CN1884330A - Synthesis method of ternary copolymer containing PEDEK and PEEK using sulfolane as solvent - Google Patents
Synthesis method of ternary copolymer containing PEDEK and PEEK using sulfolane as solvent Download PDFInfo
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- CN1884330A CN1884330A CN 200610016889 CN200610016889A CN1884330A CN 1884330 A CN1884330 A CN 1884330A CN 200610016889 CN200610016889 CN 200610016889 CN 200610016889 A CN200610016889 A CN 200610016889A CN 1884330 A CN1884330 A CN 1884330A
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Abstract
The invention relates to a method for preparing polyetheretherketone and polyetheretherketone terpolymer by using sulfolane. It comprises following steps: the mole number of 4, 4'- difluoro diphenyl ketone is more than that of eldopaque and diphenol by 0.1-1%, the solid content in reaction system is 15-30%; filling dimethylbenzene with its mass being 10-20% of that of organic solvent, stirring, heating, adding mixed salt of alkali metal carbonate when monomer is totally dissolved and the temperature is between 75 to 85 Deg. C, reacting at constant temperature 230-260 Deg. C for 1-3 hours, stopping reaction, pouring product into cold water, cooling and disintegrating and filtering, boiling solid product with deionized water for several times, drying refined powder material in baking box, and getting said final product.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of polar solvent that utilizes, particularly is that solvent prepares the method that contains biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer with the tetramethylene sulfone.
Background technology
A series of excellent comprehensive performances such as that the polyaryletherketone base polymer has is high temperature resistant, high strength, anti-irradiation.Its business-like the earliest kind is well-known polyether-ether-ketone (PEEK) resin of being introduced to the market at first in 1981 by Britain ICl company.Clearly the high-temperature solvent sulfobenzide in the patent of its preparation method.Because its polymer reaction temperature is more than 300 ℃, other solvent all can't adapt to.Afterwards the patent of Shen Qing relevant polyaryletherketone aspect none not all prolong and used this solvent.(preparation as 97101168.0 poly (aryl ether ketone) copolymers is also quoted two biphenyl contenting structure patents) also all is to adopt this traditional high-temperature solvent in our the obtained in the past relevant patent.
There is the unfavorable factor of following two aspects in this preparation method.The one, in the refinement treatment process of polymkeric substance, because solvent is water insoluble, must be earlier with organic solvent (as acetone, ethanol etc.) through repeatedly (being generally 8～10 times) the extrct sulfobenzide that desolvates, and then water is through repeatedly (generally also needing 8～10 times) extracting, to remove by-product salt, just can obtain qualified pure PEEK.Because long flow path consumes a large amount of acetone, ethanol, can increase substantially production cost undoubtedly like this; The 2nd, used a large amount of acetone, ethanol are inflammable, explosive hazardous chemical, not only will build between special hoolivan, also inevitably have hidden danger in transportation, storage, the use.
We are engaged in the research process of polyethersulfone (PES) resin at the same time, then adopt tetramethylene sulfone to make solvent always.Because tetramethylene sulfone and water dissolve each other,, obtain virgin resin with regard to solvent sulfolane and by-product salt being removed simultaneously fully so its treating process then needs only with a water extracting operation (generally also being 8～10 times).
Under the guidance of this thinking, we are through exploring repeatedly, finally finished the research of employing polar solvent tetramethylene sulfone synthesis of polyether-ether-ketone (PEEK) resin, afterwards, based on this, again through exploring repeatedly, having obtained again is the success of the synthetic biphenyl contenting structure polyaryletherketone terpolymer of solvent with the tetramethylene sulfone, thereby obtained can be solvent with tetramethylene sulfone, prepares the success of the poly (aryl ether ketone) copolymer of various different melting points according to the needs of different purposes, thereby has finished this patent.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method, be to be that polymerization solvent replaces the water-insoluble sulfobenzide solvent that generally adopts in the conventional patents adopting water-soluble tetramethylene sulfone, no longer need in the process for refining after polymerization is finished to adopt the organic solvent purification step thereby can reach, obtain containing biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer and only adopt water treatment can reach refining effect.
