CN116854679A - Novel epoxy resin containing imide unit and preparation method thereof - Google Patents
Novel epoxy resin containing imide unit and preparation method thereof Download PDFInfo
- Publication number
- CN116854679A CN116854679A CN202310697730.0A CN202310697730A CN116854679A CN 116854679 A CN116854679 A CN 116854679A CN 202310697730 A CN202310697730 A CN 202310697730A CN 116854679 A CN116854679 A CN 116854679A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- compound
- aminophenol
- solvent
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 60
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 125000005462 imide group Chemical group 0.000 title claims description 49
- 239000004593 Epoxy Substances 0.000 claims abstract description 58
- -1 phenol compound Chemical class 0.000 claims abstract description 25
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical class CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 97
- 239000000047 product Substances 0.000 claims description 70
- 238000010992 reflux Methods 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 48
- 239000012153 distilled water Substances 0.000 claims description 46
- 239000012065 filter cake Substances 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical group N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 30
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 25
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 238000000967 suction filtration Methods 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 15
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 14
- 239000012300 argon atmosphere Substances 0.000 claims description 14
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 12
- 150000002828 nitro derivatives Chemical class 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 235000009518 sodium iodide Nutrition 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- VORRYOXJWMUREO-UHFFFAOYSA-N 4-amino-3-(trifluoromethyl)phenol Chemical compound NC1=CC=C(O)C=C1C(F)(F)F VORRYOXJWMUREO-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- YVWGMAFXEJHFRO-UHFFFAOYSA-N halopropane Chemical compound FC(F)C(F)(F)CBr YVWGMAFXEJHFRO-UHFFFAOYSA-N 0.000 claims description 4
- 229950000188 halopropane Drugs 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 4
- WFUBYPSJBBQSOU-UHFFFAOYSA-M rubidium iodide Chemical compound [Rb+].[I-] WFUBYPSJBBQSOU-UHFFFAOYSA-M 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 claims description 2
- ATJGAHFTSOPTCH-UHFFFAOYSA-N 2-amino-3-(trifluoromethyl)phenol Chemical compound NC1=C(O)C=CC=C1C(F)(F)F ATJGAHFTSOPTCH-UHFFFAOYSA-N 0.000 claims description 2
- FEDLEBCVFZMHBP-UHFFFAOYSA-N 2-amino-3-methylphenol Chemical compound CC1=CC=CC(O)=C1N FEDLEBCVFZMHBP-UHFFFAOYSA-N 0.000 claims description 2
- AVJWZOLSWBETCM-UHFFFAOYSA-N 2-amino-3-phenylphenol Chemical compound NC1=C(O)C=CC=C1C1=CC=CC=C1 AVJWZOLSWBETCM-UHFFFAOYSA-N 0.000 claims description 2
- DAIZNEMAGMWZKY-UHFFFAOYSA-N 2-amino-3-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(O)=C1N DAIZNEMAGMWZKY-UHFFFAOYSA-N 0.000 claims description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- RHMYEOYYPYBQCN-UHFFFAOYSA-N 3,3,3-trichloropropanoic acid Chemical compound OC(=O)CC(Cl)(Cl)Cl RHMYEOYYPYBQCN-UHFFFAOYSA-N 0.000 claims description 2
- KSNKQSPJFRQSEI-UHFFFAOYSA-N 3,3,3-trifluoropropanoic acid Chemical compound OC(=O)CC(F)(F)F KSNKQSPJFRQSEI-UHFFFAOYSA-N 0.000 claims description 2
- RUNYOYJSBYNOMZ-UHFFFAOYSA-N 3-amino-2-(trifluoromethyl)phenol Chemical compound NC1=CC=CC(O)=C1C(F)(F)F RUNYOYJSBYNOMZ-UHFFFAOYSA-N 0.000 claims description 2
- FLROJJGKUKLCAE-UHFFFAOYSA-N 3-amino-2-methylphenol Chemical compound CC1=C(N)C=CC=C1O FLROJJGKUKLCAE-UHFFFAOYSA-N 0.000 claims description 2
- UOBWAODYTSELAE-UHFFFAOYSA-N 3-amino-2-phenylphenol Chemical compound NC1=CC=CC(O)=C1C1=CC=CC=C1 UOBWAODYTSELAE-UHFFFAOYSA-N 0.000 claims description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- OHNDAXCVWUKVHF-UHFFFAOYSA-N 4-amino-2-(trifluoromethyl)phenol Chemical compound NC1=CC=C(O)C(C(F)(F)F)=C1 OHNDAXCVWUKVHF-UHFFFAOYSA-N 0.000 claims description 2
- HDGMAACKJSBLMW-UHFFFAOYSA-N 4-amino-2-methylphenol Chemical compound CC1=CC(N)=CC=C1O HDGMAACKJSBLMW-UHFFFAOYSA-N 0.000 claims description 2
- OUIITAOCYATDMY-UHFFFAOYSA-N 4-amino-2-phenylphenol Chemical compound NC1=CC=C(O)C(C=2C=CC=CC=2)=C1 OUIITAOCYATDMY-UHFFFAOYSA-N 0.000 claims description 2
- ACTPUQAHTZXJSC-UHFFFAOYSA-N 4-amino-3-phenylphenol Chemical compound NC1=CC=C(O)C=C1C1=CC=CC=C1 ACTPUQAHTZXJSC-UHFFFAOYSA-N 0.000 claims description 2
- HWYSAVAYUJTSLU-UHFFFAOYSA-N 4-amino-3-propan-2-ylphenol Chemical compound CC(C)C1=CC(O)=CC=C1N HWYSAVAYUJTSLU-UHFFFAOYSA-N 0.000 claims description 2
- QGNGOGOOPUYKMC-UHFFFAOYSA-N 4-hydroxy-6-methylaniline Chemical compound CC1=CC(O)=CC=C1N QGNGOGOOPUYKMC-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Substances SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 58
- 239000011347 resin Substances 0.000 abstract description 58
- 150000003949 imides Chemical class 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000005191 phase separation Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 238000010907 mechanical stirring Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 10
- 239000004642 Polyimide Substances 0.000 description 9
- 229920001721 polyimide Polymers 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 7
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 239000004697 Polyetherimide Substances 0.000 description 4
- 229920001601 polyetherimide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XLQSXGGDTHANLN-UHFFFAOYSA-N 1-bromo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Br)C=C1 XLQSXGGDTHANLN-UHFFFAOYSA-N 0.000 description 3
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 3
- XFZFJQHXWJIBQV-UHFFFAOYSA-N 2-bromo-1-methyl-4-nitrobenzene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Br XFZFJQHXWJIBQV-UHFFFAOYSA-N 0.000 description 3
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 3
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000009396 hybridization Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- IKOKHHBZFDFMJW-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(2-morpholin-4-ylethoxy)pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCCN1CCOCC1 IKOKHHBZFDFMJW-UHFFFAOYSA-N 0.000 description 1
- OPVHOFITDJSMOD-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1OC1=CC=CC2=C1C(=O)OC2=O OPVHOFITDJSMOD-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
Aiming at the problems that the brittleness of the cured epoxy resin is high after the curing and the heat resistance of the cured epoxy resin is easy to be reduced or the phase separation is easy to be caused after the toughening of the epoxy resin at present, the invention provides a preparation method of novel epoxy resin containing imide primitives, which aims at realizing good compatibility between the imide and the epoxy resin on a molecular level and solving the scientific problems that the brittleness of the cured epoxy resin is high and the heat resistance is easy to be reduced after the toughening of the epoxy resin by utilizing the chemical advantages of high rigidity, high strength and high heat resistance of the imide primitives. The invention takes commercial dicarboxylic anhydride as a basic monomer unit, prepares the bisimide dihydric phenol compound by combining with a plurality of active monomers, and then reacts with epoxy halogenated propane to obtain the novel epoxy resin containing imide units. The novel epoxy resin developed by the invention has good solubility, outstanding heat resistance, excellent manufacturability and good impact toughness after curing, can meet the requirements of advanced resin matrix composite materials, and is expected to further promote and deepen the application of the epoxy resin in the technical field of high precision tips of aerospace and the like.
