CN107936205A - A kind of manufacture method of polyether-ether-ketone resin - Google Patents

A kind of manufacture method of polyether-ether-ketone resin Download PDF

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CN107936205A
CN107936205A CN201711338915.3A CN201711338915A CN107936205A CN 107936205 A CN107936205 A CN 107936205A CN 201711338915 A CN201711338915 A CN 201711338915A CN 107936205 A CN107936205 A CN 107936205A
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washing
ether
polyether
temperature
filtrate
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陈逊
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    • 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

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Abstract

The invention discloses a kind of manufacture method of polyether-ether-ketone resin, using the 4 of certain mol proportion, 4 difluoro benzophenones, bisphenol-A, hydroquinone and phenol are raw material, N, N ' dimethylacetylamides are solvent, under alkali carbonate promoter effect, under the conditions of certain temperature, polycondensation synthesis of polyether-ether-ketone resin, the resin first uses absolute methanol, acetone, the mixed solution of chloroform washs 3 times, then washed 8 times with anaerobic deionized water, then anaerobic deionized water and N are used again, after the mixed solution of N ' dimethylacetylamides purifies 2 times, washed 8 times with anaerobic deionized water after being separated by filtration, obtain the polyether-ether-ketone wet resin that water content is 3~6%wt, the resin is dried under conditions of certain temperature and vacuum, obtain high-purity polyether-ether-ketone resin.

Description

A kind of manufacture method of polyether-ether-ketone resin
Technical field
The invention belongs to high molecular material resin manufacture, more particularly to the manufacture method of polyether-ether-ketone resin.
Background technology
Polyether-ether-ketone（PEEK）Resistance to elevated temperatures, it has higher glass transition temperature (Tg=143 DEG C) and fusing point (Tm=334 DEG C), it loads heat distortion temperature and is up to 316 DEG C, and long-time service temperature is 260 DEG C, and instantaneous temperature in use is up to 300 ℃.Polyether-ether-ketone（PEEK）Mechanical property, there is rigidity and flexible, it is particularly very prominent to the fatigue resistance under alternate stress Go out, can compare favourably with alloy material, polyether-ether-ketone（PEEK）Self lubricity, there are excellent sliding properties, be suitable for stringent It is required that the occasion of low-friction coefficient and abrasion performance purposes, particularly with the PEEK of carbon resin, graphite, PTFE the slip trade mark being modified Wearability is very superior, and for corrosion resistance in addition to the concentrated sulfuric acid, PEEK does not dissolve in any solvent and strong acid, highly basic, and hydrolysis, tool There is very high chemical stability, anti-flammability PEEK has self-extinguishment, even if being not added with any fire retardant, can reach the 94V- of UL standards 0 grade, temperature flowing is good since PEEK has for workability, and the characteristics of heat decomposition temperature is very high, a variety of processing can be used Mode：Injection moulding, extrusion molding, compression molding and melt spinning, two-way drawing-off manufacture resin etc..
Since PEEK has excellent comprehensive performance, many special dimensions can with traditional materials such as alternative metals, ceramics, The high temperature resistants of the plastics, self-lubricating, wear-resistant and antifatigue etc. characteristic, make current most popular high performance engineering plastics One of, it is mainly used in the fields such as aerospace, auto industry, electric and medical instrument.
High-performance polyether-ether-ketone has the heat endurance under excellent chemical proofing and high temperature, and with fire-retardant, exhausted Edge, radiation hardness and good mechanical performance, to expand the use scope of the material, the researchers of various countries always search for being allowed to The new method that resinification uses.
PEEK synthetic routes are mainly with 4,4 '-difluoro benzophenone and bisphenol-A in solvent dimethylacetylamide and alkali gold Belonging to carbonate etc. and exist and is prepared, one of wherein PEEK production keys are exactly monomer 4, the preparation of 4 '-difluoro benzophenone, its Molecular structure is as follows：
The thermoplastic resin of its molecular backbone ether ether ketone containing phenylene chain link, has highly crystalline, the preparation method of resin is using general It is logical to melt two-way drawing-off method.
Introduced in Chinese patent number 200610016889.8 using dimethylacetylamide as solvent, with 4,4‘- difluoro two Benzophenone, be raw material to biphenol, biphenyl phenol, and the mixed system using alkali carbonate as auxiliary agent, by solvent Dimethylbenzene is added in system as synthesis of polyether-ether-ketone resin on the basis of adjuvant, since the polymer is except carbonyl and ether Again without other flexible groups beyond group, from prepared by polyether-ether-ketone resin rigidity than the polyether-ether-ketone resin obtained by the present invention Rigidity is strong, is unfavorable for manufacturing the two-way drawing-off resin sheet needed for resin.
The purification process of polyether-ether-ketone resin is introduced in Chinese patent 200410081436.4, it is by with N- methyl Pyrrolidones is solvent, and it is processing purifying polyether-ether-ketone resin on the basis of auxiliary agent to be properly added surface conjunction property agent, like this Purifying mode due to adding another material, according to the similar compatibility principle of material, this method is more or less all A part of material can be remained among polyether-ether-ketone resin, although making the small-molecule substance of polyether-ether-ketone resin locate during it Reason is fallen, but with the addition of other materials again, so purifying the result is that unsatisfactory.
The content of the invention
The object of the present invention is to provide a kind of manufacture method of polyether-ether-ketone resin, to solve in customary preparation methods, gathers The defects of its performance of ether ether ketone resin is not easy to be optimal, and qualification rate is relatively low, passes through the synthesis technique to polyether-ether-ketone resin, tree The innovation of the recovery process of fat and the purifying process of resin, obtains purity height, melt flow index index height, and crystallinity Relatively low polyether-ether-ketone resin, and improve its yield.
The purpose of the present invention is what is realized by the following means.
A kind of manufacture method of polyether-ether-ketone resin, using 4,4- difluoro benzophenones, bisphenol-A, hydroquinone and phenol For raw material, N, N '-dimethyl acetamide is solvent, the polycondensation synthesis of polyether-ether-ketone resin under alkali carbonate promoter effect, Wherein 4,4- difluoro benzophenones：Bisphenol-A+hydroquinone+phenol：The molar ratio of alkali carbonate is 1.0：1.003： 1.003 wherein bisphenol-A：Hydroquinone：The molar ratio of phenol is 1.0：32.3：0.033, its manufacture method includes：
（1）In the case where being passed through nitrogen protective condition, by 4,4- difluoro benzophenones add be stirred continuously and with N, N '-dimethyl second Acid amides carries out heating heating with conduction oil, when temperature rises to 166~168 DEG C, then distinguishes to be reacted in the polymeric kettle of solvent Alkali carbonate, bisphenol-A he hydroquinones are sequentially added, solid-liquid mass ratio is reached 0.15~0.2：1.0, then proceed to Heating, when temperature rises to 264~268 DEG C, when insulation 3.6~4.0 is small, temperature is increased to 304~308 DEG C again, insulation 6.0 ~6.6 it is small when；
（2）Mixture after insulation is poured into -8~-6 DEG C of frozen water, quick refrigeration to room temperature, filtered, then filter cake adds The mixed solution of 38~48 DEG C of absolute methanols, acetone and chloroform washes out the dimethylacetamide solvent 3 times in mixture, often washes Wash a polyether-ether-ketone resin and be intended to separating and filtering；The filtrate input that first order methanol, acetone, the mixed solution of chloroform wash is molten Agent recovery process；Wherein, specific methanol, acetone, the mixed solution washing process of chloroform are：First order wash liquid is to utilize The filter cake that filtrate after the washing of second stage polyetheretherketoneresin resin is separated by filtration out the reaction mixture that washs, second The first order washing and filtering point that level wash liquid is the filtrate after washing using third level polyether-ether-ketone resin to wash The filter cake come is separated out, third level wash liquid is to utilize fresh methanol, acetone and chloroform mixed solution；Wherein, methanol：Third Ketone：The mass ratio of chloroform is 33：14：3；
（3）By step（2）In obtained filter cake, after first order wash liquid is washed using the second stage polyetheretherketoneresin resin Filtrate carrys out washing step（1）Obtained filter cake, and supplement the deionized water of 16~18wt% second level filtrate total amount so that washing The solids content of polyether-ether-ketone resin is 26~28wt% in system, with i.e. by the temperature of charge rising in first order washing system To 96~99 DEG C, and under the temperature conditionss, 30~45min is kept the temperature, is filtered while hot, filtrate inputs the recycling of side product chlorinated sodium System, filter cake input second level washing process process；
