CN106432651A - Preparation method of polyether-ether-ketone - Google Patents
Preparation method of polyether-ether-ketone Download PDFInfo
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- CN106432651A CN106432651A CN201610853847.3A CN201610853847A CN106432651A CN 106432651 A CN106432651 A CN 106432651A CN 201610853847 A CN201610853847 A CN 201610853847A CN 106432651 A CN106432651 A CN 106432651A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
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Abstract
The invention provides a preparation method of polyether-ether-ketone. The method comprises the following steps that in a reaction kettle, nitrogen is introduced, then, a solvent is added for stirring and heating, hydroquinone, sodium hydroxide and potassium carbonate are added to continue to be stirred, then, 4,4'-difluorobenzophenone and a water-carrying agent are added, after water generated by the reaction is completely carried out, continuous heating is performed to discharge the water-carrying agent, stirring and heating are performed continuously, 3,4-difluorobenzophenone or 3-chlorin-4-fluorinated diphenyl ketones is added, and a reaction is performed to obtain a polymerized mucus; the polymerized mucus is poured into deionized water, rapid stirring is performed to obtain crude polyether-ether-ketone particles, filtering and smashing are performed, and after extraction and washing are performed inside an extractor, vacuum drying is performed to obtain the polyether-ether-ketone. According to the method, the reaction time is shortened, discharge of carbon dioxide is reduced, the subsection charging mode is adopted, the reaction temperature is easier to control, energy conservation and consumption reduction are promoted, and an end-capping agent is added before the polymerization reaction is ended, so that the thermal stability of the polyether-ether-ketone is improved.
Description
Technical field
The invention belongs to macromolecule material preparation area, particularly relate to the preparation method of a kind of polyether-ether-ketone.
Background technology
Polyether-ether-ketone is a kind of fragrance linear polymeric material, has the physical chemistry such as high temperature resistant, chemical resistance corrosion
Performance, suffers from extensive purposes in a lot of fields.It is to be raw material with 4,4 '-difluoro benzophenone and hydroquinones mostly,
Carrying out solution polycondensation reaction under a large amount of sodium carbonates' presences and preparing polyether-ether-ketone, reaction temperature is often beyond 320 DEG C, and excess
Carbonate is not only bad for reaction, and reaction produces substantial amounts of carbon dioxide and is also unfavorable for environment.If in addition, reaction end is not added with appointing
What capping monomer, then polyether-ether-ketone then blocks or phenol end group for fluorine, in order to improve the heat endurance of material further, needs
It is blocked.
It is therefore desirable to design the preparation method of a kind of polyether-ether-ketone, to overcome the problems referred to above.
Content of the invention
It is an object of the invention to overcome the defect of prior art, provide that a kind of end-blocking effect is good, product heat endurance
The preparation method of the high polyether-ether-ketone of good and purity.
The present invention is realized in：
The invention discloses the preparation method of a kind of polyether-ether-ketone, including.The method comprises the following steps that：
Step one：It in the reactor equipped with agitator, thermometer, reflux condensing tube and logical nitrogen tube, is passed through nitrogen, so
Rear addition stirring solvent is simultaneously warming up to 140-160 DEG C, and it is continuously stirred to add hydroquinones, NaOH and potassium carbonate, treats
After all dissolving, addition 4,4 '-difluoro benzophenone and water entrainer, continuously stirred reaction, the water that reaction generates is taken out of completely
After, continue to heat up and release water entrainer, more persistently overheating to 220-260 DEG C, react 2-4h；
Step 2：Continue stirring and be warming up to 300-310 DEG C, add 3,4 difluoro benzophenones or 3-chloro-4-fluorine hexichol first
Ketone, then reacts 10-20min, obtains being polymerized mucus；
Step 3：Polymerization mucus is poured in deionized water rapidly, and stirring obtains polyether-ether-ketone crude product particle, mistake rapidly
Filter is wrapped in fat-free filter paper bag after pulverizing, and puts into the extraction tube of extractor, adds the methyl alcohol of heat, keeps pressure 0.3-1Mpa model
Enclose, be heated to boiling, maintain the temperature at 100-150 DEG C, pressure release blowing after 30-40min, repressurization extraction after extract backflow
Take, repeat to extract 24-48h, be then washed with deionized 2-3 time, after being finally vacuum dried, obtain polyether-ether-ketone resin.