Be shown below in the reaction formula of the present invention:
By the terpolymer that contains biphenyl polyether ether ketone and polyether-ether-ketone of two kinds of different end groups of following formula prepared in reaction, that is:
By what (2-1) formula prepared be: the fluorine end group contains biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer.
By what (2-2) formula prepared be: the benzene end group contains biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer.
Wherein (2-2 ') formula is the pilot process of preparation (2-2) formula.
Wherein x can regulate and control arbitrarily between 0.01～0.4, and M represents K or Na, generally uses mixed salt, and it is adjustable between 10%～90% that wherein a kind of mole number of salt accounts for the ratio of mixed salt total mole number, and n is 〉=1 integer.
(2-1) synthetic method of formula product is: agitator is being housed, thermometer, logical nitrogen tube, in three mouthfuls of reaction flasks of reflux exchanger (ternary copolymerization system), add the organic solvent tetramethylene sulfone, add 4 in turn then, 4 '-difluoro benzophenone, Resorcinol, '-biphenyl diphenol, wherein 4, the mole number of 4 '-difluoro benzophenone is with respect to Resorcinol, '-biphenyl diphenol mole number and excessive 0.1～1%, the mole number of '-biphenyl diphenol accounts for Resorcinol, the '-biphenyl diphenol mole number and 1%～40%, its solid content (i.e. the ratio of the quality of the polymkeric substance of Sheng Chenging and solvent and polymer quality sum) is between 15～30%; Adding is to begin to stir behind the dimethylbenzene of organic solvent quality 10～20% again, and heat temperature raising is molten entirely at monomer, when system temperature rises to 75～85 ℃, adds a certain amount of K
2CO
3And Na
2CO
3Mixed salt.Two kinds of diphenol mole numbers of mole ratio sum of its add-on is after amount 1～5%, wherein K
2CO
3Mole number account for 10～90% of mixed salt total mole number, continue to heat up, dimethylbenzene begins azeotropic and refluxes, after treating that the whole azeotropic of water generation reaction are taken out of in the system, dimethylbenzene begins to clarify fully in the return line, at this moment stop to reflux and begin to steam dimethylbenzene, system temperature also constantly rises, isothermal reaction stopped reaction after 1～3 hour when treating that temperature reaches 230 ℃～260 ℃, pour resultant of reaction in cold water pulverizing filtration after the cooled and solidified, solid product is boiled repeatedly (8～10 times) repeatedly with the deionized water of 10 times of amounts, till solvent and by-product salt are all removed.Powder after will making with extra care is again dried in baking oven, promptly obtains the fluorine end group shown in the present invention (2-1) formula and contains biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer.
(2-2) synthetic method of formula product is: '-biphenyl diphenol, the mole dosage of Resorcinol and with respect to 4, the mole dosage of 4 '-difluoro benzophenone excessive 0.1%～1%, the mole number of '-biphenyl diphenol accounts for Resorcinol, the '-biphenyl diphenol mole number and 1%～40%, reaction is reacted with (2-1) formula early stage fully, when 230 ℃～260 ℃ isothermal reactions after 1～2 hour, adding is a '-biphenyl diphenol, Resorcinol is with respect to 4, single fluorine ketone of the several 2 times of amounts of 4 '-difluoro benzophenone molar excess, continue 0.2～1 hour stopped reaction of reaction again, thereafter refining and aftertreatment obtains benzene end group biphenyl contenting structure polyether-ether-ketone and the polyetheretherketoneterpolymer terpolymer shown in the present invention (2-2) formula fully with the post-processing step of (2-1) formula.