（4）In step（3）In obtained filter cake, after second level wash liquid is washed using third level polyether-ether-ketone resin Filtrate carrys out washing step（2）Obtained filter cake, and supplement the deionized water of 13~15wt% third level filtrate total amounts so that washing The solids content of polyether-ether-ketone resin is 26~28wt% in system, with i.e. by the temperature of charge rising in the washing system of the second level To 96~99 DEG C, and under the temperature conditionss, 30~45min is kept the temperature, is filtered while hot, filtrate input first order washing process work Sequence, filter cake input third level washing process process；
（5）In step（4）In obtained filter cake, after third level wash liquid is washed using fourth stage polyether-ether-ketone resin Filtrate carrys out washing step（3）Obtained filter cake, and supplement the deionized water of 9~12wt% fourth stage filtrate total amounts so that washing system The solids content of polyether-ether-ketone resin is 26~28wt% in system, with rising to the temperature of charge in third level washing system 96~99 DEG C, and under the temperature conditionss, keep the temperature 30~45min, filter while hot, filtrate input second level washing process process, Filter cake inputs fourth stage washing process process；
（6）In step（5）In obtained filter cake, after fourth stage wash liquid is washed using level V polyether-ether-ketone resin Filtrate carrys out washing step（4）Obtained filter cake, and supplement the deionized water of 6~9wt% level V filtrate total amounts so that washing system The solids content of polyether-ether-ketone resin is 26~28wt% in system, with rising to the temperature of charge in fourth stage washing system 96~99 DEG C, and under the temperature conditionss, keep the temperature 30~45min, filter while hot, filtrate input third level washing process process, Filter cake inputs level V washing process process；
（7）In step（6）In obtained filter cake, after level V wash liquid is washed using the 6th stage polyetheretherketoneresin resin Filtrate carrys out washing step（5）Obtained filter cake, and supplement the deionized water of the 6th grade of filtrate total amount of 6~9wt% so that washing system The solids content of polyether-ether-ketone resin is 26~28wt% in system, with rising to the temperature of charge in level V washing system 96~99 DEG C, and under the temperature conditionss, keep the temperature 30~45min, filter while hot, filtrate input fourth stage washing process process, Filter cake inputs the 6th grade of washing process process；
（8）In step（7）In obtained filter cake, after the 6th grade of wash liquid is washed using the 7th stage polyetheretherketoneresin resin Filtrate carrys out washing step（6）Obtained filter cake, and supplement the deionized water of the 7th grade of filtrate total amount of 3~6wt% so that washing system The solids content of polyether-ether-ketone resin is 26~28wt% in system, with rising to the temperature of charge in the 6th grade of washing system 96~99 DEG C, and under the temperature conditionss, keep the temperature 30~45min, filter while hot, filtrate input level V washing process process, Filter cake inputs the 7th grade of washing process process；
（9）In step（8）In obtained filter cake, after the 7th grade of wash liquid is washed using the 8th stage polyetheretherketoneresin resin Filtrate carrys out washing step（7）Obtained filter cake, and supplement the deionized water of the 8th grade of filtrate total amount of 1~3wt% so that washing system The solids content of polyether-ether-ketone resin is 26~28wt% in system, with rising to the temperature of charge in the 7th grade of washing system 96~99 DEG C, and under the temperature conditionss, keep the temperature 30~45min, filter while hot, filtrate inputs the 6th grade of washing process process, Filter cake inputs the 8th grade of washing process process；
（10）In step（9）In obtained filter cake, fresh deionized water is added so that polyether-ether-ketone resin in washing system Solids content is 26~28wt%, with the temperature of charge in the 8th grade of washing system is risen to 96~99 DEG C, and in the temperature Under the conditions of, 30~45min is kept the temperature, is filtered while hot, filtrate inputs the 7th grade of washing process process, filter cake input drying process work Sequence, this completes the washing of polyether-ether-ketone resin, so as to obtain polyether-ether-ketone resin crude product；
（11）By step（10）Obtained polyether-ether-ketone resin crude product rejoins the dimethylacetylamide containing 30% deionized water again In the washing kettle of solvent, and 210~220 DEG C are heated to, when insulation 1~2 is small；
（12）By step（11）Mixture after insulation keeps the temperature filtering while hot, repeats step（11）Operation obtain melt-flow Index is the polyether-ether-ketone resin of 10~15g/10min；
（13）By step（12）Obtained polyether-ether-ketone resin uses step（3）~（10）Identical washing process control condition into Row washing 8 times, obtains the polyether-ether-ketone wet resin that water content is 3~6%wt；
（14）By step（13）Obtained polyether-ether-ketone resin, insert temperature be dry 3 in 158~168 DEG C of vacuum drying oven~ 4h, its vacuum is -0.08~-0.09MPa, so as to obtain the polyether-ether-ketone resin of high-purity.
The beneficial effects of the invention are as follows：
After as above means, especially obtain that polydispersity coefficient is relatively low and molecular weight point using bisphenol-A, phenol as polymerizable raw material The very narrow polyether-ether-ketone resin of cloth, the crystallinity of resin is relatively low, high mechanical strength, good toughness, melting viscosity, oxygen index (OI) It is high, polydispersity coefficient is low etc., its characteristic is more excellent compared with the polyether-ether-ketone resin characteristic that conventional synthesis purification process obtains, and such as uses The polyether-ether-ketone resin of this kind of method synthesis is used to manufacture resin, and the drawing-off performance of its resin is more excellent, and the disconnected of resin is made Resistance to spalling, and other performances are further enhanced, and temperature in use and fusing point have to be improved to some extent.
Meeting after the insertion-carbonyl on the molecular structure of-Ar- and the flexible group of ether group structure and bisphenol-A of the invention Such a molecular structures of formation-Ar-B-Ar-C- Ar-D- Ar-C-Ar（B represents carbonyl, C represents ether, D represents bisphenol-A Flexible group）, and these separation structures are probably ordered arrangement, even control molecular structure by charging sequence, it is such Purpose is to improve the intensity index and toughness of polyether-ether-ketone resin, therefore the polyether-ether-ketone containing flexible group that the present invention obtains Resin be used for manufacture resin, impact strength, the tearing strength of resin can be improved, this be exactly the present invention required for reach The effect arrived.
Based on low boiling point organic solvent, they can be detergent employed in the present invention：Methanol, methanol, propyl alcohol, The organic solvents such as butanol, acetone, monochloro methane, dichloromethane, chloroform, benzene,toluene,xylene, especially with acetone, methanol, chlorine Imitative mixed solution is best.
The object of the invention is to produce polyether-ether-ketone（PEEK）A kind of new special resin, in related patents at home and abroad It is rare manufacture resin application and its pertinent literature, by the synthesis technique to polyether-ether-ketone resin, the recovery process of resin with And the innovation of the purifying process of resin, obtain purity height, melt flow index index height, and the polyethers that crystallinity is relatively low Ether ketone resin, the polyether-ether-ketone resin of high intensity, toughness, tearing strength is produced using the polyether-ether-ketone resin, meanwhile, according to The purpose of the present invention, present inventor have made the purifying and resin washing experiment of a large amount of related works, especially polyether-ether-ketone resin Work, synthetically produced polyether-ether-ketone resin mixture is washed in particular by the mixed solution of acetone, methanol, chloroform, be for The various impurity contents in polyether-ether-ketone resin crude product are reduced, in addition, the resin of excellent performance in order to obtain, manufactures like this The polyether-ether-ketone resin gone out in resin due to, there are flexible group, so as to suitably reduce the rigidity of resin, adding resin Toughness, so that expanding the application range of polyether-ether-ketone resin.
The present invention adds bisphenol-A, the purpose of phenol is to improve the finished product yield of polyether-ether-ketone resin, reduces polyether-ether-ketone tree Fat causes resin cracks and embrittlement because of objective factors such as its rigidity in the fabrication process, so not only improves the production effect of product Rate, but also the production cost of product is reduced, for this reason, finished product yield and reduction production cost of the present invention for raising product, During manufacturing polyether-ether-ketone resin, bisphenol A monomer is suitably added, its purpose is to reduce polyether-ether-ketone in manufacturing process Resin causes resin cracks and embrittlement because of objective factors such as its rigidity, improves finished product rate, present inventor is in experimentation In other materials is respectively adopted cannot reach its effect, especially add phenol as blocked with polymer agent, it is evident that carry High product yield rate, while the polydispersity coefficient of reduction molecular weight product that can also be clearly.