Description
Technical Field
The invention belongs to the field of synthesis of high-performance resin, and particularly relates to epoxy resin with high impact resistance and high heat resistance and a preparation method thereof, wherein a molecular main chain of the epoxy resin comprises imide units.
Background
Epoxy (EP) resins are recognized as the most widely used and strategically significant thermosetting materials due to their high mechanical strength, good chemical resistance, high heat resistance, outstanding electrical insulation, and strong adhesion, and have been widely used as matrix resins for anticorrosive coatings, adhesives, semiconductor encapsulating materials, electrical insulating materials, and high performance composite materials, etc. Because of its unique chemical structure, EP resins play a significant role in transportation, construction, electronics, insulation, aerospace, and other industries. In 2019, china consumed over 160 ten thousand tons of EP resin, accounting for about 51.0% of the total EP resin consumption, and Western Europe, U.S. and Korea consumed 10.3%, 8.2% and 5.7% of the total EP resin consumption, respectively. Clearly, EP resins have become an indispensable base material for various industrial fields.
However, the EP resin after curing is similar to the traditional thermosetting resin, the molecular framework is highly crosslinked, the plastic deformation is small, and the brittleness is obvious. In addition, due to the volume shrinkage of the cured resin, certain internal stress is generated in the material, so that the material has poor crack initiation resistance and crack propagation inhibition capability, and further application of the material in the field of high-performance composite materials is prevented. At present, aiming at the scientific problems of prominent brittleness and poor crack extension resistance of EP resin after curing, a great number of toughening researches are carried out by students at home and abroad, and main strategies comprise toughening of rubber (Res), toughening of Thermoplastic Polymers (TPs), toughening of Liquid Crystal Polymers (LCPs), toughening of Block Copolymers (BCPs), toughening of Nano (NMs), toughening of hyperbranched polymers (HBPs), toughening of bio-based materials (BBMs), toughening of Topological Structures (TSs) and the like. The corresponding toughening mechanism is mainly to achieve stress dissipation by constructing Interpenetrating Polymer Networks (IPNs) or semi-interpenetrating polymer networks (SIPNs).
Compared with EP resin, polyimide (PI) is used as special engineering plastic with excellent comprehensive performance, has higher heat resistance, outstanding impact toughness, excellent mechanical strength, good dielectric property and the like, and is widely applied to high-tech fields such as aerospace, electronic packaging, weaponry, microelectronics and the like as a high-performance resin matrix. Since 90 s of the last century, students at home and abroad tried to toughen and modify the cured EP resin with PI, and made a certain progress. Sue et al, university of agricultural industry, texas, USA, compounded an EP resin with a Polyetherimide (PEI) having a molecular weight of 10kg/mol to form a critical stress intensity factor (K IC ) From 0.70 MPa.m before toughening 1/2 Lifting to 1.67 MPa.m 1/2 The modification effect is obvious [ Sue, H. -J.; polymer,2023,270,125763.]. Unfortunately, due to the higher molecular weight of the PEI used and the greater chain polarity than the EP resin, the PEI toughening phase of the resin undergoes significant phase separation from the EP resin phase during cure molding and a "double glass transition" behavior [ Sue, h. -j; polymer,2023,270,125763.]. It can be seen that it is possible to toughen EP resins with PI, but because of the unavoidable phase separation, the EP resins form a phase-separated structure of "phase inversion" and "co-continuous" model after curing, destroying the homogeneity of the resins, leading to a decrease in their long-term performance, creep resistance, and solvent resistance. To avoid phase separation, university of south China university Zhiming et al [ Qiu, z.; et al J. Mater. Sci.2016,51,10833.]The amino-terminated polyamide acid (PAA, average polymerization degree n=1) is directly compounded with the EP resin, and the ring-opening reaction of active amino groups in the PAA molecular chain on epoxy groups is utilized to construct an interpenetrating network structure of PI and EP, so that the compatibility of the PI phase and the EP resin phase and the fracture toughness of the EP resin after curing are improved. However, although the theoretical polymerization degree of the amino-terminated PAA is 1, the composition is a mixture, the molecular weight distribution index is relatively wide, so that the final resin cured product does not realize the complete molecular level of PI and EP resinsAnd meanwhile, the bonding strength of PI is lower than that of epoxy, so that the finally obtained resin condensate shows poor tensile shear strength and thermal oxygen stability. In light of research and inspiring of Zhiming et al, the inventor supposes that whether to start from a problem source, imide motifs can be directly introduced into an EP resin molecular main chain, namely, an epoxy resin with the molecular main chain containing the imide motifs is developed, so that hybridization and thorough compatibility of a PI phase and an EP resin phase on a molecular scale are realized, the impact toughness and the thermal performance of the EP resin after curing are hopefully improved, and meanwhile, inherent advantages of the imide motifs such as high strength, high rigidity, high polarity and the like can be fully utilized, so that the EP resin is endowed with more excellent comprehensive physical properties, and the product types and the application range of the EP resin are further expanded.
It should be noted that extensive literature studies have found that, until now, no method for synthesizing EP resins containing imide moieties in the molecular main chain has been reported.
At present, the EP resin has large brittleness after curing, and after toughening, the heat resistance of a resin cured product is easily reduced or phase separation is easily caused, so that the application of the EP resin in the field of partial high heat resistance is limited.
Disclosure of Invention
The invention aims to overcome the defects of the existing epoxy resin, prepare the novel epoxy resin with the molecular main chain containing imide units, and improve the impact toughness and comprehensive physical properties of the EP resin after curing by utilizing the inherent advantages of the imide units such as high rigidity, strong polarity, high strength, high heat resistance and the like.
The invention provides a novel epoxy resin containing imide units, the molecular structure composition of the epoxy resin is represented by the following general formula (I),
wherein the molar ratio of the dicarboxylic anhydride moiety, the compound E moiety and the epihalohydrin moiety in formula (I) is 1:2:2; r is R 1 Represents O or S;
R 2 representative ofResidues in compound E, R 2 Is a substituted or unsubstituted phenylene group, or a structural fragment represented by formula (II):
r in formula (II) is a residue in a dihydric phenol compound, R is the same as R in formula (I) 1 Are connected; the benzene ring is connected with the N atom; m is M 1 Is O or S, Y is H, -CF 3 or-CH 3 ；
R 3 Representing residues in the dibasic anhydride.
