CN105482097A - Soluble and ultraviolet crosslinking polyetherketoneketone and preparation method thereof - Google Patents
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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
- 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
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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
- C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
- C08G65/405—(I) or (II) containing oxygen other than as phenol or carbonyl group in ring structure, e.g. phenolphtalein
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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
Abstract
The invention relates to soluble and ultraviolet crosslinking polyetherketoneketone and a preparation method thereof, belonging to the field of high polymer materials. The preparation method comprises the steps that three bisphenol monomer compounds containing allyl and vinyl and a difluoro monomer compound are taken as crosslinking points; through nucleophilic substitution, the crosslinking points are introduced in a block way, and are uniformly distributed in a polymer main chain structure; the content of the crosslinking points is controlled within 5-40 percent; methyl benzene or xylene is selected as a dehydrant; anhydrous potassium carbonate or sodium carbonate is selected as a catalyst; sulfolane, N-methyl pyrrolidone, dimethyl sulfoxide or N,N-dimethylacetamide is selected as a solvent. The soluble and ultraviolet crosslinking polyetherketoneketone has the advantages of excellent organic solvent resistance and stress cracking resistance, meanwhile the heat resistance and strength of a membrane material are further improved, the shape and size stability of the material before and after crosslinking is effectively ensured, and regulation and control on the performance of the material can be realized by changing the content of crosslinking point structures in a polymer structure, ultraviolet crosslinking time and ultraviolet light wavelength.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to one class novel solvable can UV-crosslinked polyaryletherketone high performance material and preparation method thereof.
Background technology
Polyether-ether-ketone (PEEK), as a kind of complete fragrant semicrystalline polymeric, has excellent physical and chemical performance, is thus widely used in the fields such as electronic apparatus, machinery instrument, communications and transportation, aerospace.For most of polyaryletherketone kind, due to reasons such as molecule chain rigidity, crystallinity, cause closely piling up of molecular chain, cause its solvability poor, melt temperature is high, can only adopt the method for hot briquetting, processing mode is single, limits its range of application.Along with application purpose and the different needs of applied environment, many investigators, around improving processing characteristics, improve the problems such as temperature classification, continually develop this type of novel material of excellent performance, to meet different service requirementss.On main polymer chain, such as introduce different functional groups (as naphthalene nucleus, azepine naphthalene nucleus etc.), the Phthalazinone of distortion non-co-planar be incorporated in main polymer chain and can improve structure adaptability, give the thermotolerance of polymkeric substance excellence simultaneously.Main chain is introduced side base functional group, improves the solvability of polyaryletherketone, or improve use properties and the processing characteristics of material further by copolymerization and the mode such as blended.In addition, by introducing the larger group of rigidity in polyaryletherketone backbone structure, introducing crosslinkable groups at main chain or side chain and improved resistance toheat and the use temperature of material by blended method further.Crosslinking reaction comprises chemically crosslinked and heat cross-linking, and chemically crosslinked needs to add crosslinking accelerator usually, impels polymer segment to form cross-linked network by the effect of chemical cross-linking agent.Along with adding of chemical cross-linking agent, make polymeric system complicated, also may occur with some side reactions simultaneously.Thermal crosslinking treatment and heat cross-linking toughening modifying are one of study hotspots of macromolecular material in recent years.Develop the polyaryletherketone material having excellent solubility energy, processing characteristics and high heat resistance energy concurrently, for industrial development and new technology progress, there is profound significance.
Ultraviolet light irradiation cross-linking processing technology operates under having normal temperature, condition of normal pressure, when macromolecular material is irradiated, light can be deep into polymeric inner effect, realizes macromolecular crosslinking reaction, makes linear polymer form the polymkeric substance with three-dimensional space network structure.The polymkeric substance be cross-linked is made to have more excellent high heat resistance, excellent Physical Mechanical, good organic solvent resistance.Ultraviolet light irradiation cross-linking is to polymer materials not damaged; and do not bring the feature of any residual hazard and refuse; simultaneously ultraviolet light irradiation processing technology also has energy-efficient, environmental protection, advantage that control method is easy, is a technology being suitable for industrialization and large-scale production.
