CN118240200A - Low-dielectric fluorine-containing polyarylether resin and preparation method and application thereof - Google Patents
Low-dielectric fluorine-containing polyarylether resin and preparation method and application thereof Download PDFInfo
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- CN118240200A CN118240200A CN202410459440.7A CN202410459440A CN118240200A CN 118240200 A CN118240200 A CN 118240200A CN 202410459440 A CN202410459440 A CN 202410459440A CN 118240200 A CN118240200 A CN 118240200A
- Authority
- CN
- China
- Prior art keywords
- bisphenol
- polyarylether resin
- monomer
- solvent
- fluoro
- 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.)
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- 229920000090 poly(aryl ether) Polymers 0.000 title claims abstract description 78
- 229920005989 resin Polymers 0.000 title claims abstract description 68
- 239000011347 resin Substances 0.000 title claims abstract description 68
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 37
- 239000011737 fluorine Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 73
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 33
- -1 terphenyl bisphenol Chemical compound 0.000 claims abstract description 30
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000004305 biphenyl Substances 0.000 claims abstract description 16
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 15
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 27
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000012024 dehydrating agents Substances 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- ONUFSRWQCKNVSL-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C1=C(F)C(F)=C(F)C(F)=C1F ONUFSRWQCKNVSL-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- QRFMXBKGNQEADL-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 QRFMXBKGNQEADL-UHFFFAOYSA-N 0.000 claims description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 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 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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 8
- PISLKPDKKIDMQT-UHFFFAOYSA-N [3-(4-fluorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC(C(=O)C=2C=CC(F)=CC=2)=C1 PISLKPDKKIDMQT-UHFFFAOYSA-N 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- BWQOPMJTQPWHOZ-UHFFFAOYSA-N (2,3-difluorophenyl)-phenylmethanone Chemical compound FC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1F BWQOPMJTQPWHOZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 150000003457 sulfones Chemical class 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- VOWPIDJSINRFPZ-UHFFFAOYSA-N 4-bromo-3-(trifluoromethyl)phenol Chemical compound OC1=CC=C(Br)C(C(F)(F)F)=C1 VOWPIDJSINRFPZ-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- MHKOVSRFDDLIFU-UHFFFAOYSA-N [4-hydroxy-2-(trifluoromethyl)phenyl]boronic acid Chemical compound OB(O)C1=CC=C(O)C=C1C(F)(F)F MHKOVSRFDDLIFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- OYNDLOJPYURCJG-UHFFFAOYSA-N (3-fluoro-4-hydroxyphenyl)boronic acid Chemical compound OB(O)C1=CC=C(O)C(F)=C1 OYNDLOJPYURCJG-UHFFFAOYSA-N 0.000 claims description 3
- OYIYNIONWDBJIF-UHFFFAOYSA-N (4-hydroxy-2-methylphenyl)boronic acid Chemical compound CC1=CC(O)=CC=C1B(O)O OYIYNIONWDBJIF-UHFFFAOYSA-N 0.000 claims description 3
- GZHWHLOMMPXHPW-UHFFFAOYSA-N (4-hydroxy-3-methylphenyl)boronic acid Chemical compound CC1=CC(B(O)O)=CC=C1O GZHWHLOMMPXHPW-UHFFFAOYSA-N 0.000 claims description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 3
- BLDOSVXRDMTZQE-UHFFFAOYSA-N 1,4-difluoro-2-(trifluoromethyl)benzene Chemical compound FC1=CC=C(F)C(C(F)(F)F)=C1 BLDOSVXRDMTZQE-UHFFFAOYSA-N 0.000 claims description 3
- CQXZSEXZQVKCHW-UHFFFAOYSA-N 3,5-difluorobenzonitrile Chemical compound FC1=CC(F)=CC(C#N)=C1 CQXZSEXZQVKCHW-UHFFFAOYSA-N 0.000 claims description 3
- BYZMZJIWCQTYSR-UHFFFAOYSA-N 4-bromo-2,5-difluorophenol Chemical compound OC1=CC(F)=C(Br)C=C1F BYZMZJIWCQTYSR-UHFFFAOYSA-N 0.000 claims description 3
- LZKYUWXZSBYMSA-UHFFFAOYSA-N 4-bromo-2,5-dimethylphenol Chemical compound CC1=CC(Br)=C(C)C=C1O LZKYUWXZSBYMSA-UHFFFAOYSA-N 0.000 claims description 3
- XFJGGRVZKUZFRG-UHFFFAOYSA-N 4-bromo-2-fluoro-5-(trifluoromethyl)phenol Chemical compound Oc1cc(c(Br)cc1F)C(F)(F)F XFJGGRVZKUZFRG-UHFFFAOYSA-N 0.000 claims description 3
- QDGUFFYQTIQGAJ-UHFFFAOYSA-N 4-bromo-2-fluoro-5-methylphenol Chemical compound CC1=CC(O)=C(F)C=C1Br QDGUFFYQTIQGAJ-UHFFFAOYSA-N 0.000 claims description 3
- PGJZBAVEKVWHIO-UHFFFAOYSA-N 4-bromo-3-(trifluoromethoxy)phenol Chemical compound OC1=CC=C(Br)C(OC(F)(F)F)=C1 PGJZBAVEKVWHIO-UHFFFAOYSA-N 0.000 claims description 3
- MRQYTJXVULSNIS-UHFFFAOYSA-N 4-bromo-3-fluorophenol Chemical compound OC1=CC=C(Br)C(F)=C1 MRQYTJXVULSNIS-UHFFFAOYSA-N 0.000 claims description 3
- GPOQODYGMUTOQL-UHFFFAOYSA-N 4-bromo-3-methylphenol Chemical compound CC1=CC(O)=CC=C1Br GPOQODYGMUTOQL-UHFFFAOYSA-N 0.000 claims description 3
- SHRYKVVPIPGXCZ-UHFFFAOYSA-N 4-bromo-5-fluoro-2-methylphenol Chemical compound CC1=CC(Br)=C(F)C=C1O SHRYKVVPIPGXCZ-UHFFFAOYSA-N 0.000 claims description 3
- VFONOIYZYXRMSR-UHFFFAOYSA-N OB(O)C1=CC=C(O)C=C1OC(F)(F)F Chemical compound OB(O)C1=CC=C(O)C=C1OC(F)(F)F VFONOIYZYXRMSR-UHFFFAOYSA-N 0.000 claims description 3
- LLJNTLUXOZPFQB-UHFFFAOYSA-N [4-(4-fluorobenzoyl)phenyl]-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(C(=O)C=2C=CC(F)=CC=2)C=C1 LLJNTLUXOZPFQB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- 239000003495 polar organic solvent Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims 1
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- 238000005266 casting Methods 0.000 claims 1
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 claims 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- 230000005684 electric field Effects 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007339 nucleophilic aromatic substitution reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- RARYKHVUFJIGKT-UHFFFAOYSA-N (2-fluoro-4-hydroxyphenyl)boronic acid Chemical compound OB(O)C1=CC=C(O)C=C1F RARYKHVUFJIGKT-UHFFFAOYSA-N 0.000 description 2
