CN102702506A - Soluble polyaryletherketone and preparation method thereof - Google Patents
Soluble polyaryletherketone and preparation method thereof Download PDFInfo
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- CN102702506A CN102702506A CN2012101548565A CN201210154856A CN102702506A CN 102702506 A CN102702506 A CN 102702506A CN 2012101548565 A CN2012101548565 A CN 2012101548565A CN 201210154856 A CN201210154856 A CN 201210154856A CN 102702506 A CN102702506 A CN 102702506A
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Abstract
The invention discloses soluble polyaryletherketone and a preparation method of the soluble polyaryletherketone. The soluble polyaryletherketone is a macromoleclar polymer composed of an ether bond and a ketone group connected with an aromatic ring; the average molecular weight is 15,000; the average melting point is 390 DEG C; the soluble polyaryletherketone is [poly(4,4'-difluoro-benzophenone-biphenyl diphenol)-poly(4,4'-difluoro-benzophenone-phenothalin)] segmented copolymer with high viscosity, high molecular weight, high glass transition temperature and increased dissolubility prepared by carrying out polymerization reaction on three monomers of 4,4'-difluoro-benzophenone, biphenyl diphenol and phenothalin through adopting composite catalyst Na2CO3 (sodium carbonate)/K2CO3 (potassium carbonate) and composite solvent sulfobenzide/sulfolane. The soluble polyaryletherketone disclosed by the invention solves the problems of relatively low glass transition temperature and poor dissolubility of the traditional engineering plastics (such as polyether-ether-ketone). The soluble polyaryletherketone disclosed by the invention can be used for preparing a proton exchange membrane and applied to a high-temperature fuel cell so as to expand the application range.
Description
Technical field
The present invention relates to a kind of solvable polyaryletherketone; The chemical name of its standard is: [gather (4; 4 '-difluoro benzophenone-'-biphenyl diphenol)-gather (4; 4 '-difluoro benzophenone-phenolphthalein)] segmented copolymer, the invention still further relates to the preparation method of its this solvable polyaryletherketone, it belongs to engineering polymer material science field.
Background technology
Polyetheretherketone (PEEK) is one of typical case representative of polyaryletherketone base polymer, as the thermoplastics of a kind of half hitch crystal formation (typing is arranged), normally by Resorcinol, 4,4 '-the difluoro benzophenone high-temperature polycondensation is synthetic.Because it has performances such as good thermostability, mechanical-physical property, radioresistance, electrical insulating property, in fields such as aerospace, automobile making, electronic apparatuss wide application prospect is arranged.Therefore, the concern of height since coming out with regard to having received extensively.Britain Victrex company has succeeded in developing the compound method of PEEK first in late 1970s, and with dropped into industrial production in 1987; People such as Man Li adopted microwave assisting method to synthesize polyetheretherketone in 2010; Chinese patent CN100582133C adopted the Na of single component in 2010
2CO
3Synthesized polyetheretherketone as condensing agent.But institute's synthetic polyether-ether-ketone resin second-order transition temperature is relatively low, and usually about 143 ℃, and solubility property is poor (can only be dissolved in dense H usually
2SO
4Etc. strong proton acid), machine-shaping is difficulty.At present, good solubility property and processing characteristics have become estimates the important performance index of high-temperature polymer, and no longer only performances such as temperature classification height is estimated.
Therefore, under the prerequisite that the thermotolerance of PAEK (polyaryletherketone) resin does not reduce, high-performance thermoplastics that synthesis of soluble is separated, unformed has important practical significance.
Summary of the invention
First purpose of the present invention is to overcome the low and relatively poor shortcoming of solvability of existing polyetheretherketone (PEEK) resin material second-order transition temperature, and a kind of solvable polyaryletherketone is provided.Its second-order transition temperature and solvability all are enhanced.
Another object of the present invention is to provide the preparation method of this solvable polyaryletherketone.
