CN105777519A - Bisphenol or dual amine containing benzocyclobutene structure unit, preparation and application thereof - Google Patents
Bisphenol or dual amine containing benzocyclobutene structure unit, preparation and application thereof Download PDFInfo
- Publication number
- CN105777519A CN105777519A CN201410822005.2A CN201410822005A CN105777519A CN 105777519 A CN105777519 A CN 105777519A CN 201410822005 A CN201410822005 A CN 201410822005A CN 105777519 A CN105777519 A CN 105777519A
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- lower group
- benzocyclobutene
- acid
- 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.)
- Granted
Links
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical group C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 title claims abstract description 50
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229930185605 Bisphenol Natural products 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000001412 amines Chemical class 0.000 title abstract 2
- 230000009977 dual effect Effects 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 14
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 7
- -1 aryl anion Chemical class 0.000 claims description 44
- 150000004985 diamines Chemical class 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 26
- 239000003153 chemical reaction reagent Substances 0.000 claims description 25
- 239000002798 polar solvent Substances 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 239000000376 reactant Chemical class 0.000 claims description 12
- 125000001475 halogen functional group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 3
- 239000007848 Bronsted acid Substances 0.000 claims description 3
- 239000007818 Grignard reagent Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical class NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000005917 acylation reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 150000002989 phenols Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 22
- 238000010276 construction Methods 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 230000005311 nuclear magnetism Effects 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 5
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- 0 CCc1cc([N+])c(*)c(OC)c1 Chemical compound CCc1cc([N+])c(*)c(OC)c1 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229940090181 propyl acetate Drugs 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 3
- 150000007860 aryl ester derivatives Chemical class 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 2
- FGNYRBUGQDHVQT-UHFFFAOYSA-N O=C(C(F)(F)F)c1ccc(CC2)c2c1 Chemical compound O=C(C(F)(F)F)c1ccc(CC2)c2c1 FGNYRBUGQDHVQT-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012761 high-performance material Substances 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- JNYLMODTPLSLIF-UHFFFAOYSA-N 6-(trifluoromethyl)pyridine-3-carboxylic acid Chemical group OC(=O)C1=CC=C(C(F)(F)F)N=C1 JNYLMODTPLSLIF-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LNQJASVDIVMKKZ-UHFFFAOYSA-N Cc1c(CCC2)c2ccc1C[O]1NC1 Chemical compound Cc1c(CCC2)c2ccc1C[O]1NC1 LNQJASVDIVMKKZ-UHFFFAOYSA-N 0.000 description 1
- MXDIGWDXPDXHFP-UHFFFAOYSA-N Cc1ccc(C(C(F)(F)F)(c(cc2)ccc2O)c2cc(CC3)c3cc2)cc1 Chemical compound Cc1ccc(C(C(F)(F)F)(c(cc2)ccc2O)c2cc(CC3)c3cc2)cc1 MXDIGWDXPDXHFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CSGYZZZJQMDMAG-UHFFFAOYSA-N O=C(C(CC1)CC23C1C2CC3)C(F)(F)F Chemical compound O=C(C(CC1)CC23C1C2CC3)C(F)(F)F CSGYZZZJQMDMAG-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing six-membered aromatic rings and other rings, with unsaturation outside the aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
- C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/42—Halogenated derivatives containing six-membered aromatic rings and other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
- C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
- C08G64/10—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing halogens
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides a bisphenol or dual amine containing a benzocyclobutene structure unit, preparation and application thereof. Specifically, the preparation method consists of: taking 4-halogenated benzocyclobutene as the raw material, carrying out acylation reaction to obtain 4-acyl substituted benzocyclobutene, and reacting the latter with substituted phenol or aniline to obtain a compound shown as formula I, wherein all the groups are defined as the specification. The method provided by the invention has the characteristics of simple process, convenient operation and excellent yield, and is suitable for large-scale industrial production, and the obtained product has a curable group and can be used for preparation of novel high performance organic thermosetting materials. (formula I).
