CN104530431A - Industrial synthetic method of low-color high-transmittance polysulfone resin - Google Patents
Industrial synthetic method of low-color high-transmittance polysulfone resin Download PDFInfo
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- CN104530431A CN104530431A CN201410790045.3A CN201410790045A CN104530431A CN 104530431 A CN104530431 A CN 104530431A CN 201410790045 A CN201410790045 A CN 201410790045A CN 104530431 A CN104530431 A CN 104530431A
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Abstract
The invention discloses an industrial synthetic method of low-color high-transmittance polysulfone resin. The method comprises the following steps: by taking 4,4-dichloro-diphenyl sulfone and bisphenol A as reaction monomers, a low-boiling-point organic substance as a solvent, sodium carbonate as a salt forming agent and 3,4'-dichloro-benzophenone as an end capping agent, raising the pressure in a kettle to 2.0-3.0MPa under the protection of an inert gas, and performing polymerization reaction at 200-210 DEG C to obtain a polymerized mucus; and cooling the polymerized mucus, then crushing the polymerized mucus, filtering, then washing to remove the solvent and byproduct salts, and drying. By adopting the synthetic process disclosed by the invention, the problem that the low-boiling-point solvent cannot meet requirements for polymerization during polymerization under a normal pressure condition is solved, the polymerization time is shortened, water-carrying agents including benzene, methylbenzene and dimethylbenzene and the like, which are required to be added during polymerization at normal pressure are avoided, the production cost is reduced, the process steps of recovering and separating these substances in an after treatment process are avoided, and the polysulfone resin prepared by the process disclosed by the invention has very low color and high transmittance, so that the application area of the product is enlarged.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to the Industrialized synthesis method of a kind of low color and high transmission rate polysulfone resin.
Background technology
Polysulfones is a kind of thermoplastic engineering plastic, excellent in mechanical performance, and rigidity is large, wear-resisting, high strength, thermostability is high, has higher second-order transition temperature (~ 190 DEG C), even if at high temperature also keep excellent mechanical property, life-time service temperature is 160 DEG C, short-period used temperature 190 DEG C, and hydrolysis, good stability of the dimension, molding shrinkage is little, nontoxic, radiation hardness, resistance to combustion, have self-extinguishing, in the temperature range of broadness, have excellent electrical property, chemical stability good, ability is generally sour, alkali, salt.So for a long time electronic apparatus, mechanical workout, automobile, medical apparatus, food-processing and not the field such as stickness paint be widely used.
Production technique all reaction preparations in normal pressure, open system usually of existing polysulfones, under normal temperature condition, polymerization need add point aquas such as benzene class, this adds the difficulty of aftertreatment technology undoubtedly, has also occurred because benzene class in aftertreatment technology removes unclean and has affected the performance issues such as the transparence of material; Simultaneously aftertreatment and removal process also need bulky equipment and complicated technology, cause production cost higher and production cycle to elongate.Chinese patent CN103254421A discloses a kind of high pressure synthesis method of aromatic series polysulfone resin, but the polysulfones yellowness index that this method is synthesized is higher, and transmittance is on the low side, limits its practical application in certain.Chinese patent CN100448933C discloses a kind of polysulfone compositions with very low color and high light transmittance properties and the commodity manufactured thus, but need to add blueness or purple toner or organic optical brightener in addition to mix colours, but polysulfones is more responsive to additive, thus product is easily deformed, distortion, the problem such as pressure embrittlement, reduce the work-ing life of product.
Summary of the invention
The object of the invention is to the defect overcoming above-mentioned prior art, a kind of industrialization high pressure synthesis method of polysulfone resin is provided.
The technical solution used in the present invention is:
An industrialization high pressure synthesis method for polysulfone resin, comprises the following steps:
(1) polyreaction
In reactor, add 4 successively, 4 '-dichloro diphenyl sulfone and dihydroxyphenyl propane, after salt forming agent and a certain amount of end-capping reagent, then add low boiling point organic solvent and make the solid content of solid materials reach 25 ~ 45%; Extract gas reactor out to after-0.09MPa, then pass into rare gas element and make still internal pressure rise to 0.01MPa, this process is fallen air displacement in still five times repeatedly, finally passes into rare gas element and still internal pressure is risen to 2.0 ~ 3.0MPa; Heating makes temperature in the kettle reach 200 DEG C of constant temperature must be polymerized mucus by temperature to 210 DEG C constant temperature 3 hours stopped reaction after 1 hour.
