CN105330841A - Industrialized synthesis method of end-capped modified polyaryletherketone resin - Google Patents
Industrialized synthesis method of end-capped modified polyaryletherketone resin Download PDFInfo
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- CN105330841A CN105330841A CN201510869420.8A CN201510869420A CN105330841A CN 105330841 A CN105330841 A CN 105330841A CN 201510869420 A CN201510869420 A CN 201510869420A CN 105330841 A CN105330841 A CN 105330841A
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Abstract
The invention discloses an industrialized synthesis method of end-capped modified polyaryletherketone resin. The industrialized synthesis method comprises the steps that a solvent, a bisphenol monomer, a double-fluorine monomer and a salt-forming agent are added into a reaction kettle subjected to nitrogen filled protection, then stirring is performed for temperature rise to reach the temperature of 130-140 DEG C, the solid content of a system is 15%-40%, all monomers are continuously stirred evenly after being dissolved, then temperature rise is performed to reach the temperature of 180-220 DEG C, reaction is performed for 1-2 hours, temperature rise is performed to reach the temperature of 240-270 DEG C, reaction is carried out for 0.5-2 hours, then temperature rise is performed to reach the temperature of 300-320 DEG C, polymerization is performed for 1-4 hours, an end capping agent is added, and reaction is continuously performed for 10-30 minutes to obtain polymerized viscous liquid; the polymerized viscous liquid is cooled, and then smashing, filtering, washing and drying are performed to obtain the end-capped modified polyaryletherketone resin. Alkali metal sodium carbonate is used as a catalyst, and after the end capping agent is added, the better end sealing effect is obtained, and also no depolymerization phenomenon occurs in the system. The obtained polyaryletherketone resin has the high-temperature heat stability, the crystallinity of the resin is reduced, and the solubility of the high polymer is improved.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of Industrialized synthesis method of blocking modification ketone-grouped resin.
Background technology
Polyaryletherketone is a kind of high performance engineering plastics, commercially can mainly contain polyetherketone (PEK) now, polyether-ether-ketone (PEEK), polyether ether ketone ketone (PEEKK), because they have thermotolerance, hot water resistance, wear resistance, resistance to fatigue, radioresistance, peel resistance, creep resistance, dimensional stability, shock-resistance, chemical proofing, nontoxic, the fire-retardant over-all properties waiting excellence, so for a long time at electronics, electrical equipment, machinery, automobile, medical apparatus, aircraft industry, the fields such as food-processing and not stickness paint are widely used.
But because its degree of crystallinity is high, processing temperature is high, and solubility property is poor, thus in order to obtain the low polyaryletherketone of degree of crystallinity, by molecular designing, introducing flexible group, falling low molecular degree of crystallinity, outside its original performance of guarantee, put forward high molecular solvability.Prepare polyaryletherketone as Chinese patent CN103113573A introducing bisphenol Z monomer and there is good solubility, thermostability.
Polyaryletherketone generally takes to add end-capping reagent or the excessive production technique of monomer, halogen end group, terminal hydroxy group, amino end group, metal end group and benzene end group is all contained in the ketone-grouped resin produced, as US Patent No. 5137988 (A) and Chinese patent CN2013102763332, containing terminal hydroxy group, amino end group or metal end group resin except be applied to useful in paint field except, should avoid in other Application Areass.Therefore, before reaction closes to an end, add rational end-capping reagent be very important, and adding along with end-capping reagent, the hot-work stability of product significantly improves.
From above-mentioned, existing ketone-grouped resin, degree of crystallinity is high, hot processing temperature is high, poorly soluble, and molecular weight distribution is wider, and reaction process difficulty controls, therefore, the present invention prepares the polyaryletherketone of the modification with good solubility and thermostability by adding suitable end-capping reagent and flexible group.
Summary of the invention
The present invention is intended to overcome above-mentioned prior art defect, and provide a kind of end-blocking effect better, during end-blocking, system depolymerization does not occur, and the deliquescent Industrialized synthesis method that the product ketone-grouped resin prepared has had.
