CN105482050A - Method for preparing polyether ether ketone - Google Patents
Method for preparing polyether ether ketone Download PDFInfo
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- CN105482050A CN105482050A CN201610052104.6A CN201610052104A CN105482050A CN 105482050 A CN105482050 A CN 105482050A CN 201610052104 A CN201610052104 A CN 201610052104A CN 105482050 A CN105482050 A CN 105482050A
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- polyether
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
Abstract
The invention belongs to the technical field of high molecular materials, and particularly relates to a method for preparing polyether ether ketone. The method for preparing the polyether ether ketone includes the steps of a polymerization reaction; precipitation treatment of a reaction product, wherein after the polymerization reaction is finished, reaction temperature is reduced to 210-230 DEG C, stirring is accelerated to enable a polyether ether ketone system to be evenly polymerized, trimethylbenzene is added when the temperature in a reactor is stable, the reaction system is stirred to be even, and then the reaction temperature is reduced to 90-110 DEG C to enable all polyether ether ketone to be evenly crystallized and polymerized; purification treatment, wherein a dehydrating agent and diphenyl sulfone are sequentially recycled from white slurry obtained through precipitation treatment, and then the polyether ether ketone can be obtained through washing and drying. By means of the method, the problem that in the existing production process of the polyether ether ketone, as a product needs to be smashed, technological processes are discontinuous is solved, and meanwhile the problem that in a traditional technology, as inorganic salt particles wrapped by product particles can not be completely washed away, a high molecular product is not high in purity is solved.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly a kind of preparation method of polyether-ether-ketone resin.
Background technology
The synthetic technology of current polyether-ether-ketone resin is comparatively ripe, what major part manufacturer often adopted after polyether-ether-ketone resin building-up reactions terminates is pulverize after product being released gradually polymeric kettle cooling, obtains powder so that subsequent recovery solvent and by-product salt after pulverizing.Such production technique has the following disadvantages: one is be difficult to automated operation, and on-the-spot pollution is large, lower batch of the easy remaining influence of product production in polymeric kettle; Two is obtain powder particles size after pulverizing to be difficult to evenly, and the catalyzer of synthesis and by product are still partially encased in polymeric inner and are difficult to purifying, cause product purity not high, limit the range of application of resin.Three is that mechanical disintegration understands the complete of saboteur's chain unavoidably, causes the reduction of product performance; Four is can not reduce temperature in the kettle for preventing product from luming in product blowing process, and the material of not releasing can continue reaction, and the polymeric kettle in actual production tonne causes the blowing time often longer, and this just easily causes molecular weight of product wider distribution.And the size of the purity of polymkeric substance and molecular weight, distribution often determine performance and the Application Areas of product.The stable of molecular weight product and high purity are also made every effort in the production of polymkeric substance.
ZL201110408150.2 patent of invention discloses a kind of preparation method of cyano group polyether ketone resin, and it has synthesized a kind of cyano group polyether ketone resin with brand-new reaction raw materials, adopts flash evaporation technology recycling design and impels powder product.ZL201110408150.2 patent of invention solves the difficult problem that polymer product needs to pulverize, and reduce solvent recuperation energy consumption, but 3 deficiencies below this technology also exists in actual mechanical process: is very high to whipping device requirement, stir resistance in solvent evaporates process can be multiplied, easily occur the phenomenon of motor stalling; Two is after flash distillation terminates, and because process is high temperature, is difficult to be washed off by the organic solvent of acetone and so on after organic impurity carbonization residual in polymkeric substance or oxidation; Three is that polymkeric substance is difficult to become uniform powder, and there is larger particles shape product affects later-period purification.
Summary of the invention
For above-mentioned defect, the invention provides a kind of preparation method of polyether-ether-ketone resin, the method overcome product in existing polyether-ether-ketone resin production process to need to pulverize and the discontinuous problem of technical process that causes, the inorganic salt particle simultaneously also overcoming product particle parcel in traditional technology does not wash clean clearly the problem causing macromolecule product purity not high, for amorphous polymer production field provides a kind of method of new product precipitating and purifying, simplify Production Flow Chart.