Summary of the invention
The invention provides a kind of solvable can UV-crosslinked polyaryletherketone and preparation method thereof, object introduces side based structures in polyaryletherketone segment, three kinds ultraviolet light cross-linking structure can be incorporated in polyaryletherketone backbone structure simultaneously, provide the solvable of brand new can UV-crosslinked polyaryletherketone high performance material and technology of preparing thereof.
The present invention adopts three kinds to contain allyl group and vinyl biphenol monomer compound and two fluorine monomer compound as cross-linking set, pass through nucleophilic substitution reaction, cross-linking set is introduced in the mode of block, it is made to be evenly distributed in polymer backbone conformation, cross-linking set content controls between 5 ~ 40%, prepares polymer architecture and performance before and after a series of solution processable, UV-crosslinked solidification and can carry out the polyaryletherketone high performance material regulated and controled.In preparation process, toluene or dimethylbenzene can be selected as dewatering agent, Anhydrous potassium carbonate or sodium carbonate are catalyzer, select tetramethylene sulfone, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or N,N-dimethylacetamide to be solvent.The present invention obtain novel solvable can UV-crosslinked poly aryl ether ketone polymer structural formula as follows:
In structure above, m, n are the polymerization degree, and m, n are positive integer.
Described solvable can the preparation method of UV-crosslinked polyaryletherketone: select 4,4 '-dihydroxyl cinnamophenone, 2,2 '-diallyl bisphenol, 2 '-allyl phenyl-2, it is cross-linking set that 6-difluoro M-nitro benzoic acid three kinds contains allyl group and vinyl structure bis-phenol and two fluorine monomer compound, cross-linking set is incorporated in polyaryletherketone backbone structure in the mode of block, and controls cross-linking set content between 5 ~ 40%.Select two fluorine monomer compound 4,4 '-difluoro benzophenone and 2,6-difluorobenzonilyile and biphenol monomer compound hexafluoro bisphenol-a, dihydroxyphenyl propane, phenolphthalein prepare serial poly aryl ether ketone polymer by nucleophilic substitution reaction route.With tetramethylene sulfone or N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO) or N, N-N,N-DIMETHYLACETAMIDE is solvent, solvent adding amount is advisable with solid content 20 ~ 35%, salt of wormwood or sodium carbonate are catalyzer, consumption is 1.05 ~ 1.15 times of biphenol monomer total mole number, and dewatering agent toluene or dimethylbenzene consumption are 20 ~ 30% of solvent for use cumulative volume.At 145 ~ 165 DEG C, 180 ~ 210 DEG C of temperature ranges react 2 ~ 4h and 3 ~ 6h respectively, disperse in reaction product cold water, respectively with ethanol and water washing 6 ~ 8 removings organic molecule, organic solvent and inorganic salt after pulverizing, last in 100 ~ 120 DEG C of drying 10 ~ 12h, obtain solvable can UV-crosslinked poly aryl ether ketone polymer, productive rate is 96 ~ 98%.
The present invention prepare novel solvable can UV-crosslinked polyaryletherketone series high-performance material, be by introduce in polymer segment simultaneously the side based structures that can improve polymer dissolution performance and can be UV-crosslinked allyl group or vinyl structure (cross-linking set) realize.Polymkeric substance can carry out solution processing, carries out UV-crosslinked solidification at ambient temperature after processing, obtains having the polyaryletherketone material of the UV-crosslinked solidification of more high heat resistance energy and use temperature.Utilize the ultraviolet light irradiation cross-linking technology of clean and effective to improve the use temperature of the polyaryletherketone material with excellent solution processing characteristics further, the requirement to material is main innovate point of the present invention and technical characteristics with satisfied different use temperature and use range for raising materials processing performance and thermal characteristics simultaneously.
