CN1190452C - High-performance material of soluble controlled crosslinkable polyarylether ketone and preparation thereof - Google Patents
High-performance material of soluble controlled crosslinkable polyarylether ketone and preparation thereof Download PDFInfo
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- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000012761 high-performance material Substances 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010894 electron beam technology Methods 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000012545 processing Methods 0.000 claims abstract description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 150000003384 small molecules Chemical class 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 238000004132 cross linking Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- OJLABXSUFRIXFL-UHFFFAOYSA-N (2-benzoylphenyl)-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 OJLABXSUFRIXFL-UHFFFAOYSA-N 0.000 claims description 9
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- NQMVZNZNTQCWJK-UHFFFAOYSA-N 2-phenyl-1-(trifluoromethyl)cyclohexa-3,5-diene-1,3-diol Chemical compound FC(C1(C(C(O)=CC=C1)C1=CC=CC=C1)O)(F)F NQMVZNZNTQCWJK-UHFFFAOYSA-N 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 6
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- FMAQEDRIXJLENV-UHFFFAOYSA-N 2-phenyl-3-(trifluoromethyl)benzene-1,4-diol Chemical compound FC(C=1C(=C(O)C=CC1O)C1=CC=CC=C1)(F)F FMAQEDRIXJLENV-UHFFFAOYSA-N 0.000 abstract 1
- 238000004382 potting Methods 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000010129 solution processing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种可溶可控交联聚芳醚酮类高性能材料的制备方法。通过间-三氟甲基苯基对苯二酚和4，4’-二氟二苯酮等与小分子齐聚物FKOSOKF在溶剂N-甲基吡咯烷酮或环丁砜中反应，反应产物于蒸馏水中出料，同时不断搅拌，得到白色聚合物细丝，经粉碎机粉碎后，聚合物粉料用丙酮洗涤六至八次以除去有机溶剂、蒸馏水煮沸洗涤六至八次以除去无机盐，在110-120℃干燥10-12h，产率96-98%，分子量在四万至六万之间。此类材料具有优异的加工性能，可采用常规加工方法或者溶液加工成型，成型后可以通过电子束辐照实现常温交联固化。可用于涂料材料、灌封材料及薄膜材料，尤其是可作为良好的复合材料树脂基体使用。
The invention relates to a preparation method of a soluble and controllable cross-linked polyaryletherketone high-performance material. Through the reaction of m-trifluoromethylphenylhydroquinone and 4,4'-difluorobenzophenone with the small molecule oligomer FKOSOKF in the solvent N-methylpyrrolidone or sulfolane, the reaction product is released in distilled water Stir continuously at the same time to obtain white polymer filaments. After being pulverized by a pulverizer, the polymer powder is washed with acetone six to eight times to remove organic solvents, and distilled water is boiled and washed six to eight times to remove inorganic salts. Dry at 120°C for 10-12 hours, the yield is 96-98%, and the molecular weight is between 40,000 and 60,000. This kind of material has excellent processing properties, and can be formed by conventional processing methods or solution processing. After forming, it can be cross-linked and cured at room temperature by electron beam irradiation. It can be used in coating materials, potting materials and film materials, especially as a good resin matrix for composite materials.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to the technology of preparing of the novel solvable controlled crosslinked high-performance materials of polyarylether ketones of a class and this material.
Background technology
Material is the milestone of human social development, and the scientific-technical progress of each period of history is all closely related with material, and along with science and technology development, people are more and more higher to the requirement of material, and many difficult problems of high-tech sector have the problem that much is actually material.The Application and Development that does not have novel material, new technical products and industrial progress just are far from being.Flourish along with world's new science and technology revolution, the high performance structures material has been proposed increasingly extensive and urgent demand, those have the base mateiral that high strength, high tenacity, high temperature resistant, wear-resistant, erosion-resisting structured material have become hi-tech industries such as development new forms of energy, nuclear technique, space development, oceanographic engineering, also are the critical materials of rebuilding traditional industry.The poly aryl ether ketone material has excellent physical chemistry as a kind of complete fragrant semicrystalline polymeric, thereby is widely used in fields such as electronic apparatus, machinery instrument, communications and transportation, aerospace.But the polyaryletherketone material also has the weak point of himself.As polyether-ether-ketone, though its heat decomposition temperature more than 500 ℃, its second-order transition temperature is lower, has only 142 ℃, descends very soon along with the modulus of the rising material of temperature more than second-order transition temperature, causes its use temperature lower.Therefore people adopt means such as blend, copolymerization that material is carried out modification, in the hope of further improving the performance, particularly resistance toheat of material.The second-order transition temperature of the novel polyaryletherketone material of our seminar development and fusing point are respectively up to 212 ℃ with 468 ℃ (molecular designing of Zhou Hongwei Jilin University doctorate paper 1999 polyaryletherketones and research of chain structure and condensed state structure), have the so high second-order transition temperature and the material of fusing point and can satisfy life-time service under 350 ℃ high temperature fully, but dystectic material like this is difficult to machine-shaping, therefore, the use temperature that improve material just must be sought other feasible way.