Technical scheme of the present invention:
The invention provides a kind of preparation method of polyether-ether-ketone resin, comprise precipitating and the purification process of polyreaction and reaction product, wherein:
Polyether-ether-ketone polyreaction Raw and mol ratio thereof are: 4,4 '-difluorodiphenyl Jia Tong ︰ Dui Ben bis-Fen ︰ Cuiization Ji ︰ bis-Ben Feng ︰ dewatering agent=1 ︰ 1 ︰ 1.2 ︰ 4.1 ~ 4.5 ︰ 1.4 ~ 1.6;
The precipitating of reaction product is treated to: polyreaction terminates first temperature of reaction to be down to 210 ~ 230 DEG C afterwards, accelerating stirring makes polyether-ether-ketone resin system evenly separate out, trimethylbenzene is added after reactor temperature is stable, be stirred to reaction system evenly after again temperature of reaction is down to 90 ~ 110 DEG C, make the whole homogeneously crystallized precipitation of polyether-ether-ketone resin, reaction system is in the white slurry of flowing; The add-on of trimethylbenzene is 1.3 ~ 1.5 times of sulfobenzide quality;
Purification process after precipitating: white slurry precipitating process obtained reclaims dewatering agent, solvent successively, then be less than 0.1 ‰ to its ash content namely obtain polyether-ether-ketone resin by washing.
Described polyether-ether-ketone resin polyreaction is: with water trap, sulfobenzide and dewatering agent is added in the reactor of agitator and heating unit, pass into rare gas element, open and stir, temperature of reaction first rises to 130 ~ 160 DEG C, 4 are added successively after sulfobenzide all dissolves, 4 '-difluoro benzophenone and Resorcinol, catalyzer is added after monomer dissolves, be warming up to the water that 200 ~ 240 DEG C are carried out releasing from water trap after 1.5 ~ 2.5 hours reflux react dewatering agent and generation again, final reaction temperature rises to 295 ~ 320 DEG C of polyreactions and terminates polyreaction in 2 ~ 3 hours, polymer reaction raw material and mol ratio thereof are: 4,4 '-difluorodiphenyl Jia Tong ︰ Dui Ben bis-Fen ︰ Cuiization Ji ︰ bis-Ben Feng ︰ dewatering agent=1 ︰ 1 ︰ 1.2 ︰ 4.1 ~ 4.5 ︰ 1.4 ~ 1.6.
In the present invention, described catalyzer is at least one in Anhydrous potassium carbonate or anhydrous sodium carbonate; Described dewatering agent is at least one in toluene, dimethylbenzene or trimethylbenzene.
Further, in above-mentioned precipitating process, alr mode is the composite stirring form that the stirring of ribbon screw or frame add paddle.
Further, in above-mentioned purification process, the recovery method of dewatering agent is: white slurry reclaims dewatering agent by underpressure distillation, obtains the polyether-ether-ketone powder containing sulfobenzide and by-product salt; Wherein, vacuum distillation temperature is 90 ~ 110 DEG C, and vacuum tightness is less than 0.09MPa.
Further, in above-mentioned purification process, the recovery method of solvent is: adopt the mode of organic extraction to reclaim sulfobenzide in the polyether-ether-ketone powder containing sulfobenzide and by-product salt, extraction temperature is 50 ~ 60 DEG C, at least extract 6 times, each extraction time 1 ~ 2 hour, extraction agent is acetone or alcohol, and the addition of extraction agent is 8 ~ 12 times of polyether-ether-ketone quality.
Further, in above-mentioned purification process, carrying out washing treatment is: remove the polyether-ether-ketone powder after solvent also containing by-product salt and the complete catalyzer alkaline carbonate of unreacted, deionized water is adopted to wash in this powder, temperature of washing water 80 ~ 100 DEG C, wash at least 4 times, each washing time 1 ~ 2 hour.
Further, in residing purification process, extraction after containing sulfobenzide extraction agent liquid through distillation after obtain sulfobenzide and extraction agent respectively, sulfobenzide and extraction agent re-refine respectively Posterior circle use.