The Industrialized synthesis method of a kind of blocking modification ketone-grouped resin of the present invention, comprises the following steps:
(1) polyreaction
With biphenol monomer, two fluorine monomer for reaction monomers, being solvent with high boiling organic solvent, take alkaline carbonate as salt forming agent;
In the reactor of nitrogen filled protection, start stirring after adding solvent, monomer and salt forming agent and be warming up to 130 DEG C ~ 140 DEG C, the solid content of system is 15% ~ 40%, after monomer all dissolves, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react after 1 ~ 2 hour, be warmed up to 240 DEG C ~ 270 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C polymerizations 1 ~ 4 hour again, add end-capping reagent, continue reaction 10-30 minute, obtain polymerization mucus;
Wherein, biphenol monomer comprises two classes: biphenol monomer is
in one;
Biphenol monomer 2 is a kind of in following monomer or combination:
R
1, R
2can be H, CH
3, (CH
2) nCH
3, (CH) n (CH
2) n (CH
3) n;
Two fluorine monomer is 4,4 '-difluoro benzophenone or 4,4 '-difluoro three benzophenone;
Molar weight more two fluorine monomer molar weight excessive 0.1% ~ 2% of described biphenol monomer, or two fluorine monomer molar weight excessive compared with biphenol monomer 0.1% ~ 2%;
The molar weight of described biphenol monomer 1 can be 1 ~ 0.01 with the ratio of biphenol monomer 2 molar weight;
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;
(2) aftertreatment
Polymerization mucus is ground into powder after water cooling, removes desolventizing and by-product salt with low boiling point organic solvent, deionized water boiling washing again after filtration, then namely obtain blocking modification ketone-grouped resin after drying.
Its molecular formula is as follows:
Wherein Ar is at least one in structural unit after biphenol monomer 2 removes bis-phenol.
I is modified polyetheretherketonefiber, is by 4,4 '-dihydroxy benaophenonel, 4, and 4 '-difluoro benzophenone and biphenol monomer 2 three kinds of monomer polymerizations form;
II is modified polyether ketone, is by Resorcinol, 4, and 4 '-dihydroxy benaophenonel and biphenol monomer 2 three kinds of monomer polymerizations form;
Iii is modified polyetheretherketonefiber ketone, is by Resorcinol, 4, and 4 '-difluoro three benzophenone and biphenol monomer 2 three kinds of monomer polymerizations form.
End-capping reagent of the present invention is the asymmetric aromatic ketone radical derivative of a class, and its structural formula is as follows:
Such end-capping reagent has different functions, both can react and end-blocking with terminal hydroxy group, simultaneously has again certain polymerizing power and prevents the function of system depolymerization.After the two benzophenone base end-blocking of F, polymkeric substance can be used as coupling agent, strengthens its modification purposes.In certain temperature range, such feature functionality group derivative has different substitutabilities, as 3,4 '-difluoro benzophenone, 4 '-position fluorine activity is obviously greater than 3-position fluorin radical, therefore 4 '-position fluorine participates in reaction fast plays end-blocking function, 3-position fluorin radical also has certain reactive behavior simultaneously, can participate in polyreaction, thus when ensure that end-blocking, system DeR does not occur.End-capping reagent adds before 10 – 20min before reaction terminates, and does not affect the polyreaction cycle.The add-on of end-capping reagent be bimodal molar content 0.1 ~ 5% between.
The molar weight of biphenol monomer of the present invention and two chlorine monomer controls in the scope of 1.001:1 ~ 1.2:1, when the more two fluorine monomer of molar weight of biphenol monomer excessive 0.1% ~ 2% time, produce the resin obtained and be mainly applicable to injection moulding.
When the molar weight of two fluorine monomer excessive compared with biphenol monomer 0.1% ~ 2% time, produce the resin obtained and be mainly applicable to coating.
The present invention compared with prior art, has following beneficial effect:
1) the present invention passes through the asymmetric aromatic ketone monomer of employing one class as end-capping reagent, it not only has good end-blocking effect, and can polyreaction be participated in, thus when ensure that end-blocking there is not depolymerization phenomenon in system, avoid adding again of LiCl, reduce the post-processing difficulty of production cost and system, preparation-obtained blocking modification ketone-grouped resin has high high-temp stability and good solubility simultaneously;
2) 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 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, and adopts domestic Na
2cO
3the polyaryletherketone product of explained hereafter and use import Na
2cO
3the product produced for salt forming agent is distinguished without color and luster.