Being used as the matrix material of structured material at present, is enhancing ingredients with macroscopic fiber such as glass fibre, carbon fibers normally, is that matrix is composited with thermoset or thermoplastic resin.Although the research of macroscopic fiber reinforced composite materials has obtained immense success, it is to be solved that but some problems still have, the bounding force of the most outstanding is fiber and reisn base material is not ideal enough, and both thermal expansivity differ the internal stress problem that causes more greatly.In addition, particularly in the occasion of using glass fibre as toughener, the high viscosity of batching and the not only exigent energy expenditure of high friction, and cause the damage of equipment easily.Seeking new composite system at these problems has great importance undoubtedly.
Summary of the invention
Purpose of the present invention is exactly by in the big replacement of the introducing side group in the molecular chain of polyaryletherketone, sulfide based structural is incorporated in the polyaryletherketone backbone structure as the mode of cross-linking set with block copolymerization, thereby the technology of preparing of a kind of novel solvable controlled crosslinked high-performance materials of polyarylether ketones and this material is provided.
Major technique characteristics of the present invention are:
One: by in the molecular chain of polyaryletherketone, introducing the big side group that replaces, destroy the tacticity that macromolecular chain is piled up, prepare the solubility amorphous polymer, make it in conventional organic solvent, have good solubility, as tetrahydrofuran (THF), chloroform, ethanol, acetone, butanone, methylene dichloride, DMF, NMP, DMSO, DMAc, 1,2-ethylene dichloride etc.Utilize its good solubility can adopt the solution method for processing to process.
Two: introduce when replacing side group greatly, utilize sulfide based structural that the characteristics of crosslinking reaction can take place under high temperature and electron beam irradiation condition, sulfide based structural is incorporated in the polyaryletherketone backbone structure as the mode of cross-linking set with block copolymerization, makes that it is single, be evenly distributed in the polyaryletherketone segmented structure.Adopt after the conventional working method machine-shaping crosslinkedly under high temperature, electron beam irradiation condition, solvable crosslinkable type polyaryletherketone is converted into does not dissolve not fused thermoset engineering plastics, the use temperature of material is greatly improved.In preparation process, change the content regulation and control cross-linking density of cross-linking set, the content range of cross-linking set by to controllable to crosslinked front and back material structure and performance of the controllable realization of the distribution mode of cross-linking set and cross-linking density, satisfies different service requirementss between 1%-50%.
Three: solvable controlled crosslinked polyaryletherketone can be used for coating material, Embedding Material and thin-film material, especially uses as good composite resin matrix.As preparing matrix material with carbon fiber or glass fibre.Its advantage is and can solidifies at ambient temperature that solidification value is low more, and internal stress is just more little in the fibre resin matrix material that fiber and resin difference of thermal expansion coefficients cause; After cross-link bond forms, is connected by the chemical bond of pretending firmly between layer and the layer, the interlaminar shear strength increase, the flexural strength increase can solve fiber and the not strong problem of resin bond power.Based on this imagination, solvable controlled crosslinked polyaryletherketone base polymer has been synthesized in design, the self-vulcanizing moulding, and crosslinked and fiber formation inierpeneirating network structure on the basis that keeps the original performance of polyaryletherketone, further improves the temperature classification of material after the moulding.This class novel material is in the same place the advantages of thermoplastic material and thermosetting material, has both had the good processing properties of thermoplastic material, has the high characteristics of thermosetting material use temperature simultaneously again.