The polyether-ether-ketone resin prepared by the inventive method is adopted to be thermoplastic resin, its second-order transition temperature 143 DEG C, the fusing point of product 343 DEG C, melting index 5 ~ 15 (360 DEG C, 10Kg), ash content is less than 0.1 ‰ (existing polyether-ether-ketone ash content is generally more than 0.2 ‰).
Beneficial effect of the present invention:
Instant invention overcomes product in existing polyether-ether-ketone resin production process to need to pulverize and the discontinuous problem of technical process that causes, the inorganic salt particle simultaneously also overcoming product particle parcel in traditional technology does not wash clean clearly and causes the problem (existing polyether-ether-ketone ash content is generally more than 0.2 ‰) that macromolecule product purity is not high, for field of polymer technology provides a kind of new purifying products method, simplify Production Flow Chart.The method makes polyether-ether-ketone resin naturally separate out in a solvent, material becomes powder pulpous state simultaneously, be conducive to carrying out mass transport and next step process, this does not just destroy the macromolecular chain of polyether-ether-ketone resin while solving purifying products and solvent recuperation, ensure that purity and the performance of product.Adopt that the polyether-ether-ketone resin purity prepared by preparation method of the present invention is high, stable performance, can be applicable to the fields such as aerospace, electronics, machinery, medical treatment, chemical industry.
Embodiment
The invention provides a kind of preparation method of polyether-ether-ketone resin, comprise precipitating and the purification process of polyreaction and reaction product, wherein:
Polyether-ether-ketone polyreaction Raw and mol ratio thereof are: 4,4 '-difluorodiphenyl Jia Tong ︰ Dui Ben bis-Fen ︰ Cuiization Ji ︰ bis-Ben Feng ︰ dewatering agent=1 ︰ 1 ︰ 1.2 ︰ 4.1 ~ 4.5 ︰ 1.4 ~ 1.6;
The precipitating of reaction product is treated to: polyreaction terminates first temperature of reaction to be down to 210 ~ 230 DEG C afterwards, accelerating stirring makes polyether-ether-ketone resin system evenly separate out, trimethylbenzene is added after reactor temperature is stable, be stirred to reaction system evenly after again temperature of reaction is down to 90 ~ 110 DEG C (being preferably 100 DEG C), make the whole homogeneously crystallized precipitation of polyether-ether-ketone resin, reaction system is in the white slurry of flowing; The add-on of trimethylbenzene is 1.3 ~ 1.5 times of sulfobenzide quality;
Purification process after precipitating: white slurry precipitating process obtained reclaims dewatering agent, solvent successively, then be less than 0.1 ‰ by washing to its ash content, namely obtain polyether-ether-ketone resin finally by drying treatment.
Described polyether-ether-ketone resin polyreaction is: with water trap, sulfobenzide and dewatering agent is added in the reactor of agitator and heating unit, pass into rare gas element, open and stir, temperature of reaction first rises to 130 ~ 160 (being preferably 140) DEG C, 4 are added successively after sulfobenzide all dissolves, 4 '-difluoro benzophenone and Resorcinol, catalyzer is added after monomer dissolves, be warming up to the water of releasing dewatering agent and generation after 200 ~ 240 (being preferably 220) DEG C carry out the reaction of 1.5 ~ 2.5 (being preferably 2) hours reflux from water trap again, final reaction temperature rises to 295 ~ 320 DEG C of polyreactions and terminates polyreaction in 2 ~ 3 hours, polymer reaction raw material and mol ratio thereof are: 4,4 '-difluorodiphenyl Jia Tong ︰ Dui Ben bis-Fen ︰ Cuiization Ji ︰ bis-Ben Feng ︰ dewatering agent=1 ︰ 1 ︰ 1.2 ︰ 4.1 ~ 4.5 ︰ 1.4 ~ 1.6.
In the present invention, described catalyzer is at least one in Anhydrous potassium carbonate or anhydrous sodium carbonate; Described dewatering agent is at least one in toluene, dimethylbenzene or trimethylbenzene; Sulfobenzide is as solvent, can melt after being heated beyond its fusing point 125 DEG C.