The present invention carries out polyether-ether-ketone resin to purify it using low boiling point absolute methanol, acetone, the mixed solvent of chloroform Afterwards, in addition to glass transition temperature and heat distortion temperature are stablized relatively, remaining each performance characteristic is superior to be used alone The mixed solvent of a kind of low boiling point solvent or any two kinds of low boiling point solvents, it is due to low polymer independent to trace it to its cause A kind of solubility in low boiling point solvent is big without three kinds of solvent mixed solvents, while is influenced by solvent effect so that mixed The performance characteristic of polyether-ether-ketone resin exists obvious different after bonding solvent purification process.
Brief description of the drawings
What Fig. 1 was represented is the performance characteristic of polyether-ether-ketone resin.
Embodiment
Present invention process flow is as follows：
The present invention is raw material using 4,4- difluoro benzophenones, bisphenol-A, hydroquinone and the phenol of certain mol proportion, N, N '-two Methylacetamide is solvent, under alkali carbonate promoter effect, under the conditions of certain temperature, and polycondensation synthesis of polyether-ether-ketone tree Fat, the resin were washed 3 times using the mixed solution of absolute methanol, acetone and chloroform before this, then washed 8 with anaerobic deionized water It is secondary, anaerobic deionized water and N are then used again, after the mixed solution of N '-dimethyl acetamide purifies 2 times, with anaerobic deionized water Wash 8 times after being separated by filtration, obtain the polyether-ether-ketone wet resin that water content is 3~6%wt, the resin is in certain temperature and very It is dried under conditions of reciprocal of duty cycle, obtains high-purity polyether-ether-ketone resin.
The technique of the present invention is described in further detail with reference to embodiment.
Embodiment 1：
It is raw material using 4,4- difluoro benzophenones, bisphenol-A, hydroquinone and phenol, N, N '-dimethyl acetamide is solvent, The polycondensation synthesis of polyether-ether-ketone resin under alkali carbonate promoter effect, wherein 4,4- difluoro benzophenones：Bisphenol-A+to benzene Diphenol+phenol：The molar ratio of alkali carbonate is 1.0：1.003：1.003 wherein bisphenol-A：Hydroquinone：Mole of phenol Than for 1.0：32.3：0.033, its manufacturing process includes：
（1）Under conditions of nitrogen is passed through, by 4,4- difluoro benzophenones add be stirred continuously and with N, N '-dimethyl acetyl Amine carries out heating heating with conduction oil, when temperature rises to 166 DEG C, then adds successively respectively to be reacted in the polymeric kettle of solvent Enter alkali carbonate, bisphenol-A and hydroquinone, solid-liquid ratio is reached 0.2：1.0, then proceed to heat up, when temperature rises to At 264 DEG C, when insulation 4.0 is small, temperature is increased to 304 DEG C again, when insulation 6.6 is small after, pour into -6 DEG C of frozen water, quick refrigeration To room temperature, filtering, it is 33 that then filter cake, which adds 38 DEG C of mass ratioes,：14：The mixed solution washing of 3 absolute methanol, acetone, chloroform Go out the dimethylacetamide solvent 3 times in mixture, often washed once polyether-ether-ketone resin and be intended to separating and filtering；First order first The filtrate input solvent recovery process that alcohol, acetone, the mixed solution of chloroform wash；Its specific methanol, acetone, the mixing of chloroform are molten Liquid washing process is：First order wash liquid is the filtrate after being washed using the second stage polyetheretherketoneresin resin to wash The filter cake that reaction mixture is separated by filtration out, after second level wash liquid is washed using third level polyether-ether-ketone resin The filter cake that filtrate is separated the first order washing and filtering that washs, third level wash liquid be using fresh methanol, Acetone, chloroform mixed solution；
First order wash liquid is the filtrate after being washed using the second stage polyetheretherketoneresin resin to wash the filter that the first order obtains Cake, and supplement the deionized water of 18wt% second level filtrate total amount so that the solids content of polyether-ether-ketone resin is in washing system 26wt%, with the temperature of charge in first order washing system is risen to 99 DEG C, and under the temperature conditionss, keeps the temperature 30min, Filter while hot, filtrate inputs the recovery system of side product chlorinated sodium, filter cake input second level washing process process；Wash the second level Liquid is to wash the filter cake that the first order obtains using the filtrate after the washing of third level polyether-ether-ketone resin, and supplements 13wt% The deionized water of third level filtrate total amount so that the solids content of polyether-ether-ketone resin is 28wt% in washing system, with i.e. by the Temperature of charge in two level washing system rises to 99 DEG C, and under the temperature conditionss, keeps the temperature 30min, filter while hot, filtrate is defeated Enter first order washing process process, filter cake input third level washing process process；Third level wash liquid is gathered using the fourth stage Filtrate after the washing of ether ether ketone resin washs the filter cake that the second level obtains, and supplements going for 12wt% fourth stage filtrate total amounts Ionized water so that the solids content of polyether-ether-ketone resin is 28wt% in washing system, with i.e. by the thing in third level washing system Material temperature degree rises to 99 DEG C, and under the temperature conditionss, keeps the temperature 30min, filter while hot, filtrate input second level washing process work Sequence, filter cake input fourth stage washing process process；Fourth stage wash liquid is using after the washing of level V polyether-ether-ketone resin Filtrate wash the filter cake that the third level obtains, and supplement the deionized water of 9wt% level V filtrate total amounts so that washing system The solids content of middle polyether-ether-ketone resin is 28wt%, with the temperature of charge in fourth stage washing system risen to 99 DEG C, and Under the temperature conditionss, 30min is kept the temperature, is filtered while hot, filtrate input third level washing process process, filter cake input level V is washed Wash technique process；Level V wash liquid is that the filtrate after being washed using the 6th stage polyetheretherketoneresin resin is obtained to wash the fourth stage The filter cake arrived, and supplement the deionized water of the 6th grade of filtrate total amount of 9wt% so that the solid of polyether-ether-ketone resin in washing system Content is 28wt%, with the temperature of charge in level V washing system is risen to 99 DEG C, and under the temperature conditionss, insulation 30min, is filtered while hot, and filtrate input fourth stage washing process process, filter cake inputs the 6th grade of washing process process；6th grade is washed It is to wash the filter cake that level V obtains using the filtrate after the washing of the 7th stage polyetheretherketoneresin resin to wash liquid, and supplements 6wt% The deionized water of 7th grade of filtrate total amount so that the solids content of polyether-ether-ketone resin is 28wt% in washing system, with i.e. by the Temperature of charge in six grades of washing systems rises to 99 DEG C, and under the temperature conditionss, keeps the temperature 30min, filter while hot, filtrate is defeated Enter level V washing process process, filter cake inputs the 7th grade of washing process process；7th grade of wash liquid is poly- using the 8th grade Filtrate after the washing of ether ether ketone resin washs the 6th grade of obtained filter cake, and supplement 3wt% the 8th grade of filtrate total amount go from Sub- water so that the solids content of polyether-ether-ketone resin is 28wt% in washing system, with i.e. by the material in the 7th grade of washing system Temperature rises to 99 DEG C, and under the temperature conditionss, keeps the temperature 30min, filter while hot, filtrate inputs the 6th grade of washing process work Sequence, filter cake input the 8th grade of washing process process；Fresh deionized water is added in filter cake so that polyethers ether in washing system The solids content of ketone resin is 28wt%, with the temperature of charge in the 8th grade of washing system is risen to 99 DEG C, and in the temperature Under the conditions of, 30min is kept the temperature, is filtered while hot, filtrate inputs the 7th grade of washing process process, and filter cake inputs drying process process, this Sample just completes the washing of polyether-ether-ketone resin, so as to obtain polyether-ether-ketone resin crude product；
Rejoined again in the washing kettle of the dimethylacetamide solvent containing 30% deionized water in polyether-ether-ketone resin crude product, And be heated to 210 DEG C, when insulation 2 is small after, insulation filtering while hot, the operation for repeating the step obtains melt flow index and is The polyether-ether-ketone resin of 15g/10min；Obtained polyether-ether-ketone resin is using the identical washing process of polyether-ether-ketone resin crude product Control condition carries out washing 8 times, obtains the polyether-ether-ketone wet resin that water content is 6%wt；Obtained polyether-ether-ketone resin, is inserted Dry 3h in the vacuum drying oven that temperature is 168 DEG C, its vacuum is -0.08MPa, so as to obtain the polyether-ether-ketone tree of high-purity Fat.
