CN104497239A - Industrial synthetic method of low-chromaticity high-thermal-stability end capped polyether-ether-ketone resin - Google Patents
Industrial synthetic method of low-chromaticity high-thermal-stability end capped polyether-ether-ketone resin Download PDFInfo
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Abstract
The invention discloses an industrial synthetic method of low-chromaticity high-thermal-stability end capped polyether-ether-ketone resin. The industrial synthetic method comprises the following steps: in a reaction kettle with nitrogen filled protection, adding phenyl sulfone, 4,4'-difluorobenzophenone and sodium carbonate, stirring, heating to 130-140 DEG C, adding hydroquinone into the system when monomer is completely dissolved, further uniformly stirring, implementing continuous heating reaction, heating to310-320 DEG C, polymerizing for 1-4 hours, adding an end-capping reagent to react for 10-30 minutes, thereby obtaining polymerized mucus, wherein the solid content of the system is 15-40%; cooling the polymerized mucus, crushing into powder, boiling the filtered powder with an organic solvent and deionized water, repeatedly washing, filtering to remove the solvent and byproduct salt, and drying, thereby obtaining polyether-ether-ketone resin.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of low colourity, the Industrialized synthesis method of high thermal stability end capped polyether ether ketone resin and the application of obtained polyether-ether-ketone resin.
Background technology
Polyether-ether-ketone is a kind of high performance engineering plastics, because they have thermotolerance, hot water resistance, wear resistance, resistance to fatigue, radioresistance, peel resistance, creep resistance, dimensional stability, shock-resistance, chemical proofing, the excellent over-all properties such as nontoxic, fire-retardant, so be widely used in fields such as electronics, electrical equipment, machinery, automobile, medical apparatus, aircraft industry, food-processing and non-viscous paints for a long time.
Have in the existing production technique of polyether-ether-ketone and to adopt sulfobenzide or tetramethylene sulfone to be solvent, salt forming agent comprises basic metal, alkaline earth metal carbonate and supercarbonate, alkali metal hydroxide, general salt forming agent is the described mixture of one or more, polyether-ether-ketone (PEEK) color of resin that patent US 4320224 adopts separately sodium carbonate to produce for salt forming agent is comparatively dark, more crisp and molecular weight is lower.But adopt other salt forming agent General reactions more violent, process is unstable, or the water absorbability of salt forming agent own is strong, the foreign matter content that is difficult to sieve is high, therefore in order to control reaction, generally take to add end-capping reagent or the excessive production technique of monomer, halogen end group is all contained in polyether-ether-ketone (PEEK) resin produced, terminal hydroxy group, amino end group or metal end group, as US Patent No. 5137988 (A) and Chinese patent CN2013102763332, containing terminal hydroxy group, the resin of amino end group or metal end group except be applied to useful in paint field except, should avoid in other Application Areass.Therefore, before reaction closes to an end, add rational end-capping reagent be very important, and adding along with end-capping reagent, the hot-work stability of product significantly improves.
The end-capping reagent being generally used for polyether-ether-ketone production system has CH
3cl, 4,4 '-difluoro benzophenone, 4-fluorine biphenyl, 4-fluorine benzophenone etc., as Chinese patent CN2013102763332, CN102250299B, there is following defect in the end-capping reagent that these technology adopt: (1) adopts CH in actual production
3cl as end-capping reagent, due to CH
3they be gaseous state under Cl normal temperature, and polymerization reaction late stage temperature is higher than 230 DEG C, for ensureing better end-blocking effect, therefore needs constantly to pass into a large amount of CH in system
3cl, and excessive unreacted CH
3cl needs Separation and Recovery, because of and need to increase special recovery system, equipment cost is high, so less employing CH in actual production
3cl is end-capping reagent.(2) adopt 4,4 '-difluoro benzophenone as end-capping reagent, 4,4 '-difluoro benzophenone can disposablely when initial charge excessively to add, also can the phase adds after the reaction.Disposable excessive add fashionable, unbalance meeting due to monomer ratio causes the polyreaction cycle longer, and reaction end is difficult to control, and still carrying out due to the reaction of discharging stage polymerization, thus can cause final molecular resin amount wider distribution or the higher result of viscosity.If all macromolecular chain end groups reached in design are chlorine end group, in actual production, the viscosity that system reaches will cause resin without any value added.If adopt the reaction later stage to add 4,4 '-difluoro benzophenone, depolymerization phenomenon can be caused again, a certain amount of LiCl must be added in case depolymerization in system simultaneously, which again increases the post-processing difficulty of production cost and system; And equally also there is the unmanageable difficult problem of molecular weight with disposable excessive adding in it.(3) adopt 4-fluorine biphenyl, 4-fluorine benzophenone as end-capping reagent, the phase adds for forming benzene end group after end-blocking 4-fluorine biphenyl after the reaction, and stability is better, can control the molecular weight of resin preferably.But the defect that 4-chlorobenzophenone is used for polyether-ether-ketone polymerization system maximum is also deagglomeration problems, has depolymerization phenomenon after adding and occur, also need to add the anti-depolymerization of LiCl.
