CN118878816B - PEEK resin polymer and preparation method and application thereof - Google Patents
PEEK resin polymer and preparation method and application thereof Download PDFInfo
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- CN118878816B CN118878816B CN202411354396.XA CN202411354396A CN118878816B CN 118878816 B CN118878816 B CN 118878816B CN 202411354396 A CN202411354396 A CN 202411354396A CN 118878816 B CN118878816 B CN 118878816B
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 59
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 59
- 229920000642 polymer Polymers 0.000 title claims abstract description 53
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 12
- YIHRGKXNJGKSOT-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorobutan-1-ol Chemical compound CC(F)(F)C(F)(F)C(O)(F)F YIHRGKXNJGKSOT-UHFFFAOYSA-N 0.000 claims abstract description 10
- BTTRMCQEPDPCPA-UHFFFAOYSA-N 4-chlorophthalic anhydride Chemical compound ClC1=CC=C2C(=O)OC(=O)C2=C1 BTTRMCQEPDPCPA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- BBRLKRNNIMVXOD-UHFFFAOYSA-N bis[4-(3-aminophenoxy)phenyl]methanone Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 BBRLKRNNIMVXOD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002009 diols Chemical class 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- LERREUOVCXYKGR-UHFFFAOYSA-N (2-phenoxyphenyl)-phenylmethanone Chemical compound C=1C=CC=C(OC=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 LERREUOVCXYKGR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 72
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 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 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 2
- 241000143437 Aciculosporium take Species 0.000 claims 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 abstract description 23
- 239000011737 fluorine Substances 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 16
- -1 dichlorimide phenoxybenzophenone Chemical compound 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 14
- 238000005406 washing Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 3
- 150000003949 imides Chemical group 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HJNTWZFZPOUDDG-UHFFFAOYSA-N [2-(3-aminophenoxy)phenyl]-phenylmethanone Chemical compound NC1=CC=CC(OC=2C(=CC=CC=2)C(=O)C=2C=CC=CC=2)=C1 HJNTWZFZPOUDDG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
本发明涉及高分子材料领域，公开了一种PEEK树脂聚合物及其制备方法与应用，该PEEK树脂聚合物含有式I和式II所示重复单元，其中式I所示重复单元的摩尔含量为20~30%，本发明利用六氟丁醇、异佛尔酮二异氰酸酯和二乙醇胺为原料合成含氟二元醇，以4，4'‑双（3‑氨基苯氧基）二苯甲酮和4‑氯代苯酐为原料合成双氯酰亚胺苯氧基二苯甲酮，然后通过含氟二元醇和双氯酰亚胺苯氧基二苯甲酮反应生成端羟基中间体，然后引入到PEEK树脂聚合物结构中，增强了其溶解性能，同时使其疏水性和耐热性能得到提升。
The invention relates to the field of polymer materials, and discloses a PEEK resin polymer and a preparation method and application thereof. The PEEK resin polymer contains repeating units shown in formulas I and II, wherein the molar content of the repeating units shown in formula I is 20-30%. The invention uses hexafluorobutanol, isophorone diisocyanate and diethanolamine as raw materials to synthesize fluorine-containing diols, uses 4,4'-bis(3-aminophenoxy)benzophenone and 4-chlorophthalic anhydride as raw materials to synthesize bischloroimide phenoxybenzophenone, then generates a terminal hydroxyl intermediate by reacting the fluorine-containing diol and the bischloroimide phenoxybenzophenone, and then introduces the terminal hydroxyl intermediate into the PEEK resin polymer structure, thereby enhancing the solubility thereof and improving the hydrophobicity and heat resistance thereof.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a PEEK resin polymer and a preparation method and application thereof.
Background
The polyether-ether-ketone is a semi-crystalline thermoplastic special engineering plastic, has excellent comprehensive properties such as excellent high temperature resistance, aging resistance, creep resistance, corrosion resistance, irradiation resistance, good biocompatibility and the like, is widely applied to civil fields such as aerospace, electronic and electric parts, automobile parts, precision machinery, medical appliances and the like and the fields of national defense and military industry, and gradually increases the requirements on the properties such as high-temperature modulus and strength of the polyether-ether-ketone material along with the rapid development of each field.