The optimum molar content of oligopolymer FKOSOKF is 2%-30%; be FKOSOKF/ (FKOSOKF+4; 4 '-difluoro benzophenone) mol ratio or FKOSOKF/ (FKOSOKF+4; 4 '-(4-fluorine) dibenzoyl benzene) mol ratio or the mol ratio of FKOSOKF/ (FKOSOKF+4,4 '-dichloro diphenyl sulfone) are 2%-30%.M-trifluoromethyl phenyl Resorcinol is with FKOSOKF and 4,4 '-difluoro benzophenone sum, FKOSOKF and 4, and 4 '-(4-fluorine) dibenzoyl benzene sum, FKOSOKF and 4, the mol ratio of 4 '-dichloro diphenyl sulfone sum is 1: 1; N-Methyl pyrrolidone (NMP) or tetramethylene sulfone are solvent, and the add-on of solvent is that 15-20% is the best to contain thing admittedly, and salt of wormwood is as catalyzer, and its consumption is on the basis of identical mole number with biphenol monomer, excessive 1-3%.
The synthetic reaction process of polymkeric substance is: with monomer m-trifluoromethyl phenyl Resorcinol and 4; 4 '-difluoro benzophenone (or 4; 4 '-(4-fluorine) dibenzoyl benzene or 4; 4 '-dichloro diphenyl sulfone) dropping into 1000ml has in the there-necked flask of agitator, thermometer, nitrogen protection device and water-and-oil separator; add catalysts salt of wormwood; solvent N-Methyl pyrrolidone (NMP) or tetramethylene sulfone add band aqua toluene 150-200ml at last.Reaction system is warming up to 145-160 ℃, and toluene band water refluxes, and constantly emits the water generation reaction branch, band water reaction 2-3h; Reaction system is warming up to 210-220 ℃ then, reaction 2-3h, reaction system is cooled to 100-120 ℃ then, (its synthetic method is seen Chinese patent: ZL00105146.6 to add small molecules oligopolymer FKOSOKF, the applying date: on April 1st, 2000, denomination of invention: the preparation of high-performance materials of polyarylether ketones), toluene unnecessary in the reaction system is removed in evaporation, reaction system is warming up to 220 ℃, reaction 2-3h, reaction product is discharging in distilled water, constantly stirs simultaneously, obtain the white polymer filament, after pulverizer is pulverized, polymer powders with washing with acetone six to eight times to remove organic solvent, distilled water boiling washing six to eight times is to remove inorganic salt, at 110-120 ℃ of dry 10-12h, productive rate 96-98%, molecular weight is between 40,000 to 60,000.End product carries out electron beam to irradiate crosslinked at 100-1000Kgy dosage under the 8-80min condition, obtain having a series of solvable controlled crosslinked polyaryletherketone based block copolymer of different degree of crosslinking.
The preparation of monomeric compound m-trifluoromethyl phenyl Resorcinol:
The first step: diazonium salt synthetic
Get liquid m-trifluoromethyl aniline and place the 5000ml beaker for 1 mole, under constantly stirring, add 2 moles of concentrated hydrochloric acids, form milky emulsion, temperature is controlled at 0 ℃-5 ℃, in above-mentioned system, slowly drip 1 mole of Sodium Nitrite dilute solution, after reaction finished, whole reaction system was a clear liquid, remains on 0 ℃-5 ℃.
Reaction equation is:
Second step: linked reaction
Add 1 mole of benzoquinones and 2 moles of sodium bicarbonates in having churned mechanically 10000ml reaction vessel, add 1000ml distilled water, be configured to the tawny suspension liquid, temperature of reaction system remains on 12 ℃-15 ℃.Add the colourless liquid that the first step forms in this system, in the dropping process, the dropping liquid temperature is controlled at 0 ℃-5 ℃.Dropwise the back and continue stirring reaction 1h, filter, obtain the yellow powder solid matter, repeatedly wash, become colorless until considering liquid with distilled water.
Reaction equation is:
The 3rd step: reduction reaction
The yellow solid matter that obtains is put into the there-necked flask of the 3000ml that has stirring, reflux and Dropping feeder in second step, add distilled water 600ml, add 2.5 moles of reductive agent zinc powders, constantly stir to be heated to down and begin to have the water backflow to drip constant temperature, begin to drip concentrated hydrochloric acid solution, add-on is 3.5 moles, and the dropping process must be slow, allows the hydrogen that generates have time enough to emit, after reacting completely, keep refluxing 1 hour.Heat filtering obtains red oily liquids, adds distilled water, stirs fast, and in temperature-fall period, oily matter solidifies and obtains white solid, promptly is our designed synthetic monomeric compound.