The novel epoxy resin containing imide units, wherein the dibasic acid anhydride part corresponds to any one or combination of the following acid anhydrides, and the chemical structural formula is as follows:
the novel epoxy resin containing imide units comprises the following components: any one or combination of epoxyfluoropropane, epoxychloropropane, epoxybromopropane and epoxyiodopropane.
The novel epoxy resin containing imide units comprises the amino phenol contained in the compound corresponding to the part E: para-aminophenol, ortho-aminophenol, meta-aminophenol, 2-methyl-4-aminophenol, tetramethyl para-aminophenol, 3-methyl-4-aminophenol, 2-methyl-3-aminophenol, 3-methyl-2-aminophenol, 4-amino-3-trifluoromethylphenol, 4-amino-2-trifluoromethylphenol, 3-amino-2-trifluoromethylphenol, 2-phenyl-4-aminophenol, 3-isopropyl-4-aminophenol, 2-phenyl-3-aminophenol, 3-isopropyl-2-aminophenol, 3-phenyl-4-aminophenol, 3-phenyl-2-aminophenol, 2-amino-3-trifluoromethylphenol, para-aminophenol, ortho-aminophenol, meta-aminophenthiophenol, 2-methyl-4-aminophenthiophenol, 3-methyl-4-aminophenthiophenol, 2-aminophenol, 4-amino-3-trifluoromethylphenol, 4-trifluoromethyl-2-trifluoro-aminophenol, tetramethyl-3-amino-3-trifluoro-thiophenol, or a combination thereof.
The invention also provides a preparation method of the novel epoxy resin containing imide units, which comprises the following specific steps:
step (1): adding dibasic acid anhydride into a three-neck flask provided with a water separator and a condensation reflux device, adding a carboxylic acid solvent under argon atmosphere, starting mechanical stirring, sequentially adding a compound E and cyclohexane, heating and refluxing, cooling to 20-30 ℃ after reflux reaction for 10-20 h, pouring reaction liquid into distilled water to precipitate, carrying out suction filtration, washing a filter cake for 2-3 times by using distilled water, and carrying out vacuum drying at 60-120 ℃ to obtain a powder product A;
the molar ratio of the dibasic acid anhydride to the compound E is 1:2.05-2.15;
the molar ratio of the compound E to the carboxylic acid solvent is 1:100-150;
the volume ratio of the cyclohexane to the carboxylic acid solvent is 1:3-8;
step (2): sequentially adding the prepared powder product A, epoxy halopropane, iodide and carbonic acid compound into a reactor, adding a solvent L under argon atmosphere, stirring, and heating the system to reflux; reflux-reacting for 10-15 h, cooling to 20-30 ℃, filtering out insoluble matters, concentrating the filtrate to remove the solvent L, and recrystallizing to obtain the novel epoxy resin containing imide units;
the molar ratio of the powder product A to the epoxy halopropane is 1:5-15;
the molar ratio of the carbonic acid compound to the epoxy halogenated propane is 1-3:1;
the molar ratio of the epoxy halogenated propane to the iodide is 1:0.1-0.8;
the mass fraction of the powder product A in the solvent L is 5% -20%.
Further, in the preparation method of the novel epoxy resin containing imide units, the compound E can be prepared by the following steps:
(S1): sequentially adding the nitro compound D and the solvent C into a reactor, and stirring and dissolving under the nitrogen atmosphere;
the mass of the solvent C for dissolving the nitro compound D is 2-4 times of that of the nitro compound D;
adding a carbonic acid compound into the reaction system, heating the system to 60-90 ℃, stirring for 0.5-2.0 h, and then dripping the dihydric phenol compound dissolved in the solvent C into the reaction system within 0.5-2 h; after the charging is completed, the temperature of the reaction system is raised to 100-140 ℃, the reaction is continued for 10-25 h, and then the reaction system is cooled to 10-30 ℃; pouring the reaction solution into distilled water to separate out precipitate, carrying out suction filtration, washing a filter cake with distilled water for 2-3 times, and drying the filter cake in a vacuum oven at 50-120 ℃ for 12-24 hours to obtain a product H;
the molar ratio of the nitro compound D to the dihydric phenol compound is 1:0.7-1.5;
the molar ratio of the nitro compound D to the carbonic acid compound is 1:1-2.5;
the mass of the solvent C for dissolving the dihydric phenol compound is 2-4 times of that of the dihydric phenol compound;
(S2): dissolving a product H in a solvent J, adding a palladium-carbon catalyst and a phosphorus-containing stabilizer, placing a reaction system in a high-pressure reaction kettle, and reacting for 15-20 hours at 20-60 ℃ in a hydrogen atmosphere, wherein the hydrogen pressure is maintained at 5-35 bar in the reaction process;
the mass fraction of the product H in the hydrogenation reduction system is 10% -20%;
the mass fraction of the phosphorus-containing stabilizer is 0.5% -2%;
the addition amount of the palladium-carbon catalyst is determined according to 20-50 mg of palladium-carbon catalyst corresponding to 1mmol of nitro;
filtering out the catalyst after the reaction is finished, removing the solvent J by reduced pressure distillation, washing the product with toluene for 2 to 3 times, and drying the product in a vacuum oven at 50 to 100 ℃ for 12 to 24 hours to obtain the monophenol compound E.
Further, the nitro compound D is any one or combination of p-nitrohalogenated benzene, 2-methyl-4-nitrohalogenated benzene, 3-methyl-4-nitrohalogenated benzene, 4-nitro-3-trifluoromethyl halogenated benzene and 4-nitro-2-trifluoromethyl halogenated benzene; the halogenated element is fluorine, chlorine, bromine or iodine;
the preparation method of the novel epoxy resin containing imide units is characterized in that the solvent C is any one or combination of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide;
the carbonic acid compound is any one or combination of sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate;
the phosphorus-containing stabilizer is any one or combination of triphenyl phosphite, triphenyl phosphate, triphenyl phosphorus and triphenyl phosphorus oxide;
the solvent J is any one or combination of methanol, tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane, chloroform, isopropanol, ethanol, N-dimethylformamide and N, N-dimethylacetamide;
the iodide is any one or combination of potassium iodide, sodium iodide, rubidium iodide and cesium iodide;
the carboxylic acid solvent is any one or combination of formic acid, acetic acid, propionic acid, trifluoroacetic acid, perfluoropropionic acid, trichloroacetic acid, trichloropropionic acid and trifluoropropionic acid;
the solvent L is any one or a combination of acetone, methyl ethyl ketone, acetonitrile, diethyl ketone and methyl propyl ketone;
further, in the preparation method of the novel epoxy resin containing imide units, the dihydric phenol compound is any one or a combination of the following compounds, and the chemical structural formula is as follows:
the invention also provides the use of the epoxy resin containing imide units as described above or the epoxy resin containing imide units prepared by the method for preparing epoxy resin materials.
