CN105367780A - Improvement method of preparation process of polyether-ether-ketone resin - Google Patents
Improvement method of preparation process of polyether-ether-ketone resin Download PDFInfo
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- CN105367780A CN105367780A CN201410433177.0A CN201410433177A CN105367780A CN 105367780 A CN105367780 A CN 105367780A CN 201410433177 A CN201410433177 A CN 201410433177A CN 105367780 A CN105367780 A CN 105367780A
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- ether
- polyether
- resorcinol
- ketone resin
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Abstract
The invention provides an improvement method of a preparation process of polyether-ether-ketone resin. Specifically, hydroquinone is first prepared into anhydrous hydroquinone lithium salt, and the hydroquinone lithium salt and 4,4-dichloro benzophenone perform reaction in a solvent to obtain the final product polyether-ether-ketone resin.
Description
Technical field
The present invention relates to organic polymer synthesis technical field, particularly a kind of the improving one's methods of preparation technology of polyether-ether-ketone resin.
Background technology
Polyether-ether-ketone is a kind of linear polymeric material, and its typical structure is a kind of polymkeric substance be made up of ehter bond and carbonyl, phenyl ring.Polyether-ether-ketone has excellent physicals and chemical property.There is purposes widely in a lot of fields: as aerospace field, locomotive manufacturing field, field of electronics, medical field and national defense and military fields.PEEK has good high thermal resistance, outstanding mechanical characteristics; There is rigidity and flexibility, particularly very outstanding to the fatigue resistance under repeated stress, can compare favourably with alloy material; Excellent sliding properties, is suitable for the occasion of being strict with low-friction coefficient and abrasion performance purposes, particularly uses carbon fiber, graphite, polytetrafluoroethylmodified modified PEEK wear resistance very superior; It also has high erosion resistance, and except the vitriol oil, polyether-ether-ketone is insoluble to any solvent and strong acid, highly basic, and hydrolysis, has very high chemical stability; Flame retardant resistance and self-extinguishing, even if do not add any fire retardant, just can reach the V-0 level of UL94 standard; Workability, due to PEEK, to have temperature flowing good, and the feature that heat decomposition temperature is very high, multiple processing mode can be adopted: injection molding, extrusion moulding, compression molding, melt-spinning and mechanical workout etc.
Britain Victrex company is in the late 1970s First Successful Development synthetic method of polyether-ether-ketone, with 4,4-difluoro benzophenone and Resorcinol are raw material, take sulfobenzide as solvent, under a large amount of sodium carbonates' presence, carry out solution polycondensation reaction and obtain polyether-ether-ketone, temperature of reaction is often beyond 320 DEG C.The route of the polyether-ether-ketone of current domestic synthesis and the route of Victrex company of Britain are similar to.Reaction not only needs high temperature, and needs complicated technique to remove metal-salt residual in product.We find through experimental study.4,4-difluoro benzophenone expensive, can use 4,4-dichlorobenzophenone to substitute.Old technology adopts sodium carbonate or salt of wormwood to react as catalyst, in fact has negative impact to reaction itself.Resorcinol has slightly acidic, with carbonate reaction, generates Resorcinol metal-salt and hydrogen-carbonate metal-salt.Because reaction is at high temperature carried out, supercarbonate is subject to thermally labile, easily decomposes, thus generates a large amount of carbonic acid gas and water.Easily there is hydrolysis reaction in the chlorosity in 4,4-dichlorobenzophenone, so old technology does not adopt 4,4-dichlorobenzophenone as raw material, adopts expensive 4,4-difluoro benzophenones.
In addition, Resorcinol reaction intermediate meets water, produces hydrolysis.Aqueous phase also can extract a large amount of phenates simultaneously, reduces the reaction density of phenates; The acidity of carbonic acid gas is better than Resorcinol, and Resorcinol metal-salt and carbon dioxide reaction generate Resorcinol and supercarbonate, phenates consume by side reaction.The inorganic salt generated in addition are coated in resin structure, need the cleaning repeatedly of a large amount of organic solvents and water, increase cost, contaminate environment.