- UOJCDDLTVQJPGH-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(B2OC(C)(C)C(C)(C)O2)C=C1 UOJCDDLTVQJPGH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- AESLWNQXGHIIQV-UHFFFAOYSA-N 1,4-bis[2-(trifluoromethyl)phenyl]benzene Chemical compound C1=CC=C(C(=C1)C2=CC=C(C=C2)C3=CC=CC=C3C(F)(F)F)C(F)(F)F AESLWNQXGHIIQV-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
The invention provides a low-dielectric fluorine-containing polyarylether resin, a preparation method and application thereof; the low dielectric fluorine-containing polyarylether resin has a repeating unit structure shown in a general formula I: Wherein: r a is the residue of a different biphenol or terphenyl bisphenol component; r b represents the residue of different dihalogen monomer components. By adopting the technical scheme, the polyarylether resin polymer is a polymer with a fluorine-containing structure and a rigid biphenyl or terphenyl structure, and can obviously improve the thermal stability, the hydrophobic property and the dielectric property of the resin; in particular, the dipole relaxation is reduced, and the dielectric loss is remarkably reduced, because the dipole relaxation cannot be changed along with the change of an alternating electric field in the polarization process.
Description
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to a low-dielectric fluorine-containing polyarylether resin and a preparation method and application thereof.
Background
As the communication industry moves to high frequency and high speed, the requirements on material loss are more and more severe. Since low-loss materials can bring low attenuation, low delay and high wave-transparent benefits to signals, they are indispensable materials in the communications industry, so it is important to obtain dielectric materials with excellent comprehensive properties. Polyarylether (PAE) is a high-performance polymer material, and can replace the traditional microelectronic material to prepare the 5G communication antenna material due to the excellent thermal stability, mechanical property and dielectric property.
In order to use the polyarylether resins for microelectronic materials, the main properties required are thermal stability, mechanical properties and dielectric properties. As a method for preparing a polyarylether having excellent thermal stability, mechanical properties and dielectric properties, the prior art generally improves the mechanical properties and thermal stability of a polyarylether resin by introducing a rigid side group structure having a large volume into a polymer chain, while increasing the molecular free volume of the polymer chain to reduce the density of polar groups per unit volume, thereby lowering the dielectric constant, and at the same time, dielectric loss is not significantly reduced since the number of polar groups in the polymer chain is unchanged.
On the other hand, fluorine atoms have the characteristics of low polarizability, low water absorbability and low surface energy, so that the thermal stability, chemical stability and dielectric property of the polyarylether resin can be improved, and the polyarylether resin has excellent abrasion resistance. However, the types of fluorine-containing monomers which can be used for producing the fluorine-containing polyarylether resin in the prior art are extremely limited, so that the popularization and the use of the fluorine-containing polyarylether are limited on the one hand, and on the other hand, the types of the fluorine-containing polyarylether with excellent performances are few.
Therefore, the invention develops the fluorine-containing polyarylether material with low dielectric constant based on the synthesis of the biphenyl bisphenol or the terphenyl bisphenol monomer based on the prior art, thereby solving the technical problems in the prior art.
Disclosure of Invention
In view of the above, the present invention provides a low dielectric fluorine-containing polyarylether resin, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides a low dielectric fluorine-containing polyarylether resin, which has a repeating unit structure of the general formula shown in formula I:
Wherein: r a is the residue of a different biphenol or terphenyl bisphenol component; r 1、R2 is selected from any one of hydrogen, alkyl, haloalkyl or haloalkoxy, and is the same or different; r b represents the residue of different dihalogen monomer components.
Preferably, R a is a bisphenol residue having a general structure shown in formula II or formula III:
Preferably, the dihalogen monomer component is selected from any one or more combinations of difluorodiphenyl sulfone (DFS), difluorobenzophenone (DFK), 1, 3-bis (4-fluorobenzoyl) benzene (BFBZ), decafluorobiphenyl (DFP), 4' -difluoro-3, 3' -bistrifluoromethyl-1, 1' -Biphenyl (BDTF), 1, 4-bis (4-fluorobenzoyl) benzene (DFBK), 3, 5-Difluorobenzonitrile (DFBN), 2, 5-Difluorotrifluoromethylbenzene (DFBTF), and derivatives thereof.
Preferably, the biphenol of the general structure shown in formula II is selected from at least one of the following structural formulas:
preferably, the terphenyl bisphenol of the general structure shown in formula III is selected from at least one of the following structural formulas:
In the invention, biphenol and/or terphenyl bisphenol with fluorine-containing substituent groups are preferable, along with the increase of rigid aromatic structures (benzene rings), the short-range ordered structures of polymer chains are increased, and the mutual accumulation of the polymer chains is promoted, so that the dipole orientation in the polymer is fixed, the dipole orientation cannot be changed along with the change of an alternating electric field in the polarization process, the dipole relaxation is reduced, and the dielectric loss (D f) is further obviously reduced; further, due to the introduction of fluorine-containing groups, on the one hand the low surface energy of the fluorine atoms gives the polymer excellent hydrophobicity, and on the other hand the low polarizability of the fluorine atoms and the larger free volume of the trifluoromethyl groups further gives the polymer a lower dielectric constant (D k).