Advantageous effects
The technical scheme provided by the invention has the following beneficial effects:
according to the invention, through the targeted molecular structure design, the rigid and strong polar imide unit is introduced into the molecular main chain of the EP resin, a novel synthesis method of the EP resin is developed, the hybridization of the imide and the EP resin on the molecular level is realized, and the impact toughness of the EP resin after curing is improved by utilizing the strong polarity and high rigidity of the imide unit.
The rigid imide element has outstanding thermal oxygen stability, and the heat resistance can be regulated and controlled by introducing the EP resin, so that the EP resin developed by the technology can meet the requirements of a resin matrix for an advanced resin matrix composite material.
In addition, the technical scheme provided by the invention not only can improve the impact toughness of the EP resin after solidification and improve the thermal performance of the EP resin by utilizing the strong polarity and high heat resistance of the imide unit, but also can introduce substituents such as methyl, phenyl, trifluoromethyl, isopropyl and the like into the molecular structure of the EP resin and introduce distorted non-coplanar units or bulky substituents into the imide unit so as to realize flexible regulation and control on the crystallinity, solubility, hygroscopicity, weather resistance, melt viscosity, processability and manufacturability of the EP resin. The technical route provided by the invention can provide diversified design ideas and raw material bases for the molecular structure design and preparation of the novel EP resin, and is beneficial to promoting and further deepening the wide application of the EP resin in extreme environments such as aerospace and the like.
Drawings
FIG. 1 is a schematic representation of the synthetic route to a phenolic compound containing a nitro group;
FIG. 2 is a schematic representation of the synthetic route to amino-containing phenolic compounds;
FIG. 3 is a schematic representation of the synthetic route to dihydric phenol compounds containing imide moieties;
FIG. 4 is a schematic representation of a preparation route for an epoxy resin comprising imide moieties;
FIG. 5 is a photograph of an epoxy resin containing imide moieties;
FIG. 6 is a schematic illustration of the epoxy resin prepared in example 10 in CDCl 3 Nuclear magnetic resonance hydrogen spectrum;
FIG. 7 is a DMSO-d phase of an epoxy resin prepared in example 10 6 Nuclear magnetic resonance carbon spectrum spectrogram in (2);
FIG. 8 is a high resolution mass spectrum of the epoxy resin prepared in example 10;
FIG. 9 is a graph showing the thermal weight loss of the epoxy resin prepared in example 8 in a nitrogen atmosphere;
FIG. 10 is a DSC curve of an epoxy prepared from example 6, melting point T m ＝183℃。
Detailed Description
The present invention will be described in detail by the following examples, which are to be understood as illustrative only and are not to be construed as limiting the scope of the invention. All the techniques realized based on the above-mentioned matters of the present invention are covered in the scope of the present invention, and all the compositions based on the core materials of the present invention as main components are covered in the scope of the present invention.
Unless otherwise specified, the starting materials and reagents used in the following examples are commercially available or are prepared by known methods.
Example 1
20.20g of p-bromonitrobenzene was dissolved in 50.00. 50.00g N-methylpyrrolidone and added to a three-necked flask equipped with a reflux condenser, and the mixture was stirred and dissolved under nitrogen atmosphere, followed by adding 10.60g of sodium carbonate to the solution, heating with stirring at 75℃for 1 hour, then dropping 7.01g of hydroquinone dissolved in 28.04. 28.04g N-methylpyrrolidone into the three-necked flask, after complete addition, raising the system temperature to 120℃and maintaining at this temperature for 12 hours, and cooling to 20 ℃. Pouring the reaction solution into distilled water to precipitate out precipitate, carrying out suction filtration, and washing a filter cake with distilled water for 2-3 times; drying the filter cake in a vacuum oven at 80 ℃ for 24 hours to obtain a product H with the yield of 91.9%; 23.12g of product H is dissolved in 230g of tetrahydrofuran, 5g of palladium-carbon catalyst and 2.6mL of triphenyl phosphite are added, and the reaction system is placed in a high-pressure reaction kettle to react for 18H at 20 ℃ in a hydrogen atmosphere; the hydrogen pressure is maintained at 12bar during the reaction; filtering out the catalyst after the reaction is finished, removing the solvent tetrahydrofuran by reduced pressure distillation, washing the product with toluene for 2-3 times, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain a monophenol compound E; 22.21g of 6FDA was added in one portion to a three-necked flask equipped with a water separator and a condensing reflux unit, 450g of acetic acid was added under argon atmosphere and mechanical stirring was started, 15.09g of monohydric phenol compound E and 150mL of cyclohexane were added in sequence and the system was heated to reflux. After 16h of reflux reaction, slowly cooling to 25 ℃, pouring the reaction solution into distilled water to precipitate out, carrying out suction filtration, and washing a filter cake with distilled water for 3 times. The filter cake was dried in a vacuum oven at 80 ℃ for 24h to give powder product a in 95% yield. Adding 8.107g of product A, 9.68g of anhydrous potassium carbonate, 4.98g of potassium iodide and 6.97g of epoxybromopropane into a three-neck flask, adding 405g of acetone under the protection of argon, starting mechanical stirring, and heating the system until reflux; after 16h of reflux reaction, the mixture is cooled to 25 ℃, insoluble matters are filtered off, acetone is removed by reduced pressure distillation, and the novel epoxy resin containing imide units is obtained after recrystallization, and the yield is 89.7%.
Example 2
21.60g of 2-bromo-4-nitrotoluene was dissolved in 60.00g of N, N-dimethylformamide and added to a three-necked flask equipped with a reflux condenser, and the solution was stirred and dissolved under nitrogen atmosphere, followed by adding 32.60g of cesium carbonate to the solution, heating with stirring at 85℃for 0.75 hours, then, 14.15g of 4,4' -dihydroxydiphenyl ether dissolved in 56.60g of N, N-dimethylformamide was dropped into the three-necked flask, after complete addition, the system temperature was raised to 115℃and kept at that temperature for 16 hours and then cooled to 25 ℃. Pouring the reaction solution into distilled water to precipitate out precipitate, carrying out suction filtration, and washing a filter cake with distilled water for 2-3 times; drying the filter cake in a vacuum oven at 75 ℃ for 18H to obtain a product H with the yield of 89.6%; 32.82g of product H is dissolved in 328g of tetrahydrofuran, 5g of palladium-carbon catalyst and 3.7mL of triphenyl phosphite are added, and the reaction system is placed in a high-pressure reaction kettle to react for 14H at 30 ℃ in a hydrogen atmosphere; the hydrogen pressure was maintained at 10bar during the reaction; filtering out the catalyst after the reaction is finished, removing the solvent tetrahydrofuran by reduced pressure distillation, washing the product with toluene for 2-3 times, and drying in a vacuum oven at 85 ℃ for 16 hours to obtain a monophenol compound E; 14.71. 14.71g a-BPDA was added in one portion to a three-necked flask equipped with a water separator and a condensing reflux apparatus, 450g of acetic acid was added under argon atmosphere and mechanical stirring was started, 29.42g of monophenol E and 150mL of cyclohexane were added in sequence and the system was heated to reflux. After 16h of reflux reaction, slowly cooling to 25 ℃, pouring the reaction solution into distilled water to precipitate out, carrying out suction filtration, and washing a filter cake with distilled water for 3 times. The filter cake was dried in a vacuum oven at 80 ℃ for 24h to give powder product a in 97.1% yield. Adding 8.46g of product A, 9.68g of anhydrous potassium carbonate, 4.5g of sodium iodide and 4.63g of epichlorohydrin into a three-neck flask, adding 423g of acetonitrile under the protection of argon, starting mechanical stirring, and heating the system until reflux; after 17h of reflux reaction, the mixture was cooled to 25 ℃, insoluble matters were filtered off, acetonitrile was removed by distillation under reduced pressure, and a novel epoxy resin containing imide units was obtained after recrystallization, with a yield of 92.0%.