Due to the characteristics of strong rigidity, high regularity and the like of a polyether-ether-ketone structure, the solubility of the polyether-ether-ketone is poor, the melting temperature is high, the processability of the polyether-ether-ketone material is poor, the processing cost is high, the glass transition temperature of the polyether-ether-ketone only reaches about 140 ℃, the mechanical property of the polyether-ether-ketone is greatly attenuated at a higher temperature, the application of the polyether-ether-ketone in a high-temperature severe environment is limited, the high heat-resistant fillers such as carbon nano tubes and graphite are filled with the modified polyether-ether-ketone in a melt blending mode in the prior art, but the mechanical strength and toughness of the material are obviously reduced due to the addition of the high heat-resistant fillers, and the introduced heat-conducting fillers have the problem of poor interface compatibility due to the limitation of the melt viscosity of the polyether-ether-ketone.
Disclosure of Invention
In order to solve the defects in the background art, the invention aims to provide a PEEK resin polymer, a preparation method and application thereof, wherein a hydroxyl-terminated intermediate is generated by reacting fluorine-containing dihydric alcohol and dichlorimidophenoxy benzophenone, and then the hydroxyl-terminated intermediate is introduced into a PEEK resin polymer structure, so that the dissolution performance of the PEEK resin polymer is enhanced, and meanwhile, the hydrophobicity and the heat resistance of the PEEK resin polymer are improved.
The aim of the invention can be achieved by the following technical scheme:
A PEEK resin polymer comprising repeat units of formula I and formula II:
(formula I);
(formula II);
wherein the molar content of the repeating unit shown in the formula I is 20-30%.
Preferably, the preparation method of the PEEK resin polymer comprises the following steps:
A. taking hexafluorobutanol, heating to 75-85 ℃, adding isophorone diisocyanate and dibutyltin dilaurate to react for 2-3 hours, then cooling to room temperature, adding diethanolamine to continue to react for 10-20 minutes, and washing and drying after the reaction is completed to obtain fluorine-containing dihydric alcohol;
B. Taking 4,4' -bis (3-aminophenoxy) benzophenone, 4-chlorophthalic anhydride and toluene in a reactor, heating to 130-145 ℃, carrying out reflux reaction for 3-5 hours, heating to 165-175 ℃ and continuing to react for 1-2 hours, discharging a system solution in absolute ethyl alcohol after the reaction is finished, washing with toluene, carrying out suction filtration and drying, and thus obtaining the dichlorimide phenoxybenzophenone;
C. Taking fluorine-containing dihydric alcohol and dichlorimide phenoxy benzophenone, adding tetrahydrofuran solvent into the reactor, stirring and reacting for 5-7 h, adding triethylamine in batches in the reaction process, removing hydrogen chloride generated by the reaction, and carrying out suction filtration, rotary evaporation and drying after the reaction is finished to prepare a hydroxyl-terminated intermediate;
D. And (3) taking 4,4' -difluorobenzophenone, hydroquinone and a hydroxyl-terminated intermediate in a reactor, adding alkali carbonate, sulfolane and toluene solvent, heating to 145-155 ℃ for reaction for 2-3 hours, heating to 160-180 ℃ for continuous reaction for 0.5-1 hour, heating to 195-220 ℃ for reaction for 2-3 hours, pouring the generated product into deionized water after the reaction is finished, washing, filtering and drying to obtain the PEEK resin polymer.
Preferably, in the step A, the molar ratio of the hexafluorobutanol, the isophorone diisocyanate and the diethanolamine is 1-1.05:1:1-1.02.
Preferably, in the step B, the molar ratio of the 4,4' -bis (3-aminophenoxy) benzophenone to the 4-chlorophthalic anhydride is 1:2-2.3.
Preferably, in the step C, the molar ratio of the fluorine-containing dihydric alcohol to the dichlorimide phenoxy benzophenone is 2-2.5:1.
Preferably, the molar ratio of the total molar ratio of the hydroquinone to the hydroxyl-terminated intermediate to the molar ratio of the 4,4' -difluorobenzophenone in the step D is 1-1.03:1.
Preferably, in the step D, the alkali metal carbonate is formed by mixing anhydrous potassium carbonate and anhydrous sodium carbonate according to a molar ratio of 15-19:1.
The use of PEEK resin polymers as described above for the preparation of cartridge casings, high temperature resistant electronics and aerospace structural members.