Description
Technical field
The invention belongs to the manufacture field of high-performance polymer intermediate, be specifically related to a class containing the bis-phenol of benzocyclobutene construction unit, the manufacture method of diamine and application thereof.
Background technology
Bisphenols, diamine compounds are the Organic Chemicals that two classes are important, and purposes is very extensive.At present, bisphenols or diamine compounds that this area is common have: bisphenol-A, Bisphenol F, bisphenol S, hexafluoro bisphenol-a, and 4,4 '-diaminodiphenyl ether, 4,4 '-MDA, DDS etc.:
Bisphenol compound can be used for producing the multiple macromolecular materials such as Merlon, epoxy resin, polyester resin, polysulfone resin, polyphenylene oxide resin, and diamine compounds then has important application in fields such as epoxy curing agent, polyimides, polyurethane, Merlon, polysulfone resin, phenolic aldehyde unsaturated-resins.Conventional bis-phenol, diamine such as bisphenol-A, 4,4 '-diaminodiphenyl ether etc., only two degrees of functionality, the polymer being usually formed is chain polymer, and the performance of resulting materials is closely related with molecular weight, for thermoplastic.But, thermoplastic is generally poor in high temperature resistant and rigidity, although polyimides excellent combination property therein, the fields such as Aero-Space, microelectronics, high-temperature resistant membrane it are widely used in, but the progress along with technology, the material of higher performance also shows that urgent demand, and wherein a big field is then the polyimides that research and development performance is more excellent.
Typically, improving molecular weight is a kind of conventional means improving polymer performance, lifting however as molecular weight, the aspect such as structure adaptability, machinability then has certain decline, in general, under not affecting the premise of polymer solubility and machinability, by introducing curable groups, by curing cross-linked, make polymer form network structure, be a kind of common method improving material property.For polyimides, by introducing curable end-capping group, it it is the conventional means improving its performance.The type reported mainly has norborene end-sealed type (J.App.Poly.Sci.1972,16,905.) and other are containing alkenyl segments end-sealed type, containing acetenyl end-sealed type (Macromolecules, 2003,36,6780.), maleimide end-sealed type (Polymer1996,37,5077.), cyano group and other carbon containings nitrogen unsaturated group end-sealed type (Polymer2009,50,1700.), epoxy-capped type and trialkoxysilane-capped (Polym.Prepr.1986,27,403.) type etc..
Benzocyclobutene is a kind of thermosetting group of releasing without little molecule when having high reaction activity and solidify, and its solidification temperature is low, and machinability and film property are good, and cured product color is shallower, have relatively low-k and high heat stability and receive much concern.If being introduced in little molecule by benzocyclobutene, synthesize new small molecule monomer so that it is become a part for main chain, or introduce polymer by the mode of copolymerization or doping, by a kind of controlled in the way of promote the performance of polymer.But, the cyclobutane construction unit in benzocyclobutene is very easy to open loop, therefore more difficult is introduced in polymerization single polymerization monomer.
In sum, benzocyclobutene construction unit can be effectively incorporated in bis-phenol or diamine compounds by this area in the urgent need to one, thus the method preparing polymerization single polymerization monomer.
Summary of the invention
It is an object of the invention to provide one can be effectively incorporated in bis-phenol or diamine compounds by benzocyclobutene construction unit, thus the method preparing polymerization single polymerization monomer.
A first aspect of the present invention a, it is provided that class has the compound of structure as shown in following formula I:
In formula,
Each R is each independently selected from lower group :-OH ,-NH2;
Each R1It is each independently selected from lower group: the alkyl of H, C1-C4;
R2Selected from lower group: the alkyl of H, C1-C4, C1-C4 haloalkyl (be preferably fluoro-alkyl).
In another preference, described compound of formula I is to prepare by the method comprised the following steps:
(ii) in polar solvent, carry out acylation reaction with formula III compound (4-halo benzocyclobutene), obtain formula II compound;
I (), in polar solvent, reacts with formula II compound, obtains type I compound;
Wherein, X is selected from lower group: halogen;The definition of all the other each groups is such as described in first aspect present invention.