Example 3
22.50g of 4-trifluoromethyl bromobenzene was dissolved in 50.00g of N, N-dimethylacetamide and added to a three-necked flask equipped with a reflux condenser, the solution was stirred and dissolved under nitrogen atmosphere, then 13.82g of potassium carbonate was added to the solution, the solution was stirred and heated at 75℃for 0.5 hour, then 17.52g of 4,4' -thiobisthiophenol dissolved in 70.04g of N, N-dimethylacetamide was dropped into the three-necked flask, after complete addition, the system temperature was raised to 105℃and kept at that temperature for 12 hours and then cooled to 30 ℃. Pouring the reaction solution into distilled water to precipitate out precipitate, carrying out suction filtration, and washing a filter cake with distilled water for 2-3 times; drying the filter cake in a vacuum oven at 85 ℃ for 18H to obtain a product H with the yield of 91.2%; 38.5g of product H is dissolved in 385g of tetrahydrofuran, 5g of palladium-carbon catalyst and 4.3mL of triphenyl phosphite are added, and the reaction system is placed in a high-pressure reaction kettle to react for 17H at 40 ℃ in a hydrogen atmosphere; the hydrogen pressure is maintained at 12bar during the reaction; filtering out the catalyst after the reaction is finished, removing the solvent tetrahydrofuran by reduced pressure distillation, washing the product with toluene for 2-3 times, and drying in a vacuum oven at 75 ℃ for 14 hours to obtain a monophenol compound E; 15.50g of ODPA was added in one portion to a three-necked flask equipped with a water separator and a condensing reflux apparatus, 450g of acetic acid was added under argon atmosphere and mechanical stirring was started, 18.13g of monohydric phenol compound E and 150mL of cyclohexane were added in sequence and the system was heated to reflux. After 17h of reflux reaction, slowly cooling to 25 ℃, pouring the reaction solution into distilled water to precipitate out, carrying out suction filtration, and washing a filter cake with distilled water for 3 times. The filter cake was dried in a vacuum oven at 80 ℃ for 24h to give powder product a in 97.9% yield. 9.67g of product A, 9.68g of anhydrous potassium carbonate, 4.5g of sodium iodide and 4.63g of epichlorohydrin are added into a three-neck flask, 483.5g of acetonitrile is added under the protection of argon and mechanical stirring is started, and the system is heated until reflux; after 17h of reflux reaction, the mixture was cooled to 25 ℃, insoluble matters were filtered off, acetonitrile was removed by distillation under reduced pressure, and a novel epoxy resin containing imide units was obtained after recrystallization, with a yield of 92.0%.
Example 4
20.20g of p-bromonitrobenzene was dissolved in 80.80g N-methylpyrrolidone and added to a three-necked flask equipped with a reflux condenser, and dissolved under stirring under nitrogen atmosphere, followed by adding 21.2g of sodium carbonate to the solution, heating under stirring at 75℃for 1 hour, then dropping 15.02g of hydroquinone dissolved in 30.04g N-methylpyrrolidone into the three-necked flask, after complete addition, raising the system temperature to 120℃and maintaining at that temperature for 12 hours, and cooling to 20 ℃. Pouring the reaction solution into distilled water to precipitate out precipitate, carrying out suction filtration, and washing a filter cake with distilled water for 2-3 times; drying the filter cake in a vacuum oven at 80 ℃ for 24 hours to obtain a product H with the yield of 91.9%; 23.12g of product H is dissolved in 230g of tetrahydrofuran, 10g of palladium-carbon catalyst and 1.3mL of triphenyl phosphite are added, and the reaction system is placed in a high-pressure reaction kettle to react for 18H at 50 ℃ in a hydrogen atmosphere; the hydrogen pressure is maintained at 12bar during the reaction; filtering out the catalyst after the reaction is finished, removing the solvent tetrahydrofuran by reduced pressure distillation, washing the product with toluene for 2-3 times, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain a monophenol compound E; 22.21g of 6FDA was added in one portion to a three-necked flask equipped with a water separator and a condensing reflux unit, 675g of acetic acid was added under argon atmosphere and mechanical stirring was started, 25.15g of monohydric phenol compound E and 84.4mL of cyclohexane were added in sequence and the system was heated to reflux. After 16h of reflux reaction, slowly cooling to 25 ℃, pouring the reaction solution into distilled water to precipitate out, carrying out suction filtration, and washing a filter cake with distilled water for 3 times. The filter cake was dried in a vacuum oven at 80 ℃ for 24h to give powder product a in 95% yield. Adding 8.107g of product A, 17.97g of anhydrous potassium carbonate, 11.62g of potassium iodide and 20.91g of epoxybromopropane into a three-neck flask, adding 81g of acetone under the protection of argon, starting mechanical stirring, and heating the system until reflux; after 16h of reflux reaction, the mixture was cooled to 25℃and insoluble matters were filtered off, acetone was removed by distillation under reduced pressure, and the novel epoxy resin containing imide groups was obtained after recrystallization in 89.7% yield.