The present invention has the following advantages:
One, solvable can have solution processable performance by UV-crosslinked polyaryletherketone, by UV-crosslinked curing after processing, improve the organic solvent-resistant ability of material, the temperature classification of further raising material and intensity, especially as mould material application aspect, there is outstanding feature, organic solvent solution working method can be first adopted to prepare thin-film material, then through UV-crosslinked solidification, under the prerequisite keeping thin-film material dimensional stabilizing, mould material after crosslinked has excellent organic solvent-resistant ability and anti-stress cracking, simultaneously the resistance toheat of mould material and intensity are further enhanced.
Two, UV-crosslinked curing technology, effectively can ensure stablizing in crosslinked front and back material shape and size.
Three, by changing the regulation and control that the content of Crosslink structure in polymer architecture and UV-crosslinked time and ultraviolet wavelength can realize material property.
Embodiment
Embodiment 1
By 22.04g (0.101mol) 4, 4 '-difluoro benzophenone, hexafluoro bisphenol-a 31.93g (0.095mol), 163ml tetramethylene sulfone (take tetramethylene sulfone as solvent, solvent adding amount is advisable with solid content 20 ~ 35%, the present embodiment tetramethylene sulfone consumption calculates according to solid content 20%), 14.49g (0.105mol) Anhydrous potassium carbonate, 40ml dimethylbenzene joins and mechanical stirring is housed, in the 500ml there-necked flask of thermometer and nitrogen protection, stirring is warming up to 145 ~ 165 DEG C, dimethylbenzene band water back flow reaction 2h, be warming up to 180 ~ 210 DEG C of reaction 2 ~ 3h, system is cooled to less than 100 DEG C, add 1.20g (0.005mol) 4, 4 '-dihydroxyl cinnamophenone [4, 4 '-dihydroxyl cinnamophenone is as cross-linking set, cross-linking set content is 5%, namely 4, 4 '-dihydroxyl cinnamophenone/(4, 4 '-dihydroxyl cinnamophenone+hexafluoro bisphenol-a) mol ratio be 5%], be warming up to 145 ~ 160 DEG C, dimethylbenzene band water back flow reaction 2h, then the dimethylbenzene in reaction system is removed gradually, be warming up to 180 ~ 210 DEG C of reaction 3 ~ 6h, be dispersed in water under polymers soln room temperature condition, after the thick product of strip is pulverized, respectively with ethanol and distilled water boiling washing 6 ~ 8 times to remove organic solvent tetramethylene sulfone, a small amount of organic molecule and inorganic salt, product is at 120 DEG C of dry 12h, obtain white polyaryletherketone powdered sample, productive rate 97%.
Embodiment 2
Hexafluoro bisphenol-a, as embodiment 1, is replaced with dihydroxyphenyl propane, phenolphthalein by method successively respectively, and in polymer formulae, dihydroxyphenyl propane unit or phenolphthalein unit replace hexafluoro bisphenol-a unit successively.Finally obtain respectively cross-linking set (4,4 '-dihydroxyl cinnamophenone) content be 5% white polyaryletherketone powdered sample [namely 4, the mol ratio of 4 '-dihydroxyl cinnamophenone/(4,4 '-dihydroxyl cinnamophenone+dihydroxyphenyl propane) is 5%; 4, the mol ratio of 4 '-dihydroxyl cinnamophenone/(4,4 '-dihydroxyl cinnamophenone+phenolphthalein) is 5%], productive rate is 96 ~ 98%.