(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.
Its reaction formula is as follows:
The add-on of end-capping reagent is 1 ~ 5% of dihydroxyphenyl propane molar content.
The mol ratio of DDS and dihydroxyphenyl propane is 1:1.
The consumption of salt forming agent is 1.01 ~ 1.10 times of dihydroxyphenyl propane or DDS monomer molar amount.
At least one in described low boiling point organic solvent DMF, N,N-dimethylacetamide, trichloromethane, ethylene dichloride, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane.
Described salt forming agent is sodium hydroxide, potassium hydroxide, sodium carbonate, at least one in salt of wormwood, preferred sodium carbonate.
Described rare gas element is one or both blending ingredients in nitrogen, carbonic acid gas, preferred nitrogen.
Described end-capping reagent is 3,4 '-difluoro benzophenone, 3-chloro-4-fluorine benzophenone, the fluoro-4-chlorobenzophenone of 3-or 3, the mixing of one or more in 4 '-dichloro benzophenone.
The present invention is 20% ~ 45% at the solid content of salt-forming reaction stage system, preferably 25% ~ 35%, more preferably 25% ~ 30%.
The invention has the beneficial effects as follows:
1) the present invention is polymerized energy Reaction time shorten nearly 1/4th under adopting condition of high voltage, can improve production capacity nearly 1/4th;
2) present invention eliminates a use point aqua, save energy consumption and the trouble of cost and minimizing aftertreatment and recovery process;
3) the present invention adopts ketone group end-blocking, and the polysulfone resin of preparation has lower yellowness index and higher transmittance, expands product applications;
4) salt forming agent of the present invention adopts Na
2cO
3, save purchase cost; In addition excessive Na
2cO
3be present in the form of a powder in system, hydrolyzed alkaline is obviously than KOH, NaOH and K
2cO
3system is low, weak to the toxic side effect of system.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but be not limited thereto.
Embodiment 1
In 200 liters of stainless steel cauldrons that dress leads to nitrogen tube and condensation water trap and high-efficiency stirrer, add 35.0KG4 in turn, 4 '-dichloro diphenyl sulfone, 27.8KG dihydroxyphenyl propane, 14.0KG sodium carbonate, 291.0g 3,4 '-difluoro benzophenone, add 100.00KG N again, N '-dimethyl formamide.Bleed and take out still internal pressure into after-0.09MPa, pass into nitrogen and still internal pressure is upgraded to 0.01MPa, this process vacuumizes for five times and passes into nitrogen air displacement in still is fallen repeatedly, finally passes into nitrogen and still internal pressure is promoted to 2.0MPa.Heating makes temperature in the kettle reach 200 DEG C of constant temperature salifies must be polymerized mucus by temperature to a 210 DEG C constant temperature polyase 13 hour stopped reaction after 1 hour.
Polymerization mucus water-cooled be ground into powder or directly pulverize after film forming cooling on Stainless Steel Band water cooler, again the powder after filtration is added new deionized water and boil 1 hour, so 8 ~ 10 times 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 polysulfones (PSU) virgin resin.
Gained PSU resin melting index M I=13.0g/10min (343.0 DEG C, 2.16KG).
Embodiment 2
With embodiment 1, except still internal pressure rises to 3.0MPa, the polymerization isothermal reaction time is outside 2.5 hours, and the fluoro-4-chlorobenzophenone of 3-substitutes 3, and outside 4 '-difluoro benzophenone, other conditions are identical.
Gained PSU resin melting index M I=13.2g/10min (343.0 DEG C, 2.16KG).
Embodiment 3
With embodiment 1, except solvent N, N '-N,N-DIMETHYLACETAMIDE substitutes N, N '-dimethyl formamide, 3-chloro-4-fluorine benzophenone substitutes 3, and outside 4 '-difluoro benzophenone, other conditions are identical.
Gained PSU resin melting index M I=13.1g/10min (343.0 DEG C, 2.16KG).
Embodiment 4
With embodiment 1, except solvent N, N '-N,N-DIMETHYLACETAMIDE substitutes N, N '-dimethyl formamide, still internal pressure rises to 3.0MPa, and the polymerization isothermal reaction time is outside 2.5 hours, and 3,4 '-dichloro benzophenone substitutes 3, and outside 4 '-difluoro benzophenone, other conditions are identical.