Summary of the invention
The invention provides a kind of synthetic method of new polyether-ether-ketone resin, it is characterized in that Resorcinol to make anhydrous lithium salts, then react in a solvent with 4,4-dichlorobenzophenone.Owing to controlling the generation of moisture in reaction process, so avoid the hydrolysis of 4,4-dichlorobenzophenone in high-temperature solvent, this raw material substitution 4,4-difluoro benzophenone can be used.Do not have water to produce, there is no carbonate, do not have carbonic acid gas to produce yet, avoid above-mentioned a lot of side reaction and occur, improve quality product.
Resorcinol lithium salts and 4,4-dichlorobenzophenone are polymerized, and generate side product chlorinated lithium.Lithium chloride has good solubleness in organic solvent, so relative to sodium salt and sylvite, more easily remove.
The price of 4,4-dichlorobenzophenone, lower than 4,4-difluoro benzophenone, reduces process costs.
The preparation of anhydrous Resorcinol lithium salts by azeotropic solvent backflow band water, also can use other industrial known dewatering types, such as spraying dry etc.
Owing to controlling side reaction, use low cost raw material, improve reaction mass, the low cost of manufacture of polyether-ether-ketone resin product, cleaning is simple.
The method improved is: join in conversion unit by the lithium hydroxide of Resorcinol and 2.0-2.5 times of molar weight, add azeotropic solvent, azeotropic solvent can be toluene, chlorobenzene, dimethylbenzene.Reflux, divides and goes to generate moisture.Fully after point water, filter out solvent, obtain the solid of Resorcinol dilithium salt.4,4-dichlorobenzophenone of this solid and equimolar amount, and solvent sulfolane, join in conversion unit.Heat temperature raising, is warmed up to 220 DEG C-280 DEG C and starts reaction, react after 1-3 hour, terminates reaction cooling, obtains product.
Embodiment
Three mouthfuls of glass flask that embodiment 1:1 rises, are equipped with mechanical stirring, water-and-oil separator, glass condenser and thermometer respectively.33.1 grams of Resorcinol are added, Lithium Hydroxide Monohydrate 44 grams, 150 grams of toluene in bottle.Be heated to solvent refluxing, keep reflux state, in water-and-oil separator, constantly separate moisture.React after three hours, in water-and-oil separator, no longer produce moisture.White solid is there is in reaction flask.Stop reaction, the Resorcinol sodium of white solid is carried out filter operation, filters toluene, solid is dried, and obtains 47 grams of pressed powders.Prolong is being housed, thermometer, in the four-hole boiling flask of logical N2 mouth, is adding 300 grams of tetramethylene sulfone, 67.1 gram of 4,4-difluoro benzophenone, 47 grams of above-mentioned pressed powders.Heat temperature raising, temperature rises to 280 DEG C and keeps, and continues stopped reaction after three hours.Polymkeric substance is injected cold water, and coagulate solids uses pulverizer to pulverize and filters.Powder is cleaned with water.Obtain polyether-ether-ketone powder.
Three mouthfuls of glass flask that embodiment 2:1 rises, are equipped with mechanical stirring, water-and-oil separator, glass condenser and thermometer respectively.33.1 grams of Resorcinol are added, Lithium Hydroxide Monohydrate 44 grams, 150 grams of toluene in bottle.Be heated to solvent refluxing, keep reflux state, in water-and-oil separator, constantly separate moisture.React after three hours, in water-and-oil separator, no longer produce moisture.White solid is there is in reaction flask.Stop reaction, the Resorcinol potassium of white solid is carried out filter operation, filters toluene, solid is dried, and obtains 38 grams of pressed powders.Prolong is being housed, thermometer, in the four-hole boiling flask of logical N2 mouth, is adding 200 grams of tetramethylene sulfone, 47 grams of above-mentioned pressed powders, stirring and dissolving heat temperature raising, temperature rises to 260 DEG C and keeps.4, the 4-dichlorobenzophenone of 66.9 grams are dissolved in the tetramethylene sulfone of 100 grams and use miniature volume pump, be slowly added dropwise in above-mentioned solution.Drip stopped reaction after three hours.Continue to react half an hour, polymkeric substance is injected cold water, coagulate solids uses pulverizer to pulverize and filters, and cleans powder, obtain polyether-ether-ketone powder with water.