From above-mentioned, sodium carbonate is adopted to be that polyether-ether-ketone resin molecular weight prepared by salt forming agent is lower separately, and the equal existing defects of existing various end-capping reagent, the existence of these defects directly constrains the quality of polyether-ether-ketone.Therefore, find a kind of suitable end-capping reagent and vital effect is played for the polyether-ether-ketone of high-quality.
Summary of the invention
The present invention is intended to overcome above-mentioned prior art defect, and provide a kind of end-blocking effect better, during end-blocking, system depolymerization does not occur, and the product prepared has the Industrialized synthesis method of the polyether-ether-ketone resin of high high-temp stability.
The Industrialized synthesis method of a kind of low colourity of the present invention, high thermal stability end capped polyether ether ketone resin, comprises the following steps:
(1) excluding air: get rid of the air in solvent sulfobenzide and reactor with shielding gas nitrogen;
(2) add reactant: in reactor, add sulfobenzide, 4 under agitation, 4 '-difluoro benzophenone and basic metal salt forming agent, be heated to 130 DEG C ~ 140 DEG C;
(3) moisture is discharged: system temperature is increased to moisture carburation by evaporation the protected band of gas goes out reactor from system;
(4) continue evaporation: treat sulfobenzide, 4, after 4 '-difluoro benzophenone all dissolves, then add Resorcinol in system, be warming up to 180 DEG C ~ 220 DEG C after continuing to stir, react 1 ~ 2 hour;
(5) polyreaction: with 4,4 '-difluoro benzophenone and Resorcinol for reaction monomers, being solvent with sulfobenzide, take sodium carbonate as basic metal salt forming agent;
In the reactor of nitrogen filled protection, add sulfobenzide solvent, 4, start stirring after 4 '-difluoro benzophenone and salt forming agent and be warming up to 130 DEG C ~ 140 DEG C, the solid content of system is 15% ~ 40%, treat sulfobenzide, 4, after 4 '-difluoro benzophenone all dissolves, Resorcinol is added again in system, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react 1 ~ 2 hour, be warmed up to 240 DEG C ~ 260 DEG C, react 0.5 ~ 2 hour, be warmed up to 270 DEG C ~ 280 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C again, be polymerized 1 ~ 4 hour, add end-capping reagent, continue reaction 10-30 minute, mucus must be polymerized,
Wherein, described end-capping reagent is 3,4 '-difluoro benzophenone, 3-chloro-4-fluorine benzophenone, the fluoro-4-chlorobenzophenone of 3-or 3, the mixing of one or more in 4 '-dichloro benzophenone, preferably 3, and 4 '-difluoro benzophenone;
The molar weight of described Resorcinol comparatively 4,4 '-difluoro benzophenone excessive 0.1% ~ 2%, or 4, the molar weight excessive compared with Resorcinol 0.1% ~ 2% of 4 '-difluoro benzophenone;
(6) aftertreatment: polymerization mucus is ground into powder after water cooling, boils repetitive scrubbing and crosses and filter solvent and by-product salt, then namely obtain polyether-ether-ketone resin after drying by powder organic solvent, the deionized water after filtering.
