220 ℃ ~ 240 ℃, proceed to and be full of nitrogen and be warming up in the reactor of 220 ℃ ~ 240 ℃, beginning is stirred with the stirring velocity of 50 ~ 70 turn/min, constant temperature strengthened stirring velocity to 70 ~ 90 after 0.5 ~ 1.0 hour turn/min, continue constant temperature and within 0.5 ~ 1.0 hour, arrive setting viscosity, obtain polymerization mucus;
Wherein, at the solid content of salt-forming reaction stage system, be 20% ~ 25%, at the solid content of polymerization stage system, be 35 ~ 45%;
Described 4,4 '-'-biphenyl diphenol or 4, the molar weight of 4 '-dihydroxy diphenylsulphone is compared with 4,4 '-dichloro diphenyl sulfone excessive 0.1% ~ 2%
Or, 4, the molar weight of 4 '-dichloro diphenyl sulfone is compared with 4,4 '-'-biphenyl diphenol or 4,4 '-dihydroxy diphenylsulphone excessive 0.1% ~ 2%;
(2) aftertreatment
Polymerization mucus is ground into powder after water cooling, after filtration, with deionized water boiling washing, removes desolventizing and by-product salt again, more obtain polyaryl ether sulphone resin after dry.
2. the Industrialized synthesis method of a kind of high solids content polyaryl ether sulphone resin according to claim 1, it is characterized in that, described minute aqua comprises toluene, dimethylbenzene, trimethylbenzene, durene, ethylbenzene, diethylbenzene or the mixture of one or more in diethylbenzene partially.
3. the Industrialized synthesis method of a kind of high solids content polyaryl ether sulphone resin according to claim 2, it is characterized in that, within described minute, aqua is the organic minute aqua of hypotoxicity that 200 ° of C of 160 ° of C< boiling point < and density are less than water, is specially sym-trimethylbenzene, hemimellitol, a trimethylbenzene, diethylbenzene, the mixture of one or more in diethylbenzene or durene partially.
4. the Industrialized synthesis method of a kind of high solids content polyaryl ether sulphone resin according to claim 1, is characterized in that, at the solid content of polymerization stage system, is 38 ~ 42%.
5. the Industrialized synthesis method of a kind of high solids content polyaryl ether sulphone resin according to claim 4, is characterized in that, at the solid content of polymerization stage system, is 39 ~ 41%.
6. the Industrialized synthesis method of a kind of high solids content polyaryl ether sulphone resin according to claim 1, is characterized in that, described salt forming agent is domestic sodium carbonate.
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| CN105330838A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | Industrialized synthesis method of high-transparent polyaromatic ether sulfone resin |
| CN105331080A (en) * | 2015-11-30 | 2016-02-17 | 广东优巨先进材料研究有限公司 | Method for preparing fiber reinforced polyether sulphone resin |
| CN105330863A (en) * | 2015-11-30 | 2016-02-17 | 广东优巨先进材料研究有限公司 | Method for adding chain extender to middle piece to synthesize high-strength polyether sulphone resin |
| CN105331081A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | Preparation method of high-performance modified polyethersulfone resin |
| CN105348773A (en) * | 2015-11-30 | 2016-02-24 | 广东优巨先进材料研究有限公司 | Fiber-reinforced type polyether sulphone alloy blended and modified resin and preparation method thereof |
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| CN106220853A (en) * | 2016-09-12 | 2016-12-14 | 李涛 | A kind of polysulfone resin industrialized producing technology |
| CN110483774A (en) * | 2019-08-06 | 2019-11-22 | 金发科技股份有限公司 | A kind of preparation method of aromatic sulfone polymer and aromatic sulfone polymer |
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| CN105368037A (en) * | 2015-11-30 | 2016-03-02 | 江门市优巨新材料有限公司 | Glass fiber-enhanced chain-extending modified polyether sulphone resin and preparation method therefor |
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| CN105330863A (en) * | 2015-11-30 | 2016-02-17 | 广东优巨先进材料研究有限公司 | Method for adding chain extender to middle piece to synthesize high-strength polyether sulphone resin |
| CN105331081A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | Preparation method of high-performance modified polyethersulfone resin |
| CN105348773A (en) * | 2015-11-30 | 2016-02-24 | 广东优巨先进材料研究有限公司 | Fiber-reinforced type polyether sulphone alloy blended and modified resin and preparation method thereof |
| CN105348774A (en) * | 2015-11-30 | 2016-02-24 | 广东优巨先进材料研究有限公司 | Preparation method of fiber-reinforced polyether sulphone alloy |
| CN105330838A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | Industrialized synthesis method of high-transparent polyaromatic ether sulfone resin |
| CN105348773B (en) * | 2015-11-30 | 2018-03-09 | 江门市优巨新材料有限公司 | A kind of fine enhanced polyether sulphone alloy blending and modifying resin and preparation method thereof |
| CN105368037B (en) * | 2015-11-30 | 2018-06-01 | 江门市优巨新材料有限公司 | A kind of fiberglass reinforced type chain extension modified polyarylether sulphone resin and preparation method thereof |
| CN106220853A (en) * | 2016-09-12 | 2016-12-14 | 李涛 | A kind of polysulfone resin industrialized producing technology |
| CN110483774A (en) * | 2019-08-06 | 2019-11-22 | 金发科技股份有限公司 | A kind of preparation method of aromatic sulfone polymer and aromatic sulfone polymer |
| CN113444239A (en) * | 2021-06-11 | 2021-09-28 | 天津师范大学 | High-efficiency preparation method of polyaromatic ether |
| CN113444239B (en) * | 2021-06-11 | 2022-11-04 | 天津师范大学 | High-efficiency preparation method of polyaromatic ether |
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