CN102924719A - Method for preparing polyether sulphone copolymer by adopting quadri-copolymerization technology - Google Patents
Method for preparing polyether sulphone copolymer by adopting quadri-copolymerization technology Download PDFInfo
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- CN102924719A CN102924719A CN2012104397798A CN201210439779A CN102924719A CN 102924719 A CN102924719 A CN 102924719A CN 2012104397798 A CN2012104397798 A CN 2012104397798A CN 201210439779 A CN201210439779 A CN 201210439779A CN 102924719 A CN102924719 A CN 102924719A
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Abstract
The invention discloses a method for preparing a polyether sulphone copolymer by adopting a quadri-copolymerization technology. The method comprises the steps of adding 4,4'-dichloro diphenyl sulfone, bis-(4-chlorobenzene sulfuryl) biphenyl, 4,4'-dyhydroxyl diphenyl sulfone and 4,4'-dihydroxybiphenyl in a reaction system, performing reaction of the four monomers and a salt-forming agent in the presence of a high temperature solvent at certain temperature and in a certain time to obtain a quadripolymer containing PES, PPSU, PESDS and PDEDS repetitive unit structures in molecular chains. The proportion of the four monomers can be adjusted according to demands, and a copolymer with macroscopic physical property the same as four binary homopolymers. The copolymer prepared by means of the quadri-copolymerization technology have a plurality of structures and can integrate advantages and disadvantages of structural units and endow resin with much performance, a processing window is wide, and various types of selection and adjustment can be provided according to customer requirements. The raw material cost is reduced, and the processing performance can be improved while the heat-resisting temperature is improved.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of method that adopts quaternary copolycondensation technology to prepare the polyether sulphone analog copolymer.
Background technology
The poly (ether ketone ketone) superpolymer is high temperature resistant, non-crystalline state, translucent special engineering plastics, excellent combination property, at commercialization PES, behind the PPSU, different Application Areass all proposes the service requirements of higher temperature classification gradually, keeps simultaneously its mechanical property not reduce or higher.
Under the promotion of the market requirement, Chinese patent CN200910217764.5 adopts the terpolymer technology to prepare the multipolymer that contains biphenyl sulfone ether structure of higher temperature classification by the ratio of components that changes two kinds of two chlorine monomers, on this basis, Chinese patent CN200910218086.4 has further finished the multipolymer that contains simultaneously biphenyl sulfone Biphenyl Ether structure.
Finish on the basis of above-mentioned terpolymer, we are again from molecular design theory, introduce various biphenyl structurals in the molecular chain, adjust sulfuryl, the ratio that ehter bond and biphenyl are strong, prepare the multipolymer that contains biphenyl sulfone ether structure of various high temperature resistant specifications by quaternary copolymerization technique, thereby finished the present invention.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts quaternary copolymerization technique to prepare the polyether sulphone analog copolymer.
