CN106633034B - A kind of preparation method of polyether-ether-ketone resin and polyether-ether-ketone resin obtained - Google Patents
A kind of preparation method of polyether-ether-ketone resin and polyether-ether-ketone resin obtained Download PDFInfo
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- CN106633034B CN106633034B CN201710010285.0A CN201710010285A CN106633034B CN 106633034 B CN106633034 B CN 106633034B CN 201710010285 A CN201710010285 A CN 201710010285A CN 106633034 B CN106633034 B CN 106633034B
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4018—(I) or (II) containing halogens other than as leaving group (X)
- C08G65/4025—(I) or (II) containing fluorine other than as leaving group (X)
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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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
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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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
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Abstract
The present invention relates to a kind of preparation method of polyether-ether-ketone resin and polyether-ether-ketone resins obtained.The preparation method of polyether-ether-ketone resin provided by the invention includes the following steps: (1), is chemically modified obtained schiff bases monomer to 4,4- difluoro benzophenone；(2), using the schiff bases monomer and hydroquinone as reaction monomers, using N-Methyl pyrrolidone as reaction dissolvent, aggregated obtained polyether-ether-ketone resin；The chemical structural formula of the schiff bases monomer are as follows:
Description
Technical field
The present invention relates to the preparation method of technical field of polymer materials more particularly to a kind of polyether-ether-ketone resin and it is made
Polyether-ether-ketone resin.
Background technique
Polyether-ether-ketone (PEEK) is to research and develop a kind of successfully novel semi-crystalline state aromatic series thermoplastic late 1970s
Property engineering plastics, be worker ecumenicity can one of highest thermoplastic material, because it has excellent comprehensive performance, in state
It is achieved in the high-technology fields such as anti-military project, aerospace, electronic information, the energy, automobile, household electrical appliances, health care extensive
Using.
The preparation method of polyether-ether-ketone mainly has parental materials and two kinds of nucleophilic displacement of fluorine.Parental materials route reaction condition
Mildly, but due to the disadvantages of product is easy branching, catalysts and solvents dosage is big and environment is unfriendly, main using parent
Core replaces route to prepare polyether-ether-ketone.Wherein, Britain's ICI Company most earlier than 1981 to being proposed earliest commercialization in the market
Kind polyether-ether-ketone resin.In its patent, the polymer reaction monomer of polyether-ether-ketone is 4,4- difluoro benzophenone and Isosorbide-5-Nitrae-
Hydroquinone, for reaction temperature at 300 DEG C or more, used solvent is diphenyl sulphone (DPS).
There are following two aspects unfavorable factors for the preparation method of conventional patents: first is that the reaction temperature of polymer is excessively high, needing
Special workshop is established, also inevitably there is hidden danger during the reaction；Second is that at the purification of polymer
During reason, since solvent for use diphenyl sulphone (DPS) is not soluble in water, it is necessary to solvent diphenyl sulphone (DPS) first is removed through repeatedly extracting with organic solvent,
Residual organic solvent is removed with water-soluble solvent, finally removes water-soluble solvent and by-product salt by repeatedly extracting with water,
Qualified implantation grade PEEK can just be obtained.In this way due to long flow path, a large amount of solvent is consumed, inherently improves production cost, and
The storage and processing of organic solvent are also required to establish special workshop and special personnel simultaneously, can also exist in use
Security risk.
Therefore, against the above deficiency, it is desirable to provide low, at low cost, production risk the is low polyethers of reaction temperature needed for a kind of
Ether ketone preparation method.
Summary of the invention
(1) technical problems to be solved
The invention solves using 4,4- difluoro benzophenone and Isosorbide-5-Nitrae-hydroquinone as reaction monomers, using diphenyl sulphone (DPS)
When preparing polyether-ether-ketone resin for solvent it is existing needed for reaction temperature is high, production rises this height, it is safe hidden to exist in production process
The problem of suffering from.
(2) technical solution
In order to solve the above-mentioned technical problems, the present invention provides a kind of polyether-ether-ketone resins different from conventional production methods
Preparation method.
The preparation method of polyether-ether-ketone resin provided by the invention, includes the following steps:
(1), obtained schiff bases monomer is chemically modified to 4,4- difluoro benzophenone；
(2), using the schiff bases monomer and hydroquinone as reaction monomers, using N-Methyl pyrrolidone as reaction
Solvent, aggregated obtained polyether-ether-ketone resin；
The chemical structural formula of the schiff bases monomer are as follows:
Preferably: in step (1), the chemical modification of 4,4- difluoro benzophenones is carried out using aniline.