Solvable polyaryletherketone is characterized in that it is a kind ofly to be connected the high molecular polymer that aromatic ring is formed with ketone group by ehter bond, and molecular-weight average is 15000, and fusing point is 390 ℃, and its molecular structural formula is:
The method for preparing above-mentioned solvable polyaryletherketone is characterized in that it is to adopt composite catalyst Na
2CO
3And K
2CO
3, double solvents sulfobenzide and tetramethylene sulfone add the '-biphenyl diphenol monomer of linear structure and the phenolphthalein monomer of nonlinear organization, and react the later stage and adopt the mode of '-biphenyl diphenol as chainextender, and concrete preparation process comprises the steps:
(1). in reaction vessel, add solvent sulfobenzide and tetramethylene sulfone, be warming up to its dissolving, so add 4,4 successively '-difluoro benzophenone, '-biphenyl diphenol and phenolphthalein, wherein 4,4 '-difluoro benzophenone: the mol ratio of '-biphenyl diphenol and phenolphthalein=1: 1.0～1.5;
(2). will pulverize the dry good Na of 200-300 mesh sieve in advance
2CO
3And K
2CO
3Join rapidly in the reaction system, wherein Na
2CO
3: K
2CO
3Mol ratio=18-20: 1; 4,4 '-difluoro benzophenone: Na
2CO
3And K
2CO
3Mol ratio=1: 1～5; Continue down to stir 20～40min at 100～150 ℃, make that the '-biphenyl diphenol in the system reacts generation sodium salt and sylvite with phenolphthalein monomer and yellow soda ash, salt of wormwood, then temperature of reaction system is elevated to 160～180 ℃; Sodium salt that generates and sylvite are subsequently with 4; 4 '-the difluoro benzophenone polymerization reaction take place, behind reaction 20～40min, in 15min, temperature is elevated to 220～240 ℃;
(3). react after 1～1.2 hour, temperature of reaction is elevated to 240～260 ℃, in reaction system, add the chainextender '-biphenyl diphenol immediately; Wherein 4; 4 '-difluoro benzophenone: the mol ratio of '-biphenyl diphenol=1: 0.01～1.0, strengthen speed of response simultaneously, react stop after 1～1.5 hour the heating;
(4). treat that at last polymerization mucus is cooled to room temperature, directly wash respectively that each washs three times, obtains product of the present invention after the drying to wherein adding acetone, ethanol, zero(ppm) water successively.
In technique scheme, said sulfobenzide: the mol ratio of tetramethylene sulfone is 80: 20～20: 80.
In technique scheme, said '-biphenyl diphenol: the mol ratio of phenolphthalein is 100: 10～10: 100.
In technique scheme, said Na
2CO
3: K
2CO
3Mol ratio=19.4: 1.
In technique scheme, said 4,4 '-difluoro benzophenone: the mol ratio of sulfobenzide and tetramethylene sulfone is 1: 1.5.
The present invention [gathers (4; 4 '-difluoro benzophenone-'-biphenyl diphenol)-gather (4; 4 '-difluoro benzophenone-phenolphthalein)] segmented copolymer (solvable polyaryletherketone) is shallow tea ash look or amber; Have HS, high-modulus, high-fracture toughness, characteristics such as coefficient of linear expansion is less, self is fire-retardant, tribological property is outstanding, good insulating, also have good temperature resistance ability, workability ability and easy solubility property.
This segmented copolymer of preparing is a non-crystalline type, has the character of high-performance thermoplastics, presents good thermal property and mechanical property, and has solved the relatively low and relatively poor problem of solvability of traditional engineering plastics polyetheretherketone second-order transition temperature.
The present invention is directed to the low and relatively poor problem of solvability of traditional polyetheretherketone (molecular-weight average is 7000) product second-order transition temperature; Adopt the '-biphenyl diphenol of linear coplanar structure and the phenolphthalein of non-linear non-coplanar structure to be reaction monomers jointly; This multiple performance that contains the polyaryletherketone segmented copolymer of xenyl and phenolphthalein base is simultaneously increased jointly, and its advantage is obvious.Reaction process adopts the programmed heating method; After generating corresponding prepolymer; Add '-biphenyl diphenol once more as chainextender; Reaction is prepared HV, HMW after for some time like this, second-order transition temperature is higher and solvability increases [gather (4,4 '-difluoro benzophenone-'-biphenyl diphenol)-gather (4,4 '-difluoro benzophenone-phenolphthalein)] segmented copolymer.
What this patent adopted is double solvents sulfobenzide/tetramethylene sulfone, can both fully dissolve to guarantee two kinds of biphenol monomers, helps the carrying out that reacts.That this patent adopts is composite catalyst Na
2CO
3/ K
2CO
3If, because adopt Na separately
2CO
3, the viscosity of then prepared product is lower; If adopt K separately
2CO
3Though the viscosity of prepared product increases, there is gelinite in the final product, therefore use Na
2CO
3And K
2CO
3Mixture (mol ratio 19.4: 1.0), can make and not contain gelinite in the product, and can keep product to have good toughness and color.