The invention has the beneficial effects that:
The invention uses hexafluorobutanol, isophorone diisocyanate and diethanolamine as raw materials, hydroxyl in the structure of hexafluorobutanol and isocyanato group connected with methylene in the structure of isophorone diisocyanate react to prepare fluorine-containing isocyanate substances, then the fluorine-containing isocyanate substances continuously react with diethanolamine, secondary amine in the structure of diethanolamine is active than the hydroxyl, secondary amine in the diethanolamine reacts with the isocyanato group directly connected with cyclohexane ring to generate fluorine-containing dihydric alcohol by controlling the temperature, meanwhile, 4 '-bis (3-aminophenoxy) benzophenone and 4-chlorophthalic anhydride are used as raw materials to synthesize the dichlorimide phenoxy benzophenone, then the prepared fluorine-containing dihydric alcohol and the dichlorimide phenoxy benzophenone are subjected to substitution reaction to prepare hydroxyl-terminated intermediates, and finally the hydroxyl-terminated intermediates, 4' -difluorobenzophenone and hydroquinone are used as raw materials to copolymerize to obtain the PEEK resin polymer. The flexible chain segment in the PEEK resin polymer structure enhances the solubility, the introduced fluorine-containing group enhances the hydrophobicity, the application of the PEEK resin polymer in the fields of hydrophobic coatings, electronic devices, information materials and the like is expanded, the introduced imide structure enhances the heat resistance, and the application of PEEK resin polymer in the fields of cartridge cases, high-temperature-resistant electronic devices, aerospace structural members and the like is further expanded.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to those skilled in the art that other drawings can be obtained according to these drawings without inventive effort.
FIG. 1 is an infrared spectrum of the fluorine-containing diol prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of the bischloroimidophenoxybenzophenone prepared in example 1 according to the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1a method for preparing a PEEK resin polymer includes the steps of:
A. 9.10g of hexafluorobutanol is taken and heated to 80 ℃, 11.11g of isophorone diisocyanate and 0.005g of dibutyltin dilaurate are added for reaction for 3 hours, then the reaction is cooled to room temperature, 5.26g of diethanolamine is added for continuous reaction for 20 minutes, and after the reaction is completed, the fluorine-containing dihydric alcohol is prepared through washing and drying;
The infrared test chart of the fluorine-containing diol is shown in figure 1, wherein the characteristic absorption peak of-OH at 3329cm -1, the absorption peak of C-F bond at 1242cm -1 and 2028cm -1 and the characteristic absorption peak of isocyanate group at 2268cm -1 disappear, which indicates that the fluorine-containing diol is successfully synthesized;
B. 9.91g of 4,4' -bis (3-aminophenoxy) benzophenone, 9.13g of 4-chlorophthalic anhydride and toluene are taken in a reactor, heated to 140 ℃ for reflux reaction for 5 hours, then heated to 170 ℃ for continuous reaction for 1 hour, after the reaction is completed, the system solution is discharged in absolute ethyl alcohol, washed by toluene, filtered and dried by suction, and the dichlorimide phenoxybenzophenone is prepared;
An infrared test chart of the dichlorimide phenoxy benzophenone is shown in figure 2, wherein an aromatic ring C-H telescopic vibration absorption peak is arranged at a position 3050cm -1, an imide ring carbonyl vibration absorption peak is arranged at a position 1720cm -1, a C-N vibration absorption peak is arranged at a position 1610cm -1, a benzene ring skeleton absorption peak is arranged at a position 1500cm -1, an imide benzene ring characteristic absorption peak is arranged at a position 1380cm -1, and an aromatic ether telescopic vibration absorption peak is arranged at a position 1200cm -1, so that the dichlorimide phenoxy benzophenone is successfully synthesized;
C. Taking 12.19g of fluorine-containing dihydric alcohol and 7.26g of dichlorimide phenoxy benzophenone in a reactor, adding 100mL of tetrahydrofuran, stirring and reacting for 6 hours, adding 2.12g of triethylamine in batches in the reaction process, removing hydrogen chloride generated by the reaction, and carrying out suction filtration, rotary evaporation and drying after the reaction is finished to prepare a hydroxyl-terminated intermediate;
D. 6.55g of 4,4' -difluorobenzophenone, 2.48g of hydroquinone and 12.54g of hydroxyl-terminated intermediate are taken and placed in a reactor, 3.94g of anhydrous potassium carbonate, 0.16g of anhydrous sodium carbonate, 34.8mL of sulfolane and 10mL of toluene solvent are added, the temperature is raised to 150 ℃ for reaction for 3 hours, then the temperature is raised to 170 ℃ for continuous reaction for 1 hour, the temperature is raised to 200 ℃ for reaction for 2 hours, and the product produced after the reaction is poured into deionized water, and the PEEK resin polymer is prepared through washing, filtering and drying.