Reaction equation is:
The 4th step: recrystallization
The white mass that obtains after 60 ℃ of dryings of vacuum drying oven, is put into the three mouthfuls of reaction flasks of 1000ml that have stirring, nitrogen protection and reflux for block, adds toluene 500ml; reflux, after the dissolving, heat filtering obtains light grey solution fully; cooling is filtered, and obtains white needle-like crystals.Be placed in the vacuum drying oven, maintain the temperature at 60 ℃ and carry out drying and promptly obtained us in 72 hours and design synthetic monomeric substance m-trifluoromethyl phenyl Resorcinol, purity is more than 99.
The structural formula of three kinds of polymkeric substance that the present invention obtains is as follows:
The building-up reactions formula one of polymkeric substance (I): (embodiment 1 and 2)
The building-up reactions formula two of polymkeric substance (II): (embodiment 3 and 4)
The building-up reactions formula three of polymkeric substance (III): (embodiment 5 and 6)
In reaction process, by changing the molar content of sulfide based structural FKOSOKF, promptly by adjusting n value size, can prepare sulfide based structural FKOSOKF molar content is a series of solvable controlled crosslinked polyaryletherketone segmented copolymer of 2%-30%.
Two fluorine monomers and biphenol monomer mol ratio are on 1: 1 the basis in keeping reaction system, can regulate and control the molecular weight of polymkeric substance by the concentration that increases the fluorine end group, molecular weight is with the variation tendency of fluorine end group concentration as shown in Figure 1: along with the increase of fluorine end group concentration, polymer viscosity (molecular weight) is on a declining curve, especially surpass after 1.5% at the excessive number of fluorine end group concentration, even the fluorine end group concentration differs very little, polymeric viscosity also can differ greatly, therefore can come the molecular weight of controlling polymers by fluorine end group concentration in the telomerized polymer, thereby obtain the polymkeric substance of different molecular weight, to obtain functional and to be beneficial to the polymkeric substance of the optimum weight of processing.
The cross-linking set of polymkeric substance belongs to (10
-10) order of magnitude, can't use the electron microscope direct viewing, still prove crosslinked existing with the variation of transitivity so far with the increase of insoluble part in change of molecular weight and the solvent.With sulfide based structural content in weight-average molecular weight 60,000 systems is 10% to be example explanation electron beam irradiation to effect of material performance:
Polymkeric substance (Polymers) Mn Mw Mz Mw/Mn
Without radiation polymerization thing 0KGy 34,340 61,859 98,115 1.80
(unirradiated)
Mw-6×10
4 50KGy 42,073 174,218 2,947,661 4.14
Thio-10％ 100KGy 38,847 331,451 13,398,805 8.53
Just can know from top GPC data: the viscosity cause of increased is that polymericular weight is increasing.Measure the later gel percentage composition of 10% thioether bond molar content polymer-electronics bundle irradiation in weight-average molecular weight 60,000 systems:
Irradiation dose (Dose) 100KGy 150KGy 200KGy 250KGy 300KGy 350KGy
Mw
6×10
4 Sol Sol Sol Gel Gel Gel
Content (Content) (%) 8.08 8.92 10.83
Polymkeric substance should have sufficiently high mechanical strength as Material Used and be absolutely necessary.We wish to obtain outside the needed performance after introducing functional group, also keep the favorable mechanical performance as far as possible.From experimental data as can be known: along with the increase of electron beam irradiation dosage, tensile modulus and tensile strength increase, and elongation reduces.
Irradiation dose (dose) 0KGy 100 150 200 250 300 350
Mw KGy KGy KGy KGy KGy KGy
Tensile modulus (Modulus) (GPa) 1.34 1.35 1.36 1.36 1.40 1.41 1.43
Tensile strength (Strength) (Mpa) 76.44 77.50 77.54 78.26 77.27 79.19 86.67
6 * 10
4(Elongation at 36.10 24.07 26.43 15.51 16.07 10.87 9.95 for elongation at break
break)(％)
Description of drawings
Fig. 1: excessive percentage ratio of fluorine end group and molecular weight concern synoptic diagram;
Fig. 2: the tensile modulus of 10% sulfide based structural content segmented copolymer and electron beam irradiation dose relationship figure;
Fig. 3: the tensile strength of 10% sulfide based structural content segmented copolymer and electron beam irradiation dose relationship figure;
Fig. 4: the elongation of 10% sulfide based structural content segmented copolymer and the graph of a relation of electron beam irradiation dosage.