End-capping reagent of the present invention is the asymmetric aromatic ketone radical derivative of a class, and its structural formula is as follows:
Such end-capping reagent has different functions, both can react and end-blocking with terminal hydroxy group, simultaneously has again certain polymerizing power and prevents the function of system depolymerization.In certain temperature range, such feature functionality group derivative has different substitutabilities, as 3,4 '-difluoro benzophenone, 4 '-position fluorine activity is obviously greater than 3-position fluorin radical, therefore 4 '-position fluorine participates in reaction fast plays end-blocking function, 3-position fluorin radical also has certain reactive behavior simultaneously, can participate in polyreaction, thus when ensure that end-blocking, system DeR does not occur.End-capping reagent adds before 10 – 20min before reaction terminates, and does not affect the polyreaction cycle.The add-on of end-capping reagent be Resorcinol molar content 0.1 ~ 5% between.
The molar weight of biphenol monomer of the present invention and two chlorine monomer controls in the scope of 1.001 ~ 1.2:1, when the molar weight comparatively 4 of Resorcinol, 4 '-difluoro benzophenone excessive 0.1% ~ 2% time, produce the resin obtained and be mainly applicable to injection moulding.
When the molar weight of 4,4 '-difluoro benzophenone excessive compared with Resorcinol 0.1% ~ 2% time, produce the resin obtained and be mainly applicable to coating.
The present invention compared with prior art, has following beneficial effect:
1) the present invention passes through the asymmetric aromatic ketone monomer of employing one class as end-capping reagent, it not only has good end-blocking effect, and can polyreaction be participated in, thus when ensure that end-blocking there is not depolymerization phenomenon in system, avoid adding again of LiCl, reduce the post-processing difficulty of production cost and system, preparation-obtained end capped polyether sulphone resin has high high-temp stability simultaneously;
2) salt forming agent of the present invention adopts the Na that is produced from China's Mainland
2cO
3, save purchase cost; In addition excessive Na
2cO
3be present in the form of a powder in system, hydrolyzed alkaline is obviously than KOH, NaOH and K
2cO
3system is low, weak to the toxic side effect of system, and adopts domestic Na
2cO
3the polyether-ether-ketone product of explained hereafter and use import Na
2cO
3the product produced for salt forming agent is distinguished without color and luster.
3) the polyether-ether-ketone range of molecular weight distributions prepared by the present invention is narrow, and has low colourity, high thermal stability.
Although be described specific embodiment of the invention scheme, those skilled in the art will appreciate that and can carry out multiple change and modification to the present invention under the prerequisite not departing from scope of the present invention or spirit.Thus, this invention is intended to contain all these dropping within the scope of claims and coordinator thereof change and modify.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the concrete embodiment of the present invention, but embodiments of the present invention are by the restriction of following embodiment.
embodiment 1
In 200 liters of stainless steel cauldrons that nitrogen tube and high-efficiency stirrer are housed, first add 90.00KG sulfobenzide, 30.000KG 4, start to be warming up to 130-140 DEG C after 4 '-difluoro benzophenone and 16.000KG sodium carbonate, after monomer all dissolves, 14.000KG Resorcinol is added again in system, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react 1 ~ 2 hour, be warmed up to 240 DEG C ~ 260 DEG C, react 0.5 ~ 2 hour, be warmed up to 270 DEG C ~ 280 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C again, be polymerized 1 ~ 4 hour, add 283.7g 3, 4 '-difluoro benzophenone, continue reaction 10-30 minute, mucus must be polymerized, polymerization mucus water-cooled be ground into powder or directly pulverize after film forming cooling on Stainless Steel Band water cooler, again the powder after filtration is added alcohol reflux and boil 1h, so 10 times repeatedly, 1 hour is boiled again with new deionized water, so 8 ~ 10 times repeatedly, in water, chloride ion content is till below 5ppm, by filter after polymkeric substance vacuum-drying to moisture weight content lower than 0.5%, obtain polyether-ether-ketone (PEEK) virgin resin.
Gained PEEK resin melting index M I=15.5g/10min (365.0 DEG C, 5KG, 5 minutes);
MI=15.0g/10min (365.0 DEG C, 5KG, 30 minutes).
embodiment 2
With embodiment 1, except increasing 3, outside 4 '-difluoro benzophenone amount to 340.3g, other conditions are identical.
Gained PEEK resin melting index M I=20.7g/10min (365.0 DEG C, 5KG, 5 minutes);
MI=20.0g/10min (365.0 DEG C, 5KG, 30 minutes).
embodiment 3
With embodiment 2, except strengthening 3, outside 4 '-difluoro benzophenone amount to 397.3g, other conditions are identical.