In another preference, each described R1It is identical.
In another preference, each described R is identical.
In another preference, each described R is each independently selected from lower group :-OH ,-NH2;
Each R1It is each independently selected from lower group: H ,-CH3;
R2Selected from lower group: H ,-CH3、-CF3。
A second aspect of the present invention, it is provided that the preparation method of a kind of compounds I as described in the first aspect of the invention, described method includes step:
I (), in atent solvent, with reactant salt formed by formula II compound and Formulas I V compound or itself and acid, obtains type I compound;
Wherein, the definition of each group is such as described in first aspect present invention;Preferably, in described step (i), the mol ratio of formula II compound and Formulas I V compound is 1:1.5~5, it is preferred that for 1:2.5~3.
In another preference, described step (i) carries out in presence of an acid catalyst;It is preferred that in described step, formula II compound is 1:0.1~1 with sour ratio.
In another preference, in described step (i), described atent solvent is polar solvent;It is preferred that described polar solvent is selected from lower group: CH2Cl2、CHCl3、ClCH2CH2Cl, toluene, or its combination.
In another preference, in described step (i), described atent solvent is aniline.In another preference, in described step, the temperature of described reaction is 0~180 DEG C.
In another preference, in described step, the time of described reaction is 24~72 hours.
In another preference, salt formed by described Formulas I V compound and acid is the protic acid salt of Formulas I V compound.
In another preference, when each R is-OH, described method includes step:
(ia) in polar solvent, react with Formulas I V compound with formula II compound, obtain type I compound, and described step (ia) carries out in presence of an acid;It is preferred that described acid is Bronsted acid, more preferably selected from lower group: HCl, HBr, H2SO4、CH3SO3H、CF3SO3H, or its combination.
In another preference, in described step (ia), formula II compound is 1:0.1~1 with sour ratio.
In another preference, in described step (ia), the ratio of formula II compound and fortified phenol is 1:1.5~5, it is preferred that, ratio is 1:2.5~3.
In another preference, in described step (ia), described solvent is polar solvent;It is preferred that described polar solvent is selected from lower group: CH2Cl2, CHCl3, ClCH2CH2Cl, toluene, or its combination.
In another preference, in described step (ia), the temperature of described reaction is 0~80 DEG C.
In another preference, in described step (ia), the time of described reaction is 24~72 hours.
In another preference, when each R is-NH2Time, described method includes step:
(ib) in polar solvent, with reactant salt formed by formula II compound and Formulas I V compound or itself and acid, type I compound is obtained;
Preferably, described step (ib) carries out in presence of an acid;It is preferred that described acid is selected from lower group: HCl, HBr, H2SO4、CH3SO3H、CF3SO3H, or its combination.
In another preference, in described step (ib), formula II compound is 1:0.1~1 with sour ratio.
In another preference, in described step (ib), described solvent is Formulas I V compound (namely corresponding reactant aniline).
In another preference, in described step (ib), the temperature of described reaction is 100~180 DEG C.
In another preference, in described step (ib), the time of described reaction is 24~72 hours.
In another preference, when reactant is formula II compound and Formulas I V compound, described step (ib) carries out in presence of an acid.
In another preference, when reactant be formula II compound with Formulas I V compound and acid formed by salt time, described step (ib) carries out under not having sour existent condition.
In another preference, described method further comprises the steps of:
(ii) in polar solvent, react with formula III compound (4-halo benzocyclobutene) and acylating reagent, obtain formula II compound;
Wherein, X is selected from lower group: halogen;The definition of all the other each groups is such as described in first aspect present invention.
In another preference, described R2Selected from lower group: H ,-CH3、-CF3。
In another preference, described X is selected from lower group: Cl, Br.
In another preference, in described step (ii), described solvent is selected from lower group: oxolane, ether, methyltetrahydrofuran, methylcyclohexyl ether, or its combination.