Further, hydroquinones and the mol ratio of salt forming agent are 1:2-3.
Further, solvent is diphenyl sulphone (DPS) or sulfolane.
Further, water entrainer is toluene or dimethylbenzene.
Further, 4,4 '-difluoro benzophenone is 1 with the mol ratio of hydroquinones:1.01-1.1.
Further, 3,4 difluoro benzophenones or 3-chloro-4-fluorine benzophenone account for the 0.1%-3% of hydroquinones content.
Further, 4,4 '-difluoro benzophenone is 1.01-1.1 with the mol ratio of hydroquinones：1.
Further, 3,4 difluoro benzophenones or 3-chloro-4-fluorine benzophenone account for 4,4 '-difluoro benzophenone content
0.1%-3%.
The present invention has the advantages that：
It is salt forming agent that the present invention uses NaOH and potassium carbonate, replaces traditional carbonate, shortens the reaction time, subtracts
Having lacked the discharge of carbon dioxide, the mode of employing subsection charging, reaction temperature is easier to control, is conducive to energy-saving and cost-reducing, is gathering
Close and add end-capping reagent to block before reaction terminates, improve the heat endurance of polyether-ether-ketone further, and the extracted device of product carries
Take rear purity higher.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
The invention discloses the preparation method of a kind of polyether-ether-ketone, comprise the steps：
Step one：It in the reactor equipped with agitator, thermometer, reflux condensing tube and logical nitrogen tube, is passed through nitrogen, so
Rear addition stirring solvent is simultaneously warming up to 140-160 DEG C, and it is continuously stirred to add hydroquinones, NaOH and potassium carbonate, treats
After all dissolving, addition 4,4 '-difluoro benzophenone and water entrainer, continuously stirred reaction, the water that reaction generates is taken out of completely
After, continue to heat up and release water entrainer, more persistently overheating to 220-260 DEG C, react 2-4h；
Step 2：Continue stirring and be warming up to 300-310 DEG C, add 3,4 difluoro benzophenones or 3-chloro-4-fluorine hexichol first
Ketone, then reacts 10-20min, obtains being polymerized mucus；
Step 3：Polymerization mucus is poured in deionized water rapidly, and stirring obtains polyether-ether-ketone crude product particle, mistake rapidly
Filter is wrapped in fat-free filter paper bag after pulverizing, and puts into the extraction tube of extractor, adds the methyl alcohol of heat, keeps pressure 0.3-1Mpa model
Enclose, be heated to boiling, maintain the temperature at 100-150 DEG C, pressure release blowing after 30-40min, repressurization extraction after extract backflow
Take, repeat to extract 24-48h, be then washed with deionized 2-3 time, after being finally vacuum dried, obtain polyether-ether-ketone resin.
Hydroquinones is 1 with the mol ratio of salt forming agent:2-3.
Solvent is diphenyl sulphone (DPS) or sulfolane.
Water entrainer is toluene or dimethylbenzene.
4,4 '-difluoro benzophenone is 1 with the mol ratio of hydroquinones:1.01-1.1.
3,4 difluoro benzophenones or 3-chloro-4-fluorine benzophenone account for the 0.1%-3% of hydroquinones content.
4,4 '-difluoro benzophenone is 1.01-1.1 with the mol ratio of hydroquinones：1.
3,4 difluoro benzophenones or 3-chloro-4-fluorine benzophenone account for the 0.1%-3% of 4,4 '-difluoro benzophenone content.