Further, in above-mentioned precipitating process, alr mode is the composite stirring form that the stirring of ribbon screw or frame add paddle; These two kinds of modes can be good at the homogeneity ensureing that high-viscosity material stirs, to guarantee precipitating effect.
Further, in above-mentioned purification process, the recovery method of dewatering agent is: white slurry reclaims dewatering agent by underpressure distillation, obtains the polyether-ether-ketone powder containing sulfobenzide and by-product salt; Wherein, vacuum distillation temperature is 90 ~ 110 DEG C (being preferably 100 DEG C), and vacuum tightness is less than 0.09MPa.
Further, in above-mentioned purification process, the recovery method of solvent is: adopt the mode of organic extraction to reclaim sulfobenzide in the polyether-ether-ketone powder containing sulfobenzide and by-product salt, extraction temperature is 50 ~ 60 DEG C, at least extract 6 times, each extraction time 1 ~ 2 (being preferably 1.5) hour, extraction agent is acetone or alcohol, and the addition of extraction agent is 8 ~ 12 (being preferably 10) times of polyether-ether-ketone quality.
Further, in above-mentioned purification process, carrying out washing treatment is: remove the polyether-ether-ketone powder after solvent also containing by-product salt and the complete catalyzer alkaline carbonate of unreacted, deionized water is adopted to wash in this powder, temperature of washing water 80 ~ 100 DEG C, wash at least 4 times, each washing time 1 ~ 2 (being preferably 1.5) hour.
Further, in residing purification process, extraction after containing sulfobenzide extraction agent liquid through distillation after obtain sulfobenzide and extraction agent respectively, sulfobenzide and extraction agent re-refine respectively Posterior circle use.
Further, drying treatment is namely in 150 DEG C of vacuum-dryings 12 hours.
The polyether-ether-ketone resin prepared by the inventive method is adopted to be thermoplastic resin, its second-order transition temperature 143 DEG C, the fusing point of product 343 DEG C, melting index 5 ~ 15 (360 DEG C, 10Kg), ash content is less than 0.1 ‰ (existing polyether-ether-ketone ash content is generally more than 0.2 ‰).Due to little and evenly, be easy to washing at product particle diameter after precipitating, solve the problem that the high and difficult removing of alkali metal ion content measured in the product of traditional method causes product quality low.
The precipitating that the technology of the present invention adopts and purification process ultimate principle are following 3 points: one is the feature utilizing polyether-ether-ketone resin cooling meeting crystallization in sulfobenzide solvent, suitably system temperature is reduced after molecular weight product reaches preset value, polyreaction stops automatically, avoids molecular weight distribution wider.Meanwhile due to the suitable reduction of system temperature, polyether-ether-ketone resin solubleness in sulfobenzide solvent reduces meeting crystallization gradually, has both reduced stirring difficulty, and has also achieved product and evenly separate out; Two is when after polyether-ether-ketone resin gradually crystallization, agitator motor load can strengthen gradually, in polymeric kettle, trimethylbenzene organic solvent is added gradually when motor load acquires a certain degree, both agitator motor load had been reduced, simultaneously because sulfobenzide has certain solvability in trimethylbenzene, after it also avoid sulfobenzide cooling, product condensation is become block; Three is that to complete post polymerization still material be pulp-like to precipitation process, and organic monomer residual in polymkeric substance or impurity are all in soluble state in the above conditions, are dissolved in organic solvent completely, is easy to be purified clean.