Claims (3)
1. a synthetic method for polyether-ether-ketone resin, its step is as follows:
(1) Resorcinol and alkaline, lithium reactant salt, make Resorcinol dilithium salt
(2) Resorcinol disalt and the temperature reaction in a solvent of 2 times of mole number 4,4-dichlorobenzophenone, obtain polyether-ether-ketone resin powder.
2. the synthetic method of polyether-ether-ketone resin according to claim 1, is characterized in that the mixture of one or several in the alkaline lithium salts selection lithium hydroxide in above-mentioned steps (1), salt of wormwood, Lithamide.
3. the synthetic method of polyether-ether-ketone resin according to claim 1, is characterized in that the Resorcinol dilithium salt in above-mentioned steps (2) is the Resorcinol dilithium salt dehydrated.
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| CN201410433177.0A CN105367780A (en) | 2014-08-29 | 2014-08-29 | Improvement method of preparation process of polyether-ether-ketone resin |
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| CN201410433177.0A CN105367780A (en) | 2014-08-29 | 2014-08-29 | Improvement method of preparation process of polyether-ether-ketone resin |
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| CN105367780A true CN105367780A (en) | 2016-03-02 |
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| CN201410433177.0A Pending CN105367780A (en) | 2014-08-29 | 2014-08-29 | Improvement method of preparation process of polyether-ether-ketone resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113774497A (en) * | 2021-09-13 | 2021-12-10 | 广州傲群刷业科技有限公司 | PEEK material wire drawing process and application thereof in electronic cigarette cleaning hairbrush |
| CN114031770A (en) * | 2021-06-25 | 2022-02-11 | 赵学强 | Method for preparing polyether-ether-ketone by using ionic liquid as solvent |
| CN115612092A (en) * | 2022-09-08 | 2023-01-17 | 重庆沃特智成新材料科技有限公司 | Synthesis method of polyether-ether-ketone |
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| JPS62151421A (en) * | 1985-12-26 | 1987-07-06 | Toray Ind Inc | Thermoplastic aromatic polyether ketone copolymer and production thereof |
| CN102391447A (en) * | 2011-09-07 | 2012-03-28 | 金发科技股份有限公司 | Preparation method of polyether ketone/sulfone high-temperature resistant material |
| CN102627747A (en) * | 2012-04-10 | 2012-08-08 | 赵延辉 | Method for synthesizing polyether ether ketone |
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2014
- 2014-08-29 CN CN201410433177.0A patent/CN105367780A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62151421A (en) * | 1985-12-26 | 1987-07-06 | Toray Ind Inc | Thermoplastic aromatic polyether ketone copolymer and production thereof |
| CN102391447A (en) * | 2011-09-07 | 2012-03-28 | 金发科技股份有限公司 | Preparation method of polyether ketone/sulfone high-temperature resistant material |
| CN102627747A (en) * | 2012-04-10 | 2012-08-08 | 赵延辉 | Method for synthesizing polyether ether ketone |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031770A (en) * | 2021-06-25 | 2022-02-11 | 赵学强 | Method for preparing polyether-ether-ketone by using ionic liquid as solvent |
| CN113774497A (en) * | 2021-09-13 | 2021-12-10 | 广州傲群刷业科技有限公司 | PEEK material wire drawing process and application thereof in electronic cigarette cleaning hairbrush |
| CN115612092A (en) * | 2022-09-08 | 2023-01-17 | 重庆沃特智成新材料科技有限公司 | Synthesis method of polyether-ether-ketone |
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