Gained PSU resin melting index M I=12.8g/10min (343.0 DEG C, 2.16KG).
Comparative example 1
In 200 liters of stainless steel cauldrons that dress leads to nitrogen tube and condensation water trap and high-efficiency stirrer, add 35.0KG4 in turn, 4 '-dichloro diphenyl sulfone, 27.8KG dihydroxyphenyl propane, 14.0KG sodium carbonate, 291.0g 3,4 '-difluoro benzophenone, add 100.00KG N again, N '-dimethyl formamide.In system, 20.0 liters of dimethylbenzene are added again when being warming up to 100 DEG C, 200 DEG C are warming up under continuing stirring, salt-forming reaction starts, the water generated in system and xylenes, start have water coolant to drip in prolong, layering in water trap, treats that upper strata dimethylbenzene becomes clarification from muddiness and continues backflow 20 minutes again to ensure that salt-forming reaction is complete, salt-forming reaction time 2 h; Be warming up to 230 DEG C again after salt-forming reaction completes, constant temperature ensures that polyreaction is complete for 6 hours; Polymerization mucus water-cooled be ground into powder or directly pulverize after film forming cooling on Stainless Steel Band water cooler, again the powder after filtration is added new deionized water and boil 1 hour, so 8 ~ 10 times 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 polysulfones (PSU) virgin resin.
Gained PSU resin melting index M I=12.7g/10min (343.0 DEG C, 2.16KG).
Comparative example 2
In 200 liters of stainless steel cauldrons that dress leads to nitrogen tube and condensation water trap and high-efficiency stirrer, add 35.0KG4 in turn, 4 '-dichloro diphenyl sulfone, 27.8KG dihydroxyphenyl propane, 14.0KG sodium carbonate, 291.0g 3,4 '-difluoro benzophenone, add 100.00KG N again, N '-N,N-DIMETHYLACETAMIDE.In system, 20.0 liters of dimethylbenzene are added again when being warming up to 100 DEG C, 200 DEG C are warming up under continuing stirring, salt-forming reaction starts, the water generated in system and xylenes, start have water coolant to drip in prolong, layering in water trap, treats that upper strata dimethylbenzene becomes clarification from muddiness and continues backflow 20 minutes again to ensure that salt-forming reaction is complete, salt-forming reaction time 2 h; Be warming up to 230 DEG C again after salt-forming reaction completes, constant temperature ensures that polyreaction is complete for 6 hours; Polymerization mucus water-cooled be ground into powder or directly pulverize after film forming cooling on Stainless Steel Band water cooler, again the powder after filtration is added new deionized water and boil 1 hour, so 8 ~ 10 times 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 polysulfones (PSU) virgin resin.
Gained PSU resin melting index M I=12.6g/10min (343.0 DEG C, 2.16KG).
By embodiment 1-4 and comparative example 1-2 comparative analysis result as shown in table 1:
Table 1 embodiment 1 ~ 4 and comparative example 1 ~ 2 comparing result
As can be seen from the above results, the present invention, in the industrial production can Reaction time shorten 3-4 hour by selecting high-pressure polymerization process, saves use and the post-processing step of point aqua simultaneously, substantially increases production capacity, and reduction energy consumption is cost-saving.
Above embodiment is only introduces preferred case of the present invention, to those skilled in the art, not deviating from any apparent changes and improvements of carrying out in the scope of spirit of the present invention, all should be regarded as a part of the present invention.
Claims (9)
1. an industrialization high pressure synthesis method for polysulfone resin, is characterized in that, comprise the following steps:
(1) polyreaction
In reactor, add DDS and dihydroxyphenyl propane successively, salt forming agent, a certain amount of end-capping reagent, then add low boiling point organic solvent and make the solid content of solid materials reach 25 ~ 45%; Extract gas reactor out, then pass into rare gas element air displacement in still is fallen, finally pass into rare gas element and still internal pressure is risen to 2.0 ~ 3.0MPa; Heating makes temperature in the kettle reach 180 ~ 210 DEG C of constant temperature after 1 ~ 3 hour by temperature to 210 ~ 250 DEG C constant temperature 1 ~ 5 hour, obtains polymerization mucus;
(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 polysulfone resin after drying.