The preparation method of a kind of polyether-ether-ketone resin provided by the present invention, can adopt following embodiment to carry out:
A, polyether-ether-ketone polyreaction
By above-mentioned recipe ingredient correct amount respectively, sulfobenzide and dewatering agent is added in the reactor with water trap, agitator and heating unit, pass into protection of inert gas, open and stir, reactor jacket is heated to 140 DEG C, 4 are added successively after sulfobenzide all dissolves, 4 '-difluoro benzophenone and Resorcinol, catalyzer is added after monomer dissolves, reactor jacket temperature rise to 220 DEG C carry out 2 hours reflux reactions after from water trap, release dewatering agent and generate water, reactor jacket temperature rises to 295 ~ 320 DEG C of polyreactions 2 ~ 3 hours and terminates polyreaction; Polymer reaction raw material and proportioning thereof are: 4, and 4 '-difluorodiphenyl first ketone ︰ is to urging of benzene two phenol ︰ agent ︰ bis-phenol ︰ dewatering agent=1 ︰ 1 ︰ 1.2 ︰ 4.1 ~ 4.5 ︰ 1.4 ~ 1.6;
B, polyether-ether-ketone precipitating method
After polyreaction reaches terminal, reactor jacket temperature is down to 210 ~ 230 DEG C, accelerate stirring velocity to promote that polyether-ether-ketone resin system lowering temperature uniform is separated out, agitator need select ribbon screw whipped form or frame to add the composite stirring form of paddle, the trimethylbenzene of sulfobenzide quality 1.3 ~ 1.5 times is added after reactor temperature is stablized, to be mixed evenly after reactor jacket temperature is down to 100 DEG C, the now whole homogeneously crystallized precipitation of polyether-ether-ketone resin, whole material system becomes runny white slurry under trimethylbenzene effect.
In the underpressure distillation still that slurry transferring to band is stirred, still kettle jacket temperature set is 100 DEG C, and open and stir and vacuum system, in still kettle, relative vacuum degree is less than 0.09MPa, trimethylbenzene is recycled by Distillation recovery, and trimethylbenzene has steamed rear material and has been rendered as uniform powdery;
C, polyether-ether-ketone purification process
Polyether-ether-ketone powder containing sulfobenzide and by-product salt is delivered in organic extraction still, utilize acetone or alcohol extraction and recovery sulfobenzide solvent, the each add-on of acetone or alcohol is 10 times of polyether-ether-ketone quality, extraction temperature is 50 ~ 60 DEG C, each extraction time 1.5 hours, iterative cycles 6 times, the acetone or alcohol liquid containing sulfobenzide obtains sulfobenzide and organic solvent-acetone or ethanol respectively after distillation, and above raw material uses through refining Posterior circle.
Remove the polyether-ether-ketone powder after solvent also containing by-product salt and the complete catalyzer alkaline carbonate of unreacted, this powder is delivered in washing kettle and adds deionized water and carry out heated scrub, wash temperature is 80 ~ 100 DEG C, each washing time 1.5 hours, iterative cycles 4 times, the powder drying after washing can obtain highly purified polyether-ether-ketone resin.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
The preparation of embodiment 1 polyether-ether-ketone resin
For the polymeric kettle of 200L, prepare starting material by following quality: 4,4 '-difluoro benzophenone (10.9Kg), Resorcinol (5.5Kg), salt of wormwood (4.96Kg), sodium carbonate (2.54Kg), sulfobenzide 46.8Kg), trimethylbenzene (9.3Kg).
By above-mentioned recipe ingredient correct amount respectively, with water trap, sulfobenzide and trimethylbenzene is added in the 200L polymeric kettle of agitator (frame adds paddle two-way stirring) and heating unit, pass into inert nitrogen gas protection, open and stir (frame type stirring 30r/min, paddle stirs 60r/min), reactor jacket is heated to 140 DEG C, after 40 minutes, sulfobenzide all dissolves, add 4 successively, 4 '-difluoro benzophenone and Resorcinol, continue to add catalyzer salt of wormwood and sodium carbonate mixed salt after stirring 10 minutes monomers dissolve, jacket of polymerization temperature is risen to 220 DEG C carry out 2 hours reflux reactions after release from water trap trimethylbenzene and generate water, jacket of polymerization temperature rises to 310 DEG C of polyreactions and terminates polyreaction in 2.5 hours.
After polyreaction completes, jacket of polymerization temperature is down to 220 DEG C, accelerate stirring velocity (frame type stirring 50r/min, paddle stirs 120r/min), polyether-ether-ketone resin major part precipitation after 30 minutes, temperature drop to 220 DEG C in reactor, now adds the trimethylbenzene of 70Kg, stirs, after 30 minutes, jacket of polymerization temperature is down to 100 DEG C, the now whole homogeneously crystallized precipitation of polyether-ether-ketone resin, whole material system becomes runny white slurry under trimethylbenzene effect.