Embodiment 3
Method is as embodiment 1 and embodiment 2, change 4 successively, the molar content of 4 '-dihydroxyl cinnamophenone is 10%, 15%, 20%, 25%, 30%, 35%, 40%, [4, 4 '-dihydroxyl cinnamophenone/(4, 4 '-dihydroxyl cinnamophenone+hexafluoro bisphenol-a), 4, 4 '-dihydroxyl cinnamophenone/(4, 4 '-dihydroxyl cinnamophenone+dihydroxyphenyl propane), 4, 4 '-dihydroxyl cinnamophenone/(4, 4 '-dihydroxyl cinnamophenone+phenolphthalein) mol ratio be respectively 10%, 15%, 20%, 25%, 30%, 35%, 40%], prepare a series of soluble poly aromatic ether ketone polymer with different cross-linking set content, productive rate is 96 ~ 98%.Embodiment 1 to embodiment 3 polymer architecture is see polymer architecture (I).
Embodiment 4
Method is as embodiment 1, by 4,4 '-dihydroxyl cinnamophenone replaces with 2,2 '-diallyl bisphenol, obtains 2, and 2 '-diallyl bisphenol is cross-linking set, cross-linking set content is 5% [2,2 '-diallyl bisphenol/(2,2 '-diallyl bisphenol+hexafluoro bisphenol-a) mol ratio is 5%] solvable can UV-crosslinked poly aryl ether ketone polymer, productive rate 98%.
Embodiment 5
Hexafluoro bisphenol-a, as embodiment 4, is replaced with dihydroxyphenyl propane, phenolphthalein by method successively respectively, and in polymer formulae, dihydroxyphenyl propane unit or phenolphthalein unit replace hexafluoro bisphenol-a unit successively.Obtain 2 respectively, 2 '-diallyl bisphenol cross-linking set content is 5%, respectively containing dihydroxyphenyl propane and phenolphthalein structure two kinds of polymkeric substance [2,2 '-diallyl bisphenol/(2,2 '-diallyl bisphenol+dihydroxyphenyl propane); 2,2 '-diallyl bisphenol/(2,2 '-diallyl bisphenol+phenolphthalein) mol ratio is 5%].Productive rate 96 ~ 98%.
Embodiment 6
Method is as embodiment 4 and embodiment 5, change 2 successively, the molar content of 2 '-diallyl bisphenol is 10%, 15%, 20%, 25%, 30%, 35%, 40%, prepare a series of 2,2 '-diallyl bisphenol is that the different a series of solubilities of cross-linking set, cross-linking set content can UV-crosslinked solidification poly aryl ether ketone polymer.Embodiment 4 to embodiment 6 polymer architecture is see polymer architecture (II).
Embodiment 7
By 33.60g (0.10mol) hexafluoro bisphenol-a, 20.95g (0.096mol) 4, 4 '-difluoro benzophenone, 165ml tetramethylene sulfone (solid content calculates according to 20%), 14.49g (0.105mol) Anhydrous potassium carbonate, 40ml dimethylbenzene joins and mechanical stirring is housed, in the 500ml there-necked flask of thermometer and nitrogen protection, stirring is warming up to 145 ~ 160 DEG C, dimethylbenzene band water back flow reaction 2h, be warming up to 180 ~ 210 DEG C of reaction 3 ~ 6h, system is cooled to less than 100 DEG C, add 1.37g (0.005mol) 2 '-allyl phenyl-2, 6-difluoro M-nitro benzoic acid [2 '-allyl phenyl-2, 6-difluoro M-nitro benzoic acid is as cross-linking set, cross-linking set content is 5%, i.e. 2 '-allyl phenyl-2, 6-difluoro M-nitro benzoic acid/(2 '-allyl phenyl-2, 6-difluoro M-nitro benzoic acid+4, 4 '-difluoro benzophenone) mol ratio be 5%], be warming up to 145 ~ 160 DEG C, dimethylbenzene band water back flow reaction 2h, remove the dimethylbenzene in reaction system gradually, be warming up to 180 ~ 210 DEG C of reaction 3 ~ 6h, polymers soln dispersed at room temperature is in water, after the thick product of strip is pulverized, respectively with ethanol and distilled water boiling washing 6 ~ 8 times to remove organic solvent tetramethylene sulfone, a small amount of organic molecule and inorganic salt, product is at 120 DEG C of dry 12h, obtain white polyaryletherketone powdered sample, productive rate 97%.