Embodiment
Embodiment 1
In three mouthfuls of reaction flasks that thermometer, logical nitrogen tube, condensation water trap, agitator are housed, add the 490g tetramethylene sulfone earlier, add 66.11g (0.303mol) 4 then in turn, 4 '-difluoro benzophenone
0.558g (0.003mol) '-biphenyl diphenol
32.70g (0.297mol) Resorcinol
Can about 86g polymkeric substance, its solid content (calculate do not comprise by-product salt with polymer content) is about 15%.After adding 74g dimethylbenzene (solvent 15%) again, stir, heating (reaction flask is put into the respective electrical hot jacket), when treating that it all dissolves and treating that temperature is raised to 80 ℃, add 25.73g (0.153mol, excessive 2%) K
2CO
3And 16.2g (0.153mol, excessive 2%) Na
2CO
3, continue again to heat up, when treating that temperature rises to 150 ℃, system begins azeotropic, and dimethylbenzene and water condensation are arranged in the water trap, the upper strata refluxing xylene, lower layer of water is constantly emitted, and when treating that water is recovered to theoretical amount, upper strata dimethylbenzene begins clear, continue to reflux 20 minutes again, begin to steam dimethylbenzene then from system, this moment, system temperature was constantly risen by heating, when temperature reaches 260 ℃, keep constant temperature, system viscosity carries out viscosity with polyreaction and constantly increases, and continues stopped reaction after 3 hours.Polymkeric substance mucus is injected cold water cool off, after treating fully to cool off, pulverize and filter with pulverizer.The gained powder is added water, in there-necked flask, boiled 1 hour, refilter.Boil so repeatedly 8 times, after solvent in material and by-product salt are all removed, get final product.
The 140 ℃ of oven dry 12 hours in baking oven of powder after refining make moisture content be lower than 0.5%, obtain fluorine end group biphenyl contenting structure polyether-ether-ketone and the polyetheretherketoneterpolymer terpolymer of x=0.01 shown in (2-1) formula at last.Record with DSC:
Tg＝144℃
Tm=335 ℃, suitable with PEEK.
Embodiment 2:
Change the ratio of components of embodiment 1, after adding the 490g tetramethylene sulfone, add 66.11g (0.303mol) 4 in turn, 4 '-difluoro benzophenone, 11.17g (0.06mol) '-biphenyl diphenol, 26.43g (0.24mol) Resorcinol, feeding quantity thereafter, order of addition(of ingredients) and reaction conditions and aftertreatment are refining all with embodiment 1.Then obtain fluorine end group biphenyl contenting structure polyether-ether-ketone and the polyetheretherketoneterpolymer terpolymer of x=0.2 shown in (2-1) formula, record with DSC:
Tg＝149℃
Tm＝298℃
Embodiment 3:
Change the ratio of components of embodiment 1, after adding the 490g tetramethylene sulfone, add 66.11g (0.303mol) 4 in turn, 4 '-difluoro benzophenone, 22.33g (0.120mol) '-biphenyl diphenol, 19.82g (0.180mol) Resorcinol, feeding quantity thereafter, order of addition(of ingredients) and reaction conditions and aftertreatment are refining all with embodiment 1.Then obtain fluorine end group biphenyl contenting structure polyether-ether-ketone and the polyetheretherketoneterpolymer terpolymer of x=0.4 shown in (2-1) formula, record with DSC:
Tg＝155℃
Tm＝302℃
Embodiment 4:
Change the ratio of components of embodiment 1, after adding the 490g tetramethylene sulfone, add 65.46g (0.30mol) 4 in turn, 4 '-difluoro benzophenone, 0.564g (0.00303mol) '-biphenyl diphenol, 33.03g (0.29997mol) Resorcinol, thereafter feeding quantity, order of addition(of ingredients) and reaction conditions are fully with embodiment 1, just isothermal reaction 1.5 hours, add the single fluorine ketone of 1.195g (0.006mol) and (promptly add Resorcinol, '-biphenyl diphenol is relative 4,2 times of amounts of 4 '-difluoro benzophenone molar excess number), continue reaction 0.5 hour, stopped reaction, refining and aftertreatment thereafter is fully with embodiment 1.Then obtain benzene end group biphenyl contenting structure polyether-ether-ketone and the polyetheretherketoneterpolymer terpolymer of x=0.01 shown in (2-2) formula, record with DSC:
Tg＝144℃
Tm=334 ℃, suitable with PEEK.