3) the modified polyarylether ketone range of molecular weight distributions prepared by the present invention is narrow, and has good solubility and high thermal stability.
4) the modified polyarylether ketone solid content prepared by the present invention is 15% ~ 40%, preferably 20% ~ 30%, and the input of solvent can be reduced, reduce production cost.
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 200 liters of stainless steel cauldrons that nitrogen tube and high-efficiency stirrer are housed, first add 90.00KG sulfobenzide, 30.000KG4, 4 '-difluoro benzophenone, start to be warming up to 130-140 DEG C after 3.68KG bisphenol Z and 16.000KG sodium carbonate, after monomer all dissolves, 7.420KG Resorcinol is added again in system, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react 1 ~ 2 hour, be warmed up to 240 DEG C ~ 270 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C again, be polymerized 1 ~ 4 hour, add 283.7g3, 4 '-difluoro benzophenone, continue reaction 10-30 minute, mucus must be polymerized, 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 alcohol reflux and boil 1h, so 10 times repeatedly, 1 hour is boiled again with new deionized water, so 8 ~ 10 times repeatedly, in water, chloride ion content is till below 5ppm, by the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain containing bisphenol Z type polyether-ether-ketone (PEEK) resin.Concrete physical property is in table one.
Gained end-blocking is containing bisphenol Z type PEEK resin melting index M I=15.5g/10min (400.0 DEG C, 5KG, 5 minutes);
MI=15.0g/10min (400.0 DEG C, 5KG, 30 minutes).
Embodiment 2
With embodiment 1, except adding 3, outside 4 '-difluoro benzophenone to 340.3g, other conditions are identical.Concrete physical property is in table one.
Gained end-blocking is containing bisphenol Z type PEEK resin melting index M I=20.7g/10min (400.0 DEG C, 5KG, 5 minutes);
MI=20.0g/10min (400.0 DEG C, 5KG, 30 minutes).
Embodiment 3
In 200 liters of stainless steel cauldrons that nitrogen tube and high-efficiency stirrer are housed, first add 90.00KG sulfobenzide, 30.000KG4, 4 '-difluoro benzophenone, 3.68KG bisphenol Z, 28.000KG4, start to be warming up to 130-140 DEG C after 4 '-dihydroxy benaophenonel and 16.000KG sodium carbonate, after monomer all dissolves, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react 1 ~ 2 hour, be warmed up to 240 DEG C ~ 270 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C again, be polymerized 1 ~ 4 hour, add 283.7g3, 4 '-difluoro benzophenone, continue reaction 10-30 minute, mucus must be polymerized, 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 alcohol reflux and boil 1h, so 10 times repeatedly, 1 hour is boiled again with new deionized water, so 8 ~ 10 times repeatedly, in water, chloride ion content is till below 5ppm, by the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain containing bisphenol Z type polyetherketone (PEK) resin.Concrete physical property is in table one.
Gained end-blocking is containing bisphenol Z type PEK resin melting index M I=15.5g/10min (400.0 DEG C, 5KG, 5 minutes);
MI=15.0g/10min (400.0 DEG C, 5KG, 30 minutes).
Embodiment 4
With embodiment 3, except adding 3, outside 4 '-difluoro benzophenone to 340.3g, other conditions are identical.Concrete physical property is in table one.
Gained end-blocking is containing bisphenol Z type PEK resin melting index M I=20.7g/10min (400.0 DEG C, 5KG, 5 minutes);
MI=20.0g/10min (400.0 DEG C, 5KG, 30 minutes).