Preferably, R b is selected from residues of two or more dihalogen monomers of difluorodiphenyl sulfone (DFS), difluorobenzophenone (DFK), 1, 3-bis (4-fluorobenzoyl) benzene (BFBZ), decafluorobiphenyl (DFP), 4' -difluoro-3, 3' -bistrifluoromethyl-1, 1' -Biphenyl (BDTF).
Preferably, the molecular weight of the polyarylether resin is greater than 5000g/mol; more preferably, the molecular weight is 10000-300000g/mol.
Preferably, the molecular weight distribution of the polyarylether resin is 1.2-2.5;
Preferably, the polyarylether resin film has a glass transition temperature (T g) greater than 170 ℃ and a dielectric constant (D k) less than 3, with a dielectric loss less than 0.007.
As another object, the present invention also provides a preparation method of the low dielectric fluorine-containing polyarylether resin, which specifically comprises the following steps:
S1, providing bisphenol monomers; adding borate monomers, dihalogen monomers and catalysts into a first solvent in an inert gas atmosphere, uniformly mixing, and then carrying out coupling reaction at 70-110 ℃ to obtain biphenyl bisphenol or terphenyl bisphenol monomers, namely the bisphenol monomers;
S2, preparing polyarylether resin; comprises dissolving the biphenyl bisphenol or the terphenyl bisphenol, a dihalogen monomer and an alkaline catalyst in a second solvent under the inert gas atmosphere, and carrying out nucleophilic aromatic substitution reaction at 25-180 ℃, wherein the reaction product is the polyarylether resin.
Preferably, in S1, the molar ratio of the borate monomer, the dihalogen monomer, the catalyst and the first solvent is 1:1-1.2:0.03-0.1:30-100.
Preferably, the borate monomer is selected from any one of 4-hydroxy-2-trifluoromethylphenylboronic acid, 4-hydroxy-2-methylphenylboronic acid, (2-fluoro-4-hydroxyphenyl) boronic acid, 4-hydroxy-2-trifluoromethoxybenzeneboronic acid, 3-methyl-4-hydroxyphenylboronic acid, 3-fluoro-4-hydroxyphenylboronic acid, 1, 4-benzenediboronic acid bis (pinacol) ester.
Preferably, the dihalogen monomer is selected from any one or a combination of more of 3-trifluoromethyl-4-bromophenol, 2-bromo-4-fluoro-5-hydroxytrifluorotoluene, 4-bromo-3-methylphenol, 4-bromo-2, 5-dimethylphenol, 4-bromo-2-fluoro-5-methylphenol, 3-fluoro-4-bromophenol, 4-bromo-5-fluoro-2-methylphenol, 5-bromo-4-fluoro-2-hydroxytrifluorotoluene, 4-bromo-2, 5-difluorophenol, 4-bromo-3-trifluoromethoxy-phenol, 4-bromo-2-fluoro-5-trifluoromethoxy-phenol.
Preferably, the catalyst comprises any one or a combination of more of tetra-triphenylphosphine palladium, DPPF palladium dichloride, palladium acetate, bis-triphenylphosphine palladium dichloride, (1, 1' -bis (diphenylphosphine) ferrocene) nickel dichloride.
Preferably, the first solvent comprises any one or more than two of dioxane, toluene, xylene and tetrahydrofuran.
Preferably, in S2, the bisphenol monomer and the dihalogen monomer are used as raw materials, the alkaline catalyst, the second solvent and the dehydrating agent are added into a reaction vessel, the temperature is increased to 140 ℃ in a nitrogen or argon protection atmosphere under the stirring condition, so that the dehydrating agent flows back, the reaction is carried out for 4 to 6 hours, the azeotropic dehydrating agent is discharged in batches, and then the temperature is increased to 175 to 180 ℃ for reaction for 6 to 8 hours; and separating out the obtained polymer in a 1% hydrochloric acid aqueous solution, washing, redissolving, filtering, carrying out cable extraction and drying to obtain the polyarylether resin with low dielectric constant.
Preferably, the mol ratio of bisphenol monomer, dihalogen monomer, alkaline catalyst, second solvent and dehydrating agent is 1:1-1.05:2.2-3:20-30:30-50.
Preferably, the second solvent is a high boiling point polar organic solvent; more preferably, the second solvent is selected from any one of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, sulfolane.
Preferably, the dehydrating agent is selected from one of toluene, xylene and ethanol.
Preferably, the bisphenol monomer and the dihalogen monomer are taken as raw materials, the alkaline catalyst and the second solvent are added into a reaction vessel, and the mixture is stirred in a nitrogen or argon protection atmosphere and reacts for 24 hours at room temperature; and separating out the obtained polymer in a mixed solution of ethanol and water, washing, redissolving, filtering, carrying out cable extraction and drying to obtain the low dielectric constant polyarylether resin.
The mol ratio of the bisphenol monomer to the dihalogen monomer to the alkaline catalyst to the second solvent is 1:1-1.05:2.2-3:20-30.
Preferably, the alkaline catalyst is selected from any one of potassium carbonate, cesium fluoride, sodium carbonate, sodium fluoride, and sodium bicarbonate.
The beneficial technical effects obtained by the invention are as follows:
1. By adopting the technical scheme, the polyarylether resin polymer is a polymer with a fluorine-containing structure and a rigid biphenyl or terphenyl structure, and can obviously improve the thermal stability, the hydrophobic property and the dielectric property of the resin; in particular, the dipole relaxation is reduced, and the dielectric loss is remarkably reduced, because the dipole relaxation cannot be changed along with the change of an alternating electric field in the polarization process.