The polyether-ether-ketone resin of acquisition, specific performance feature are listed in Fig. 1.
Embodiment 2
It is raw material using 4,4- difluoro benzophenones, bisphenol-A, hydroquinone and phenol, N, N '-dimethyl acetamide is solvent, The polycondensation synthesis of polyether-ether-ketone resin under alkali carbonate promoter effect, wherein 4,4- difluoro benzophenones：Bisphenol-A+to benzene Diphenol+phenol：The molar ratio of alkali carbonate is 1.0：1.003：1.003 wherein bisphenol-A：Hydroquinone：Mole of phenol Than for 1.0：32.3：0.033, its manufacturing process includes：
1）Under conditions of nitrogen is passed through, by 4,4- difluoro benzophenones add be stirred continuously and with N, N '-dimethyl acetyl Amine carries out heating heating with conduction oil, when temperature rises to 168 DEG C, then adds successively respectively to be reacted in the polymeric kettle of solvent Enter alkali carbonate, bisphenol-A, hydroquinone；Solid-liquid mass ratio is set to reach 0.15：1.0, then proceed to heat up, when in temperature When being raised to 268 DEG C, when insulation 3.6 is small, temperature is increased to 308 DEG C again, when insulation 6.0 is small after, pour into -8 DEG C of frozen water, drastically Room temperature is cooled to, is filtered, then 48 DEG C of mass ratioes of filter cake addition reach 33：14：3 absolute methanol, acetone, the mixing of chloroform are molten Liquid washes out the dimethylacetamide solvent 3 times in mixture, often washed once polyether-ether-ketone resin and is intended to separating and filtering；First The filtrate input solvent recovery process that level methanol, acetone, the mixed solution of chloroform wash；Its specific methanol, acetone, chloroform it is mixed Closing solution washing process is：First order wash liquid is the filtrate after being washed using the second stage polyetheretherketoneresin resin to wash To the reaction mixture filter cake that is separated by filtration out, second level wash liquid is to wash it using third level polyether-ether-ketone resin The filter cake that filtrate afterwards is separated the first order washing and filtering that washs, third level wash liquid is to utilize fresh first Alcohol, acetone, chloroform mixed solution；
First order wash liquid is the filtrate after being washed using the second stage polyetheretherketoneresin resin to wash the filter that the first order obtains Cake, and supplement the deionized water of 16wt% second level filtrate total amount so that the solids content of polyether-ether-ketone resin is in washing system 28wt%, with the temperature of charge in first order washing system is risen to 96 DEG C, and under the temperature conditionss, keeps the temperature 45min, Filter while hot, filtrate inputs the recovery system of accessory substance-sodium chloride, filter cake input second level washing process process；The second level is washed It is to wash the filter cake that the first order obtains using the filtrate after the washing of third level polyether-ether-ketone resin to wash liquid, and is supplemented The deionized water of 15wt% third level filtrate total amounts so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, with The temperature of charge in the washing system of the second level is risen to 96 DEG C, and under the temperature conditionss, keeps the temperature 45min, filters while hot, Filtrate inputs first order washing process process, filter cake input third level washing process process；Third level wash liquid is to utilize the Filtrate after the washing of four stage polyetheretherketoneresin resins washs the filter cake that the second level obtains, and supplements 9wt% fourth stage filtrate total amounts Deionized water so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, with i.e. by third level washing system Temperature of charge rise to 96 DEG C, and under the temperature conditionss, keep the temperature 45min, filter while hot, filtrate input second level washers Skill process, filter cake input fourth stage washing process process；Fourth stage wash liquid is washed using level V polyether-ether-ketone resin Filtrate afterwards washs the filter cake that the third level obtains, and supplements the deionized water of 6wt% level V filtrate total amounts so that washing The solids content of polyether-ether-ketone resin is 26wt% in system, with the temperature of charge in fourth stage washing system is risen to 96 DEG C, and under the temperature conditionss, 45min is kept the temperature, is filtered while hot, filtrate input third level washing process process, filter cake input the Pyatyi washing process process；Level V wash liquid is the filtrate after being washed using the 6th stage polyetheretherketoneresin resin to wash the The filter cake that level Four obtains, and supplement the deionized water of the 6th grade of filtrate total amount of 6wt% so that polyether-ether-ketone resin in washing system Solids content be 26wt%, with the temperature of charge in level V washing system is risen to 96 DEG C, and in the temperature conditionss Under, 45min is kept the temperature, is filtered while hot, filtrate input fourth stage washing process process, filter cake inputs the 6th grade of washing process process； 6th grade of wash liquid is to wash the filter cake that level V obtains using the filtrate after the washing of the 7th stage polyetheretherketoneresin resin, and Supplementing the deionized water of the 7th grade of filtrate total amount of 3wt% so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, With the temperature of charge in the 6th grade of washing system is risen to 96 DEG C, and under the temperature conditionss, 30min is kept the temperature, while hot mistake Filter, filtrate input level V washing process process, filter cake input the 7th grade of washing process process；7th grade of wash liquid is to utilize Filtrate after the washing of 8th stage polyetheretherketoneresin resin washs the 6th grade of obtained filter cake, and to supplement the 8th grade of filtrates of 1wt% total The deionized water of amount so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, with i.e. by the 7th grade of washing system In temperature of charge rise to 96 DEG C, and under the temperature conditionss, keep the temperature 45min, filter while hot, filtrate inputs the 6th grade of washing Technique process, filter cake input the 8th grade of washing process process；Fresh deionized water is added in filter cake so that in washing system The solids content of polyether-ether-ketone resin is 26wt%, with the temperature of charge in the 8th grade of washing system risen to 96 DEG C, and Under the temperature conditionss, 45min is kept the temperature, is filtered while hot, filtrate inputs the 7th grade of washing process process, filter cake input drying process work Sequence；This completes the washing of polyether-ether-ketone resin, so as to obtain polyether-ether-ketone resin crude product；
Rejoined again in the washing kettle of the dimethylacetamide solvent containing 30% deionized water in polyether-ether-ketone resin crude product, And be heated to 220 DEG C, insulation 1 it is small when after；Insulation filtering while hot, the operation for repeating the step obtain melt flow index and are The polyether-ether-ketone resin of 10g/10min；Obtained polyether-ether-ketone resin is using the identical washing process of polyether-ether-ketone resin crude product Control condition carries out washing 8 times, obtains the polyether-ether-ketone wet resin that water content is 3%wt；Obtained polyether-ether-ketone resin, is inserted Dry 4h in the vacuum drying oven that temperature is 158 DEG C, its vacuum is -0.09MPa；So as to obtain the polyether-ether-ketone tree of high-purity Fat.
The polyether-ether-ketone resin of acquisition, specific performance feature are listed in Fig. 1.
Comparison example 1
In addition to the mixture after a kind of low boiling point solvent processing polyether-ether-ketone resin synthesis is used alone, remaining is adopted this example With the process conditions and composition of raw materials synthesis of polyether-ether-ketone resin of embodiment 1, so as to obtain the not high polyether-ether-ketone resin of purity.