Embodiment 1
It in the reactor equipped with agitator, thermometer, reflux condensing tube and logical nitrogen tube, is passed through nitrogen, is subsequently adding
65.4g diphenyl sulphone (DPS) stirs and is warming up to 140 DEG C, and adds 11.2g hydroquinones, 6.2g NaOH and 6.9g potassium carbonate and hold
Continuous stirring, after all dissolving, adds 21.8g4,4 '-difluoro benzophenone and 150ml toluene, continuously stirred reaction, will react
After the water generating is taken out of completely, continue to heat up and release toluene, more persistently overheating to 220 DEG C, react 2.5h；Continue stirring to be warming up to
300 DEG C, add 0.3g 3,4 ' difluoro benzophenone, then react 15min, obtain being polymerized mucus；Polymerization mucus is poured into rapidly
In deionized water, and stirring obtains polyether-ether-ketone crude product particle rapidly, filters and wraps in fat-free filter paper bag after pulverizing, puts into extraction
In the extraction tube of device, add the methyl alcohol of heat, keep pressure 0.3Mpa scope, be heated to boiling, maintain the temperature at 140 DEG C, 40min
Rear pressure release blowing, repressurization extraction after extract backflow, repeats to extract 48h, is then washed with deionized 2 times, very finally
Sky obtains polyether-ether-ketone resin after being dried, and productivity is 89%.
Embodiment 2
It in the reactor equipped with agitator, thermometer, reflux condensing tube and logical nitrogen tube, is passed through nitrogen, is subsequently adding
36.0g sulfolane stirs and is warming up to 160 DEG C, and adds 11.0g hydroquinones, 6.0g NaOH and 13.8g potassium carbonate>
Continuously stirred, after all dissolving, addition 24.0g 4,4 '-difluoro benzophenone and 150ml dimethylbenzene, continuously stirred reaction,
After the water that reaction generates is taken out of completely, continue to heat up and release dimethylbenzene, more persistently overheating to 240 DEG C, react 3h；Continue stirring
It is warming up to 310 DEG C, add 0.25g 3-chloro-4-fluorine benzophenone, then react 20min, obtain being polymerized mucus；Mucus will be polymerized
Pour in deionized water rapidly, and stirring obtain polyether-ether-ketone crude product particle rapidly, filter and wrap in fat-free filter paper bag after pulverizing,
Put into the extraction tube of extractor, add the methyl alcohol of heat, keep pressure 0.8Mpa scope, be heated to boiling, maintain the temperature at 110
DEG C, pressure release blowing after 30min, repressurization extraction after extract backflow, repeats to extract 24h, is then washed with deionized 3
Secondary, obtain polyether-ether-ketone resin after being finally vacuum dried, productivity is 85%.
In sum, the present invention uses NaOH and potassium carbonate is salt forming agent, replaces traditional carbonate, shortens anti-
Between Ying Shi, decreasing the discharge of carbon dioxide, using the mode of subsection charging, reaction temperature is easier to control, beneficially energy-conservation
Consumption reduction, adds end-capping reagent to block before polymerisation terminates, improves the heat endurance of polyether-ether-ketone, and product warp further
After extractor extracts, purity is higher.
Being described in detail the specific embodiment of the present invention above, but it being intended only as example, the present invention does not limit
It is formed on particular embodiments described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should cover within the scope of the invention.
Claims (8)
1. the preparation method of a polyether-ether-ketone, it is characterised in that the method comprises the following steps that：
Step one：It in the reactor equipped with agitator, thermometer, reflux condensing tube and logical nitrogen tube, is passed through nitrogen, then adds
Enter stirring solvent and be warming up to 140-160 DEG C, and it is continuously stirred to add hydroquinones, NaOH and potassium carbonate, treating all
After dissolving, addition 4,4 '-difluoro benzophenone and water entrainer, continuously stirred reaction, after taking the water that reaction generates completely out of, continues
Temperature of continuing rising releases water entrainer, more persistently overheating to 220-260 DEG C, reacts 2-4h；
Step 2：Continue stirring and be warming up to 300-310 DEG C, add 3,4 difluoro benzophenones or 3-chloro-4-fluorine benzophenone, so
Rear reaction 10-20min, obtains being polymerized mucus；
Step 3：Polymerization mucus is poured in deionized water rapidly, and stirring obtains polyether-ether-ketone crude product particle rapidly, filter powder
After broken, bag is in fat-free filter paper bag, puts into the extraction tube of extractor, adds the methyl alcohol of heat, keeps pressure 0.3-1Mpa scope,
It is heated to boiling, maintain the temperature at 100-150 DEG C, pressure release blowing after 30-40min, repressurization extraction, weight after extract backflow
Extract 24-48h again, be then washed with deionized 2-3 time, after being finally vacuum dried, obtain polyether-ether-ketone resin.