The present invention is achieved by the following technical solutions:
In reaction system, add successively:
I:4,4 '-dichloro diphenyl sulfone:
,
II: two-(4-chlorobenzene sulfuryl) biphenyl:
,
III:4,4 '-dihydroxy diphenylsulphone:
,
IV:4,4 '-dihydroxybiphenyl:
,
Four kinds of monomers react the tetrapolymer that namely can obtain containing simultaneously in the molecular chain following structural unit with alkaline carbonate at certain temperature and time in the presence of high-temperature solvent:
I+III：PES：
，
I+IV：PPSU：
，
II+III：PESDS：
，
II+IV：PDEDS：
。
Its concrete preparation method comprises the steps:
A) thermometer is being housed, logical nitrogen tube, the condensation water trap, in the there-necked flask of agitator, add successively 4,4 '-dichloro diphenyl sulfone, two-(4-chlorobenzene sulfuryl) biphenyl, 4,4 '-dihydroxy diphenylsulphone, 4,4 '-dihydroxybiphenyl, add again the stirring of high temperature organic solvent and be warming up to 80-110 ℃ of dissolved monomer transparent to solution, the salt forming agent that adds the total excessive 5-20% of relative terminal hydroxy group monomer molar, be incorporated as subsequently solvent volume 10-30%(v/v) dimethylbenzene, continue to stir and to be warming up to salt-forming reaction and to begin down, holding temperature is 200-210 ℃ scope, when the collection water yield during near theoretical value, continued again backflow 10-30 minute, do not have the globule to fall when observing, be expressed as reactant salt and finish, redistillation is also emitted dimethylbenzene, be warming up to gradually 225-240 ℃ of beginning polyreaction, constant temperature 2-4 hour;
B) stop to stir and heating, material slowly poured into be cooled to white strip solid in the deionized water, be broken into again Powdered with pulverizer, boiled 1 hour with deionized water, filtration is anhydrated minute, so repeatedly, until filtrate is detected constant muddiness with Silver Nitrate, after filtering polymkeric substance vacuum-drying to constant weight, namely get the tetrapolymer that contains simultaneously PES, PPSU, PESDS and PDEDS repeat unit structure in the molecular chain.
Described high temperature organic solvent is tetramethylene sulfone, dimethyl sulfoxide (DMSO) or n-formyl sarcolysine base pyrrolidone.
Described salt forming agent is alkali, alkaline carbonate, alkali metal hydrocarbonate or its mixture, is preferably KOH, NaOH, K
2CO
3, Na
2CO
3, KHCO
3, NaHCO
3, or its mixture.
Of the present invention 4,4 '-dichloro diphenyl sulfone, two-(4-chlorobenzene sulfuryl) biphenyl, 4,4 '-dihydroxy diphenylsulphone, 4, the add-on of 4 '-dihydroxybiphenyl only need satisfy halogen end group mole total amount than terminal hydroxy group mole total amount excessive getting final product a little, preferred halogen end group mole total amount more preferably is excessive 0.5%-3.5% than the excessive 0.1%-5.0% of terminal hydroxy group mole total amount.
The present invention can be as required by 4,4 '-dichloro diphenyl sulfone, two-(4-chlorobenzene sulfuryl) biphenyl, 4,4 '-dihydroxy diphenylsulphone, 4, the regulation and control of four kinds of monomer ratios of 4 '-dihydroxybiphenyl, prepare macroscopic properties and four kinds of binary homopolymer, be polyethersulfone (PES), poly biphenyl ether sulfone (PPSU), poly-biphenyl sulfone ether sulfone (PESDS), the suitable multipolymer of poly biphenyl ether biphenyl sulfone (PDEDS), the second-order transition temperature of this analog copolymer can be regulated arbitrarily between 220 ℃ to 281 ℃.
The present invention compared with prior art has following advantage:
1) the present invention adopts the structure of multipolymer of quaternary copolymerization technique preparation more, gives resin more performance, process window
Wider, can multiple choices be arranged and adjust leeway according to client's needs;
2) reduce raw materials cost, two-(4-chlorobenzene sulfuryl) biphenyl price is high, apparent availability is little, and 4,4 '-dichloro diphenyl sulfone price is low, and apparent availability is large, under the suitable prerequisite of resin property, 4,4 '-dichloro diphenyl sulfone Partial Replacement is two-and (4-chlorobenzene sulfuryl) biphenyl obviously can reduce cost of material;
3) relative merits that the quarternary copolymerized system of the present invention preparation can soft each structural unit can be improved processing characteristics again when improving heat resisting temperature.
Embodiment
Further specify the present invention below by embodiment, following examples are the better embodiment of the present invention, but embodiments of the present invention are not subjected to the restriction of following embodiment.