Further preferably: in step (1), the preparation method of the schiff bases monomer specifically comprises the following steps:
It is heated to reflux after 4,4- difluoro benzophenone and organic solvent are mixed, instills aniline, react 3~6h, Schiff is made
Alkali monomer.
More specifically, the organic solvent used in step (1) is preferably dry toluene and acetic acid.The dosage of the two
Depending on (in terms of milliliter) is according to the dosage (in terms of molal quantity) of 4,4- difluoro benzophenone, it is preferable that dry toluene used, acetic acid
Amount ratio with 4,4- difluoro benzophenone is (16-50): (2-10): (0.02-1).
After reacting 3-6h, reactant obtained in reaction system is concentrated under reduced pressure into the 1/3~1/2 of original volume, adds water 50
White solid is precipitated in~100ml, filters, and gained precipitating is washed with water for several times, dry that crude product, crude product obtain after recrystallizing
The schiff bases monomer of high-purity, can be used in subsequent preparation step.
Recrystallization is carried out using 95% ethyl alcohol.
Further preferably: in step (1), 4,4- difluoro benzophenone used and aniline are respectively in terms of mol and mL, the two
Amount ratio be (0.02~1): (1~10).
Preferably: step (2) specifically comprises the following steps:
(21), schiff bases monomer, hydroquinone are sequentially added into N-Methyl pyrrolidone, add alkali metal carbonic acid
It stirs after salt, toluene, be heated to 160~180 DEG C and react 2~3 hours within this temperature range, polymer powder is made
Material；
(22), N-Methyl pyrrolidone is added into the polymer powders, adds strong acid, heat, reach to temperature
At 60~100 DEG C, isothermal reaction 2~5 hours, polyether-ether-ketone resin is made.
Specifically, in step (21), after source chemicals are all added, with continuous heat temperature raising, toluene starts
Azeotropic reflux, after the water whole azeotropic after react generation in system is taken out of, toluene starts to clarify completely in return pipe, stops reflux
And start to evaporate remaining methylbenzene water-taking agent in system, while system temperature also constantly rises, when rising to 160~180 DEG C,
It reacts 2~3 hours within this temperature range, reaction product is polymer powders crude product.By purifying, polymer powder can be made
Expect fine work, that is, is used for the polymer powders of subsequent reactions step.
For purification step, the following technical solution can be selected: the reaction product of acquisition being poured into distilled water, is stirred simultaneously
Cooling is mixed, the polymer after solidification is crushed into filtering, the deionized water that solid product is measured with 6~10 times is boiled 10~12 repeatedly
It is secondary, polymer powders are obtained in drying in oven until removing solvent and by-product, then by powder.
In step (21), when sequentially adding schiff bases monomer, hydroquinone into N-Methyl pyrrolidone, alkali is added
After metal carbonate, toluene, the solid content of system is preferably 20~25%.
For step (22), specifically, N-Methyl pyrrolidone is added into polymer powders made from step (21),
Strong acid is added, is heated, when temperature reaches 60~100 DEG C, isothermal reaction 2~5 hours, reaction product is polyether-ether-ketone
Resin crude product.By purifying, polyether-ether-ketone resin provided by the invention can be made.
For strong acid used in this step, preferably inorganic acid.The inorganic acid can be selected from sulfuric acid, nitre
One of acid, perchloric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, permanganic acid are a variety of.
For the purifying in this step, purifying in the same step of concrete operations (21) is not described in detail here.
Preferably: in step (21), for the mole dosage of hydroquinone, the schiff bases monomer mole with
Amount excessive 0.1~2%, the mole dosage excessive 1~10% of the alkali carbonate.
If being single use potassium carbonate, product has branching, crosslinking phenomena, and color is partially deep, and if being single use carbonic acid
Sodium needs big excessive (excessive 30~50%), and otherwise polymerization will fail, preferably: in step (21), the alkali carbonate
For sodium carbonate and potassium carbonate mixtures, wherein the molal quantity of sodium carbonate is the 10~80% of the mixture total moles.
Preferably: in step (22), after N-Methyl pyrrolidone is added, the solid content of system is 40~80%.
Preferably: in step (22), the quality of the strong acid is the 20~50% of the polymer powders quality.
The present invention also provides a kind of using polyether-ether-ketone resin made from this method.
(3) beneficial effect
Above-mentioned technical proposal of the invention has the advantages that
By being chemically modified to 4,4- difluoro benzophenone, it is prepared for schiff bases monomer, is used for preparing polyethers ether
In the polymerization reaction of ketone resin, temperature needed for reducing reaction reduces the security risk in production process.