The solvable polyaryletherketone of the present invention is compared with polyetheretherketone (PEEK), biphenyl type polyetheretherketone (DPEEK) and is dissolved in the number of chemical medicine; Be not only soluble in the vitriol oil; Also be dissolved in polar solvent, for example acetone, N-Methyl pyrrolidone (NMP), N (DMF), N,N-DIMETHYLACETAMIDE (DMAc), DMSO 99.8MIN. (DMSO); Non-polar solvent, for example THF (THF), chloroform (CHCl
3).
The present invention [gathers (4; 4 '-difluoro benzophenone-'-biphenyl diphenol)-gather (4; 4 '-difluoro benzophenone-phenolphthalein)] segmented copolymer removes in the sophisticated technology fields such as being used in aerospace, automobile making, electric, medical facilities; Can also prepare PEM, be used for high-temperature fuel cell, enlarge range of application.
Embodiment
Below in conjunction with embodiment the present invention is done detailed explanation and explanation, but also non exhaustive, the present invention is not done any restriction, simultaneously through explaining that advantage of the present invention will become clear more and easy and understand.
Solvable polyaryletherketone is characterized in that it is a kind ofly to be connected the high molecular polymer that aromatic ring is formed with ketone group by ehter bond, and molecular-weight average is 15000, and fusing point is 390 ℃, and its molecular structural formula is:
The method for preparing above-mentioned solvable polyaryletherketone is characterized in that it is to adopt composite catalyst Na
2CO
3And K
2CO
3, double solvents sulfobenzide and tetramethylene sulfone add the '-biphenyl diphenol monomer of linear structure and the phenolphthalein monomer of nonlinear organization, and react the later stage and adopt the mode of '-biphenyl diphenol as chainextender, and concrete preparation process comprises the steps:
(1). in reaction vessel, add solvent sulfobenzide and tetramethylene sulfone, be warming up to its dissolving, so add 4,4 successively '-difluoro benzophenone, '-biphenyl diphenol and phenolphthalein, wherein 4,4 '-difluoro benzophenone: the mol ratio of '-biphenyl diphenol and phenolphthalein=1: 1.0～1.5;
(2). will pulverize the dry good Na of 200-300 mesh sieve in advance
2CO
3And K
2CO
3Join rapidly in the reaction system, wherein Na
2CO
3: K
2CO
3Mol ratio=18-20: 1; 4,4 '-difluoro benzophenone: Na
2CO
3And K
2CO
3Mol ratio=1: 1～5; Continue down to stir 20～40min at 100～150 ℃, make that the '-biphenyl diphenol in the system reacts generation sodium salt and sylvite with phenolphthalein monomer and yellow soda ash, salt of wormwood, then temperature of reaction system is elevated to 160～180 ℃; Sodium salt that generates and sylvite are subsequently with 4; 4 '-the difluoro benzophenone polymerization reaction take place, behind reaction 20～40min, in 15min, temperature is elevated to 220～240 ℃;
(3). react after 1～1.2 hour, temperature of reaction is elevated to 240～260 ℃, in reaction system, add the chainextender '-biphenyl diphenol immediately; Wherein 4; 4 '-difluoro benzophenone: the mol ratio of '-biphenyl diphenol=1: 0.01～1.0, strengthen speed of response simultaneously, react stop after 1～1.5 hour the heating;
(4). treat that at last polymerization mucus is cooled to room temperature, directly wash respectively that each washs three times, obtains product of the present invention after the drying to wherein adding acetone, ethanol, zero(ppm) water successively.
Said sulfobenzide: the mol ratio of tetramethylene sulfone is 80: 20～20: 80.Said '-biphenyl diphenol: the mol ratio of phenolphthalein is 100: 10～10: 100.Said Na
2CO
3: K
2CO
3Mol ratio=19.4: 1.Said 4,4 '-difluoro benzophenone: the mol ratio of sulfobenzide and tetramethylene sulfone is 1: 1.5.