2. Bisphenol monomer with fluorine-containing structure and rigid biphenyl or terphenyl structure synthesized by adopting the technical scheme of the invention, bisphenol monomer and dihalogenated monomer realize the synthesis of polymer resin containing fluorine group and biphenyl or terphenyl group with rigid aromatic structure in the polymer main chain by a high-temperature or room-temperature nucleophilic aromatic substitution polymerization method, and the molecular weight of the resin is controllable; moreover, the low surface energy of fluorine atoms on the one hand gives polymers with excellent hydrophobicity and on the other hand the low polarizability of fluorine atoms and the larger free volume of trifluoromethyl groups further gives polymers with lower dielectric constants due to the introduction of fluorine containing groups. Particularly, most fluorine atoms in the fluorine-containing polyarylether resin come from-CF 3 of bisphenol monomers, and the combination of large-volume-CF 3 into a polymer skeleton can not only enhance the solubility, flame retardance, thermal stability and glass transition temperature of the polymer, but also reduce the crystallinity, dielectric constant and water absorption of the polymer, so that the fluorine-containing polyarylether resin has great application prospect in low dielectric constant insulating materials, in particular to the proton exchange membrane, the optical waveguide device, the gas separation membrane and the like.
3. The bisphenol monomer with the rigid biphenyl or terphenyl structure synthesized by adopting the technical scheme of the invention can also provide good mechanical properties for the polymer, so that the synthesized polymer has good dielectric properties, hydrophobic properties and thermal stability, and also has good mechanical properties, thus obtaining a polyarylether resin product with excellent comprehensive properties.
4. The process provided by the invention has the characteristics of simple process, low energy consumption and the like, and the obtained polyarylether resin has the characteristics of low dielectric property, and is suitable for large-scale production.
Drawings
FIG. 1 is a 1 H NMR chart of 2,2' -bis (trifluoromethyl) diphenol biphenyl monomer prepared in example 1 of the present invention.
FIG. 2 is a schematic illustration of 2,2 "-bis (trifluoromethyl) - [1,1': 1 H NMR of 4',1 "-terphenyl ] -4, 4" -diphenol.
FIG. 3 is an infrared spectrum of the polyarylether resins prepared in examples 3 to 7 of the present invention.
FIG. 4 is a graph showing the thermal stability of the polyarylether resins prepared in examples 3 to 7 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application.
One aspect of an embodiment of the present invention provides a polyarylether having a repeating unit structure of formula I:
Wherein: r a represents the residue of a different biphenol or terphenyl bisphenol component, and R a is a bisphenol residue having the general structure of formula II or formula III;
R b represents the residue of different dihalogen monomer components, and R b is the residue of difluorodiphenyl sulfone (DFS), difluorobenzophenone (DFK), 1, 3-bis (4-fluorobenzoyl) benzene (BFBZ), decafluorobiphenyl (DFP), 4' -difluoro-3, 3' -bistrifluoromethyl-1, 1' -Biphenyl (BDTF);
Wherein R 1 in different substitution positions can be the same or different, R 2 in different substitution positions can be the same or different, and R 1 and R 2 can also be the same or different; r 1 and R 2 are selected from at least one or a combination of more of hydrogen, halogen, alkyl, haloalkyl or haloalkoxy.
The molecular weight of the polyarylether resin polymer is more than 5000g/mol, more preferably 10000-300000g/mol, and the molecular weight distribution is 1.2-2.5.
Another aspect of the embodiment of the present invention further provides a method for preparing the foregoing polyarylether resin, including:
Under the inert gas atmosphere, biphenyl bisphenol or terphenyl bisphenol, dihalogenated monomer, alkaline catalyst, high boiling point polar solvent and dehydrating agent are subjected to nucleophilic aromatic substitution reaction in the solvent at 25-180 ℃ to obtain the low dielectric constant polyarylether resin.
In some preferred embodiments, the molar ratio of biphenyl bisphenol or terphenyl bisphenol, dihalogenated monomer, basic catalyst, high boiling polar solvent to dehydrating agent is 1:1-1.05:2.2-3:20-30:30-50.
In some preferred embodiments, the biphenol satisfying the general structure of formula II may be selected from structures shown in any one or more of the following formulas:
In some more preferred embodiments, the biphenol satisfying the general structure of formula II may be selected from the structures shown in the following formulas:
in some preferred embodiments, the terphenyl bisphenol satisfying the general structure of formula III may be selected from at least one of the following formulas
In some more preferred embodiments, the terphenyl bisphenol satisfying the general structure of formula III is of the structure shown in the following formula:
In some preferred embodiments, the dihalogen monomer may be selected from structures shown in any one or more of the following formulas: one or more dihalogen monomers selected from difluorodiphenyl sulfone (DFS), difluorobenzophenone (DFK), 1, 3-bis (4-fluorobenzoyl) benzene (BFBZ), decafluorobiphenyl (DFP), 4' -difluoro-3, 3' -bistrifluoromethyl-1, 1' -Biphenyl (BDTF), 1, 4-bis (4-fluorobenzoyl) benzene (DFBK), 3, 5-Difluorobenzonitrile (DFBN), 2, 5-difluorotrifluoromethyl benzene (DFBTF) and derivatives thereof, are not limited thereto.
In some more preferred embodiments, the dihalogen monomer is difluorodiphenyl sulfone (DFS), difluorobenzophenone (DFK), 1, 3-bis (4-fluorobenzoyl) benzene (BFBZ), decafluorobiphenyl (DFP), 4' -difluoro-3, 3' -bistrifluoromethyl-1, 1' -Biphenyl (BDTF).
In some preferred embodiments, the basic catalyst may be selected from one of potassium carbonate, cesium fluoride, sodium carbonate, sodium fluoride, sodium bicarbonate, but is not limited thereto.
In some more preferred embodiments, the basic catalyst is potassium carbonate, cesium fluoride.
In some preferred embodiments, the high boiling polar solvent may be at least one selected from the group consisting of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, sulfolane, but is not limited thereto.