Embodiment
Embodiment one
Mechanical stirring is being housed; add 17.46g (0.08mol) 4 in the 1000ml three-necked bottle of thermometer and nitrogen protection; 4 '-difluoro benzophenone; 22.88g (0.09mol) m-trifluoromethylphenyl Resorcinol; add 12.24g (0.09mol) Anhydrous potassium carbonate; add solvent sulfolane 200ml; band aqua toluene 100ml stirs and heats up, and reaction system is warming up to 160 ℃; toluene band water refluxes; band water reaction 2h, reaction system is warming up to 220 ℃ then, reaction 2h; reaction system is cooled to 100 ℃ then; add small molecules oligopolymer (FKOSOKF) 6.15g (0.01mol), be warming up to 160 ℃ of evaporations and remove toluene in the reaction system, reaction system is warming up to 220 ℃; continue reaction 3h; reactant is annotated discharging in 5000ml distilled water, and constantly stirs, and obtains white strip solid.Thick product is after organizing the pulverizer pulverizing, with washing with acetone eight times to remove the organic solvent in the polymkeric substance, distilled water boiling washing eight times is to remove inorganic salt, final product is at 120 ℃ of dry 10h, obtain the FKOSOKF molar content and be 10% white polymer powdered sample, the mol ratio that is FKOSOKF/ (FKOSOKF+4,4 '-difluoro benzophenone) is 10%.Productive rate 97%.
Embodiment two
Method such as embodiment one, changing the molar content of FKOSOKF in reaction system is 2%, 5%, 15%, 20%, 25%, 30%, be FKOSOKF/ (FKOSOKF+4,4 '-difluoro benzophenone) mol ratio is 2%, 5%, 15%, 20%, 25%, 30%, the polyreaction formula is referring to reaction formula one, polymer architecture formula and embodiment one are similar, and difference is FKOSOKF molar content difference, the chain length difference of polyaryletherketone between the cross-linking set.Prepare the solvable controlled crosslinked polyaryletherketone segmented copolymer of the different molar content of a series of FKOSOKF, productive rate 96-98%.
Embodiment three
Method such as embodiment one; with 4; 4 '-difluoro benzophenone replaces with 4,4 '-(4-fluorine) dibenzoyl benzene, and the polyreaction formula is referring to polyreaction formula two; with 4; 4 '-(4-fluorine) dibenzoyl benzene monomer replaces 4, and 4 '-difluoro benzophenone is in the polymer architecture formula 4; 4 '-(4-fluorine) dibenzoyl benzene unit replaces 4,4 '-difluoro benzophenone unit.Obtain the FKOSOKF molar content and be 10% white polymer powdered sample, promptly the mol ratio of FKOSOKF/ (FKOSOKF+4,4 '-(4-fluorine) dibenzoyl benzene) is 10%, productive rate 97%.
Embodiment four
Method such as embodiment three, changing the molar content of FKOSOKF in reaction system is 2%, 5%, 15%, 20%, 25%, 30%, be FKOSOKF/ (FKOSOKF+4,4 '-difluoro benzophenone) mol ratio is 2%, 5%, 15%, 20%, 25%, 30%, polymer architecture formula and embodiment three are similar, difference is FKOSOKF molar content difference, the chain length difference of polyaryletherketone between the cross-linking set.Prepare the solvable controlled crosslinked polyaryletherketone segmented copolymer of a series of FKOSOKF different contents, productive rate 96-98%.
Embodiment five
Method such as embodiment one, with 4,4 '-difluoro benzophenone replaces with 4,4 '-dichloro diphenyl sulfone, and the polyreaction formula is referring to polyreaction formula three, with 4,4 '-dichloro diphenyl sulfone monomer replaces 4, and 4 '-difluoro benzophenone is in the polymer architecture formula 4,4 '-dichloro diphenyl sulfone unit replaces 4,4 '-difluoro benzophenone unit.Obtain the FKOSOKF molar content and be 10% white polymer powdered sample, promptly the mol ratio of FKOSOKF/ (FKOSOKF+4,4 '-dichloro diphenyl sulfone) is 10%, productive rate 97%.