It selects water-soluble solvent N-Methyl pyrrolidone as reaction dissolvent in the present invention simultaneously, facilitates the pure of late-stage products
Change, reduces the security risk in production cost and purification process.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Technical solution in bright is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention,
Instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative labor
Every other embodiment obtained under the premise of dynamic, shall fall within the protection scope of the present invention.
Embodiment one
1, prepared by schiff bases monomer
Blender is being housed, thermometer leads in the three-neck flask of nitrogen tube, and 4,4- difluoro benzophenone 4.364g is added
(0.02mol), dry toluene 16mL, acetic acid 2mL are heated to reflux, and slowly instill aniline 1mL, are reacted 3h, are concentrated under reduced pressure into substance
Long-pending 1/2, adds water 50mL, and white solid is precipitated, white solid is filtered, and precipitating is washed with water 8 times, dry crude product.
The schiff bases monomer of high-purity is obtained with 95% re crystallization from toluene.
2, polymerization reaction
(21), organic solvent is added in equipped with blender, thermometer, logical nitrogen tube, the reaction system of reflux condensing tube
Then N-Methyl pyrrolidone sequentially adds 0.303mol schiff bases monomer, excessive relative to hydroquinone dosage 0.30mol
The hydroquinone of 1%, 0.30mol are added 0.153mol potassium carbonate and 0.153mol sodium carbonate, start after adding 60mL toluene
Stirring (solid content that wherein, the dosage of the organic solvent N-Methyl pyrrolidone of addition meets system is 20~25%), heating
Heating, when temperature rises to 110 DEG C, system starts azeotropic, there is toluene and water condensation, upper toluene reflux, lower layer in water segregator
Water is constantly released, and toluene starts to clarify completely return pipe at the middle and upper levels, is further continued for reflux 20 minutes, is then started to be evaporated off from system
Toluene, while system temperature also constantly rises, and when temperature reaches 160~180 DEG C, keeps constant temperature, system viscosity is anti-with polymerization
That answers be continuously increased, and stops reaction after reaction 3 hours, reaction product is poured into distilled water, while stirring cooling, will coagulated
Gu polymer after is crushed with high speed disintegrator and is filtered, and comminuted solids product is boiled and mistake with the deionized water of 6~10 times of amounts
Filter, boils 1h every time, continues to boil after filtering, and filtering 10 times is boiled in repetition, until solvent and by-product all removals, then
By powder in baking oven 140 DEG C of drying 12h.
(22), the polymer powders 200g obtained in step 21 is put into equipped with blender, thermometer, logical nitrogen tube,
In the three-neck flask of reflux condensing tube, N-Methyl pyrrolidone (solid content for ensuring system is 40~80%) is added, 40g is added
Concentrated hydrochloric acid (mass fraction 37.5%) after mixing slowly uniformly, increases mixing speed and simultaneously opens heating, reach 60 to temperature~
At 100 DEG C, stops reaction after isothermal reaction 2~5 hours, reaction product is poured into distilled water, while stirring cooling, will solidified
Polymer afterwards crushes filtering, and the deionized water that comminuted solids product is measured with 6~10 times is boiled and filtered, boils 1h every time,
Continue to boil after filtering, filtering 10 times is boiled in repetition, until solvent and by-product all removals, then by powder in baking oven
140 DEG C of drying 12h, can be obtained polyether-ether-ketone resin.
In the present embodiment, the reaction equation being related to is as follows:
The preparation of schiff bases monomer:
Its reaction principle are as follows:
In acid condition, aniline protonates, as the amino nucleopilic reagent attack 4 for having positive particles, 4- difluoro two
Carbonyl in benzophenone generates the transition state intermediate containing C-N key, and then transition state intermediate is by generating after dehydrogenation step
Schiff bases monomer containing C=N key.
The preparation of polyetheretherketonepolymer polymer:
Its reaction principle are as follows:
Benzenediol, at salt, sloughs hydrogen ion under the action of alkali metal, as nucleophilic displacement of fluorine reagent, attack 4,4- difluoro two
In benzophenone be connected with F in electropositive carbon atom (because the polarity of F atom is greater than C atom, therefore in 4,4- difluoro benzophenone
In this C atom at electropositive) generate reaction intermediate, then F ion is left away.
Embodiment two and embodiment three are basically the same as the first embodiment, and something in common repeats no more, the difference is that respectively
There may be differences for source chemicals type and dosage used in step, specific as shown in Table 1 and Table 2.