Embodiment 1:
Thermometer is being housed, logical nitrogen tube, the condensation water trap, add successively 44.37g(0.1545mol in the there-necked flask of agitator, the terminal hydroxy group monomer molar total excessive 1.5% relatively) 4,4 '-dichloro diphenyl sulfone, 75.51g(0.15mol) two-(4-chlorobenzene sulfuryl) biphenyl, 37.54g(0.15mol) 4,4 '-dihydroxy diphenylsulphone, 27.93(0.15mol) 4,4 '-dihydroxybiphenyl, add again the 490.3g solvent sulfolane, stir and to be warming up to 100 ℃ of dissolved monomer transparent to solution, add 34.98g(0.33mol, the terminal hydroxy group monomer molar total excessive 10% relatively) anhydrous sodium carbonate, add subsequently 70mL dimethylbenzene, being warming up to salt-forming reaction under continuing to stir begins, the protected air-blowing of azeotrope that the water of producing in the system and dimethylbenzene generate goes out that condensation drips to layering in the water trap to the prolong, and the dimethylbenzene on upper strata is back to again in the system; Holding temperature is 200-210 ℃ scope, when collecting the water yield near theoretical value (5.4g), continue again to reflux 20 minutes, not observing has the globule to fall, and proves that salify is complete, and redistillation is also emitted dimethylbenzene, be warming up to gradually 230 ℃ of beginning polyreactions, constant temperature 3 hours, the agitator motor moment of torsion is constant, and the system viscosity substantially constant is described; Stop to stir and heating, material slowly poured into be cooled to white strip solid in the deionized water, be broken into again Powdered with pulverizer, boiled 1 hour with deionized water, filter and to anhydrate minute, so repeat 10 times, until filtrate is detected constant muddiness with Silver Nitrate, illustrate that the by-product salt eccysis is clean in the powder, after filtering polymkeric substance is dried to constant weight with 120 ℃ of vacuum drying ovens, namely get tetrapolymer.
Survey its Tg=259.9 ℃ with DSC.
Embodiment 2:
In the reaction kit identical with embodiment 1, add respectively 143.58g(0.5mol by the same operation order, the terminal hydroxy group monomer molar total excessive 1.0% relatively) 4,4 '-dichloro diphenyl sulfone, 2.52g(0.005mol) two-(4-chlorobenzene sulfuryl) biphenyl, 123.89g(0.495mol) 4,4 '-dihydroxy diphenylsulphone, 0.93(0.005mol) 4,4 '-dihydroxybiphenyl, add again the 547.0g solvent sulfolane, stir and to be warming up to 80 ℃ of dissolved monomer transparent to solution, add 58.3g(0.55mol, the terminal hydroxy group monomer molar total excessive 10% relatively) anhydrous sodium carbonate, add subsequently 80mL dimethylbenzene, step namely gets tetrapolymer according to embodiment 1 operation afterwards.
Survey its Tg=226.1 ℃ with DSC, PES is suitable with polyethersulfone.
Embodiment 3:
In the reaction kit identical with embodiment 1, add respectively 143.58g(0.5mol by the same operation order, the terminal hydroxy group monomer molar total excessive 0.5% relatively) 4,4 '-dichloro diphenyl sulfone, 1.26g(0.0025mol) two-(4-chlorobenzene sulfuryl) biphenyl, 1.25g(0.005mol) 4,4 '-dihydroxy diphenylsulphone, 92.17(0.495mol) 4,4 '-dihydroxybiphenyl, add again the 558.9g solvent sulfolane, stir and to be warming up to 80 ℃ of dissolved monomer transparent to solution, add 63.6g(0.6mol, the terminal hydroxy group monomer molar total excessive 10% relatively) anhydrous sodium carbonate, add subsequently 80mL dimethylbenzene, step namely gets tetrapolymer according to embodiment 1 operation afterwards.
Survey its Tg=220.6 ℃ with DSC, PPSU is suitable with PPSU.