Embodiment 5
In 200 liters of stainless steel cauldrons that nitrogen tube and high-efficiency stirrer are housed, first add 90.00KG sulfobenzide, 44.200KG4, 4 '-difluoro triphen diketone, 3.68KG start to be warming up to 130-140 DEG C after bisphenol Z and 16.000KG sodium carbonate, after monomer all dissolves, 7.420KG Resorcinol is added again in system, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react 1 ~ 2 hour, be warmed up to 240 DEG C ~ 270 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C again, be polymerized 1 ~ 4 hour, add 283.7g3, 4 '-difluoro benzophenone, continue reaction 10-30 minute, mucus must be polymerized, 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 alcohol reflux and boil 1h, so 10 times repeatedly, 1 hour is boiled again with new deionized water, so 8 ~ 10 times repeatedly, in water, chloride ion content is till below 5ppm, by the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain containing bisphenol Z type polyether ether ketone ketone (PEEKK) resin.Concrete physical property is in table one.
Gained end-blocking is containing bisphenol Z type PEEKK resin melting index M I=15.5g/10min (400.0 DEG C, 5KG, 5 minutes);
MI=15.0g/10min (400.0 DEG C, 5KG, 30 minutes).
Embodiment 6
With embodiment 5, except strengthening 3, outside 4 '-difluoro benzophenone amount to 340.3g, other conditions are identical.Concrete physical property is in table one.
Gained end-blocking is containing bisphenol Z type PEEKK resin melting index M I=20.4g/10min (400.0 DEG C, 5KG, 5 minutes);
MI=20.0g/10min (400.0 DEG C, 5KG, 30 minutes).
Comparative example 1
In 200 liters of stainless steel cauldrons that nitrogen tube and high-efficiency stirrer are housed, first add 90.00KG sulfobenzide, 30.000KG4, start to be warming up to 130-140 DEG C after 4 '-difluoro benzophenone and 16.000KG sodium carbonate, after monomer all dissolves, 7.420KG Resorcinol is added again in system, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react 1 ~ 2 hour, be warmed up to 240 DEG C ~ 270 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C polymerizations 1 ~ 4 hour again, add 283.7g3,4 '-difluoro benzophenone; 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 alcohol reflux and boil 1h, so 10 times repeatedly, 1 hour is boiled again with new deionized water, so 8 ~ 10 times repeatedly, in water, chloride ion content is till below 5ppm, by the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain end capped polyether ether ketone (PEEK) virgin resin.
Gained end-blocking PEEK resin melting index M I=15.5g/10min (400.0 DEG C, 5KG, 5 minutes);
MI=15.0g/10min (400.0 DEG C, 5KG, 30 minutes).
Comparative example 2
In 200 liters of stainless steel cauldrons that nitrogen tube and high-efficiency stirrer are housed, first add 90.00KG sulfobenzide, 30.000KG4, 4 '-difluoro benzophenone, 28.000KG4, start to be warming up to 130-140 DEG C after 4 '-dihydroxy benaophenonel and 16.000KG sodium carbonate, after monomer all dissolves, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react 1 ~ 2 hour, be warmed up to 240 DEG C ~ 270 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C again, be polymerized 1 ~ 4 hour, add 283.7g3, 4 '-difluoro benzophenone, continue reaction 10-30 minute, mucus must be polymerized, 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 alcohol reflux and boil 1h, so 10 times repeatedly, 1 hour is boiled again with new deionized water, so 8 ~ 10 times repeatedly, in water, chloride ion content is till below 5ppm, by the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain end capped polyether ketone (PEK) resin.Concrete physical property is in table one.
Gained end-blocking PEK resin melting index M I=15.5g/10min (400.0 DEG C, 5KG, 5 minutes);
MI=15.0g/10min (400.0 DEG C, 5KG, 30 minutes).
Comparative example 3
In 200 liters of stainless steel cauldrons that nitrogen tube and high-efficiency stirrer are housed, first add 90.00KG sulfobenzide, 44.200KG4, start to be warming up to 130-140 DEG C after 4 '-difluoro triphen diketone and 16.000KG sodium carbonate, after monomer all dissolves, 7.420KG Resorcinol is added again in system, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react 1 ~ 2 hour, be warmed up to 240 DEG C ~ 270 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C again, be polymerized 1 ~ 4 hour, add 283.7g3, 4 '-difluoro benzophenone, continue reaction 10-30 minute, mucus must be polymerized, 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 alcohol reflux and boil 1h, so 10 times repeatedly, 1 hour is boiled again with new deionized water, so 8 ~ 10 times repeatedly, in water, chloride ion content is till below 5ppm, by the polymkeric substance vacuum-drying after filtering to moisture weight content lower than 0.5%, obtain end capped polyether ether ketone ketone (PEEKK) resin.Concrete physical property is in table one.