Embodiment 5:
With embodiment 4, after adding the 490g tetramethylene sulfone, add 65.46g (0.30mol) 4 in turn, 4 '-difluoro benzophenone, 11.72g (0.063mol) '-biphenyl diphenol, 26.42g (0.240mol) Resorcinol, feeding quantity thereafter, order of addition(of ingredients) and reaction conditions are fully with embodiment 4, then obtain benzene end group biphenyl contenting structure polyether-ether-ketone and the polyetheretherketoneterpolymer terpolymer of x=0.208 shown in (2-2) formula, record with DSC:
Tg＝150℃
Tm＝298℃
Embodiment 6:
With embodiment 4, after adding the 490g tetramethylene sulfone, add 65.46g (0.30mol) 4 in turn, 4 '-difluoro benzophenone, 22.33g (0.12mol) '-biphenyl diphenol, 20.15g (0.183mol) Resorcinol, feeding quantity thereafter, order of addition(of ingredients) and reaction conditions are fully with embodiment 4, then obtain benzene end group biphenyl contenting structure polyether-ether-ketone and the polyetheretherketoneterpolymer terpolymer of x=0.396 shown in (2-2) formula, record with DSC:
Tg＝155℃
Tm＝301℃
Embodiment 7:
With embodiment 4, change the usage ratio of '-biphenyl diphenol and Resorcinol, can obtain any benzene end group biphenyl contenting structure polyether-ether-ketone and polyetheretherketoneterpolymer terpolymer between the x=0.01-0.40 shown in (2-2) formula respectively.
Claims (4)
1, be the method that the synthetic fluorine end group of solvent contains biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer with the tetramethylene sulfone, its reaction formula is as follows:
Wherein x is between 0.01～0.4, and M represents K or Na, and n is 〉=1 integer.
2, as claimed in claim 1 is the method that the synthetic fluorine end group of solvent contains biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer with the tetramethylene sulfone, it is characterized in that: in ternary copolymerization system, add the organic solvent tetramethylene sulfone, add 4 in turn then, 4 '-difluoro benzophenone, Resorcinol, '-biphenyl diphenol, wherein 4, the mole number of 4 '-difluoro benzophenone is with respect to Resorcinol, '-biphenyl diphenol mole number and excessive 0.1～1%, the mole number of '-biphenyl diphenol account for Resorcinol, '-biphenyl diphenol mole number and 1%～40%, the reaction system solid content is 15～30%; Adding is to begin to stir behind the dimethylbenzene of organic solvent quality 10～20% again, and heat temperature raising is molten entirely at monomer, when system temperature rises to 75～85 ℃, adds the K of mole number with respect to Resorcinol, '-biphenyl diphenol mole number and excessive 1～5%
2CO
3And Na
2CO
3The mixed salt of alkaline carbonate, wherein K
2CO
3Mole number account for 10～90% of mixed salt total mole number, continue to heat up, dimethylbenzene begins azeotropic and refluxes, after treating that the whole azeotropic of water generation reaction are taken out of in the system, stop to reflux and begin to steam dimethylbenzene, isothermal reaction stopped reaction after 1～3 hour when treating that temperature reaches 230 ℃～260 ℃, pour resultant of reaction in cold water pulverizing filtration after the cooled and solidified, the deionized water of solid product with 10 times of amounts boiled repeatedly repeatedly, till solvent and by-product salt are all removed, powder after will making with extra care is again dried in baking oven, promptly obtains the fluorine end group and contains biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer.
3, be the method that the synthetic benzene end group of solvent contains biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer with the tetramethylene sulfone, its reaction formula is as follows:
Wherein x is between 0.01～0.4, and M represents K or Na, and n is 〉=1 integer.