Example 2 a method for preparing a PEEK resin polymer includes the steps of:
A. 9.10g of hexafluorobutanol is taken and heated to 80 ℃, 11.11g of isophorone diisocyanate and 0.005g of dibutyltin dilaurate are added for reaction for 3 hours, then the reaction is cooled to room temperature, 5.26g of diethanolamine is added for continuous reaction for 20 minutes, and after the reaction is completed, the fluorine-containing dihydric alcohol is prepared through washing and drying;
B. 9.91g of 4,4' -bis (3-aminophenoxy) benzophenone, 9.13g of 4-chlorophthalic anhydride and toluene are taken in a reactor, heated to 140 ℃ for reflux reaction for 5 hours, then heated to 170 ℃ for continuous reaction for 1 hour, after the reaction is completed, the system solution is discharged in absolute ethyl alcohol, washed by toluene, filtered and dried by suction, and the dichlorimide phenoxybenzophenone is prepared;
C. Taking 12.19g of fluorine-containing dihydric alcohol and 7.26g of dichlorimide phenoxy benzophenone in a reactor, adding 100mL of tetrahydrofuran, stirring and reacting for 6 hours, adding 2.12g of triethylamine in batches in the reaction process, removing hydrogen chloride generated by the reaction, and carrying out suction filtration, rotary evaporation and drying after the reaction is finished to prepare a hydroxyl-terminated intermediate;
D. 6.55g of 4,4' -difluorobenzophenone, 2.31g of hydroquinone and 15.04g of hydroxyl-terminated intermediate are taken and placed in a reactor, 3.94g of anhydrous potassium carbonate, 0.16g of anhydrous sodium carbonate, 34.8mL of sulfolane and 10mL of toluene solvent are added, the temperature is raised to 150 ℃ for reaction for 3 hours, then the temperature is raised to 170 ℃ for continuous reaction for 1 hour, the temperature is raised to 200 ℃ for reaction for 2 hours, and the product produced after the reaction is poured into deionized water, and the PEEK resin polymer is prepared through washing, filtering and drying.
Example 3a method of preparing a PEEK resin polymer includes the steps of:
A. 9.10g of hexafluorobutanol is taken and heated to 80 ℃, 11.11g of isophorone diisocyanate and 0.005g of dibutyltin dilaurate are added for reaction for 3 hours, then the reaction is cooled to room temperature, 5.26g of diethanolamine is added for continuous reaction for 20 minutes, and after the reaction is completed, the fluorine-containing dihydric alcohol is prepared through washing and drying;
B. 9.91g of 4,4' -bis (3-aminophenoxy) benzophenone, 9.13g of 4-chlorophthalic anhydride and toluene are taken in a reactor, heated to 140 ℃ for reflux reaction for 5 hours, then heated to 170 ℃ for continuous reaction for 1 hour, after the reaction is completed, the system solution is discharged in absolute ethyl alcohol, washed by toluene, filtered and dried by suction, and the dichlorimide phenoxybenzophenone is prepared;
C. Taking 12.19g of fluorine-containing dihydric alcohol and 7.26g of dichlorimide phenoxy benzophenone in a reactor, adding 100mL of tetrahydrofuran, stirring and reacting for 6 hours, adding 2.12g of triethylamine in batches in the reaction process, removing hydrogen chloride generated by the reaction, and carrying out suction filtration, rotary evaporation and drying after the reaction is finished to prepare a hydroxyl-terminated intermediate;
D. 6.55g of 4,4' -difluorobenzophenone, 2.64g of hydroquinone and 10.03g of hydroxyl-terminated intermediate are taken and put into a reactor, 3.94g of anhydrous potassium carbonate, 0.16g of anhydrous sodium carbonate, 34.8mL of sulfolane and 10mL of toluene solvent are added, the temperature is raised to 150 ℃ for reaction for 3 hours, then the temperature is raised to 170 ℃ for continuous reaction for 1 hour, the temperature is raised to 200 ℃ for reaction for 2 hours, and the product generated after the reaction is poured into deionized water, and the PEEK resin polymer is prepared through washing, filtering and drying.