2. the preparation method of a kind of polyether-ether-ketone as claimed in claim 1, it is characterised in that：Described hydroquinones with described become
The mol ratio of salt agent is 1:2-3.
3. the preparation method of a kind of polyether-ether-ketone as claimed in claim 1, it is characterised in that：Described solvent is diphenyl sulphone (DPS) or ring
Fourth sulfone.
4. the preparation method of a kind of polyether-ether-ketone as claimed in claim 1, it is characterised in that：Described water entrainer is toluene or two
Toluene.
5. the preparation method of a kind of polyether-ether-ketone as claimed in claim 1, it is characterised in that：Described 4,4 '-difluorodiphenyl first
Ketone is 1 with the mol ratio of described hydroquinones:1.01-1.1.
6. the preparation method of a kind of polyether-ether-ketone as claimed in claim 5, it is characterised in that：Described 3,4 difluoro benzophenones
Or 3-chloro-4-fluorine benzophenone accounts for the 0.1%-3% of described hydroquinones content.
7. the preparation method of a kind of polyether-ether-ketone as claimed in claim 1, it is characterised in that：Described 4,4 '-difluorodiphenyl first
Ketone is 1.01-1.1 with the mol ratio of described hydroquinones：1.
8. the preparation method of a kind of polyether-ether-ketone as claimed in claim 7, it is characterised in that：Described 3,4 difluoro benzophenones
Or 3-chloro-4-fluorine benzophenone accounts for the 0.1%-3% of described 4,4 '-difluoro benzophenone content.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107611322A (en) * | 2017-08-22 | 2018-01-19 | 界首市天鸿新材料股份有限公司 | A kind of High-strength lithium battery diaphragm and its production technology |
| CN108384193A (en) * | 2018-03-13 | 2018-08-10 | 如皋市非标轴承有限公司 | A kind of high molecular material bearing and preparation method thereof |
| 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 |
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| CN101104684A (en) * | 2007-07-06 | 2008-01-16 | 吉林大学 | Fluorine-containing poly(ether-ether-ketone) terpolymer and synthetic method thereof |
| CN102627747A (en) * | 2012-04-10 | 2012-08-08 | 赵延辉 | Method for synthesizing polyether ether ketone |
| CN104497239A (en) * | 2014-12-17 | 2015-04-08 | 江门市优巨新材料有限公司 | Industrial synthetic method of low-chromaticity high-thermal-stability end capped polyether-ether-ketone resin |
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2016
- 2016-09-27 CN CN201610853847.3A patent/CN106432651A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104684A (en) * | 2007-07-06 | 2008-01-16 | 吉林大学 | Fluorine-containing poly(ether-ether-ketone) terpolymer and synthetic method thereof |
| CN102627747A (en) * | 2012-04-10 | 2012-08-08 | 赵延辉 | Method for synthesizing polyether ether ketone |
| CN104497239A (en) * | 2014-12-17 | 2015-04-08 | 江门市优巨新材料有限公司 | Industrial synthetic method of low-chromaticity high-thermal-stability end capped polyether-ether-ketone resin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107611322A (en) * | 2017-08-22 | 2018-01-19 | 界首市天鸿新材料股份有限公司 | A kind of High-strength lithium battery diaphragm and its production technology |
| CN108384193A (en) * | 2018-03-13 | 2018-08-10 | 如皋市非标轴承有限公司 | A kind of high molecular material bearing and preparation method thereof |
| 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 |
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Application publication date: 20170222 |