Example 5
21.60g of 2-bromo-4-nitrotoluene was dissolved in 86.4g of N, N-dimethylformamide and added to a three-necked flask equipped with a reflux condenser, and the solution was stirred and dissolved under nitrogen atmosphere, followed by adding 65.2g of cesium carbonate to the solution, heating under stirring at 85℃for 0.75 hours, then 28.30g of 4,4' -dihydroxydiphenyl ether dissolved in 56.60g of N, N-dimethylformamide was dropped into the three-necked flask, after complete addition, the system temperature was raised to 115℃and kept at that temperature for 16 hours and then cooled to 25 ℃. Pouring the reaction solution into distilled water to precipitate out precipitate, carrying out suction filtration, and washing a filter cake with distilled water for 2-3 times; drying the filter cake in a vacuum oven at 75 ℃ for 18H to obtain a product H with the yield of 89.6%; 32.82g of product H is dissolved in 164g of tetrahydrofuran, 10g of palladium-carbon catalyst and 1.8mL of triphenyl phosphite are added, and the reaction system is placed in a high-pressure reaction kettle to react for 14H at 40 ℃ in a hydrogen atmosphere; the hydrogen pressure was maintained at 10bar during the reaction; filtering out the catalyst after the reaction is finished, removing the solvent tetrahydrofuran by reduced pressure distillation, washing the product with toluene for 2-3 times, and drying in a vacuum oven at 85 ℃ for 16 hours to obtain a monophenol compound E; 14.71. 14.71g a-BPDA was added in one portion to a three-necked flask equipped with a water separator and a condensing reflux apparatus, 675g of acetic acid was added under argon atmosphere and mechanical stirring was started, 49.03g of monohydric phenol compound E and 84.4mL of cyclohexane were added in sequence, and the system was heated to reflux. After 16h of reflux reaction, slowly cooling to 25 ℃, pouring the reaction solution into distilled water to precipitate out, carrying out suction filtration, and washing a filter cake with distilled water for 3 times. The filter cake was dried in a vacuum oven at 80 ℃ for 24h to give powder product a in 97.1% yield. 8.46g of product A, 17.97g of anhydrous potassium carbonate, 10.5g of sodium iodide and 13.89g of epichlorohydrin are added into a three-neck flask, 84.6g of acetonitrile is added under the protection of argon, mechanical stirring is started, and the system is heated until reflux; after 17h of reflux reaction, the mixture was cooled to 25℃and insoluble matters were filtered off, acetonitrile was removed by distillation under reduced pressure, and a novel epoxy resin containing imide groups was obtained after recrystallization in 92.0% yield.
Example 6
22.50g of 4-trifluoromethyl bromobenzene was dissolved in 90g of N, N-dimethylacetamide and added to a three-necked flask equipped with a reflux condenser, and dissolved under stirring under nitrogen atmosphere, followed by adding 27.64g of potassium carbonate to the solution, heating under stirring at 75℃for 0.5 hours, then, 35.04g of 4,4' -thiobisthiophenol dissolved in 70.08g of N, N-dimethylacetamide was dropped into the three-necked flask, after complete addition, the system temperature was raised to 105℃and kept at that temperature for 12 hours and then cooled to 30 ℃. Pouring the reaction solution into distilled water to precipitate out precipitate, carrying out suction filtration, and washing a filter cake with distilled water for 2-3 times; drying the filter cake in a vacuum oven at 85 ℃ for 18H to obtain a product H with the yield of 91.2%; 38.5g of product H is dissolved in 192.5g of tetrahydrofuran, 10g of palladium-carbon catalyst and 2.1mL of triphenyl phosphite are added, and the reaction system is placed in a high-pressure reaction kettle to react for 17H at 60 ℃ in a hydrogen atmosphere; the hydrogen pressure is maintained at 12bar during the reaction; filtering out the catalyst after the reaction is finished, removing the solvent tetrahydrofuran by reduced pressure distillation, washing the product with toluene for 2-3 times, and drying in a vacuum oven at 75 ℃ for 14 hours to obtain a monophenol compound E; 26.00g of BPADA was added in one portion to a three-necked flask equipped with a water separator and a condensing reflux apparatus, 675g of acetic acid was added under argon atmosphere and mechanical stirring was started, and 30.21g of monohydric phenol compound E and 84.4mL of cyclohexane were added in sequence and the system was heated to reflux. After 17h of reflux reaction, slowly cooling to 25 ℃, pouring the reaction solution into distilled water to precipitate out, carrying out suction filtration, and washing a filter cake with distilled water for 3 times. The filter cake was dried in a vacuum oven at 80 ℃ for 24h to give powder product a in 97.9% yield. 9.67g of product A, 17.97g of anhydrous potassium carbonate, 10.5g of sodium iodide and 13.89g of epichlorohydrin are added into a three-neck flask, 96.6g of acetonitrile is added under the protection of argon, mechanical stirring is started, and the system is heated until reflux; after 17h of reflux reaction, the mixture was cooled to 25℃and insoluble matters were filtered off, acetonitrile was removed by distillation under reduced pressure, and a novel epoxy resin containing imide groups was obtained after recrystallization in 92.0% yield.
Example 7
20.20g of p-bromonitrobenzene was dissolved in 40.4. 40.4g N-methylpyrrolidone and added to a three-necked flask equipped with a reflux condenser, and the mixture was stirred and dissolved under nitrogen atmosphere, followed by adding 10.70g of sodium carbonate to the solution, heating with stirring at 75℃for 1 hour, then dropping 11.01g of hydroquinone dissolved in 30.00. 30.00g N-methylpyrrolidone into the three-necked flask, after complete addition, raising the system temperature to 120℃and maintaining at this temperature for 12 hours, and cooling to 20 ℃. Pouring the reaction solution into distilled water to precipitate out precipitate, carrying out suction filtration, and washing a filter cake with distilled water for 2-3 times; drying the filter cake in a vacuum oven at 80 ℃ for 24 hours to obtain a product H with the yield of 91.9%; 23.12g of product H is dissolved in 230g of tetrahydrofuran, 7.5g of palladium-carbon catalyst and 2.2mL of triphenyl phosphorus oxide are added, and the reaction system is placed in a high-pressure reaction kettle to react for 18H at 50 ℃ in a hydrogen atmosphere; the hydrogen pressure is maintained at 12bar during the reaction; filtering out the catalyst after the reaction is finished, removing the solvent tetrahydrofuran by reduced pressure distillation, washing the product with toluene for 2-3 times, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain a monophenol compound E; 22.21g of 6FDA was added to a three-necked flask equipped with a water separator and a condensing reflux unit at one time, 500g of acetic acid was added under argon atmosphere and mechanical stirring was started, 22.13g of monohydric phenol compound E and 100mL of cyclohexane were added in sequence and the system was heated to reflux. After 16h of reflux reaction, slowly cooling to 25 ℃, pouring the reaction solution into distilled water to precipitate out, carrying out suction filtration, and washing a filter cake with distilled water for 3 times. The filter cake was dried in a vacuum oven at 80 ℃ for 24h to give powder product a in 95% yield. Adding 8.107g of product A, 12.13g of anhydrous potassium carbonate, 6.73g of potassium iodide and 14.52g of epoxybromopropane into a three-neck flask, adding 300g of acetone under the protection of argon, starting mechanical stirring, and heating the system until reflux; after 16h of reflux reaction, the mixture was cooled to 25℃and insoluble matters were filtered off, acetone was removed by distillation under reduced pressure, and the novel epoxy resin containing imide groups was obtained after recrystallization in 89.7% yield.