Embodiment 4:
In the reaction kit identical with embodiment 1, add respectively 1.44g(0.005mol by the same operation order) 4,4 '-dichloro diphenyl sulfone, 256.74g(0.51mol, the terminal hydroxy group monomer molar total excessive 3.0% relatively) two-(4-chlorobenzene sulfuryl) biphenyl, 123.89g(0.495mol) 4,4 '-dihydroxy diphenylsulphone, 0.93(0.005mol) 4,4 '-dihydroxybiphenyl, add again the 796.7g solvent sulfolane, stir and to be warming up to 110 ℃ of dissolved monomer transparent to solution, add 55.65g(0.525mol, the terminal hydroxy group monomer molar total excessive 5% relatively) anhydrous sodium carbonate, add subsequently 100mL dimethylbenzene, step namely gets the poly-biphenyl sulfone ether sulfone of tetrapolymer according to embodiment 1 operation afterwards.
Survey its Tg=271.8 ℃ with DSC.
Embodiment 5:
In the reaction kit identical with embodiment 1, add respectively 1.44g(0.005mol by the same operation order) 4,4 '-dichloro diphenyl sulfone, 251.71g(0.5mol, the terminal hydroxy group monomer molar total excessive 1.0% relatively) two-(4-chlorobenzene sulfuryl) biphenyl, 1.25g(0.005mol) 4,4 '-dihydroxy diphenylsulphone, 92.17(0.495mol) 4,4 '-dihydroxybiphenyl, add again the 808.7g solvent sulfolane, stir and to be warming up to 110 ℃ of dissolved monomer transparent to solution, add 58.3g(0.55mol, the terminal hydroxy group monomer molar total excessive 10% relatively) anhydrous sodium carbonate, add subsequently 100mL dimethylbenzene, step namely gets tetrapolymer poly biphenyl ether biphenyl sulfone according to embodiment 1 operation afterwards.
Survey its Tg=280.3 ℃ with DSC.
Embodiment 6:
In the reaction kit identical with embodiment 1, add respectively 66.87g(0.232875mol by the same operation order, the terminal hydroxy group monomer molar total excessive 3.5% relatively) 4,4 '-dichloro diphenyl sulfone, 39.08g(0.077625mol) two-(4-chlorobenzene sulfuryl) biphenyl, 74.33g(0.297mol) 4,4 '-dihydroxy diphenylsulphone, 0.56(0.003mol) 4,4 '-dihydroxybiphenyl, add again the 469g solvent sulfolane, stir and to be warming up to 110 ℃ of dissolved monomer transparent to solution, add 35.0g(0.33mol, the terminal hydroxy group monomer molar total excessive 10% relatively) anhydrous sodium carbonate, add subsequently 70mL dimethylbenzene, step namely gets tetrapolymer according to embodiment 1 operation afterwards.
Survey its Tg=247.4 ℃ with DSC.
Embodiment 7:
In the reaction kit identical with embodiment 1, add respectively 19.02g(0.06625mol by the same operation order, the terminal hydroxy group monomer molar total excessive 1.5% relatively) 4,4 '-dichloro diphenyl sulfone, 94.39g(0.1875mol) two-(4-chlorobenzene sulfuryl) biphenyl, 61.94g(0.2475mol) 4,4 '-dihydroxy diphenylsulphone, 0.46(0.0025mol) 4,4 '-dihydroxybiphenyl, add again 464g solvent n-formyl sarcolysine base pyrrolidone, stir and to be warming up to 100 ℃ of dissolved monomer transparent to solution, add 29.15g(0.33mol, the terminal hydroxy group monomer molar total excessive 10% relatively) anhydrous sodium carbonate, add subsequently 100mL dimethylbenzene, step is according to embodiment 1 operation afterwards, wherein be with water temp to maintain 180-190 ℃, polymerization temperature finally obtains tetrapolymer at 198-200 ℃.
Survey its Tg=267.2 ℃ with DSC.