In some more preferred embodiments, the high boiling polar solvents are N-methylpyrrolidone and sulfolane.
In some preferred embodiments, the dehydrating agent may be selected from one of toluene, xylene, ethanol.
In some more preferred embodiments, the dehydrating agent is toluene.
Another aspect of the embodiment of the present invention further provides a method for synthesizing the Ra monomer, including:
In an inert gas atmosphere, carrying out coupling reaction on a borate monomer, a dihalogenated monomer, a catalyst and a solvent in the solvent at 70-110 ℃ to obtain the biphenyl bisphenol or terphenyl bisphenol monomer.
In some preferred embodiments, the molar ratio of borate monomer, halogenated monomer, catalyst, and solvent is 1:1-1.2:0.03-0.1:30-100.
In some preferred embodiments, the borate monomer may be selected from one of 4-hydroxy-2-trifluoromethylphenylboronic acid, 4-hydroxy-2-methylphenylboronic acid, (2-fluoro-4-hydroxyphenyl) boronic acid, 4-hydroxy-2-trifluoromethoxybenzeneboronic acid, 3-methyl-4-hydroxyphenylboronic acid, 3-fluoro-4-hydroxyphenylboronic acid, 1, 4-benzenediboronic acid bis (pinacol) ester.
In some more preferred embodiments, the borate monomers are 4-hydroxy-2-trifluoromethyl phenylboronic acid and 1, 4-phenyldiboronic acid bis (pinacol) ester.
In some preferred embodiments, the halogenated monomer may be selected from one of 3-trifluoromethyl-4-bromophenol, 2-bromo-4-fluoro-5-hydroxytrifluorotoluene, 4-bromo-3-methylphenol, 4-bromo-2, 5-dimethylphenol, 4-bromo-2-fluoro-5-methylphenol, 3-fluoro-4-bromophenol, 4-bromo-5-fluoro-2-methylphenol, 5-bromo-4-fluoro-2-hydroxytrifluorotoluene, 4-bromo-2, 5-difluorophenol, 4-bromo-3-trifluoromethoxy-phenol, 4-bromo-2-fluoro-5-trifluoromethoxyphenol.
In some more preferred embodiments, the halogenated monomer is 3-trifluoromethyl-4-bromophenol.
In some preferred embodiments, the catalyst may be selected from any one or a combination of two or more of tetra-triphenylphosphine palladium, DPPF palladium dichloride, palladium acetate, bis-triphenylphosphine palladium dichloride, (1, 1' -bis (diphenylphosphine) ferrocene) nickel dichloride. The catalyst is tetraphenylphosphine palladium and palladium acetate.
In some preferred embodiments, the solvent may be selected from any one or a combination of two or more of dioxane, toluene, xylene, tetrahydrofuran.
In some more preferred embodiments, the solvent is dioxane.
The polyarylether resin prepared by the invention can form a film on a glass plate, a metal surface or a silicon wafer by a tape casting method, and can be applied to the fields of aerospace, 5G communication antenna materials, gas separation films, hydrophobic materials and the like because the prepared polyarylether resin has low dielectric constant, low water absorption, high thermal stability and good mechanical properties.
According to the invention, trifluoromethyl is introduced into biphenyl bisphenol monomer and reacts with dihalogen monomer to obtain a series of low dielectric constant polyarylether, and the free volume of the polymer can be increased due to the bulky trifluoromethyl, so that the glass transition temperature (more than 170 ℃) is increased while the thermal stability (5% thermal decomposition temperature T d5％ is more than 550 ℃) is not reduced, and the low dielectric constant (less than 2.7) and low dielectric loss (less than 0.007) are also provided for the polymer.
The technical scheme of the invention is further described in detail through specific examples.
Example 1
The embodiment provides a method for synthesizing a monomer of 2,2 '-bis (trifluoromethyl) diphenol biphenyl, wherein the molecular structural formula of the 2,2' -bis (trifluoromethyl) diphenol biphenyl) is as follows:
The specific steps of synthesis include: concentrated sulfuric acid (80 mL) was poured into the reaction vessel, and 2,2' -bis (trifluoromethyl) diaminobiphenyl (32.0 g) was added to the concentrated sulfuric acid in portions of 5 to 10mg at room temperature, followed by magnetic stirring for 2 to 4 hours; at 0-5 ℃, naNO 2 (17 g) is dissolved in concentrated sulfuric acid (80 mL) in batches of 5-10 mg, and the solution is magnetically stirred until the solution is blue-violet; dripping NaNO 2 sulfuric acid solution prepared in the steps into the 2,2 '-bis (trifluoromethyl) diaminobiphenyl sulfuric acid solution prepared in the steps at the speed of 1-5 drops/second at the temperature of 0-5 ℃, magnetically stirring for 10 minutes, and standing for 2 hours to obtain 2,2' -bis (trifluoromethyl) diaminobiphenyl sulfuric acid diazonium salt solution with the yield of 72%; dropping the 2,2' -di (trifluoromethyl) diaminobiphenyl sulfate diazonium salt solution obtained in the step into 400mL of deionized water at a speed of 2 mL/sec; and pouring the solution into a reaction vessel, and refluxing for 3 hours at 120 ℃ to obtain black sticky solid with the yield of 65%. The nuclear magnetic hydrogen spectrum of the product prepared by the above reaction is shown in fig. 1: 1H NMR(400MHz,CDCl3 ppm) δ:10.19 (s, 2H), 7.11 (s, 2H), 7.10 (d, 2H), 7.01 (d, 2H), and the molecular structural formula synthesized in this example is shown in the graph
Washing the black sticky solid in the step with 400mL of ionized water at 120 ℃, pouring out the upper acidic solution, and washing for 3-4 times; the remaining black viscous solid was extracted with ethyl acetate (400 mL), and anhydrous magnesium sulfate (20 g) was added to remove water; spin-drying ethyl acetate by a rotary evaporator, and performing vacuum sublimation to obtain yellow crystals; the yellow crystals were washed in toluene, filtered and dried to give 2,2' -bis (trifluoromethyl) diphenol biphenyl in 26% yield.