Embodiment 1:
Under nitrogen protection, to be equipped with mechanical stirrer, TM and condensing surface reactor drum in, add 261.6 gram sulfobenzides (1.2 moles) and restrain tetramethylene sulfone (0.3 mole) with 36; Be heated to 60 ℃ treat its dissolving after, add 218 grams 4,4 '-difluoro benzophenone (1.0 moles); Be heated to 80 ℃ and make its dissolving; Add 169.07 gram '-biphenyl diphenols (0.909 mole), be heated to 120 ℃ and make its dissolving, 28.94 gram phenolphthalein (0.091 mole); Be heated to 150 ℃ and make its dissolving, with pulverizing dry 102.1 good gram (0.951 mole) Na of 300 mesh sieves in advance
2CO
3With 6.762 gram (0.049 mole) K
2CO
3Join rapidly in the reaction system, stir and made the also dissolving of itself and diphenol salify in 20 minutes, rapidly system temperature is elevated to 180 ℃, react after 20 minutes; Slowly temperature is elevated to 240 ℃, reacted 1 hour, rapidly elevated temperature to 260 ℃; And add 4.65 gram '-biphenyl diphenols (0.01 mole) immediately as chainextender, and strengthen stirring velocity reaction 1 hour, stop heating; After treating that at last polymerization mucus is cooled to room temperature, directly wash each repeated washing three times respectively to wherein adding acetone, ethanol, zero(ppm) water successively; Obtain after the drying [gather (4,4 '-difluoro benzophenone-'-biphenyl diphenol)-gather (4,4 '-difluoro benzophenone-phenolphthalein)] the segmented copolymer product.Test its physical properties, the result is as shown in table 1.
Embodiment 2
Under the reaction conditions identical with embodiment 1; In the time of will be for the first time reinforced 4; 4 '-mol ratio of difluoro benzophenone and ('-biphenyl diphenol and phenolphthalein) is 1: 1.2, and other conditions do not change, and '-biphenyl diphenol is 202.74 grams (1.09 moles) when promptly reinforced for the first time; Phenolphthalein is 34.66 grams (0.109 mole), and experimental result is as shown in table 1.
Embodiment 3
Under the reaction conditions identical with embodiment 1; In the time of will be for the first time reinforced 4; 4 '-mol ratio of difluoro benzophenone and ('-biphenyl diphenol and phenolphthalein) is 1: 1.5, and other conditions do not change, and '-biphenyl diphenol is 252.96 grams (1.36 moles) when promptly reinforced for the first time; Phenolphthalein is 43.25 grams (0.136 mole), and experimental result is as shown in table 1.
Embodiment 4
Under the reaction conditions identical with embodiment 1, the mol ratio of '-biphenyl diphenol and phenolphthalein is 100: 100 when reinforced for the first time, with Na
2CO
3And K
2CO
3Mol ratio be adjusted into 18:1, other conditions do not change, '-biphenyl diphenol is 111.6 grams (0.6 mole) when promptly for the first time reinforced, phenolphthalein is 190.8 grams (0.6 mole), with pulverizing dry 100.38 good gram (0.947 mole) Na of 300 mesh sieves in advance
2CO
3With 7.31 gram (0.053 mole) K
2CO
3Join rapidly in the reaction system, experimental result is as shown in table 1.
Embodiment 5
Under the reaction conditions identical with embodiment 1; The mol ratio of '-biphenyl diphenol and phenolphthalein was 10: 100 when fed in raw material the first time, and other conditions do not change, and '-biphenyl diphenol is 16.93 grams (0.091 mole) when promptly reinforced for the first time; Phenolphthalein is 289.06 grams (0.909 mole), and experimental result is as shown in table 1.
Embodiment 6
Under the reaction conditions identical with embodiment 1; In the time of will be for the second time reinforced 4,4 '-mol ratio of difluoro benzophenone and '-biphenyl diphenol (chainextender) is 1: 0.1, other conditions do not change; '-biphenyl diphenol is 18.6 grams (0.1 mole) when promptly reinforced for the second time, and experimental result is as shown in table 1.
Embodiment 7
Under the reaction conditions identical with embodiment 1, in the time of will be reinforced for the second time 4,4 '-mol ratio of difluoro benzophenone and '-biphenyl diphenol (chainextender) is 1: 1.0, with Na
2CO
3And K
2CO
3Mol ratio be adjusted into 20:1, other conditions do not change, '-biphenyl diphenol is 186 grams (1.0 moles) when promptly for the second time reinforced, with pulverizing dry 100.95 good gram (0.952 mole) Na of 300 mesh sieves in advance
2CO
3With 6.62 gram (0.048 mole) K
2CO
3Join rapidly in the reaction system, experimental result is as shown in table 1.