2. the industrialization high pressure synthesis method of polysulfone resin according to claim 1, it is characterized in that, described low boiling point organic solvent DMF, N, at least one in N-N,N-DIMETHYLACETAMIDE, trichloromethane, ethylene dichloride, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane.
3. the industrialization high pressure synthesis method of polysulfone resin according to claim 1, is characterized in that, described salt forming agent is sodium hydroxide, potassium hydroxide, sodium carbonate, at least one in salt of wormwood, preferred sodium carbonate.
4. the industrialization high pressure synthesis method of polysulfone resin according to claim 1, is characterized in that, described rare gas element is one or both blending ingredients in nitrogen, carbonic acid gas, preferred nitrogen.
5. the industrialization high pressure synthesis method of polysulfone resin according to claim 1, it is characterized in that, described end-capping reagent is 3,4 '-difluoro benzophenone, 3-chloro-4-fluorine benzophenone, the fluoro-4-chlorobenzophenone of 3-or 3, the mixing of one or more in 4 '-dichloro benzophenone.
6. the industrialization high pressure synthesis method of polysulfone resin according to claim 1 or 5, it is characterized in that, the add-on of described end-capping reagent is 1 ~ 5% of dihydroxyphenyl propane molar content.
7. the industrialization high pressure synthesis method of polysulfone resin according to claim 1, is characterized in that, the mol ratio of DDS and dihydroxyphenyl propane is 1:1.
8. the industrialization high pressure synthesis method of polysulfone resin according to claim 1, is characterized in that, the consumption of described salt forming agent is 1.01 ~ 1.10 times of dihydroxyphenyl propane or DDS monomer molar amount.
9. the industrialization high pressure synthesis method of polysulfone resin according to claim 1, it is characterized in that, in polyreaction, the concrete operations that air displacement in still is fallen be: extract gas reactor out extremely--after 0.09MPa, passing into rare gas element again makes still internal pressure rise to 0.01MPa, and this process falls air displacement in still repeatedly.
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| CN105331082A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | Method for preparing fiber reinforced low-viscidity polysulfone resin |
| CN105330837A (en) * | 2015-11-30 | 2016-02-17 | 广东优巨先进材料研究有限公司 | Star type polysulfone resin industrial synthesis method |
| CN105330862A (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 polysulfone resin |
| CN105330839A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | High-pressure synthesis method of high-light-transmittance polyether sulfone resin narrow in molecular weight distribution |
| CN105330861A (en) * | 2015-11-30 | 2016-02-17 | 广东优巨先进材料研究有限公司 | High-transparent polysulfone resin and preparation method thereof |
| CN105348513A (en) * | 2015-11-30 | 2016-02-24 | 广东优巨先进材料研究有限公司 | Industrialized synthesis method of cladodification high-strength polysulfone resin |
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| CN105860078A (en) * | 2016-05-12 | 2016-08-17 | 金发科技股份有限公司 | Sulfone polymer composition, preparation method thereof and thermoplastic molding composition formed by sulfone polymer composition |
| CN105968357A (en) * | 2016-06-29 | 2016-09-28 | 江苏傲伦达科技实业股份有限公司 | Preparation method of polyether sulphone |
| CN106189235A (en) * | 2016-07-21 | 2016-12-07 | 金发科技股份有限公司 | A kind of sulfone polymer composition and consisting of thermoplastic composition and application |
| CN112159526A (en) * | 2020-09-08 | 2021-01-01 | 威海金泓管材有限公司 | Industrial preparation method for reducing water absorption of PPSU pipe |
| CN113004521A (en) * | 2019-12-19 | 2021-06-22 | 万华化学集团股份有限公司 | Polysulfone and preparation method thereof |
| WO2023016487A1 (en) * | 2021-08-13 | 2023-02-16 | 吉林省中研高分子材料股份有限公司 | High-strength and low-chroma polyether ether ketone and preparation method therefor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070049724A1 (en) * | 2004-09-27 | 2007-03-01 | General Electric Company | Polyethersulfone compositions with high heat and good impact resistance |