Gained PEEK resin melting index M I=30.4g/10min (365.0 DEG C, 5KG, 5 minutes);
MI=30.0g/10min (365.0 DEG C, 5KG, 30 minutes).
comparative example 1
In 200 liters of stainless steel cauldrons that nitrogen tube and high-efficiency stirrer are housed, first add 90.00KG sulfobenzide, 30.000KG 4, start to be warming up to 130-140 DEG C after 4 '-difluoro benzophenone and 16.000KG sodium carbonate, after monomer all dissolves, 14.000KG Resorcinol is added again in system, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react 1 ~ 2 hour, be warmed up to 240 DEG C ~ 260 DEG C, react 0.5 ~ 2 hour, be warmed up to 270 DEG C ~ 280 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C polymerizations 1 ~ 4 hour again, add 340.3g 4, 4 '-difluoro benzophenone, continue reaction 20 minutes,
add again liCl, reacts 60 minutes, polymerization mucus water-cooled be ground into powder or directly pulverize after film forming cooling on Stainless Steel Band water cooler, again the powder after filtration is added alcohol reflux and boil 1h, so 10 times repeatedly, 1 hour is boiled again with new deionized water, so 8 ~ 10 times repeatedly, in water, chloride ion content is till below 5ppm, by filter after polymkeric substance vacuum-drying to moisture weight content lower than 0.5%, obtain polyether-ether-ketone (PEEK) virgin resin.
Gained PEEK resin melting index M I=26.0g/10min (365.0 DEG C, 5KG, 5 minutes);
MI=23.2g/10min (365.0 DEG C, 5KG, 30 minutes).
comparative example 2
In 200 liters of stainless steel cauldrons that nitrogen tube and high-efficiency stirrer are housed, first add 90.00KG sulfobenzide, 30.000KG 4, start to be warming up to 130-140 DEG C after 4 '-difluoro benzophenone and 16.000KG sodium carbonate, after monomer all dissolves, 14.000KG Resorcinol is added again in system, 180 DEG C ~ 220 DEG C are warming up to after continuing to stir, react 1 ~ 2 hour, be warmed up to 240 DEG C ~ 260 DEG C, react 0.5 ~ 2 hour, be warmed up to 270 DEG C ~ 280 DEG C, react 0.5 ~ 2 hour, be warming up to 310 DEG C ~ 320 DEG C polymerizations 1 ~ 4 hour again, add 312.3g 4-fluorine benzophenone, continue reaction 30 minutes,
add LiCl again, react 60 minutes, polymerization mucus water-cooled be ground into powder or directly pulverize after film forming cooling on Stainless Steel Band water cooler, again the powder after filtration is added alcohol reflux and boil 1h, so 10 times repeatedly, 1 hour is boiled again with new deionized water, so 8 ~ 10 times repeatedly, in water, chloride ion content is till below 5ppm, by filter after polymkeric substance vacuum-drying to moisture weight content lower than 0.5%, obtain polyether-ether-ketone (PEEK) virgin resin.
Gained PEEK resin melting index M I=25.8g/10min (365.0 DEG C, 5KG, 5 minutes);
MI=22.0g/10min (365.0 DEG C, 5KG, 30 minutes).
Claims (10)
1. a polyether-ether-ketone resin Industrialized synthesis method for low colourity, high thermal stability, end-blocking, comprises the following steps:
1) excluding air: get rid of the air in sulfobenzide and reactor with nitrogen;
2) add reactant: in reactor, add sulfobenzide, 4 under agitation, 4 '-difluoro benzophenone and basic metal salt forming agent, be heated to 130 DEG C ~ 140 DEG C;
3) moisture is discharged: system temperature is increased to moisture carburation by evaporation the protected band of gas goes out reactor from system;
4) continue evaporation: treat sulfobenzide, 4, after 4 '-difluoro benzophenone all dissolves, then add Resorcinol in system, be warming up to 180 DEG C ~ 220 DEG C after continuing to stir, react 1 ~ 2 hour;
5) polyreaction: heat up and carry out polyreaction, add end-capping reagent, continues reaction 10-30 minute, obtains polymerization mucus;
6) aftertreatment: polymerization mucus is ground into powder after water cooling, powder organic solvent, the deionized water after filtering is boiled repetitive scrubbing and cross and filter solvent and by-product salt, then namely drying obtains polyether-ether-ketone resin.