It is raw material using 4,4- difluoro benzophenones, bisphenol-A, hydroquinone and phenol, N, N '-dimethyl acetamide is molten Agent, the polycondensation synthesis of polyether-ether-ketone resin under alkali carbonate promoter effect, wherein 4,4- difluoro benzophenones：Bisphenol-A+right Benzenediol+phenol：The molar ratio of alkali carbonate reaches 1.0：1.003：1.003 wherein bisphenol-A：Hydroquinone：Phenol Molar ratio reaches 1.0：32.3：0.033, its manufacturing process includes：
Under conditions of nitrogen is passed through, by 4,4- difluoro benzophenones add be stirred continuously and with N, N '-dimethyl acetamide To be reacted in the polymeric kettle of solvent, heating heating is carried out with conduction oil, when temperature rises to 168 DEG C, then is sequentially added into Alkali carbonate, bisphenol-A, hydroquinone；Solid-liquid mass ratio is set to reach 0.15：1.0, then proceed to heat up, when temperature rises During to 268 DEG C, when insulation 3.60 is small, temperature is increased to 308 DEG C again, when insulation 6.0 is small after, pour into -6 DEG C of frozen water, drastically Room temperature is cooled to, is filtered, then 48 DEG C of quality of filter cake addition wash out the dimethyl in mixture for 100% absolute methanol solution Acetyl amine solvent 3 times, often washed once polyether-ether-ketone resin and is intended to separating and filtering；The filtrate input of first order methanol solution washing Solvent recovery process；Its specific methanol solution washing process is：First order wash liquid is to utilize the second stage polyetheretherketoneresin resin The filter cake that filtrate after washing is separated by filtration out the reaction mixture that washs, second level wash liquid are to utilize the The filter cake that filtrate after the washing of three stage polyetheretherketoneresin resins is separated the first order washing and filtering that washs, the third level Wash liquid is to utilize fresh methanol solution；
First order wash liquid is the filtrate after being washed using the second stage polyetheretherketoneresin resin to wash the filter that the first order obtains Cake, and supplement the deionized water of 18wt% second level filtrate total amount so that the solids content of polyether-ether-ketone resin is in washing system 26wt%, with the temperature of charge in first order washing system is risen to 96 DEG C, and under the temperature conditionss, keeps the temperature 45min, Filter while hot, filtrate inputs the recovery system of accessory substance-sodium chloride, filter cake input second level washing process process；The second level is washed It is to wash the filter cake that the first order obtains using the filtrate after the washing of third level polyether-ether-ketone resin to wash liquid, and is supplemented The deionized water of 15wt% third level filtrate total amounts so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, with The temperature of charge in the washing system of the second level is risen to 96 DEG C, and under the temperature conditionss, keeps the temperature 45min, filters while hot, Filtrate inputs first order washing process process, filter cake input third level washing process process；Third level wash liquid is to utilize the Filtrate after the washing of four stage polyetheretherketoneresin resins washs the filter cake that the second level obtains, and supplements 9wt% fourth stage filtrate total amounts Deionized water so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, with i.e. by third level washing system Temperature of charge rise to 96 DEG C, and under the temperature conditionss, keep the temperature 45min, filter while hot, filtrate input second level washers Skill process, filter cake input fourth stage washing process process；Fourth stage wash liquid is washed using level V polyether-ether-ketone resin Filtrate afterwards washs the filter cake that the third level obtains, and supplements the deionized water of 9wt% level V filtrate total amounts so that washing The solids content of polyether-ether-ketone resin is 26wt% in system, with the temperature of charge in fourth stage washing system is risen to 96 DEG C, and under the temperature conditionss, 45min is kept the temperature, is filtered while hot, filtrate input third level washing process process, filter cake input the Pyatyi washing process process；Level V wash liquid is the filtrate after being washed using the 6th stage polyetheretherketoneresin resin to wash the The filter cake that level Four obtains, and supplement the deionized water of the 6th grade of filtrate total amount of 6wt% so that polyether-ether-ketone resin in washing system Solids content be 26wt%, with the temperature of charge in level V washing system is risen to 96 DEG C, and in the temperature conditionss Under, 45min is kept the temperature, is filtered while hot, filtrate input fourth stage washing process process, filter cake inputs the 6th grade of washing process process； 6th grade of wash liquid is to wash the filter cake that level V obtains using the filtrate after the washing of the 7th stage polyetheretherketoneresin resin, and Supplementing the deionized water of the 7th grade of filtrate total amount of 3wt% so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, With the temperature of charge in the 6th grade of washing system is risen to 96 DEG C, and under the temperature conditionss, 45min is kept the temperature, while hot mistake Filter, filtrate input level V washing process process, filter cake input the 7th grade of washing process process；7th grade of wash liquid is to utilize Filtrate after the washing of 8th stage polyetheretherketoneresin resin washs the 6th grade of obtained filter cake, and to supplement the 8th grade of filtrates of 1wt% total The deionized water of amount so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, with i.e. by the 7th grade of washing system In temperature of charge rise to 96 DEG C, and under the temperature conditionss, keep the temperature 45min, filter while hot, filtrate inputs the 6th grade of washing Technique process, filter cake input the 8th grade of washing process process；Fresh deionized water is added in filter cake so that in washing system The solids content of polyether-ether-ketone resin is 26wt%, with the temperature of charge in the 8th grade of washing system risen to 96 DEG C, and Under the temperature conditionss, 45min is kept the temperature, is filtered while hot, filtrate inputs the 7th grade of washing process process, filter cake input drying process work Sequence；This completes the washing of polyether-ether-ketone resin, so as to obtain polyether-ether-ketone resin crude product；
Rejoined again in the washing kettle of the dimethylacetamide solvent containing 30% deionized water in polyether-ether-ketone resin crude product, And be heated to 220 DEG C, insulation 1 it is small when after；Insulation filtering while hot, the operation for repeating the step obtain melt flow index and are The polyether-ether-ketone resin of 10g/10min；Obtained polyether-ether-ketone resin is using the identical washing process of polyether-ether-ketone resin crude product Control condition carries out washing 8 times, obtains the polyether-ether-ketone wet resin that water content is 6%wt；Obtained polyether-ether-ketone resin, is inserted Dry 3h in the vacuum drying oven that temperature is 168 DEG C, its vacuum is -0.08MPa, so as to obtain the polyether-ether-ketone tree of high-purity Fat.
The polyether-ether-ketone resin of acquisition, specific performance feature are listed in Fig. 1.
Embodiment 3
It is raw material using 4,4- difluoro benzophenones, bisphenol-A, hydroquinone and phenol, N, N '-dimethyl acetamide is solvent, The polycondensation synthesis of polyether-ether-ketone resin under alkali carbonate promoter effect, wherein 4,4- difluoro benzophenones：Bisphenol-A+to benzene Diphenol+phenol：The molar ratio of alkali carbonate reaches 1.0：1.003：1.003 wherein bisphenol-A：Hydroquinone：Phenol rubs You reach 1.0 by ratio：32.3：0.033, its manufacturing process includes：
Under conditions of nitrogen is passed through, by 4,4- difluoro benzophenones add be stirred continuously and with N, N '-dimethyl acetamide To be reacted in the polymeric kettle of solvent, heating heating is carried out with conduction oil, when temperature rises to 167 DEG C, then is sequentially added into Alkali carbonate, bisphenol-A, hydroquinone；Solid-liquid mass ratio is set to reach 0.17：1.0, then proceed to heat up, when temperature rises During to 266 DEG C, when insulation 3.8 is small, temperature is increased to 306 DEG C again, when insulation 6.2 is small after；Pour into -7 DEG C of frozen water, it is drastically cold But room temperature is arrived, is filtered, then 41 DEG C of mass ratioes of filter cake addition reach 33：14：3 absolute methanol, acetone, the mixed solution of chloroform The dimethylacetamide solvent 3 times in mixture is washed out, polyether-ether-ketone resin is often washed once and is intended to separating and filtering；The first order The filtrate input solvent recovery process that methanol, acetone, the mixed solution of chloroform wash；The mixing of its specific methanol, acetone, chloroform Solution washing process is：First order wash liquid is the filtrate after being washed using the second stage polyetheretherketoneresin resin to wash to obtain The reaction mixture filter cake that is separated by filtration out, second level wash liquid is using after the washing of third level polyether-ether-ketone resin The filter cake separated the first order washing and filtering that washs of filtrate, third level wash liquid is to utilize fresh first Alcohol, acetone, chloroform mixed solution；
First order wash liquid is the filtrate after being washed using the second stage polyetheretherketoneresin resin to wash the filter that the first order obtains Cake, and supplement the deionized water of 17wt% second level filtrate total amount so that the solids content of polyether-ether-ketone resin is in washing system 27wt%, with the temperature of charge in first order washing system is risen to 97 DEG C, and under the temperature conditionss, keeps the temperature 38min, Filter while hot, filtrate inputs the recovery system of accessory substance-sodium chloride, filter cake input second level washing process process；The second level is washed It is to wash the filter cake that the first order obtains using the filtrate after the washing of third level polyether-ether-ketone resin to wash liquid, and is supplemented The deionized water of 14wt% third level filtrate total amounts so that the solids content of polyether-ether-ketone resin is 27wt% in washing system, with The temperature of charge in the washing system of the second level is risen to 97 DEG C, and under the temperature conditionss, keeps the temperature 9min, filters while hot, Filtrate inputs first order washing process process, filter cake input third level washing process process；Third level wash liquid is to utilize the Filtrate after the washing of four stage polyetheretherketoneresin resins washs the filter cake that the second level obtains, and to supplement 11wt% fourth stage filtrates total The deionized water of amount so that the solids content of polyether-ether-ketone resin is 27wt% in washing system, with i.e. by third level washing system In temperature of charge rise to 97 DEG C, and under the temperature conditionss, keep the temperature 41min, filter while hot, filtrate input second level washing Technique process, filter cake input fourth stage washing process process；Fourth stage wash