Comparative example one
Polyether-ether-ketone resin is prepared using the preparation method mentioned in conventional patents.Specifically comprise the following steps:
With 4,4- difluoro benzophenone and hydroquinone sylvite for raw material, diphenyl sulphone (DPS) is solvent, in anhydrous conditions in 300~
340 DEG C of carry out solution polycondensations, obtained polymer through desolventizing, desalt, wash, be then dried in vacuo in 140 DEG C, obtain high score
Son amount PEEK resin.
Tables 1 and 2 is the type and dosage of each embodiment used reagent during the preparation process.Wherein, table 1 and table
2 be respectively reagent type and quantity used in schiff bases monomer preparation process and polymerization process.
The each embodiment of table 1 reagent type and quantity used in schiff bases monomer preparation process
| 4,4- difluoro benzophenone | Aniline | Organic solvent | |
| Embodiment one | 0.02mol | 1mL | Dry toluene 16mL, acetic acid 2mL |
| Embodiment two | 1mol | 10mL | Dry toluene 50mL, acetic acid 10mL |
| Embodiment three | 0.3mol | 5mL | Dry toluene 40mL, acetic acid 7.5mL |
Reagent type and quantity of each embodiment of table 2 used in polymerization process
Note: NMP, that is, N-Methyl pyrrolidone in table 2, agents useful for same volume purity are that analysis is pure.
Polyether-ether-ketone resin made from each embodiment and comparative example is carried out to DSC detection and heat stability test respectively,
Testing result is as shown in table 3.
3 physical property testing result of table
| Tg | Tm | 400 DEG C of heating, 5 minutes survey MI values | 400 DEG C of heating, 30 minutes survey MI values | |
| Embodiment one | 146℃ | 332℃ | 21.4g/10 minutes | 17.8g/10 minutes |
| Embodiment two | 145℃ | 330℃ | 21.2g/10 minutes | 17.5g/10 minutes |
| Embodiment three | 146℃ | 334℃ | 20.8g/10 minutes | 17.3g/10 minutes |
| Comparative example one | 147℃ | 338℃ | 21.7g/10 minutes | 18.0g/10 minutes |
Note: the MI value in table 3 refers to melt index.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (4)
1. a kind of preparation method of polyether-ether-ketone resin, it is characterised in that:
(1) obtained schiff bases monomer is chemically modified to 4,4- difluoro benzophenone, specifically comprised the following steps: 4,4- difluoro
It is heated to reflux after benzophenone, dry toluene and acetic acid mixing, instills aniline, react 3~6h, schiff bases monomer is made；
(2) using the schiff bases monomer and hydroquinone as reaction monomers, using N-Methyl pyrrolidone as reaction dissolvent,
Aggregated obtained polyether-ether-ketone resin, specifically comprises the following steps:
(21) schiff bases monomer, hydroquinone are sequentially added into N-Methyl pyrrolidone, add alkali carbonate, toluene
After stir evenly, be heated to 160~180 DEG C and within this temperature range react 2~3 hours, be made polymer powders；Its
In, for the mole dosage of hydroquinone, the mole dosage excessive 0.1~2% of the schiff bases monomer, the alkali gold
Belong to the mole dosage excessive 1~10% of carbonate；The alkali carbonate is sodium carbonate and potassium carbonate mixtures, wherein carbonic acid
The molal quantity of sodium is the 10~80% of the mixture total moles；
(22) N-Methyl pyrrolidone is added into the polymer powders, adds strong acid, be heated to 60~100 DEG C simultaneously
It reacts 2~5 hours at such a temperature, polyether-ether-ketone resin is made；
The chemical structural formula of the schiff bases monomer are as follows:
2. preparation method according to claim 1, it is characterised in that: in step (1), 4,4- difluoro benzophenone used and
For aniline respectively in terms of mol and mL, the amount ratio of the two is (0.02~1): (1~10).
3. preparation method according to claim 1, it is characterised in that: in step (22), when addition N-Methyl pyrrolidone
Afterwards, the solid content of system is 40~80%.
4. preparation method according to claim 1, it is characterised in that: in step (22), the quality of the strong acid is described
The 20~50% of polymer powders quality.
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| CN110052178B (en) * | 2019-05-23 | 2020-09-25 | 中国科学院长春应用化学研究所 | High-tolerance organic solvent separation membrane and preparation method thereof |
| CN115558066B (en) * | 2022-10-13 | 2024-03-26 | 中国科学院长春应用化学研究所 | Polyaryletherketone ketone precursor resin and preparation method of polyaryletherketone ketone resin |
| CN117801446B (en) * | 2024-02-29 | 2024-05-07 | 无锡市中天塑料保持架制造有限公司 | High-strength plastic retainer based on polyether-ether-ketone and preparation method thereof |
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