In another preference, in described step (ii), described in the ratio of the aryl anion made and acylating reagent be 1:1~1.5.
In another preference, in described step (ii), the temperature of described reaction is-78~30 DEG C.
In another preference, in described step (ii), the time of described reaction is 1~10 hour.
In another preference, described step (ii) also includes: in polar solvent, prepares aryl anion with 4-halo benzocyclobutene, then reacts with acylating reagent, obtains formula II compound;Preferably, in described step (ii), described prepares the method for aryl anion selected from lower group with 4-halo benzocyclobutene:
(1) carry out lithium halogen exchange with formula III compound with alkyl lithium reagents (being preferably n-BuLi), obtain aryl lithium salts;Preferably, when preparing aryl anion by described method (1), described X is Br;Or
(2) react with formula III compound and magnesium metal, obtain aryl grignard reagent;Preferably, when preparing aryl anion by described method (2), described X is Cl or Br.
In another preference, in described method (1), described method carries out (being preferably-78 DEG C~-30 DEG C) at low temperatures.
In another preference, in described step (ii), described acylating reagent isWherein, R2Definition such as described in first aspect present invention;R is selected from lower group :-N (R ')2,-OR ', wherein, the alkyl that described R ' is C1-C4.
In another preference, described acylating reagent is selected from lower group: DMF, N,N-dimethylacetamide, ethyl acetate, propyl acetate, methyl acetate, Trifluoroacetic Acid Ethyl Ester, trifluoro-acetate.
In another preference, work as R2During for H, described acylating reagent is DMF.
In another preference, work as R2For CH3Time, described acylating reagent is selected from lower group: N,N-dimethylacetamide, ethyl acetate, propyl acetate, methyl acetate, or its combination.
In another preference, work as R2For CF3Time, described acylating reagent is selected from lower group: Trifluoroacetic Acid Ethyl Ester, trifluoro-acetate, or its combination.
A third aspect of the present invention, it is provided that a kind of compound as shown in Formula Il:
Wherein, described R2Haloalkyl (being preferably fluoro-alkyl) selected from lower group: C1-C4.
A fourth aspect of the present invention, it is provided that the purposes of a kind of compounds I as described in the first aspect of the invention, is used for:
A () prepares thermosets;
B existing goods are modified by () as the additive of bis-phenol or diamine goods, or prepare new material;
C () is used for preparing intermediate polymer.
A fifth aspect of the present invention, it is provided that a kind of polymer, described polymer is that use compound I as described in the first aspect of the invention carries out homopolymerization as monomer or prepared by copolymerization;Preferably, described polymer has the structure selected from lower group:
In another preference, described polymer is selected from lower group: polyester, polyethers, polyether-ether-ketone, polyimides, Polyurethane, polyisocyanate, poly-aryl esters, or Merlon.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus constituting new or preferred technical scheme.As space is limited, tired no longer one by one state at this.
Detailed description of the invention
The present inventor through long-term and deep research, is prepared for a kind of novel containing the bis-phenol of benzocyclobutene construction unit, diamine.Described bis-phenol, diamine contain curable groups, after as main material or additive, thermoplastic can be changed into thermosets.And said method reactions steps is simple, productivity is high, is especially suitable for industrialized production.Described bis-phenol, diamine can substitute existing raw material of industry bis-phenol, diamine, or jointly be polymerized with existing bis-phenol, diamine, thus preparing novel hot setting material, and then preparation has the cured product of property.Based on above-mentioned discovery, inventor completes the present invention.
Term
As used herein, term " bis-phenol " refers to the compound containing two phenolic hydroxyl groups, for instance conventional commercialization raw material of industry bisphenol-A, Bisphenol F, bisphenol S, hexafluoro bisphenol-a etc..Especially, a preferred bis-phenol of class is the bis-phenol containing benzocyclobutene construction unit provided by the present invention.
Term " diamine " refers to the compound with two aminophenyls, for instance the conventional commercialization raw material of industry 4,4 '-diaminodiphenyl ether, 4, and 4 '-MDA, DDS etc..Especially, a preferred diamine of class is the diamine containing benzocyclobutene construction unit provided by the present invention.