Claims (8)
1. adopt quaternary copolymerization technique to prepare the method for polyether sulphone analog copolymer, it is characterized in that, comprise the steps:
A) thermometer is being housed, logical nitrogen tube, the condensation water trap, in the there-necked flask of agitator, add successively 4,4 '-dichloro diphenyl sulfone, two-(4-chlorobenzene sulfuryl) biphenyl, 4,4 '-dihydroxy diphenylsulphone, 4,4 '-dihydroxybiphenyl, add again the stirring of high temperature organic solvent and be warming up to 80-110 ℃ of dissolved monomer transparent to solution, the salt forming agent that adds the total excessive 5-20% of relative terminal hydroxy group monomer molar, be incorporated as subsequently solvent volume 10-30%(v/v) dimethylbenzene, continue to stir and to be warming up to salt-forming reaction and to begin down, holding temperature is 200-210 ℃ scope, when the collection water yield during near theoretical value, continued again backflow 10-30 minute, do not have the globule to fall when observing, be expressed as reactant salt and finish, redistillation is also emitted dimethylbenzene, be warming up to gradually 225-240 ℃ of beginning polyreaction, constant temperature 2-4 hour;
B) stop to stir and heating, material slowly poured into be cooled to white strip solid in the deionized water, be broken into again Powdered with pulverizer, boiled 1 hour with deionized water, filter and to anhydrate minute, so repeatedly, until filtrate is detected constant muddiness with Silver Nitrate, after filtering polymkeric substance vacuum-drying to constant weight, namely get the tetrapolymer that contains simultaneously PES, PPSU, PESDS and PDEDS repeat unit structure in the molecular chain
PES：
，
PPSU：
，
PESDS：
，
PDEDS：
。
2. employing quaternary copolymerization technique as claimed in claim 1 prepares the method for polyether sulphone analog copolymer, it is characterized in that, described high temperature organic solvent is tetramethylene sulfone, dimethyl sulfoxide (DMSO) or n-formyl sarcolysine base pyrrolidone.
3. employing quaternary copolymerization technique as claimed in claim 1 prepares the method for polyether sulphone analog copolymer, it is characterized in that, described salt forming agent is alkali, alkaline carbonate, alkali metal hydrocarbonate or its mixture.
4. employing quaternary copolymerization technique as claimed in claim 3 prepares the method for polyether sulphone analog copolymer, it is characterized in that, described salt forming agent is KOH, NaOH, K
2CO
3, Na
2CO
3, KHCO
3, NaHCO
3, or its mixture.
5. employing quaternary copolymerization technique as claimed in claim 1 prepares the method for polyether sulphone analog copolymer, it is characterized in that, described 4,4 '-dichloro diphenyl sulfone, two-(4-chlorobenzene sulfuryl) biphenyl, 4, it is more excessive than terminal hydroxy group mole total amount that 4 '-dihydroxy diphenylsulphone, 4, the add-on of 4 '-dihydroxybiphenyl satisfy halogen end group mole total amount.
6. employing quaternary copolymerization technique as claimed in claim 5 prepares the method for polyether sulphone analog copolymer, it is characterized in that, described 4,4 '-dichloro diphenyl sulfone, two-(4-chlorobenzene sulfuryl) biphenyl, 4,4 '-dihydroxy diphenylsulphone, 4, the add-on of 4 '-dihydroxybiphenyl satisfy halogen end group mole total amount than the excessive 0.1%-5.0% of terminal hydroxy group mole total amount.
7. employing quaternary copolymerization technique as claimed in claim 6 prepares the method for polyether sulphone analog copolymer, it is characterized in that, described 4,4 '-dichloro diphenyl sulfone, two-(4-chlorobenzene sulfuryl) biphenyl, 4,4 '-dihydroxy diphenylsulphone, 4, the add-on of 4 '-dihydroxybiphenyl satisfy halogen end group mole total amount than the excessive 0.5%-3.5% of terminal hydroxy group mole total amount.