Embodiment 8
Method is as embodiment 7, replace the hexafluoro bisphenol-a in embodiment 7 successively with dihydroxyphenyl propane and phenolphthalein, preparing two kinds of 2 '-allyl phenyl-2,6-difluoro M-nitro benzoic acids is cross-linking set, cross-linking set content is 5% and contains the poly aryl ether ketone polymer of dihydroxyphenyl propane and phenolphthalein structure respectively, and productive rate is 96 ~ 98%.
Embodiment 9
Method is as embodiment 7 and embodiment 8, change 2 '-allyl phenyl-2 successively, the molar content of 6-difluoro M-nitro benzoic acid is 10%, 15%, 20%, 25%, 30%, 35%, 40%, prepare a series of 2,2 '-diallyl bisphenol is that different solvable of cross-linking set, cross-linking set content can UV-crosslinked serial poly aryl ether ketone polymer, and productive rate is 96 ~ 98%.Embodiment 7 to embodiment 9 polymer architecture is see polymer architecture (III).
Embodiment 10:
By 7.02g (0.0505mol) 2, 6-difluorobenzonilyile, 11.02g (0.0505mol) 4, 4 '-difluoro benzophenone, 31.93g (0.095mol) hexafluoro bisphenol-a, 190ml tetramethylene sulfone (solid content calculates according to 20%), 14.49g (0.105mol) Anhydrous potassium carbonate, 40ml dimethylbenzene joins and mechanical stirring is housed, in the 500ml there-necked flask of thermometer and nitrogen protection, stirring is warming up to 145 ~ 160 DEG C, dimethylbenzene band water back flow reaction 2h, be warming up to 180 ~ 210 DEG C of reaction 3 ~ 6h, system is cooled to less than 100 DEG C, add 1.20g (0.005mol) 4, 4 '-dihydroxyl cinnamophenone [4, 4 '-dihydroxyl cinnamophenone is as cross-linking set, cross-linking set content is 5%, namely 4, 4 '-dihydroxyl cinnamophenone/(4, 4 '-dihydroxyl cinnamophenone+hexafluoro bisphenol-a) mol ratio be 5%], be warming up to 145 ~ 160 DEG C, dimethylbenzene band water back flow reaction 2h, remove the dimethylbenzene in reaction system gradually, be warming up to 180 ~ 210 DEG C of reaction 3 ~ 6h, polymers soln dispersed at room temperature is in water, after the thick product of strip is pulverized, respectively with ethanol and distilled water boiling washing 6 ~ 8 times to remove organic solvent tetramethylene sulfone, a small amount of organic molecule and inorganic salt, product is at 120 DEG C of dry 12h, obtain white polyaryletherketone powdered sample, productive rate 97%.
Embodiment 11:
Method is as embodiment 10, linking agent is replaced with 2 successively, 2 '-diallyl bisphenol, 2 '-allyl phenyl-2,6-difluoro M-nitro benzoic acid, prepare two kinds of content of crosslinking agent be 5% and can UV-crosslinked poly aryl ether ketone polymer containing hexafluoro bisphenol-a and the solvable of cyano group structure.
Embodiment 12:
Hexafluoro bisphenol-a, as embodiment 10 and embodiment 11, is replaced with dihydroxyphenyl propane and phenolphthalein by method successively, prepares a series of different cross-linking set content and is 5% and containing the solvable of homonymy based structures can UV-crosslinked polyaryletherketone series polymer.
Embodiment 13:
Method, as embodiment 10 to embodiment 12, adjusts three kinds of different cross-linking set content for being 10%, 15%, 20%, 25%, 30%, 35%, 40%, prepares a series of different Crosslink structure and the solvable of content can UV-crosslinked poly aryl ether ketone polymer.Embodiment 10 to embodiment 13 polymer architecture is see polymer architecture (IV).