Example 2
This example provides 2,2 "-bis (trifluoromethyl) - [1,1': method for synthesizing monomers of 4',1 "-terphenyl ] -4, 4" -diphenol, 2 "-bis (trifluoromethyl) - [1,1': the molecular structural formula of the 4', 1' -terphenyl ] -4, 4' -diphenol is as follows:
the specific steps of synthesis include:
1, 4-Benzodiboronic acid bis (pinacol) ester (3.4 g), 3-trifluoromethyl-4-bromophenol (5.0 g), cs 2CO3 (10.2 g) and dioxane (19 mL) were added to a reaction vessel and oxygen and water were removed from the system using anhydrous anaerobic operation; then adding 0.6g Pd (PPh 3)4) into a reaction vessel, adopting anhydrous and anaerobic operation again to remove oxygen and water in the system, placing the reaction vessel in the above-mentioned steps into an oil bath kettle, heating and refluxing at 120 deg.C for 24 hr under the protection of nitrogen gas, and making the obtained product implement nuclear magnetic analysis, and the nuclear magnetic hydrogen spectrum of the monomer obtained by means of the above-mentioned reaction is shown in figure 2, 1 H NMR (400 MHz, DMSO, ppm) delta: 10.19 (s, 2H), 7.30 (s, 4H), 7.27 (d, 2H), 7.17 (s, 2H) and 7.09 (s, 2H), and the structural formula of the monomer obtained by means of synthesis of this example is
The solid-liquid mixture obtained in the above step was extracted with a mixed solution of deionized water (200 mL) and methylene chloride (200 mL); the aqueous phase was extracted four times with dichloromethane (4×200 mL), the organic phase was collected and solid precipitated at low temperature, filtered by suction to give pale yellow crystals, dried and sublimated in vacuo to give 2,2 "-bis (trifluoromethyl) - [1,1':4',1 "-terphenyl ] -4, 4" -diphenol in 28% yield.
Example 3
This example provides a method for preparing polyarylether resin (FPAE-1).
The molecular structural formula of the polyarylether resin (FPAE-1) is as follows:
the preparation method comprises the following specific steps:
2,2' -bis (trifluoromethyl) diphenol biphenyl 2.9g (0.009 mol), difluorodiphenyl sulfone 2.3g (0.009 mol), 3.0g anhydrous potassium carbonate, 20 mLN-methylpyrrolidone and 30mL dry toluene were added to a 100mL three-neck flask equipped with a magnetic stirrer and a water separator, the temperature was raised to 140℃under the protection of nitrogen to reflux toluene, the azeotropic dehydrating agent was discharged in portions after 4 hours of reaction, and the temperature was raised to 180℃to react for 6 hours. The obtained polymer is separated out in 1% hydrochloric acid aqueous solution, and the fluorine-containing polyarylether is obtained after washing, redissolving, filtering, cable extracting and drying, and the yield is 93%.
Referring to FIG. 3, the infrared spectrograms of the products obtained by the preparation method show that characteristic absorption peaks of trifluoromethyl groups and aromatic ether bonds are respectively positioned at 1095cm -1 and 1205cm -1, and the FPAE-1 is successfully synthesized.
The polyarylether resin is formed into a film on a glass plate by adopting a tape casting method, and the film is not repeated in the prior art.
The thermal properties, dielectric properties and hydrophobic properties of the films were tested and the specific results are shown in table 1.
The dielectric constant of the film in this example was 2.59; the DMA measured a glass transition temperature of 226℃and the thermogravimetric analyzer measured a T d5％ of 514 ℃.
Example 4
The embodiment provides a preparation method of polyarylether resin (FPAE-2), wherein the molecular formula structure of the polyarylether resin is as follows
The preparation method comprises the following specific steps:
2,2' -bis (trifluoromethyl) diphenol biphenyl 2.7g (0.008 mol), difluorobenzophenone 1.8329g (0.008 mol), anhydrous potassium carbonate 2.5569g, 15mL of N-methylpyrrolidone and 30mL of dry toluene were added to a 100mL three-necked flask equipped with a magnetic stirrer and a water separator, the temperature was raised to 140℃under the protection of nitrogen to reflux toluene, the azeotropic dehydrating agent was discharged in portions after 4 hours of reaction, and the temperature was raised to 180℃to react for 6 hours. The obtained polymer is separated out in 1% hydrochloric acid aqueous solution, and the fluorine-containing polyarylether is obtained after washing, redissolving, filtering, cable extracting and drying, and the yield is 95%.
The infrared spectrogram of the product has characteristic absorption peaks of trifluoromethyl group and aromatic ether bond at 1095cm -1 and 1205cm -1 respectively, which proves that FPAE-2 is successfully synthesized.
The thermal properties, dielectric properties and hydrophobic properties of the films were tested and the specific results are shown in table 1.
The dielectric constant of the film was 2.80; the DMA measured a glass transition temperature of 187℃and the thermogravimetric analyzer measured a T d5％ of 529 ℃.
Example 5
The embodiment provides a preparation method of polyarylether resin (FPAE-3), wherein the molecular formula structure of the polyarylether resin is as follows:
the preparation method comprises the following specific steps:
2,2' -bis (trifluoromethyl) diphenol biphenyl 2.7g (0.008 mol), 1, 3-bis (4-fluorobenzoyl) benzene 2.7g (0.008 mol), 2.6g anhydrous potassium carbonate, 18 mLN-methylpyrrolidone and 30mL dry toluene were added to a 100mL three-necked flask equipped with a magnetic stirrer and a water separator, the temperature was raised to 140℃under nitrogen protection to reflux toluene, the azeotropic dehydrating agent was discharged in portions after the reaction for 6 hours, and the temperature was raised to 180℃to react for 6 hours. The obtained polymer is separated out in 1% hydrochloric acid aqueous solution, and the fluorine-containing polyarylether is obtained after washing, redissolving, filtering, cable extracting and drying, and the yield is 94%.