liquid is washed using level V polyether-ether-ketone resin Filtrate after washing washs the filter cake that the third level obtains, and supplements the deionized water of 7wt% level V filtrate total amounts so that washes The solids content for washing polyether-ether-ketone resin in system is 27wt%, with rising to the temperature of charge in fourth stage washing system 97 DEG C, and under the temperature conditionss, keep the temperature 33min, filter while hot, filtrate input third level washing process process, filter cake input Level V washing process process；Level V wash liquid is the filtrate after being washed using the 6th stage polyetheretherketoneresin resin to wash The filter cake that the fourth stage obtains, and supplement the deionized water of the 6th grade of filtrate total amount of 7wt% so that polyether-ether-ketone tree in washing system The solids content of fat is 27wt%, with the temperature of charge in level V washing system is risen to 97 DEG C, and in the temperature conditionss Under, 43min is kept the temperature, is filtered while hot, filtrate input fourth stage washing process process, filter cake inputs the 6th grade of washing process process； 6th grade of wash liquid is to wash the filter cake that level V obtains using the filtrate after the washing of the 7th stage polyetheretherketoneresin resin, and Supplementing the deionized water of the 7th grade of filtrate total amount of 4wt% so that the solids content of polyether-ether-ketone resin is 24wt% in washing system, With the temperature of charge in the 6th grade of washing system is risen to 94 DEG C, and under the temperature conditionss, 41min is kept the temperature, while hot mistake Filter, filtrate input level V washing process process, filter cake input the 7th grade of washing process process；7th grade of wash liquid is to utilize Filtrate after the washing of 8th stage polyetheretherketoneresin resin washs the 6th grade of obtained filter cake, and to supplement the 8th grade of filtrates of 2wt% total The deionized water of amount so that the solids content of polyether-ether-ketone resin is 27wt% in washing system, with i.e. by the 7th grade of washing system In temperature of charge rise to 97 DEG C, and under the temperature conditionss, keep the temperature 36min, filter while hot, filtrate inputs the 6th grade of washing Technique process, filter cake input the 8th grade of washing process process；Fresh deionized water is added in filter cake so that in washing system The solids content of polyether-ether-ketone resin is 27wt%, with the temperature of charge in the 8th grade of washing system risen to 97 DEG C, and Under the temperature conditionss, 43min is kept the temperature, is filtered while hot, filtrate inputs the 7th grade of washing process process, filter cake input drying process work Sequence；This completes the washing of polyether-ether-ketone resin, so as to obtain polyether-ether-ketone resin crude product；
Rejoined again in the washing kettle of the dimethylacetamide solvent containing 30% deionized water in polyether-ether-ketone resin crude product, And be heated to 213 DEG C, insulation 1.5 it is small when after；Insulation filtering while hot, the operation for repeating the step obtain melt flow index and are The polyether-ether-ketone resin of 13g/10min；Obtained polyether-ether-ketone resin is using the identical washing process of polyether-ether-ketone resin crude product Control condition carries out washing 8 times, obtains the polyether-ether-ketone wet resin that water content is 5%wt；Obtained polyether-ether-ketone resin, is inserted Dry 3.3h in the vacuum drying oven that temperature is 164 DEG C, its vacuum is -0.083MPa, so as to obtain the polyether-ether-ketone of high-purity Resin.
The polyether-ether-ketone resin of acquisition, specific performance feature are listed in Fig. 1.
Embodiment 4
It is raw material using 4,4- difluoro benzophenones, bisphenol-A, hydroquinone and phenol, N, N '-dimethyl acetamide is solvent, The polycondensation synthesis of polyether-ether-ketone resin under alkali carbonate promoter effect, wherein 4,4- difluoro benzophenones：Bisphenol-A+to benzene Diphenol+phenol：The molar ratio of alkali carbonate reaches 1.0：1.003：1.003 wherein bisphenol-A：Hydroquinone：Phenol rubs You reach 1.0 by ratio：32.3：0.033, its manufacturing process includes：
Under conditions of nitrogen is passed through, by 4,4- difluoro benzophenones add be stirred continuously and with N, N '-dimethyl acetamide To be reacted in the polymeric kettle of solvent, heating heating is carried out with conduction oil, when temperature rises to 168 DEG C, then is sequentially added into Alkali carbonate, bisphenol-A, hydroquinone；Solid-liquid mass ratio is set to reach 0.19：1.0, then proceed to heat up, when temperature rises During to 267 DEG C, when insulation 3.9 is small, temperature is increased to 307 DEG C again, when insulation 6.5 is small after；Pour into -7.5 DEG C of frozen water, drastically Room temperature is cooled to, is filtered, then 44 DEG C of mass ratioes of filter cake addition reach 33：14：3 absolute methanol, acetone, the mixing of chloroform are molten Liquid washes out the dimethylacetamide solvent 3 times in mixture, often washed once polyether-ether-ketone resin and is intended to separating and filtering；First The filtrate input solvent recovery process that level methanol, acetone, the mixed solution of chloroform wash；Its specific methanol, acetone, chloroform it is mixed Closing solution washing process is：First order wash liquid is the filtrate after being washed using the second stage polyetheretherketoneresin resin to wash To the reaction mixture filter cake that is separated by filtration out, second level wash liquid is to wash it using third level polyether-ether-ketone resin The filter cake that filtrate afterwards is separated the first order washing and filtering that washs, third level wash liquid is to utilize fresh first Alcohol, acetone, chloroform mixed solution；
First order wash liquid is the filtrate after being washed using the second stage polyetheretherketoneresin resin to wash the filter that the first order obtains Cake, and supplement the deionized water of 17.6wt% second level filtrate total amount so that the solids content of polyether-ether-ketone resin in washing system For 26.8wt%, with the temperature of charge in first order washing system is risen to 98 DEG C, and under the temperature conditionss, insulation 44min, is filtered while hot, and filtrate inputs the recovery system of accessory substance-sodium chloride, filter cake input second level washing process process；The Two level wash liquid is to wash the filter cake that the first order obtains using the filtrate after the washing of third level polyether-ether-ketone resin, and is mended Fill the deionized water of 14.3wt% third level filtrate total amounts so that the solids content of polyether-ether-ketone resin is in washing system 27.1wt%, with the temperature of charge in the washing system of the second level is risen to 98 DEG C, and under the temperature conditionss, insulation 39min, is filtered while hot, filtrate input first order washing process process, filter cake input third level washing process process；The third level is washed It is to wash the filter cake that the second level obtains using the filtrate after the washing of fourth stage polyether-ether-ketone resin to wash liquid, and is supplemented The deionized water of 11.3wt% fourth stage filtrate total amounts so that the solids content of polyether-ether-ketone resin is in washing system 27.4wt%, with the temperature of charge in third level washing system is risen to 97.5 DEG C, and under the temperature conditionss, insulation 45min, is filtered while hot, filtrate input second level washing process process, filter cake input fourth stage washing process process；The fourth stage is washed It is to wash the filter cake that the third level obtains using the filtrate after the washing of level V polyether-ether-ketone resin to wash liquid, and supplements 8wt% The deionized water of level V filtrate total amount so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, with i.e. by the Temperature of charge in level Four washing system rises to 96.8 DEG C, and under the temperature conditionss, keeps the temperature 42min, filter while hot, filtrate Input third level washing process process, filter cake input level V washing process process；Level V wash liquid is to utilize the 6th grade Filtrate after polyether-ether-ketone resin washing washs the filter cake that the fourth stage obtains, and supplements the 6th grade of filtrate total amount of 8.3wt% Deionized water so that the solids content of polyether-ether-ketone resin is 27.4wt% in washing system, with i.e. by level V washing system Temperature of charge rise to 98 DEG C, and under the temperature conditionss, keep the temperature 43.5min, filter while hot, filtrate input fourth stage washing Technique process, filter cake input the 6th grade of washing process process；6th grade of wash liquid is washed using the 7th stage polyetheretherketoneresin resin Filtrate after washing washs the filter cake that level V obtains, and supplements the deionized water of the 7th grade of filtrate total amount of 5.5wt% so that The solids content of polyether-ether-ketone resin is 26.9wt% in washing system, with i.e. by the temperature of charge in the 6th grade of washing system 98.5 DEG C are risen to, and under the temperature conditionss, keeps the temperature 42.3min, filters while hot, filtrate input level V washing process process, Filter cake inputs the 7th grade of washing process process；7th grade of wash liquid is to utilize the filter after the washing of the 8th stage polyetheretherketoneresin resin Liquid washs the 6th grade of obtained filter cake, and supplements the deionized water of the 8th grade of filtrate total amount of 2.3wt% so that in washing system The solids content of polyether-ether-ketone resin is 26.4wt%, with the temperature of charge in the 7th grade of washing system is risen to 98.1 DEG C, And under the temperature conditionss, keep the temperature 44.3min, filter while hot, filtrate inputs the 6th grade of washing process process, filter cake input the 8th Level washing process process；Fresh deionized water is added in filter cake so that the solid of polyether-ether-ketone resin contains in washing system Measure as 27.5wt%, with the temperature of charge in the 8th grade of washing system is risen to 98.4 DEG C, and under the temperature conditionss, protect Warm 43.1min, is filtered while hot, and filtrate inputs the 7th grade of washing process process, filter cake input drying process process；Thus complete The washing of polyether-ether-ketone resin, so as to obtain polyether-ether-ketone resin crude product；
Rejoined again in the washing kettle of the dimethylacetamide solvent containing 30% deionized water in polyether-ether-ketone resin crude product, And be heated to 216 DEG C, insulation 1.8 it is small when after；Insulation filtering while hot, the operation for repeating the step obtain melt flow index and are 14.1g/10min polyether-ether-ketone resin；Obtained polyether-ether-ketone resin is using the identical washers of polyether-ether-ketone resin crude product Skill control condition carries out washing 8 times, obtains the polyether-ether-ketone wet resin that water content is 4.8%wt；Obtained polyether-ether-ketone resin, Dry 3.8h in the vacuum drying oven that temperature is 163 DEG C is inserted, its vacuum is -0.088MPa, so as to obtain the polyethers of high-purity Ether ketone resin.