Embodiment six
Method such as embodiment five, changing the molar content of FKOSOKF in reaction system is 2%, 5%, 15%, 20%, 25%, 30%, be FKOSOKF/ (FKOSOKF+4,4 '-dichloro diphenyl sulfone) mol ratio is 2%, 5%, 15%, 20%, 25%, 30%, polymer architecture formula and embodiment five are similar, difference is FKOSOKF molar content difference, the chain length difference of polyaryletherketone between the cross-linking set.Prepare the solvable controlled crosslinked polyaryletherketone segmented copolymer of a series of FKOSOKF different contents, productive rate 96-98%.
Embodiment seven
The segmented copolymer of the different cross-linking set content (2%, 5%, 15%, 20%, 25%, 30%) of embodiment one to embodiment six preparation, irradiation dose at 100KGy, irradiation time is to carry out electron beam to irradiate crosslinked under the 8min condition, obtains having a series of crosslinked polyaryletherketone segmented copolymer of different degree of crosslinking.
Embodiment eight
Method such as embodiment seven, the segmented copolymer of the different cross-linking set content (2%, 5%, 15%, 20%, 25%, 30%) of embodiment one to embodiment six preparation, change the irradiation dose of electron beam irradiation, irradiation dose at 150-1000KGy, irradiation time is to carry out electron beam to irradiate crosslinked under the 12-80min condition, obtains having a series of crosslinked polyaryletherketone segmented copolymer of different degree of crosslinking.
Claims (3)
1, solvable controlled crosslinked poly aryl ether ketone material, its structural formula is as follows:
Or
2, the described solvable controlled crosslinked poly aryl ether ketone preparation methods of claim 1 the steps include:
(1) with mol ratio is 1: 1 monomer m-trifluoromethyl phenyl Resorcinol and 4,4 '-difluoro benzophenone or 4,4 '-(4-fluorine) dibenzoyl benzene or 4,4 '-dichloro diphenyl sulfone, dropping into 1000ml has in the there-necked flask of agitator, thermometer, nitrogen protection device and water-and-oil separator, add catalysts salt of wormwood with the excessive 1-3% of monomer mole ratio, solvent N-Methyl pyrrolidone or tetramethylene sulfone, the add-on of solvent is 15-20% to contain thing admittedly, adds band aqua toluene 150-200ml;
(2) reaction system is warming up to 145-160 ℃, and toluene band water refluxes, and constantly emits the water generation reaction branch, band water reaction 2-3h; Reaction system is warming up to 210-220 ℃, reaction 2-3h, reaction system is cooled to 100-120 ℃ then, add small molecules oligopolymer FKOSOKF, the molar content of oligopolymer FKOSOKF is 2%-30%, be FKOSOKF/ (FKOSOKF+4,4 '-difluoro benzophenone) or FKOSOKF/ (FKOSOKF+4,4 '-(4-fluorine) dibenzoyl benzene) or FKOSOKF/ (FKOSOKF+4,4 '-dichloro diphenyl sulfone) mol ratio is 2%-30%, toluene unnecessary in the reaction system is removed in evaporation, and reaction system is warming up to 220 ℃, reaction 2-3h;
(3) reaction product discharging in distilled water, constantly stir simultaneously, obtain the white polymer filament, after pulverizer is pulverized, polymer powders with washing with acetone six to eight times to remove organic solvent, distilled water boiling washing six to eight times to remove inorganic salt, at 110-120 ℃ of dry 10-12h, get productive rate 96-98%, molecular weight is the white polymer powder between 40,000 to 60,000;
(4) product carries out electron beam to irradiate crosslinked at 100-1000Kgy dosage under the 8-80min condition, obtains having a series of solvable controlled crosslinked poly aryl ether ketone block copolymer material of different degree of crosslinking.
3, solvable controlled crosslinked poly aryl ether ketone preparation methods as claimed in claim 2 is characterized in that:
Can come the molecular weight of controlling polymers by fluorine end group concentration in the telomerized polymer, thereby obtain the polymkeric substance of different molecular weight, to obtain functional and to be beneficial to the polymkeric substance of the optimum weight of processing.
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