The infrared spectrogram of the product has characteristic absorption peaks of trifluoromethyl group and aromatic ether bond at 1095cm -1 and 1205cm -1 respectively, which proves that FPAE-3 is successfully synthesized.
The thermal properties, dielectric properties and hydrophobic properties of the films were tested and the specific results are shown in table 1.
The dielectric constant of the film is 2.64; the DMA measured a glass transition temperature of 178℃and the thermogravimetric analyzer measured a T d5％ of 534 ℃.
Example 6
The embodiment provides a preparation method of polyarylether resin (FPAE-4), wherein the molecular formula structure of the polyarylether resin is as follows:
the preparation method comprises the following specific steps:
1.5g (0.005 mol) of 2,2 '-bis (trifluoromethyl) diphenol biphenyl, 1.5g (0.005 mol) of 4,4' -difluoro-3, 3 '-bis (trifluoromethyl) -1,1' -biphenyl, 1.5g of anhydrous potassium carbonate, 10 mLN-methylpyrrolidone and 30mL of dry toluene were added to a 100mL three-necked flask equipped with a magnetic stirrer and a water separator, the temperature was raised to 140℃under the protection of nitrogen, the toluene was refluxed, the azeotropic dehydrating agent was discharged in portions after the reaction for 6 hours, and the reaction was carried out at 180℃for 6 hours. The obtained polymer is separated out in 1% hydrochloric acid aqueous solution, and the fluorine-containing polyarylether is obtained after washing, redissolving, filtering, cable extracting and drying, wherein the yield is 96%.
The infrared spectrogram of the product has characteristic absorption peaks of trifluoromethyl group and aromatic ether bond at 1095cm -1 and 1205cm -1 respectively, which proves that FPAE-4 is successfully synthesized.
The thermal properties, dielectric properties and hydrophobic properties of the films were tested and the specific results are shown in table 1.
The dielectric constant of the film is 2.06; the DMA measured a glass transition temperature of 195℃and the thermogravimetric analyzer measured a T d5％ of 555 ℃.
Example 7
The embodiment provides a preparation method of polyarylether resin (FPAE-4), wherein the molecular formula structure of the polyarylether resin is as follows:
the preparation method comprises the following specific steps:
1.4g (0.004 mol) of 2,2' -bis (trifluoromethyl) diphenol biphenyl, 1.4g (0.0042 mol) of decafluorobiphenyl, 1.9g (0.013 mol) of anhydrous cesium fluoride and 9 mLN-methylpyrrolidone were charged into a 100mL three-necked flask equipped with a magnetic stirrer and a water separator, and reacted at room temperature under the protection of nitrogen for 24 hours. And separating out the obtained polymer in a mixed solution of ethanol and water, washing, redissolving, filtering, carrying out cable extraction and drying to obtain the fluorine-containing polyarylether.
The infrared spectrogram of the product has characteristic absorption peaks of trifluoromethyl group and aromatic ether bond at 1095cm -1 and 1205cm -1 respectively, which proves that FPAE-5 is successfully synthesized.
The thermal properties, dielectric properties and hydrophobic properties of the films were tested and the specific results are shown in table 1.
The dielectric constant of the film is 2.27; the DMA measured a glass transition temperature of 200℃and the thermogravimetric analyzer measured a T d5％ of 548 ℃.
Table 1 examples provide thermal and dielectric properties of fluorine-containing polyarylether films
As can be seen from the above embodiments, the fluorine-containing polyarylether resin can be prepared by adopting the technical scheme provided by the technical scheme of the invention; meanwhile, as can be seen from table 1, the film prepared from the fluorine-containing polyarylether resin has low dielectric constant (D k is less than 3) and low dielectric loss (D f is less than 0.007), and has good dielectric properties; the glass transition temperature is higher than 170 ℃, and the glass transition temperature can maintain that the 5% thermal decomposition temperature (T d5％) is higher than 550 ℃, so that the glass transition temperature has good thermal stability; the polymer has excellent hydrophobic performance due to the introduction of a large amount of fluorine-containing groups, the water contact angle is more than 92.4 degrees, and the water absorption is less than 0.87.
The above is only a preferred embodiment of the present invention, which is not to be construed as limiting the scope of the present invention, and various modifications and variations of the present invention will be apparent to those skilled in the art. Variations, modifications, substitutions, integration and parameter changes may be made to these embodiments by conventional means or may be made to achieve the same functionality within the spirit and principles of the present invention without departing from such principles and spirit of the invention.
Claims (10)
1. A low dielectric fluorine-containing polyarylether resin is characterized in that the resin has a repeating unit structure shown in a general formula I:
wherein: r a is the residue of a different biphenol or terphenyl bisphenol component;
R b represents the residue of different dihalogen monomer components.
2. The low dielectric fluorine-containing polyarylether resin of claim 1,
R a is a bisphenol residue having a general structure shown in formula II or formula III:
Wherein R 1 in different substitution positions can be the same or different, R 2 in different substitution positions can be the same or different, and R 1 and R 2 can also be the same or different; r 1 and R 2 are selected from at least one or a combination of more of hydrogen, halogen, alkyl, haloalkyl or haloalkoxy;
The dihalogen monomer component is selected from any one or a combination of a plurality of difluoro diphenyl sulfone (DFS), difluoro diphenyl ketone (DFK), 1, 3-bis (4-fluoro benzoyl) benzene (BFBZ), decafluoro Diphenyl (DFP), 1' -biphenyl, 4' -difluoro-3, 3' -bis trifluoromethyl (BDTF), 1, 4-bis (4-fluoro benzoyl) benzene (DFBK), 3, 5-difluoro benzonitrile (DFBN), 2, 5-difluoro trifluoromethyl benzene (DFBTF) and derivatives thereof.