The polyether-ether-ketone resin of acquisition, specific performance feature are listed in Fig. 1.
Comparison example 2
In addition to the mixture after being used in mixed way two kinds of low boiling point solvent processing polyether-ether-ketone resin synthesis, remaining is adopted this example With the process conditions and composition of raw materials synthesis of polyether-ether-ketone resin of embodiment 1, so as to obtain the not high polyether-ether-ketone resin of purity.
It is raw material using 4,4- difluoro benzophenones, bisphenol-A, hydroquinone and phenol, N, N '-dimethyl acetamide is molten Agent, the polycondensation synthesis of polyether-ether-ketone resin under alkali carbonate promoter effect, wherein 4,4- difluoro benzophenones：Bisphenol-A+right Benzenediol+phenol：The molar ratio of alkali carbonate reaches 1.0：1.003：1.003 wherein bisphenol-A：Hydroquinone：Phenol Molar ratio reaches 1.0：32.3：0.033, its manufacturing process includes：
Under conditions of nitrogen is passed through, by 4,4- difluoro benzophenones add be stirred continuously and with N, N '-dimethyl acetamide To be reacted in the polymeric kettle of solvent, heating heating is carried out with conduction oil, when temperature rises to 168 DEG C, then is sequentially added into Alkali carbonate, bisphenol-A, hydroquinone；Solid-liquid mass ratio is set to reach 0.2：1.0, then proceed to heat up, when temperature rises to At 26468 DEG C, when insulation 4.0 is small, temperature is increased to 308 DEG C again, when insulation 6.0 is small after；Pour into -8 DEG C of frozen water, it is drastically cold But room temperature is arrived, is filtered, then 38 DEG C of mass ratioes of filter cake addition reach 33：The mixing of 17 acetone, chloroform or methanol and chloroform is molten Liquid washes out the dimethylacetamide solvent 3 times in mixture, often washed once polyether-ether-ketone resin and is intended to separating and filtering；First The filtrate input solvent recovery process that grade acetone, the mixed solution of chloroform wash；The mixed solution washing of its specific acetone, chloroform Technique is：First order wash liquid is that the filtrate after being washed using the second stage polyetheretherketoneresin resin is mixed come the reaction washed The filter cake that compound is separated by filtration out, second level wash liquid be using third level polyether-ether-ketone resin wash after filtrate come The filter cake that obtained first order washing and filtering is separated is washed, third level wash liquid is mixed using fresh acetone, chloroform Close solution；
First order wash liquid is the filtrate after being washed using the second stage polyetheretherketoneresin resin to wash the filter that the first order obtains Cake, and supplement the deionized water of 16wt% second level filtrate total amount so that the solids content of polyether-ether-ketone resin is in washing system 28wt%, with the temperature of charge in first order washing system is risen to 96 DEG C, and under the temperature conditionss, keeps the temperature 45min, Filter while hot, filtrate inputs the recovery system of accessory substance-sodium chloride, filter cake input second level washing process process；The second level is washed It is to wash the filter cake that the first order obtains using the filtrate after the washing of third level polyether-ether-ketone resin to wash liquid, and is supplemented The deionized water of 13wt% third level filtrate total amounts so that the solids content of polyether-ether-ketone resin is 28wt% in washing system, with The temperature of charge in the washing system of the second level is risen to 96 DEG C, and under the temperature conditionss, keeps the temperature 45min, filters while hot, Filtrate inputs first order washing process process, filter cake input third level washing process process；Third level wash liquid is to utilize the Filtrate after the washing of four stage polyetheretherketoneresin resins washs the filter cake that the second level obtains, and supplements 9wt% fourth stage filtrate total amounts Deionized water so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, with i.e. by third level washing system Temperature of charge rise to 96 DEG C, and under the temperature conditionss, keep the temperature 45min, filter while hot, filtrate input second level washers Skill process, filter cake input fourth stage washing process process；Fourth stage wash liquid is washed using level V polyether-ether-ketone resin Filtrate afterwards washs the filter cake that the third level obtains, and supplements the deionized water of 6wt% level V filtrate total amounts so that washing The solids content of polyether-ether-ketone resin is 26wt% in system, with the temperature of charge in fourth stage washing system is risen to 96 DEG C, and under the temperature conditionss, 45min is kept the temperature, is filtered while hot, filtrate input third level washing process process, filter cake input the Pyatyi washing process process；Level V wash liquid is the filtrate after being washed using the 6th stage polyetheretherketoneresin resin to wash the The filter cake that level Four obtains, and supplement the deionized water of the 6th grade of filtrate total amount of 6wt% so that polyether-ether-ketone resin in washing system Solids content be 26wt%, with the temperature of charge in level V washing system is risen to 96 DEG C, and in the temperature conditionss Under, 45min is kept the temperature, is filtered while hot, filtrate input fourth stage washing process process, filter cake inputs the 6th grade of washing process process； 6th grade of wash liquid is to wash the filter cake that level V obtains using the filtrate after the washing of the 7th stage polyetheretherketoneresin resin, and Supplementing the deionized water of the 7th grade of filtrate total amount of 3wt% so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, With the temperature of charge in the 6th grade of washing system is risen to 96 DEG C, and under the temperature conditionss, 45min is kept the temperature, while hot mistake Filter, filtrate input level V washing process process, filter cake input the 7th grade of washing process process；7th grade of wash liquid is to utilize Filtrate after the washing of 8th stage polyetheretherketoneresin resin washs the 6th grade of obtained filter cake, and to supplement the 8th grade of filtrates of 1wt% total The deionized water of amount so that the solids content of polyether-ether-ketone resin is 26wt% in washing system, with i.e. by the 7th grade of washing system In temperature of charge rise to 96 DEG C, and under the temperature conditionss, keep the temperature 45min, filter while hot, filtrate inputs the 6th grade of washing Technique process, filter cake input the 8th grade of washing process process；Fresh deionized water is added in filter cake so that in washing system The solids content of polyether-ether-ketone resin is 26wt%, with the temperature of charge in the 8th grade of washing system risen to 96 DEG C, and Under the temperature conditionss, 45min is kept the temperature, is filtered while hot, filtrate inputs the 7th grade of washing process process, filter cake input drying process work Sequence；This completes the washing of polyether-ether-ketone resin, so as to obtain polyether-ether-ketone resin crude product；
Rejoined again in the washing kettle of the dimethylacetamide solvent containing 30% deionized water in polyether-ether-ketone resin crude product, And be heated to 210 DEG C, insulation 2 it is small when after；Insulation filtering while hot, the operation for repeating the step obtain melt flow index and are The polyether-ether-ketone resin of 15g/10min；Obtained polyether-ether-ketone resin is using the identical washing process of polyether-ether-ketone resin crude product Control condition carries out washing 8 times, obtains the polyether-ether-ketone wet resin that water content is 3%wt；Obtained polyether-ether-ketone resin, is inserted Dry 3h in the vacuum drying oven that temperature is 168 DEG C, its vacuum is -0.09MPa, so as to obtain the polyether-ether-ketone tree of high-purity Fat.