Embodiment 8
Under the reaction conditions identical with embodiment 1, with 4,4 '-difluoro benzophenone and composite catalyst (Na
2CO
3And K
2CO
3) mol ratio is 1: 3, promptly add 218 gram (1.0 moles) 4,4 '-difluoro benzophenone, 302.10 gram (2.85 moles) Na
2CO
3With 20.42 gram (0.148 mole) K
2CO
3, other conditions do not change, and experimental result is as shown in table 1.
Embodiment 9
Under the reaction conditions identical with embodiment 1, with 4,4 '-difluoro benzophenone and composite catalyst (Na
2CO
3And K
2CO
3) mol ratio is 1: 5, promptly add 218 gram (1.0 moles) 4,4 '-difluoro benzophenone, 503.29 gram (4.748 moles) Na
2CO
3With 33.95 gram (0.246 mole) K
2CO
3, other conditions do not change, and experimental result is as shown in table 1.
Embodiment 10
Under the reaction conditions identical with embodiment 1, be 1: 1 with double solvents sulfobenzide and tetramethylene sulfone mol ratio, promptly add 163.5 gram sulfobenzides (0.75 mole) and restrain tetramethylene sulfone (0.75 mole) with 90, other conditions do not change, and experimental result is as shown in table 1.
Embodiment 11
Under the reaction conditions identical with embodiment 1, be 20: 80 with double solvents sulfobenzide and tetramethylene sulfone mol ratio, promptly add 65.4 gram sulfobenzides (0.3 mole) and restrain tetramethylene sulfone (1.2 moles) with 144, other conditions do not change, and experimental result is as shown in table 1.
Table 1
Wherein: ++, room temperature is solvable; +, the dissolving of room temperature lower section is heated to 30 ℃ of dissolvings fully;
+-, is heated to 45 ℃, dissolving fully in the 0.5h.
As known from Table 1: this block copolymer is compared with PEEK, has not only improved glass transition temperature but also has improved solubility property.
Claims (6)
1. solvable polyaryletherketone is characterized in that it is a kind ofly to be connected the high molecular polymer that aromatic ring is formed with ketone group by ehter bond, and molecular-weight average is 15000, and average fusing point is 390 ℃, and its molecular structural formula is:
2. the method for preparing the said solvable polyaryletherketone of claim 1 is characterized in that it is to adopt composite catalyst Na
2CO
3And K
2CO
3, double solvents sulfobenzide and tetramethylene sulfone add the '-biphenyl diphenol monomer of linear structure and the phenolphthalein monomer of nonlinear organization, and react the later stage and adopt the mode of '-biphenyl diphenol as chainextender, and concrete preparation process comprises the steps:
(1). in reaction vessel, add solvent sulfobenzide and tetramethylene sulfone, be warming up to its dissolving, so add 4,4 successively '-difluoro benzophenone, '-biphenyl diphenol and phenolphthalein, wherein 4,4 '-difluoro benzophenone: the mol ratio of '-biphenyl diphenol and phenolphthalein=1: 1.0～1.5;
(2). will pulverize the dry good Na of 200-300 mesh sieve in advance
2CO
3And K
2CO
3Join rapidly in the reaction system, wherein Na
2CO
3: K
2CO
3Mol ratio=18-20: 1; 4,4 '-difluoro benzophenone: Na
2CO
3And K
2CO
3Mol ratio=1: 1～5; Continue down to stir 20～40min at 100～150 ℃, make that the '-biphenyl diphenol in the system reacts generation sodium salt and sylvite with phenolphthalein monomer and yellow soda ash, salt of wormwood, then temperature of reaction system is elevated to 160～180 ℃; Sodium salt that generates and sylvite are subsequently with 4; 4 '-the difluoro benzophenone polymerization reaction take place, behind reaction 20～40min, in 15min, temperature is elevated to 220～240 ℃;
(3). react after 1～1.2 hour, temperature of reaction is elevated to 240～260 ℃, in reaction system, add the chainextender '-biphenyl diphenol immediately; Wherein 4; 4 '-difluoro benzophenone: the mol ratio of '-biphenyl diphenol=1: 0.01～1.0, strengthen speed of response simultaneously, react stop after 1～1.5 hour the heating;
(4). treat that at last polymerization mucus is cooled to room temperature, directly wash respectively that each washs three times, obtains product of the present invention after the drying to wherein adding acetone, ethanol, zero(ppm) water successively.