Comparative example 1a method for preparing a PEEK resin polymer includes the steps of:
A. 9.91g of 4,4' -bis (3-aminophenoxy) benzophenone, 9.13g of 4-chlorophthalic anhydride and toluene are taken in a reactor, heated to 140 ℃ for reflux reaction for 5 hours, then heated to 170 ℃ for continuous reaction for 1 hour, after the reaction is completed, the system solution is discharged in absolute ethyl alcohol, washed by toluene, filtered and dried by suction, and the dichlorimide phenoxybenzophenone is prepared;
B. 6.55g of 4,4' -difluorobenzophenone, 2.48g of hydroquinone and 5.44g of bischloroimide phenoxy benzophenone are taken and placed in a reactor, 3.94g of anhydrous potassium carbonate, 0.16g of anhydrous sodium carbonate, 34.8mL of sulfolane and 10mL of toluene solvent are added, the temperature is raised to 150 ℃ for reaction for 3 hours, then the temperature is raised to 170 ℃ for continuous reaction for 1 hour, the temperature is raised to 200 ℃ for reaction for 2 hours, and the product generated after the reaction is poured into deionized water, and the PEEK resin polymer is prepared through washing, filtering and drying.
Comparative example 2 a method for preparing a PEEK resin polymer includes the steps of:
6.55g of 4,4' -difluorobenzophenone, 2.48g of hydroquinone and 0.93g of 2, 5-dihydroxytoluene are taken and placed in a reactor, 3.94g of anhydrous potassium carbonate, 0.16g of anhydrous sodium carbonate, 34.8mL of sulfolane and 10mL of toluene solvent are added, the temperature is raised to 150 ℃ for reaction for 3 hours, then the temperature is raised to 170 ℃ for continuous reaction for 1 hour, the temperature is raised to 200 ℃ for reaction for 2 hours, and the product produced after the reaction is poured into deionized water, and the PEEK resin polymer is prepared through washing, filtering and drying.
Performance detection
PEEK resin polymers prepared in examples 1-3 and comparative examples 1-2 were subjected to performance test:
(1) Dissolution test, namely, at normal temperature, 0.01g of PEEK resin polymer prepared in examples 1-3 is added into 1mL of solvent respectively, and the dissolution performance of a sample is tested, and the test results are shown in Table 1.
Note that +is dissolved and-is insoluble
As can be seen from the data results in Table 1, the PEEK resin polymers prepared in examples 1-3 of the present invention are soluble in most common organic solvents, and the polymer solubility is strong, because the introduction of trifluoromethyl in fluorine-containing dihydric alcohol enhances the flexibility of molecular chains, and the introduction of imide structure in the dichlorimide phenoxy benzophenone destroys the regularity of the polyether ether ketone structure, increases the free volume of the polymer main chain, makes the solvent molecules more easily penetrate, thereby improving the solubility of PEEK resin polymer.
(2) And (2) measuring the glass transition temperature (Tg) of the PEEK resin polymer by using a differential scanning calorimeter, weighing 8mg of sample in the test process, setting the temperature range to 50-380 ℃, heating twice under the protection of nitrogen, and the temperature rise and fall rate to 10 ℃ per minute, testing the PEEK resin polymer sample by using a thermogravimetric analyzer under the nitrogen atmosphere, and testing the PEEK resin polymer sample to 800 ℃ at the temperature rise rate of 10 ℃ per minute, and testing the water contact angle by using a contact angle measuring instrument, wherein the data result is shown in Table 2.
As can be seen from the data in Table 2, the PEEK resin polymers prepared in examples 1-3 of the present invention have glass transition temperatures of more than 170 ℃,5% thermal weight loss temperatures and 10% thermal weight loss temperatures of more than 550 ℃, and have strong heat resistance because the PEEK resin polymers have high heat stability determined by the polymer chain structure, the polarity of the imide structure introduced by the hydroxyl-terminated intermediate is strong, intermolecular forces exist between the molecular chains, so that the PEEK resin polymers have high thermal decomposition temperatures, and water contact angles of more than 120 DEG, because fluorine has strong electronegativity, and the introduction of fluorine atoms enhances the hydrophobic property of the PEEK resin polymers. Wherein no fluorine-containing dihydric alcohol is introduced in comparative example 1, the measured hydrophobic property is reduced compared with examples 1-3, no hydroxyl-terminated intermediate is introduced in comparative example 2, and the measured water contact angle, glass transition temperature and thermal decomposition temperature are reduced compared with examples 1-3, which shows that the introduction of the hydroxyl-terminated intermediate can improve the hydrophobic property and heat resistance of PEEK resin polymer to a certain extent.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (8)
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