In the underpressure distillation still that slurry transferring to band is stirred, still kettle jacket temperature set is 100 DEG C, open and stir and vacuum system, in still kettle, relative vacuum degree is less than 0.09MPa, it is for subsequent use that trimethylbenzene is delivered to trimethylbenzene storage tank by the whole recovery of distillation in 3 hours, and trimethylbenzene has steamed rear material and has been rendered as flat-white powdery.
Polyether-ether-ketone powder containing sulfobenzide and by-product salt is delivered in organic extraction still, acetone extract is utilized to reclaim sulfobenzide solvent, the each add-on of acetone is 10 times of polyether-ether-ketone quality, extraction temperature is 50 DEG C, each extraction time 1.5 hours, iterative cycles extracts 6 times, and the acetone liquid containing sulfobenzide obtains sulfobenzide and organic solvent-acetone or ethanol respectively after distillation, and above raw material uses through refining Posterior circle.
Be delivered in washing kettle and add deionized water by removing the polyether-ether-ketone powder after solvent and carry out heated scrub, wash temperature is 100 DEG C, each washing time 1.5 hours, iterative cycles washs 4 times, and the powder after washing can obtain highly purified polyether-ether-ketone resin in 12 hours through 150 DEG C of vacuum-dryings.
Table 1 polyether-ether-ketone resin performance
Embodiment 2
Concrete grammar is with reference to embodiment 1, and be only with the difference of embodiment: reflux time is extended 30 minutes, polyreaction extends 30 minutes; The performance of gained polyether-ether-ketone resin is as shown in table 1.
Embodiment 3
Concrete grammar is with reference to embodiment 1, and be only with the difference of embodiment: reflux time is shortened 30 minutes, polyreaction shortens 30 minutes; The performance of gained polyether-ether-ketone resin is as shown in table 1.
From above-described embodiment, along with the proper extension of back flow reaction and polymerization reaction time, polyether-ether-ketone resin molecular weight increases to some extent, its mechanical property is increased to some extent, processing fluidity is deteriorated, and its purification effect of equal post-treating method slightly declines, otherwise suitably shortens reflux time and polymerization reaction time, although mechanical property slightly declines, processing fluidity and purification effect increase to some extent.
Claims (10)
1. the preparation method of polyether-ether-ketone resin, is characterized in that, comprises precipitating and the purification process of polyreaction and reaction product, wherein:
The raw material of polyether-ether-ketone polyreaction and mol ratio thereof are: 4,4 '-difluorodiphenyl Jia Tong ︰ Dui Ben bis-Fen ︰ Cuiization Ji ︰ bis-Ben Feng ︰ dewatering agent=1 ︰ 1 ︰ 1.2 ︰ 4.1 ~ 4.5 ︰ 1.4 ~ 1.6;
The precipitating of reaction product is treated to: polyreaction terminates first temperature of reaction to be down to 210 ~ 230 DEG C afterwards, accelerating stirring makes polyether-ether-ketone resin system evenly separate out, trimethylbenzene is added after reactor temperature is stable, be stirred to reaction system evenly after again temperature of reaction is down to 90 ~ 110 DEG C, make the whole homogeneously crystallized precipitation of polyether-ether-ketone resin, reaction system is in the white slurry of flowing; The add-on of trimethylbenzene is 1.3 ~ 1.5 times of sulfobenzide quality;
Purification process after precipitating: the white slurry that precipitating process obtains reclaims dewatering agent, sulfobenzide successively, then be less than 0.1 ‰ to its ash content namely obtain polyether-ether-ketone resin by washing.