Example 8
21.60g of 2-bromo-4-nitrotoluene was dissolved in 43.20g of N, N-dimethylformamide and added to a three-necked flask equipped with a reflux condenser, and the solution was stirred and dissolved under nitrogen atmosphere, followed by adding 34.25g of cesium carbonate to the solution, heating with stirring at 85℃for 0.75 hours, then 20.17g of 4,4' -dihydroxydiphenyl ether dissolved in 45.00g of N, N-dimethylformamide was dropped into the three-necked flask, after complete addition, the system temperature was raised to 115℃and kept at that temperature for 16 hours and then cooled to 25 ℃. Pouring the reaction solution into distilled water to precipitate out precipitate, carrying out suction filtration, and washing a filter cake with distilled water for 2-3 times; drying the filter cake in a vacuum oven at 75 ℃ for 18H to obtain a product H with the yield of 89.6%; 32.82g of product H is dissolved in 300g of tetrahydrofuran, 7.9g of palladium-carbon catalyst and 2.7mL of triphenyl phosphorus oxide are added, and the reaction system is placed in a high-pressure reaction kettle to react for 14H at 30 ℃ in a hydrogen atmosphere; the hydrogen pressure was maintained at 10bar during the reaction; filtering out the catalyst after the reaction is finished, removing the solvent tetrahydrofuran by reduced pressure distillation, washing the product with toluene for 2-3 times, and drying in a vacuum oven at 85 ℃ for 16 hours to obtain a monophenol compound E; 14.71. 14.71g a-BPDA was added in one portion to a three-necked flask equipped with a water separator and a condensing reflux apparatus, 600g of acetic acid was added under argon atmosphere and mechanical stirring was started, 37.16g of monohydric phenol compound E and 110mL of cyclohexane were added in sequence and the system was heated to reflux. After 16h of reflux reaction, slowly cooling to 25 ℃, pouring the reaction solution into distilled water to precipitate out, carrying out suction filtration, and washing a filter cake with distilled water for 3 times. The filter cake was dried in a vacuum oven at 80 ℃ for 24h to give powder product a in 97.1% yield. 8.46g of product A, 13.66g of anhydrous potassium carbonate, 7.30g of sodium iodide and 10.20g of epichlorohydrin are added with 260g of acetonitrile under the protection of argon and are stirred mechanically, and the system is heated to reflux; after 17h of reflux reaction, the mixture was cooled to 25 ℃, insoluble matters were filtered off, acetonitrile was removed by distillation under reduced pressure, and a novel epoxy resin containing imide units was obtained after recrystallization, with a yield of 92.0%.
Example 9
22.50g of 4-trifluoromethyl bromobenzene was dissolved in 45.00g of N, N-dimethylacetamide and added to a three-necked flask equipped with a reflux condenser, the solution was stirred and dissolved under nitrogen atmosphere, then 14.73g of potassium carbonate was added to the solution, the solution was stirred and heated at 75℃for 0.5 hour, then 25.36g of 4,4' -thiobisthiophenol dissolved in 55.23g of N, N-dimethylacetamide was dropped into the three-necked flask, after complete addition, the system temperature was raised to 105℃and kept at that temperature for 12 hours and then cooled to 30 ℃. Pouring the reaction solution into distilled water to precipitate out precipitate, carrying out suction filtration, and washing a filter cake with distilled water for 2-3 times; drying the filter cake in a vacuum oven at 85 ℃ for 18H to obtain a product H with the yield of 91.2%; 38.5g of product H is dissolved in 225g of tetrahydrofuran, 7.3g of palladium-carbon catalyst and 2.7mL of triphenyl phosphite are added, and the reaction system is placed in a high-pressure reaction kettle to react for 17H at 20 ℃ in a hydrogen atmosphere; the hydrogen pressure is maintained at 12bar during the reaction; filtering out the catalyst after the reaction is finished, removing the solvent tetrahydrofuran by reduced pressure distillation, washing the product with toluene for 2-3 times, and drying in a vacuum oven at 75 ℃ for 14 hours to obtain a monophenol compound E; 15.50-g a-ODPA was added to a three-necked flask equipped with a water separator and a condensing reflux unit at a time, 550g of acetic acid was added under argon atmosphere and mechanical stirring was started, 22.42g of monophenol E and 100mL of cyclohexane were added in sequence, and the system was heated to reflux. After 17h of reflux reaction, slowly cooling to 25 ℃, pouring the reaction solution into distilled water to precipitate out, carrying out suction filtration, and washing a filter cake with distilled water for 3 times. The filter cake was dried in a vacuum oven at 80 ℃ for 24h to give powder product a in 97.9% yield. 9.67g of product A, 10.36g of anhydrous potassium carbonate, 7.20g of sodium iodide and 11.83g of epichlorohydrin are added into a three-neck flask, 320.5g of acetonitrile is added under the protection of argon and mechanical stirring is started, and the system is heated until reflux; after 17h of reflux reaction, the mixture was cooled to 25 ℃, insoluble matters were filtered off, acetonitrile was removed by distillation under reduced pressure, and a novel epoxy resin containing imide units was obtained after recrystallization, with a yield of 92.0%.
Example 10
11.10g of 6FDA was added in one portion to a three-necked flask equipped with a water separator and a condensing reflux apparatus, 200g of acetic acid was added under argon atmosphere and mechanical stirring was started, 5.45g of p-aminophenol and 50mL of cyclohexane were sequentially added and the system was heated to reflux. After 18h of reflux reaction, slowly cooling to 25 ℃, pouring the reaction solution into distilled water to precipitate out, carrying out suction filtration, and washing a filter cake with distilled water for 3 times. The filter cake was dried in a vacuum oven at 80 ℃ for 24h to give powder product a in 96.9% yield. 9.67g of product A, 20.72g of anhydrous potassium carbonate, 12.45g of potassium iodide and 20.70g of epichlorohydrin are added into a three-neck flask, 300g of acetone is added under the protection of argon, mechanical stirring is started, and the system is heated until reflux; reflux reaction for 17h, cooling to 25 ℃, filtering out insoluble matters, distilling off acetone under reduced pressure, and recrystallizing to obtain the novel epoxy resin containing imide units, wherein the yield is 91.7%.
Example 11
The mechanical and thermal properties of the EP resin prepared according to the present invention after curing are shown in Table 1, which are compared with those of EP resin cured products reported in part of the trade mark or part of the subject group.
Table 1. Impact Properties (Critical stress Strength factor) and thermal performance data of EP resins prepared according to the invention and other brands of EP resin cured products vs:
as shown in the above table, the resin material provided by the invention shows a significantly improved critical stress intensity factor (K IC ) Up to 2.03 MPa.m 1/2 The elongation at break exceeds 6%, while the glass transition temperature and the 5% thermal decomposition temperature are not reduced, even a small increase is exhibited, so that the technical solution claimed by the invention has significant advantages in improving the impact toughness of EP resins.
The above examples illustrate exemplary embodiments of the invention. However, the scope of the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A novel epoxy resin comprising imide moieties, characterized in that: the molecular structure of the epoxy resin is represented by the following general formula (I),
wherein the molar ratio of the dicarboxylic anhydride moiety, the compound E moiety and the epihalohydrin moiety in formula (I) is 1:2:2; r is R 1 Represents O or S;
R 2 represents a residue in compound E, R 2 Is a substituted or unsubstituted phenylene group, or is a structural fragment represented by the following formula (II):
wherein R in formula (II) is a residue in a dihydric phenol compound, R is the same as R in formula (I) 1 Are connected; m is M 1 Is O or S, Y is H, -CF 3 or-CH 3 ；R 3 Representing residues in the dibasic anhydride.