Gained end-blocking PEEKK resin melting index M I=15.5g/10min (400.0 DEG C, 5KG, 5 minutes);
MI=15.0g/10min (400.0 DEG C, 5KG, 30 minutes).
Table one embodiment 1 ~ 6 and comparative example 1 ~ 3 physical property table
Claims (10)
1. an Industrialized synthesis method for blocking modification ketone-grouped resin, is characterized in that, comprises the following steps:
(1) polyreaction
With biphenol monomer, two fluorine monomer for reaction monomers, being solvent with high boiling organic solvent, take alkaline carbonate as salt forming agent;
In the reactor of nitrogen filled protection, start stirring after adding solvent, reaction monomers and salt forming agent and be warming up to 130 DEG C ~ 140 DEG C, the solid content of system is 15% ~ 40%, after monomer all dissolves, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react after 1 ~ 2 hour, be warmed up to 240 DEG C ~ 270 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C polymerizations 1 ~ 4 hour again, add end-capping reagent, continue reaction 10-30 minute, obtain polymerization mucus;
Wherein, biphenol monomer comprises two classes: biphenol monomer 1 is
in one;
Biphenol monomer 2 is a kind of in following monomer or combination:
R
1, R
2can be H, CH
3, (CH
2) nCH
3, (CH) n (CH
2) n (CH
3) n;
Two fluorine monomer is 4,4 '-difluoro benzophenone or 4,4 '-difluoro three benzophenone;
Molar weight more two fluorine monomer molar weight excessive 0.1% ~ 2% of described biphenol monomer, or two fluorine monomer molar weight excessive compared with biphenol monomer 0.1% ~ 2%;
The molar weight of described biphenol monomer 1 can be 1 ~ 0.01 with the ratio of biphenol monomer 2 molar weight;
Described end-capping reagent is 3,4 '-difluoro benzophenone, 3-chloro-4-fluorine benzophenone, the fluoro-4-chlorobenzophenone of 3-and 3, the mixing of one or more in 4 '-dichloro benzophenone;
(2) aftertreatment
Polymerization mucus is ground into powder after water cooling, removes desolventizing and by-product salt with low boiling point organic solvent, deionized water boiling washing again after filtration, then after drying, namely obtain the polymkeric substance of blocking modification ketone-grouped resin.
2. the Industrialized synthesis method of a kind of blocking modification ketone-grouped resin according to claim 1, is characterized in that, described salt forming agent is one or several the mixture in potassium hydroxide, sodium hydroxide, sodium carbonate and salt of wormwood.
3. the Industrialized synthesis method of a kind of blocking modification ketone-grouped resin according to claim 1, is characterized in that, the molar weight of described end-capping reagent is the molar weight excessive 0.1% ~ 5% compared with biphenol monomer 1 or two fluorine monomer.
4. the Industrialized synthesis method of a kind of blocking modification ketone-grouped resin according to claim 1, is characterized in that, the molar weight of described biphenol monomer 2 accounts for 0% ~ 99.9% of biphenol monomer molar weight.
5. the Industrialized synthesis method of a kind of blocking modification ketone-grouped resin according to claim 1, is characterized in that, when 4,4 '-dihydroxy benaophenonel, 4, when 4 '-difluoro benzophenone and biphenol monomer 2 react, it is modified PE K resin.
6. the Industrialized synthesis method of a kind of blocking modification ketone-grouped resin according to claim 1, is characterized in that, when Resorcinol and 4, when 4 '-difluoro benzophenone and biphenol monomer 2 react, it is modified PE EK resin.