| CN102888003A (en) * | 2012-10-10 | 2013-01-23 | 四川飞亚新材料有限公司 | High polymer material precipitation method and industrial production method of polysulfone resin |
| CN103087309A (en) * | 2013-01-18 | 2013-05-08 | 山东浩然特塑有限公司 | High-pressure synthetic method of polyaryl sulfone resin of terpolymer and quadripolymer |
| CN103254421A (en) * | 2013-01-18 | 2013-08-21 | 山东浩然特塑有限公司 | High pressure synthesis method for aromatic polysulfone resin |
| CN103613752A (en) * | 2013-11-25 | 2014-03-05 | 威海洁瑞医用制品有限公司 | Synthesis method of polysulfone resin |
| CN103626992A (en) * | 2013-11-27 | 2014-03-12 | 江门市优巨新材料有限公司 | Industrialized synthesis method of high-heat-stability blocked polyether sulfone resin |
-
2014
- 2014-12-17 CN CN201410790045.3A patent/CN104530431A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070049724A1 (en) * | 2004-09-27 | 2007-03-01 | General Electric Company | Polyethersulfone compositions with high heat and good impact resistance |
| CN102888003A (en) * | 2012-10-10 | 2013-01-23 | 四川飞亚新材料有限公司 | High polymer material precipitation method and industrial production method of polysulfone resin |
| CN103087309A (en) * | 2013-01-18 | 2013-05-08 | 山东浩然特塑有限公司 | High-pressure synthetic method of polyaryl sulfone resin of terpolymer and quadripolymer |
| CN103254421A (en) * | 2013-01-18 | 2013-08-21 | 山东浩然特塑有限公司 | High pressure synthesis method for aromatic polysulfone resin |
| CN103613752A (en) * | 2013-11-25 | 2014-03-05 | 威海洁瑞医用制品有限公司 | Synthesis method of polysulfone resin |
| CN103626992A (en) * | 2013-11-27 | 2014-03-12 | 江门市优巨新材料有限公司 | Industrialized synthesis method of high-heat-stability blocked polyether sulfone resin |
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| CN105330862B (en) * | 2015-11-30 | 2018-04-20 | 江门市优巨新材料有限公司 | A kind of preparation method of high-performance modified polysulfone resin |
| CN105330837A (en) * | 2015-11-30 | 2016-02-17 | 广东优巨先进材料研究有限公司 | Star type polysulfone resin industrial synthesis method |
| CN105330862A (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 polysulfone resin |
| CN105330839A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | High-pressure synthesis method of high-light-transmittance polyether sulfone resin narrow in molecular weight distribution |
| CN105330861A (en) * | 2015-11-30 | 2016-02-17 | 广东优巨先进材料研究有限公司 | High-transparent polysulfone resin and preparation method thereof |
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| CN105418910A (en) * | 2015-11-30 | 2016-03-23 | 广东优巨先进材料研究有限公司 | Method for synthesizing end-capped bisphenol A polyaryletherketone resin with semi-flexible structure |
| CN105331082A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | Method for preparing fiber reinforced low-viscidity polysulfone resin |
| CN105860078A (en) * | 2016-05-12 | 2016-08-17 | 金发科技股份有限公司 | Sulfone polymer composition, preparation method thereof and thermoplastic molding composition formed by sulfone polymer composition |
| CN105968357A (en) * | 2016-06-29 | 2016-09-28 | 江苏傲伦达科技实业股份有限公司 | Preparation method of polyether sulphone |
| CN106189235A (en) * | 2016-07-21 | 2016-12-07 | 金发科技股份有限公司 | A kind of sulfone polymer composition and consisting of thermoplastic composition and application |
| CN113004521A (en) * | 2019-12-19 | 2021-06-22 | 万华化学集团股份有限公司 | Polysulfone and preparation method thereof |
| CN113004521B (en) * | 2019-12-19 | 2022-08-05 | 万华化学集团股份有限公司 | Polysulfone and preparation method thereof |
| CN112159526A (en) * | 2020-09-08 | 2021-01-01 | 威海金泓管材有限公司 | Industrial preparation method for reducing water absorption of PPSU pipe |
| CN112159526B (en) * | 2020-09-08 | 2023-04-25 | 威海金泓管材有限公司 | Industrial preparation method for reducing water absorption rate of PPSU (polyphenylene sulfide) pipe |
| WO2023016487A1 (en) * | 2021-08-13 | 2023-02-16 | 吉林省中研高分子材料股份有限公司 | High-strength and low-chroma polyether ether ketone and preparation method therefor |
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Application publication date: 20150422 |