2. the preparation method of polyether-ether-ketone resin according to claim 1, it is characterized in that, polyether-ether-ketone polyreaction is: with water trap, sulfobenzide and dewatering agent is added in the reactor of agitator and heating unit, pass into rare gas element, open and stir, temperature of reaction first rises to 130 ~ 160 DEG C, monomer 4 is added successively after sulfobenzide all dissolves, 4 '-difluoro benzophenone and Resorcinol, catalyzer is added after monomer dissolves, be warming up to 200 ~ 240 DEG C of back flow reaction again after 1.5 ~ 2.5 hours, the water of dewatering agent and generation is released from water trap, final reaction temperature rises to 295 ~ 320 DEG C of polyreactions and terminates polyreaction in 2 ~ 3 hours.
3. the preparation method of polyether-ether-ketone resin according to claim 2, it is characterized in that, in polyether-ether-ketone polyreaction, temperature of reaction first rises to 140 DEG C, monomer 4 is added successively after sulfobenzide all dissolves, 4 '-difluoro benzophenone and Resorcinol, add catalyzer, then be warming up to 220 DEG C of back flow reaction after monomer dissolves.
4. the preparation method of the polyether-ether-ketone resin according to any one of claims 1 to 3, is characterized in that, described catalyzer is at least one in Anhydrous potassium carbonate or anhydrous sodium carbonate; Described dewatering agent is at least one in toluene, dimethylbenzene or trimethylbenzene.
5. the preparation method of the polyether-ether-ketone resin according to any one of Claims 1 to 4, is characterized in that, in described precipitating process, alr mode is that ribbon screw stirs, frame adds paddle composite stirring.
6. the preparation method of the polyether-ether-ketone resin according to any one of Claims 1 to 5, it is characterized in that, in residing purification process, the recovery method of dewatering agent is: white slurry reclaims dewatering agent by underpressure distillation, obtains the polyether-ether-ketone powder containing sulfobenzide and by-product salt; Wherein, vacuum distillation temperature is 90 ~ 110 DEG C, and vacuum tightness is less than 0.09MPa.
7. the preparation method of the polyether-ether-ketone resin according to any one of claim 1 ~ 6, it is characterized in that, in residing purification process, the recovery method of sulfobenzide is: adopt the mode of organic extraction to reclaim sulfobenzide in the polyether-ether-ketone powder containing sulfobenzide and by-product salt, extraction temperature is 50 ~ 60 DEG C, at least extracts 6 times, each extraction time 1 ~ 2 hour, extraction agent is acetone or alcohol, and the addition of extraction agent is 8 ~ 12 times of polyether-ether-ketone quality.
8. the preparation method of polyether-ether-ketone resin according to claim 7, it is characterized in that, in residing purification process, the extraction agent liquid containing sulfobenzide after extraction obtains sulfobenzide and extraction agent respectively after distillation, and sulfobenzide and extraction agent Posterior circle of re-refining respectively uses.
9. the preparation method of the polyether-ether-ketone resin according to any one of claim 1 ~ 8, it is characterized in that, in residing purification process, washing methods is: remove the polyether-ether-ketone powder after sulfobenzide also containing by-product salt and the complete catalyzer alkaline carbonate of unreacted, deionized water is adopted to wash in this powder, temperature of washing water 80 ~ 100 DEG C, washs at least 4 times, each washing time 1 ~ 2 hour.
10. adopt the polyether-ether-ketone resin that the preparation method of the polyether-ether-ketone resin described in any one of claim 1 ~ 9 obtains, its ash content≤0.1 ‰.
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| CN106810652A (en) * | 2017-01-12 | 2017-06-09 | 苏州大学 | A kind of polyether-ether-ketone and preparation method thereof |
| CN107383293A (en) * | 2017-08-16 | 2017-11-24 | 宜宾天原集团股份有限公司 | A kind of preparation method of polyether-ether-ketone suitable for 3D printing |
| CN110256643A (en) * | 2019-06-26 | 2019-09-20 | 南京清研高分子新材料有限公司 | A method of preparing polyether-ether-ketone resin |
| CN113402723A (en) * | 2021-06-03 | 2021-09-17 | 宁夏清研高分子新材料有限公司 | Super-hydrophobic polyether-ether-ketone material and preparation method thereof |
| CN113461932A (en) * | 2021-07-29 | 2021-10-01 | 浙江大学 | Preparation method of polyaryletherketone |
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