4, as claimed in claim 3 is the method that the synthetic benzene end group of solvent contains biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer with the tetramethylene sulfone, it is characterized in that: in ternary copolymerization system, add the organic solvent tetramethylene sulfone, add 4 in turn then, 4 '-difluoro benzophenone, Resorcinol, '-biphenyl diphenol, the mole dosage of '-biphenyl diphenol, Resorcinol and with respect to 4, the mole dosage of 4 '-difluoro benzophenone excessive 0.1%～1%, the mole number of '-biphenyl diphenol account for Resorcinol, '-biphenyl diphenol mole number and 1%～40%, the reaction system solid content is 15～30%; Adding is to begin to stir behind the dimethylbenzene of organic solvent quality 10～20% again, and heat temperature raising is molten entirely at monomer, when system temperature rises to 75～85 ℃, adds the K of mole number with respect to Resorcinol, '-biphenyl diphenol mole number and excessive 1～5%
2CO
3And Na
2CO
3The mixed salt of alkaline carbonate, wherein K
2CO
3Mole number account for 10～90% of mixed salt total mole number, continue to heat up, dimethylbenzene begins azeotropic and refluxes, after treating that the whole azeotropic of water generation reaction are taken out of in the system, stop to reflux and begin to steam dimethylbenzene, 230 ℃～260 ℃ isothermal reactions are after 1～2 hour, adding is a '-biphenyl diphenol, Resorcinol is with respect to 4, single fluorine ketone of the several 2 times of amounts of 4 '-difluoro benzophenone molar excess, continue 0.2～1 hour stopped reaction of reaction again, pour resultant of reaction in cold water pulverizing filtration after the cooled and solidified, the deionized water of solid product with 10 times of amounts boiled repeatedly repeatedly, till solvent and by-product salt were all removed, the powder after will making with extra care was again dried in baking oven, promptly obtains the benzene end group and contains biphenyl polyether ether ketone and polyetheretherketoneterpolymer terpolymer.
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| CNB2006100168898A CN100389139C (en) | 2006-05-30 | 2006-05-30 | Synthesis method of ternary copolymer containing PEDEK and PEEK using sulfolane as solvent |
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| WO2010149040A1 (en) * | 2009-06-26 | 2010-12-29 | 金发科技股份有限公司 | Method for preparing polyaryletherketone-based copolymer by using quaternary copolymerization technology |
| WO2011075942A1 (en) * | 2009-12-23 | 2011-06-30 | 金发科技股份有限公司 | Method for preparing poly (diphenyl ether sulfone) and poly (diphenyl ether diphenyl sulfone) ternary polymer |
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| US4766197A (en) * | 1986-10-28 | 1988-08-23 | Amoco Corporation | Modified poly(aryl ether ketones) derived from biphenol |
| DE3901072A1 (en) * | 1989-01-16 | 1990-07-19 | Basf Ag | Process for the preparation of polyaryl ether ketones |
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| CN1050616C (en) * | 1997-02-26 | 2000-03-22 | 吉林大学 | Synthesizing for high-viscosity polyether-ether-ketone keto-resin containing biphenyl structure |
| CN1050615C (en) * | 1997-02-26 | 2000-03-22 | 吉林大学 | Synthesis of high viscosity polyether-ether-ketone resin having biphenyl structure |
| CN1141330C (en) * | 2001-02-02 | 2004-03-10 | 吉林大学 | Preparation of poly aromatic ether ketone liquid crystal copolymer |
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| WO2011075942A1 (en) * | 2009-12-23 | 2011-06-30 | 金发科技股份有限公司 | Method for preparing poly (diphenyl ether sulfone) and poly (diphenyl ether diphenyl sulfone) ternary polymer |
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| CN105593267A (en) * | 2013-09-27 | 2016-05-18 | 威格斯制造有限公司 | Polymeric material |
| CN109476837B (en) * | 2016-04-29 | 2021-12-21 | 索尔维特殊聚合物美国有限责任公司 | High flow polyetherimide compositions |
| WO2017186921A1 (en) * | 2016-04-29 | 2017-11-02 | Solvay Specialty Polymers Usa, Llc | High-flow polyetherimide compositions |
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