8. employing quaternary copolymerization technique as claimed in claim 1 prepares the method for polyether sulphone analog copolymer, it is characterized in that, the second-order transition temperature of described tetrapolymer is between 220 ℃ to 281 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105504263A (en) * | 2015-12-30 | 2016-04-20 | 金发科技股份有限公司 | Composition of sulfone polymer as well as preparation method and application thereof |
| CN105601926A (en) * | 2015-06-08 | 2016-05-25 | 四川理工学院 | Preparing method for polyethylene sulfone resin |
| CN108285535A (en) * | 2018-01-30 | 2018-07-17 | 上海帕斯砜材料科技有限公司 | A kind of ternary, the synthetic method of multi-component copolymer polysulfone resin |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1844196A (en) * | 2006-03-29 | 2006-10-11 | 长春吉大高科技股份有限公司 | Process for preparing copolymer containing biphenyl polyether ether-sulfone and poly(ether sulfone) |
| CN101580583A (en) * | 2009-06-26 | 2009-11-18 | 吴忠文 | Method for preparing poly aryl ether ketone copolymers by adopting quaternary copolymerization technique |
| CN101704951A (en) * | 2009-10-27 | 2010-05-12 | 金发科技股份有限公司 | Method for preparing terpolymer of poly-diphenyl sulphone ether and polyether sulfone |
| CN101735459A (en) * | 2009-12-23 | 2010-06-16 | 金发科技股份有限公司 | Method for preparing poly(biphenyl ether sulfone) and poly(biphenyl ether biphenyl sulfone) terpolymer |
| CN102167811A (en) * | 2011-01-18 | 2011-08-31 | 长春博文特塑技术咨询服务有限责任公司 | Method for preparing polyether benzophenone copolymers by adopting quaternionic copolycondensation technology |
-
2012
- 2012-11-07 CN CN201210439779.8A patent/CN102924719B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1844196A (en) * | 2006-03-29 | 2006-10-11 | 长春吉大高科技股份有限公司 | Process for preparing copolymer containing biphenyl polyether ether-sulfone and poly(ether sulfone) |
| CN101580583A (en) * | 2009-06-26 | 2009-11-18 | 吴忠文 | Method for preparing poly aryl ether ketone copolymers by adopting quaternary copolymerization technique |
| CN101704951A (en) * | 2009-10-27 | 2010-05-12 | 金发科技股份有限公司 | Method for preparing terpolymer of poly-diphenyl sulphone ether and polyether sulfone |
| CN101735459A (en) * | 2009-12-23 | 2010-06-16 | 金发科技股份有限公司 | Method for preparing poly(biphenyl ether sulfone) and poly(biphenyl ether biphenyl sulfone) terpolymer |
| CN102167811A (en) * | 2011-01-18 | 2011-08-31 | 长春博文特塑技术咨询服务有限责任公司 | Method for preparing polyether benzophenone copolymers by adopting quaternionic copolycondensation technology |
Cited By (8)
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|---|---|---|---|---|
| CN105601926A (en) * | 2015-06-08 | 2016-05-25 | 四川理工学院 | Preparing method for polyethylene sulfone resin |
| CN105601926B (en) * | 2015-06-08 | 2018-10-12 | 四川理工学院 | The preparation method of polyphenylene sulfone resins |
| 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 |
| 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 |
| CN105504263A (en) * | 2015-12-30 | 2016-04-20 | 金发科技股份有限公司 | Composition of sulfone polymer as well as preparation method and application thereof |
| CN105504263B (en) * | 2015-12-30 | 2018-07-27 | 金发科技股份有限公司 | A kind of composition of sulfone polymer and the preparation method and application thereof |
| CN108285535A (en) * | 2018-01-30 | 2018-07-17 | 上海帕斯砜材料科技有限公司 | A kind of ternary, the synthetic method of multi-component copolymer polysulfone resin |
| CN108285535B (en) * | 2018-01-30 | 2023-11-10 | 上海帕斯砜材料科技有限公司 | Synthesis method of ternary and polynary copolymerized polysulfone resin |
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