7. the Industrialized synthesis method of a kind of blocking modification ketone-grouped resin according to claim 1, is characterized in that, when Resorcinol and 4, when 4 '-difluoro three benzophenone and biphenol monomer 2 react, it is modified PE EKK resin.
8. the Industrialized synthesis method of a kind of blocking modification ketone-grouped resin according to claim 1, is characterized in that, described high boiling solvent is tetramethylene sulfone or sulfobenzide.
9. the Industrialized synthesis method of a kind of blocking modification ketone-grouped resin according to claim 1, is characterized in that, the solid content of system is 20% ~ 30%.
10. the Industrialized synthesis method of a kind of blocking modification ketone-grouped resin according to claim 1, is characterized in that, described low boiling point solvent is methyl alcohol, ethanol, acetone.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107936205A (en) * | 2017-12-14 | 2018-04-20 | 陈逊 | A kind of manufacture method of polyether-ether-ketone resin |
| CN108440751A (en) * | 2018-03-19 | 2018-08-24 | 吉林大学 | 2,6- dimethyl -4- (three (3,5- 3,5-dimethylphenyls) methyl) phenol, preparation and end group functional polyarylether |
| CN110184744A (en) * | 2019-05-09 | 2019-08-30 | 吉林大学 | A kind of crystal type poly(aryl ether ketone) nano fibrous membrane, preparation method and applications |
| CN114989416A (en) * | 2022-06-14 | 2022-09-02 | 中国科学院长春应用化学研究所 | Polyaryletherketone heat-shrinkable material and preparation method thereof |
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| DE4016711A1 (en) * | 1990-05-24 | 1991-11-28 | Bayer Ag | New thermoplastic aromatic polyether-sulphone¨ prods. - and polyether-ketone prods., contain units derived from 1,1-bis-4-hydroxyphenyl-3-alkyl-cyclohexane cpd. |
| CN104479089A (en) * | 2014-12-17 | 2015-04-01 | 江门市优巨新材料有限公司 | Industrial synthesis method of high-thermal-stability blocked binphenyl-structure-containing polyaryletherketone resin |
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| JPS63256620A (en) * | 1987-04-14 | 1988-10-24 | Asahi Chem Ind Co Ltd | Noncrystalline polyether ketone |
| DE4016711A1 (en) * | 1990-05-24 | 1991-11-28 | Bayer Ag | New thermoplastic aromatic polyether-sulphone¨ prods. - and polyether-ketone prods., contain units derived from 1,1-bis-4-hydroxyphenyl-3-alkyl-cyclohexane cpd. |
| CN104479089A (en) * | 2014-12-17 | 2015-04-01 | 江门市优巨新材料有限公司 | Industrial synthesis method of high-thermal-stability blocked binphenyl-structure-containing polyaryletherketone resin |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107936205A (en) * | 2017-12-14 | 2018-04-20 | 陈逊 | A kind of manufacture method of polyether-ether-ketone resin |
| CN108440751A (en) * | 2018-03-19 | 2018-08-24 | 吉林大学 | 2,6- dimethyl -4- (three (3,5- 3,5-dimethylphenyls) methyl) phenol, preparation and end group functional polyarylether |
| CN108440751B (en) * | 2018-03-19 | 2020-09-18 | 吉林大学 | 2, 6-dimethyl-4- (tri (3, 5-dimethylphenyl) methyl) phenol, preparation and end group functionalized polyarylether |
| CN110184744A (en) * | 2019-05-09 | 2019-08-30 | 吉林大学 | A kind of crystal type poly(aryl ether ketone) nano fibrous membrane, preparation method and applications |
| CN110184744B (en) * | 2019-05-09 | 2022-01-21 | 吉林大学 | Crystalline polyaryletherketone nanofiber membrane, and preparation method and application thereof |
| CN114989416A (en) * | 2022-06-14 | 2022-09-02 | 中国科学院长春应用化学研究所 | Polyaryletherketone heat-shrinkable material and preparation method thereof |
| CN114989416B (en) * | 2022-06-14 | 2023-10-10 | 中国科学院长春应用化学研究所 | Polyaryletherketone heat-shrinkable material and preparation method thereof |
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Application publication date: 20160217 |