The polyether-ether-ketone resin of acquisition, specific performance feature are listed in Fig. 1.

Claims (1)

1. a kind of manufacture method of polyether-ether-ketone resin, is using 4,4- difluoro benzophenones, bisphenol-A, hydroquinone and phenol Raw material, N, N '-dimethyl acetamide are solvent, the polycondensation synthesis of polyether-ether-ketone resin under alkali carbonate promoter effect, its It is characterized in that：4, the 4- difluoro benzophenones：Bisphenol-A+hydroquinone+phenol：The molar ratio of alkali carbonate is 1.0： 1.003：1.003 the bisphenol-A：Hydroquinone：The molar ratio of phenol is 1.0：32.3：0.033；The tool of the manufacture method Body step is：
（1）In the case where being passed through nitrogen protective condition, by 4,4- difluoro benzophenones add be stirred continuously and with N, N '-dimethyl second Acid amides carries out heating heating with conduction oil, when temperature rises to 166~168 DEG C, then distinguishes to be reacted in the polymeric kettle of solvent Alkali carbonate, bisphenol-A and hydroquinone are sequentially added, solid-liquid mass ratio is reached 0.15~0.2：1.0, then proceed to rise Temperature, when temperature rises to 264~268 DEG C, when insulation 3.6~4.0 is small, temperature is increased to 304~308 DEG C again, and insulation 6.0~ 6.6 it is small when；
（2）Mixture after insulation is poured into -8~-6 DEG C of frozen water, quick refrigeration to room temperature, filtered, then filter cake adds The mixed solution of 38~48 DEG C of absolute methanols, acetone and chloroform washes out the dimethylacetamide solvent 3 times in mixture, often washes Wash a polyether-ether-ketone resin and be intended to separating and filtering；The filtrate that the first order methanol, acetone, the mixed solution of chloroform wash is defeated Enter solvent recovery process；The methanol, acetone, the mixed solution washing process of chloroform are to utilize second for first order wash liquid The filter cake that filtrate after stage polyetheretherketoneresin resin washing is separated by filtration out the reaction mixture that washs, the second level is washed It is that the filtrate after being washed using third level polyether-ether-ketone resin is isolated come the first order washing and filtering washed to wash liquid The filter cake come, third level wash liquid is to utilize fresh methanol, acetone and chloroform mixed solution；The methanol：Acetone：Chloroform Mass ratio be 33：14：3；
（3）In step（2）In obtained filter cake, after first order wash liquid is washed using the second stage polyetheretherketoneresin resin Filtrate carrys out washing step（1）Obtained filter cake, and supplement the deionized water of 16~18wt% second level filtrate total amount so that washing The solids content of polyether-ether-ketone resin is 26~28wt% in system, with i.e. by the temperature of charge rising in first order washing system To 96~99 DEG C, and under the temperature conditionss, 30~45min is kept the temperature, is filtered while hot, filtrate inputs the recycling of side product chlorinated sodium System, filter cake input second level washing process process；
（4）In step（3）In obtained filter cake, after second level wash liquid is washed using third level polyether-ether-ketone resin Filtrate carrys out washing step（2）Obtained filter cake, and supplement the deionized water of 13~15wt% third level filtrate total amounts so that washing The solids content of polyether-ether-ketone resin is 26~28wt% in system, with i.e. by the temperature of charge rising in the washing system of the second level To 96~99 DEG C, and under the temperature conditionss, 30~45min is kept the temperature, is filtered while hot, filtrate input first order washing process work Sequence, filter cake input third level washing process process；
（5）In step（4）In obtained filter cake, after third level wash liquid is washed using fourth stage polyether-ether-ketone resin Filtrate carrys out washing step（3）Obtained filter cake, and supplement the deionized water of 9~12wt% fourth stage filtrate total amounts so that washing system The solids content of polyether-ether-ketone resin is 26~28wt% in system, with rising to the temperature of charge in third level washing system 96~99 DEG C, and under the temperature conditionss, keep the temperature 30~45min, filter while hot, filtrate input second level washing process process, Filter cake inputs fourth stage washing process process；
（6）In step（5）In obtained filter cake, after fourth stage wash liquid is washed using level V polyether-ether-ketone resin Filtrate carrys out washing step（4）Obtained filter cake, and supplement the deionized water of 6~9wt% level V filtrate total amounts so that washing system The solids content of polyether-ether-ketone resin is 26~28wt% in system, with rising to the temperature of charge in fourth stage washing system 96~99 DEG C, and under the temperature conditionss, keep the temperature 30~45min, filter while hot, filtrate input third level washing process process, Filter cake inputs level V washing process process；
（7）In step（6）In obtained filter cake, after level V wash liquid is washed using the 6th stage polyetheretherketoneresin resin Filtrate carrys out washing step（5）Obtained filter cake, and supplement the deionized water of the 6th grade of filtrate total amount of 6~9wt% so that washing system The solids content of polyether-ether-ketone resin is 26~28wt% in system, with rising to the temperature of charge in level V washing system 96~99 DEG C, and under the temperature conditionss, keep the temperature 30~45min, filter while hot, filtrate input fourth stage washing process process, Filter cake inputs the 6th grade of washing process process；
（8）In step（7）In obtained filter cake, after the 6th grade of wash liquid is washed using the 7th stage polyetheretherketoneresin resin Filtrate carrys out washing step（6）Obtained filter cake, and supplement the deionized water of the 7th grade of filtrate total amount of 3~6wt% so that washing system The solids content of polyether-ether-ketone resin is 26~28wt% in system, with rising to the temperature of charge in the 6th grade of washing system 96~99 DEG C, and under the temperature conditionss, keep the temperature 30~45min, filter while hot, filtrate input level V washing process process, Filter cake inputs the 7th grade of washing process process；
（9）In step（8）In obtained filter cake, after the 7th grade of wash liquid is washed using the 8th stage polyetheretherketoneresin resin Filtrate carrys out washing step（7）Obtained filter cake, and supplement the deionized water of the 8th grade of filtrate total amount of 1~3wt% so that washing system The solids content of polyether-ether-ketone resin is 26~28wt% in system, with rising to the temperature of charge in the 7th grade of washing system 96~99 DEG C, and under the temperature conditionss, keep the temperature 30~45min, filter while hot, filtrate inputs the 6th grade of washing process process, Filter cake inputs the 8th grade of washing process process；
（10）In step（9）In obtained filter cake, fresh deionized water is added so that polyether-ether-ketone resin in washing system Solids content is 26~28wt%, with the temperature of charge in the 8th grade of washing system is risen to 96~99 DEG C, and in the temperature Under the conditions of, 30~45min is kept the temperature, is filtered while hot, filtrate inputs the 7th grade of washing process process, filter cake input drying process work Sequence, that is, complete the washing of polyether-ether-ketone resin, so as to obtain polyether-ether-ketone resin crude product；
（11）By step（10）Obtained polyether-ether-ketone resin crude product adds the dimethylacetamide solvent containing 30% deionized water Washing kettle in, 210~220 DEG C are heated to, when insulation 1~2 is small；
（12）By step（11）Mixture after insulation keeps the temperature filtering while hot, repeats step 11）Operation obtain melt-flow Index is the polyether-ether-ketone resin of 10~15g/10min；
（13）By step（12）Obtained polyether-ether-ketone resin uses step（3）~（10）Identical washing process control condition into Row washing 8 times, obtains the polyether-ether-ketone wet resin that water content is 3~6%wt；
（14）By step（13）Obtained polyether-ether-ketone resin, insert temperature be dry 3 in 158~168 DEG C of vacuum drying oven~ 4h, its vacuum is -0.08~-0.09MPa, so as to obtain the polyether-ether-ketone resin of high-purity.
CN201711338915.3A 2017-12-14 2017-12-14 A kind of manufacture method of polyether-ether-ketone resin Pending CN107936205A (en)

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