Embodiment 14:
Method is as embodiment 1 to embodiment 13, and sulfolane solvent is replaced with successively N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO) or N,N-dimethylacetamide, solvent adding amount is to be advisable between solid content 20 ~ 35%.
Claims (2)
1. one kind solvable can UV-crosslinked polyaryletherketone and preparation method thereof, its structural formula is as follows:
In structure above, m, n are the polymerization degree, and m, n are positive integer.
2. as claimed in claim 1 a kind of solvable can the preparation method of UV-crosslinked polyaryletherketone, it is characterized in that: select 4,4 '-dihydroxyl cinnamophenone, 2,2 '-diallyl bisphenol, 2 '-allyl phenyl-2, it is cross-linking set that 6-difluoro M-nitro benzoic acid three kinds contains allyl group and vinyl structure bis-phenol and two fluorine monomer compound, cross-linking set is incorporated in polyaryletherketone backbone structure in the mode of block, and controls cross-linking set content between 5 ~ 40%; Select two fluorine monomer compound 4,4 '-difluoro benzophenone and 2,6-difluorobenzonilyile and biphenol monomer compound hexafluoro bisphenol-a, dihydroxyphenyl propane, phenolphthalein prepare serial poly aryl ether ketone polymer by nucleophilic substitution reaction route; With tetramethylene sulfone or N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO) or N, N-N,N-DIMETHYLACETAMIDE is solvent, solvent adding amount is advisable with solid content 20 ~ 35%, salt of wormwood or sodium carbonate are catalyzer, consumption is 1.05 ~ 1.15 times of biphenol monomer total mole number, and dewatering agent toluene or dimethylbenzene consumption are 20 ~ 30% of solvent for use cumulative volume; At 145 ~ 165 DEG C, 180 ~ 210 DEG C of temperature ranges react 2 ~ 4h and 3 ~ 6h respectively, disperse in reaction product cold water, respectively with ethanol and water washing 6 ~ 8 removings organic molecule, organic solvent and inorganic salt after pulverizing, finally in 100 ~ 120 DEG C of drying 10 ~ 12h.
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| CN111732724A (en) * | 2020-06-30 | 2020-10-02 | 东北师范大学 | Polyaryletherketone single-ion polymer and single-ion gel polymer electrolyte |
| CN115417986A (en) * | 2022-10-09 | 2022-12-02 | 中国科学院兰州化学物理研究所 | Allyl grafted polyaryletherketone oligomer and preparation method thereof, photosensitive material and application thereof |
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| CN1482158A (en) * | 2003-07-08 | 2004-03-17 | 吉林大学 | High-performance material of soluble controlled crosslinkable polyarylether ketone and preparation thereof |
| CN102532517A (en) * | 2011-12-28 | 2012-07-04 | 吉林省聚科高新材料有限公司 | Soluble and ultraviolet-crosslinked-cured polyaryletherketone and preparation method thereof |
| CN102558544A (en) * | 2011-12-28 | 2012-07-11 | 吉林省聚科高新材料有限公司 | Soluble and ultraviolet crosslinking polyaryl ether nitrile and preparation method thereof |
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| CN111732724A (en) * | 2020-06-30 | 2020-10-02 | 东北师范大学 | Polyaryletherketone single-ion polymer and single-ion gel polymer electrolyte |
| CN111732724B (en) * | 2020-06-30 | 2023-01-03 | 东北师范大学 | Polyaryletherketone single-ion polymer and single-ion gel polymer electrolyte |
| CN115417986A (en) * | 2022-10-09 | 2022-12-02 | 中国科学院兰州化学物理研究所 | Allyl grafted polyaryletherketone oligomer and preparation method thereof, photosensitive material and application thereof |
| CN115417986B (en) * | 2022-10-09 | 2023-08-18 | 中国科学院兰州化学物理研究所 | Allyl grafted polyaryletherketone oligomer, preparation method thereof, photosensitive material and application thereof |
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