2. The novel epoxy resin containing imide moieties according to claim 1, wherein the dibasic anhydride moiety corresponds to any one or a combination of the following anhydrides, having the chemical structural formula:
3. the novel epoxy resin comprising imide moieties of claim 1, wherein the epihalohydrin is: any one or combination of epoxyfluoropropane, epoxychloropropane, epoxybromopropane and epoxyiodopropane.
4. A novel epoxy resin comprising imide moieties according to any one of claims 1 to 3 wherein the compound corresponding to the moiety E comprises an aminophenol of: para-aminophenol, ortho-aminophenol, meta-aminophenol, 2-methyl-4-aminophenol, tetramethyl para-aminophenol, 3-methyl-4-aminophenol, 2-methyl-3-aminophenol, 3-methyl-2-aminophenol, 4-amino-3-trifluoromethylphenol, 4-amino-2-trifluoromethylphenol, 3-amino-2-trifluoromethylphenol, 2-phenyl-4-aminophenol, 3-isopropyl-4-aminophenol, 2-phenyl-3-aminophenol, 3-isopropyl-2-aminophenol, 3-phenyl-4-aminophenol, 3-phenyl-2-aminophenol, 2-amino-3-trifluoromethylphenol, para-aminophenol, ortho-aminophenol, meta-aminophenthiophenol, 2-methyl-4-aminophenthiophenol, 3-methyl-4-aminophenthiophenol, 2-aminophenol, 4-amino-3-trifluoromethylphenol, 4-trifluoromethyl-2-trifluoro-aminophenol, tetramethyl-3-amino-3-trifluoro-thiophenol, or a combination thereof.
5. A process for preparing the novel epoxy resins comprising imide moieties according to claims 1 to 4, characterized by the following specific steps:
step (1): adding dibasic acid anhydride into a reactor, adding a carboxylic acid solvent under argon atmosphere, stirring, sequentially adding a compound E and cyclohexane, heating and refluxing, cooling to 20-30 ℃ after reflux reaction for 10-20 hours, pouring reaction liquid into distilled water to precipitate, filtering, washing a filter cake with distilled water for 2-3 times, and vacuum drying at 60-120 ℃ to obtain a powder product A;
the molar ratio of the dibasic acid anhydride to the compound E is 1:2.05-2.15;
the molar ratio of the compound E to the carboxylic acid solvent is 1:100-150;
the volume ratio of the cyclohexane to the carboxylic acid solvent is 1:3-8;
step (2):
sequentially adding the prepared powder product A, epoxy halopropane, iodide and carbonic acid compound into a reactor, adding a solvent L under argon atmosphere, stirring, and heating the system to reflux; reflux-reacting for 10-15 h, cooling to 20-30 ℃, filtering out insoluble matters, concentrating the filtrate to remove the solvent L, and recrystallizing to obtain the novel epoxy resin containing imide units;
the molar ratio of the powder product A to the epoxy halopropane is 1:5-15;
the molar ratio of the carbonic acid compound to the epoxy halogenated propane is 1-3:1;
the molar ratio of the epoxy halogenated propane to the iodide is 1:0.1-0.8;
the mass fraction of the powder product A in the solvent L is 5% -20%.
6. The method for producing a novel epoxy resin containing an imide moiety according to claim 5, wherein said compound E is produced by:
(S1): adding the nitro compound D and the solvent C into a reactor, and stirring and dissolving under the nitrogen atmosphere; the mass of the solvent C for dissolving the nitro compound D is 2-4 times of that of the nitro compound D;
adding a carbonic acid compound into the reaction system, heating the system to 60-90 ℃, stirring for 0.5-2.0 h, and then dripping the dihydric phenol compound dissolved in the solvent C into the reaction system within 0.5-2 h; after the charging is completed, the temperature of the reaction system is raised to 100-140 ℃, the reaction is continued for 10-25 h, and then the reaction system is cooled to 10-30 ℃; pouring the reaction solution into distilled water to separate out precipitate, carrying out suction filtration, washing a filter cake with distilled water for 2-3 times, and drying the filter cake in a vacuum oven at 50-120 ℃ for 12-24 hours to obtain a product H;
the molar ratio of the nitro compound D to the dihydric phenol compound is 1:0.7-1.5;
the molar ratio of the nitro compound D to the carbonic acid compound is 1:1-2.5;
the mass of the solvent C for dissolving the dihydric phenol compound is 2-4 times of that of the dihydric phenol compound;
(S2): dissolving the prepared product H in a solvent J, adding a palladium-carbon catalyst and a phosphorus-containing stabilizer, placing the reaction system in a high-pressure reaction kettle, and reacting for 15-20H at 20-60 ℃ in a hydrogen atmosphere, wherein the hydrogen pressure is maintained at 5-35 bar in the reaction process;
the mass fraction of the product H in the hydrogenation reduction system is 10% -20%;
the mass fraction of the phosphorus-containing stabilizer is 0.5% -2%;
the addition amount of the palladium-carbon catalyst is determined according to 20-50 mg of palladium-carbon catalyst corresponding to 1mmol of nitro;
filtering out the catalyst after the reaction is finished, removing the solvent J by reduced pressure distillation, washing the product with toluene for 2 to 3 times, and drying the product in a vacuum oven at 50 to 100 ℃ for 12 to 24 hours to obtain the monophenol compound E.
7. The method for producing a novel epoxy resin containing an imide moiety according to claim 5 or 6, wherein the nitro compound D is any one of p-nitrohalogenated benzene, 2-methyl-4-nitrohalogenated benzene, 3-methyl-4-nitrohalogenated benzene, 4-nitro-3-trifluoromethyl halogenated benzene, 4-nitro-2-trifluoromethyl halogenated benzene, or a combination thereof; the halogenated element is fluorine, chlorine, bromine or iodine.
8. The method for producing a novel epoxy resin containing an imide moiety according to claim 5 or 6, wherein the solvent C is any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, or a combination thereof;
the carbonic acid compound is any one or combination of sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate;
the phosphorus-containing stabilizer is any one or combination of triphenyl phosphite, triphenyl phosphate, triphenyl phosphorus and triphenyl phosphorus oxide;
the solvent J is any one or combination of methanol, tetrahydrofuran, ethyl acetate, acetonitrile, dichloromethane, chloroform, isopropanol, ethanol, N-dimethylformamide and N, N-dimethylacetamide;
the iodide is any one or combination of potassium iodide, sodium iodide, rubidium iodide and cesium iodide;
the carboxylic acid solvent is any one or combination of formic acid, acetic acid, propionic acid, trifluoroacetic acid, perfluoropropionic acid, trichloroacetic acid, trichloropropionic acid and trifluoropropionic acid;
the solvent L is any one or combination of acetone, methyl ethyl ketone, acetonitrile, diethyl ketone and methyl propyl ketone.
9. The method for preparing a novel epoxy resin containing imide units according to claim 5 or 6, wherein the dihydric phenol compound is any one of the following compounds or a combination thereof, and has the following chemical structural formula:
10. use of an epoxy resin comprising imide moieties according to any one of claims 1 to 4 or an epoxy resin comprising imide moieties prepared by the method of any one of claims 5 to 9 for the preparation of an epoxy resin material.
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