3. according to the method for the solvable polyaryletherketone of the described preparation of claim 2, it is characterized in that said sulfobenzide: the mol ratio of tetramethylene sulfone is 80: 20～20: 80.
4. according to the method for the solvable polyaryletherketone of right 2 described preparations, it is characterized in that said '-biphenyl diphenol: the mol ratio of phenolphthalein is 100: 10～10: 100.
5. according to the method for the solvable polyaryletherketone of right 2 described preparations, it is characterized in that said Na
2CO
3: K
2CO
3Mol ratio be 19.4: 1.
6. according to the method for the solvable polyaryletherketone of right 2 described preparations, it is characterized in that said 4,4 '-difluoro benzophenone: the mol ratio of sulfobenzide and tetramethylene sulfone is 1: 1.5.
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| CN105348774A (en) * | 2015-11-30 | 2016-02-24 | 广东优巨先进材料研究有限公司 | Preparation method of fiber-reinforced polyether sulphone alloy |
| CN107805305A (en) * | 2017-11-24 | 2018-03-16 | 江门市优巨新材料有限公司 | A kind of Industrialized synthesis method of film level polyaryl ether sulphone resin |
| CN108239245A (en) * | 2017-12-05 | 2018-07-03 | 宜宾天原集团股份有限公司 | A kind of preparation method of dissolvable polyether-ether-ketone |
| CN109096485A (en) * | 2018-07-23 | 2018-12-28 | 大连理工大学 | The novel crystallizable polyether-ether-ketone keto-resin and preparation method that can dissolve the side group containing phthalein |
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| CN103554478A (en) * | 2013-10-13 | 2014-02-05 | 吉林大学 | Phosphorus-containing polyaryletherketone capable of increasing interlaminar toughness of bismaleimide resin based composite material and its toughening film |
| CN105348774A (en) * | 2015-11-30 | 2016-02-24 | 广东优巨先进材料研究有限公司 | Preparation method of fiber-reinforced polyether sulphone alloy |
| CN107805305A (en) * | 2017-11-24 | 2018-03-16 | 江门市优巨新材料有限公司 | A kind of Industrialized synthesis method of film level polyaryl ether sulphone resin |
| CN108239245A (en) * | 2017-12-05 | 2018-07-03 | 宜宾天原集团股份有限公司 | A kind of preparation method of dissolvable polyether-ether-ketone |
| CN109096485B (en) * | 2018-07-23 | 2020-09-25 | 大连理工大学 | Crystallizable and dissolvable polyether-ether-ketone resin containing phthalein side group and preparation method thereof |
| CN109096485A (en) * | 2018-07-23 | 2018-12-28 | 大连理工大学 | The novel crystallizable polyether-ether-ketone keto-resin and preparation method that can dissolve the side group containing phthalein |
| CN109280188A (en) * | 2018-11-22 | 2019-01-29 | 吉林大学 | Continuous fiber reinforcement poly(aryl ether ketone) unidirectional prepreg tape and preparation method thereof |
| CN109280188B (en) * | 2018-11-22 | 2021-04-30 | 吉林大学 | Continuous fiber reinforced polyaryletherketone unidirectional prepreg tape and preparation method thereof |
| CN112979940A (en) * | 2021-02-23 | 2021-06-18 | 吉林大学 | All-biphenyl polyaryletherketone precursor as well as preparation method and application thereof |
| CN113929844A (en) * | 2021-08-13 | 2022-01-14 | 吉林省中研高分子材料股份有限公司 | Polyether-ether-ketone and preparation method thereof |
| CN113929844B (en) * | 2021-08-13 | 2024-03-08 | 吉林省中研高分子材料股份有限公司 | Polyether-ether-ketone and preparation method thereof |
| CN113861408A (en) * | 2021-10-19 | 2021-12-31 | 中国科学院大连化学物理研究所 | Preparation method for industrial production of amorphous polyaryletherketone resin |
| CN113861408B (en) * | 2021-10-19 | 2023-10-13 | 中国科学院大连化学物理研究所 | Preparation method of amorphous polyaryletherketone resin for industrial production |
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Application publication date: 20121003 |