3. The low dielectric fluorine-containing polyarylether resin of claim 1, wherein the biphenyl bisphenol of the general structure of formula II is selected from at least one of the following structural formulas:
and/or, the terphenyl bisphenol with the general structure shown in the formula III is selected from at least one of the following structural formulas:
Wherein R b is selected from residues of two or more dihalogen monomers in difluorodiphenyl sulfone (DFS), difluorobenzophenone (DFK), 1, 3-bis (4-fluorobenzoyl) benzene (BFBZ), decafluorobiphenyl (DFP), 4' -difluoro-3, 3' -bistrifluoromethyl-1, 1' -Biphenyl (BDTF).
4. A low dielectric fluorine-containing polyarylether resin according to any one of claims 1 to 3, wherein the polyarylether resin has a molecular weight of more than 5000g/mol, preferably 10000 to 300000g/mol; the molecular weight distribution is 1.2-2.5.
5. A method for preparing the low dielectric fluorine-containing polyarylether resin according to any one of claims 1 to 4, comprising the following steps:
S1, providing bisphenol monomers; adding borate monomers, dihalogen monomers and catalysts into a first solvent in an inert gas atmosphere, uniformly mixing, and then carrying out coupling reaction at 70-110 ℃ to obtain biphenyl bisphenol or terphenyl bisphenol monomers, namely the bisphenol monomers;
S2, preparing polyarylether resin; comprises dissolving the biphenyl bisphenol or the terphenyl bisphenol, a dihalogen monomer and an alkaline catalyst in a second solvent under the inert gas atmosphere, and carrying out nucleophilic substitution reaction at 25-180 ℃, wherein the reaction product is the polyarylether resin.
6. The method for preparing a low dielectric fluorine-containing polyarylether resin according to claim 5, wherein in S1, the molar ratio of the borate monomer, the dihalogen monomer, the catalyst and the first solvent is 1:1-1.2:0.03-0.1:30-100;
And/or the borate monomer is selected from any one of 4-hydroxy-2-trifluoromethyl phenylboronic acid, 4-hydroxy-2-methyl phenylboronic acid, (2-fluoro-4-hydroxyphenyl) boric acid, 4-hydroxy-2-trifluoromethoxy phenylboronic acid, 3-methyl-4-hydroxy phenylboronic acid, 3-fluoro-4-hydroxy phenylboronic acid and 1, 4-phenyldiboronic acid bis (pinacol) ester;
And/or the dihalogen monomer is selected from any one or a combination of a plurality of 3-trifluoromethyl-4-bromophenol, 2-bromo-4-fluoro-5-hydroxytrifluorotoluene, 4-bromo-3-methylphenol, 4-bromo-2, 5-dimethylphenol, 4-bromo-2-fluoro-5-methylphenol, 3-fluoro-4-bromophenol, 4-bromo-5-fluoro-2-methylphenol, 5-bromo-4-fluoro-2-hydroxytrifluorotoluene, 4-bromo-2, 5-difluorophenol, 4-bromo-3-trifluoromethoxy-phenol, 4-bromo-2-fluoro-5-trifluoromethoxy-phenol;
And/or the catalyst comprises any one or a combination of a plurality of tetraphenylphosphine palladium, DPPF palladium dichloride, palladium acetate, bis triphenylphosphine palladium dichloride, (1, 1' -bis (diphenylphosphine) ferrocene) nickel dichloride;
And/or the first solvent comprises any one or more than two of dioxane, toluene, xylene and tetrahydrofuran.
7. The method for preparing a low dielectric fluorine-containing polyarylether resin according to claim 5, wherein in S2, the bisphenol monomer and the dihalogen monomer are taken as raw materials, the alkaline catalyst, the second solvent and the dehydrating agent are added into a reaction vessel, the temperature is raised to 140 ℃ in a nitrogen or argon protection atmosphere under the stirring condition so that the dehydrating agent flows back, the reaction is carried out for 4 to 6 hours, the azeotropic dehydrating agent is discharged in batches, and then the temperature is raised to 175 to 180 ℃ for reaction for 6 to 8 hours; separating out the obtained polymer in a 1% hydrochloric acid aqueous solution, washing, redissolving, filtering, carrying out cable extraction and drying to obtain the polyarylether resin with low dielectric constant;
And/or the mol ratio of bisphenol monomer, dihalogen monomer, alkaline catalyst, second solvent and dehydrating agent is 1:1-1.05:2.2-3:20-30:30-50;
And/or the alkaline catalyst is selected from any one of potassium carbonate, cesium fluoride, sodium carbonate, sodium fluoride and sodium bicarbonate;
And/or the second solvent is a high boiling point polar organic solvent; preferably, the second solvent is selected from any one of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, sulfolane.
And/or the dehydrating agent is selected from one of toluene, xylene and ethanol.
8. The method for preparing polyarylether resin according to claim 5, wherein in S2, the bisphenol monomer and the dihalogen monomer are used as raw materials, the alkaline catalyst and the second solvent are added into a reaction vessel, and the mixture is stirred in a nitrogen or argon protection atmosphere and reacted for 24 hours at room temperature; separating out the obtained polymer in a mixed solution of ethanol and water, washing, redissolving, filtering, carrying out cable extraction and drying to obtain the low dielectric constant polyarylether resin;
the mol ratio of the bisphenol monomer to the dihalogen monomer to the alkaline catalyst to the second solvent is 1:1-1.05:2.2-3:20-30;
And/or the alkaline catalyst is selected from any one of potassium carbonate, cesium fluoride, sodium carbonate, sodium fluoride and sodium bicarbonate;
and/or the second solvent is a high boiling point polar organic solvent, preferably, the second solvent is selected from any one of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide and sulfolane.
9. A polyarylether resin film, characterized by comprising being formed on a glass plate, a metal surface or a silicon wafer by a casting method with the polyarylether resin of any one of claims 1 to 3;
The glass transition temperature (T g) of the polyarylether resin film is more than 170 ℃, the dielectric constant (D k) is less than 3, and the dielectric loss is less than 0.007.
10. Use of the polyarylether resin of any one of claims 1-4 or the polyarylether resin film of claim 9 in the fields of aerospace, 5G communication antenna materials, gas separation membranes, and hydrophobic materials.
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