2. the Industrialized synthesis method of the polyether-ether-ketone resin of a kind of low colourity according to claim 1, high thermal stability, end-blocking, is characterized in that, described basic metal salt forming agent is carbonate.
3. the Industrialized synthesis method of the polyether-ether-ketone resin of a kind of low colourity according to claim 1, high thermal stability, end-blocking, is characterized in that, described basic metal salt forming agent is sodium carbonate and salt of wormwood or both different ratios mixtures.
4. the Industrialized synthesis method of the polyether-ether-ketone resin of a kind of low colourity according to claim 1, high thermal stability, end-blocking, it is characterized in that, the molar weight of described Resorcinol is compared with 4,4 '-difluoro benzophenone excessive 0.1% ~ 2%, or 4, the molar weight excessive compared with Resorcinol 0.1% ~ 2% of 4 '-difluoro benzophenone.
5. the Industrialized synthesis method of the polyether-ether-ketone resin of a kind of low colourity according to claim 1, high thermal stability, end-blocking, is characterized in that, the low boiling point organic solvent of described post-processing step comprises methyl alcohol, ethanol, acetone.
6. the Industrialized synthesis method of the polyether-ether-ketone resin of a kind of low colourity according to claim 1, high thermal stability, end-blocking, it is characterized in that, described end-capping reagent comprises 3,4 '-difluoro benzophenone, 3-chloro-4-fluorine benzophenone, the fluoro-4-chlorobenzophenone of 3-or 3, a kind of or above-mentioned several mixing in 4 '-dichloro benzophenone.
7. the Industrialized synthesis method of the polyether-ether-ketone resin of a kind of low colourity according to claim 1, high thermal stability, end-blocking, is characterized in that, described end-capping reagent 10 – 20min before reaction terminates add.
8. the Industrialized synthesis method of the polyether-ether-ketone resin of a kind of low colourity according to claim 1, high thermal stability, end-blocking, is characterized in that, the add-on of described end-capping reagent be Resorcinol molar content 0.1 ~ 5% between.
9. the Industrialized synthesis method of the polyether-ether-ketone resin of a kind of low colourity according to claim 1, high thermal stability, end-blocking, it is characterized in that, added sulfobenzide and 4,4 '-difluoro benzophenone and salt forming agent are solid-state, account for system solid content 15% ~ 40%.
10. the Industrialized synthesis method of the polyether-ether-ketone resin of a kind of low colourity according to claim 1, high thermal stability, end-blocking, it is characterized in that, the temperature of polyreaction is 240 DEG C ~ 260 DEG C, react 0.5 ~ 2 hour, be warmed up to 270 DEG C ~ 280 DEG C, react 0.5 ~ 2 hour, then be warming up to 310 DEG C ~ 320 DEG C, react 1 ~ 4 hour.
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| CN105348531A (en) * | 2015-11-30 | 2016-02-24 | 广东优巨先进材料研究有限公司 | Method for preparing polyaryl ether ketone sulfone random copolymer through quaternary copolycondensation technology |
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| CN113912799A (en) * | 2021-09-16 | 2022-01-11 | 吉林省中研高分子材料股份有限公司 | Polyether-ether-ketone and preparation method thereof |
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| CN105524239A (en) * | 2016-01-28 | 2016-04-27 | 淄博迈特瑞工程材料有限公司 | Method for modifying PEEK (polyether-ether-ketone) by titanium |
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| CN107474201A (en) * | 2017-08-16 | 2017-12-15 | 宜宾天原集团股份有限公司 | A kind of preparation method of high thermal stability end capped polyether ether ketone resin |
| 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 |
| CN113583232A (en) * | 2021-08-13 | 2021-11-02 | 吉林省中研高分子材料股份有限公司 | High-strength low-chroma polyether-ether-ketone and preparation method thereof |
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| WO2023040819A1 (en) * | 2021-09-16 | 2023-03-23 | 吉林省中研高分子材料股份有限公司 | Polyetheretherketone and preparation method therefor |
| CN114437338A (en) * | 2022-01-24 | 2022-05-06 | 吉林省聚科高新材料有限公司 | Synthesis method of polyether-ether-ketone |
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