Term " halogen " refers to fluorine, chlorine, bromine, iodine.
Term " halo " refers to that the one or more hydrogen atoms on group are replaced by halogen.
Term " alkyl of C1~C6 " refers to the straight or branched alkyl with 1~6 carbon atom, such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, or similar group.
Bis-phenol or diamine containing benzocyclobutene construction unit
Consider that in industrialization, route is succinct, the features such as method is simple, the present inventor devise a class novel containing the bis-phenol of benzocyclobutene construction unit, diamine, using its as existing commercialization bis-phenol, diamine substitute or as additive be added on containing commercialization bis-phenol, diamine goods in, by the crosslinking that is heating and curing, to the new material that performance to be obtained is more excellent.
Provided by the invention containing the bis-phenol of benzocyclobutene construction unit, diamine, there is the structure shown in below formula I:
In formula,
Each R is each independently selected from lower group :-OH ,-NH2;
Each R1It is each independently selected from lower group: the alkyl of H, C1-C4;
R2Selected from lower group: the alkyl of H, C1-C4, C1-C4 haloalkyl (be preferably fluoro-alkyl).
In above-mentioned monomer, each R or R1May each be identical or different, it is preferable that each described R1It is identical;And/or each described R is identical.In a kind of highly preferred structure, each R1It is all identical with each R.
In a class preferred embodiment of the present invention, each described R is each independently selected from lower group :-OH ,-NH2;Each R1It is each independently selected from lower group: H ,-CH3;And R2Selected from lower group: H ,-CH3、-CF3。
Described bis-phenol or diamine can substitute existing bis-phenol or diamine, for the existing preparation using bis-phenol or diamine as the polymer of monomer, for instance polyester, polyethers, polyether-ether-ketone, polyimides, Polyurethane, polyisocyanate etc..The enforcement of preferred polymer is such as: poly-aryl esters, or Merlon.
Bis-phenol containing benzocyclobutene construction unit or the preparation of diamine
The preparation method that present invention also offers the above-mentioned compounds I of a class; described method is with 4-halo benzocyclobutene for raw material; obtaining the benzocyclobutene of 4-acyl substituted after acylation reaction, the latter obtains bis-phenol, the diamine monomer that benzocyclobutene is modified in acid condition with fortified phenol, aniline reaction.Described method reaction scheme is short, and productivity is high, it is adaptable to industrialized production.
Specifically, described method includes step:
I (), in atent solvent, is reacted with Formulas I V compound with formula II compound, is obtained type I compound;
Wherein, described in the literary composition as defined above of each group.
In above-mentioned reaction, the ratio of each raw material has no particular limits, it is preferable that in described step (i), and the mol ratio of formula II compound and Formulas I V compound is 1:1.5~5, it is preferred that for 1:2.5~3.
In another preference, described step (i) carries out in presence of an acid;Especially, due to the very easily open loop of cyclobutane construction unit, therefore, described acid preferably should possess moderate acidity, in order to enables this reaction to carry out, and will not make cyclobutane construction unit open loop.Inventor finds after screening, and Bronsted acid is (such as HCl, HBr, H2SO4、CH3SO3H、CF3SO3H etc.) less for the impact of benzocyclobutene construction unit in the reaction, substantially without causing benzocyclobutene open loop (still remaining stable for when the highest 150 DEG C) in course of reaction, and lewis acid is (such as ZnCl2、Al(OPh)3Deng) can cause that open loop occurs in benzocyclobutene construction unit at a higher temperature, cause that product yield is relatively low.For different reactants, it is possible to select corresponding most suitable acid.It is preferred that in described step, formula II compound is 1:0.1~1 with sour molar ratio.
Atent solvent in described step (i) has no particular limits, it is preferred that for polar solvent or phenyl amines solvent.In a preference of the present invention, described polar solvent is selected from lower group: CH2Cl2、CHCl3、ClCH2CH2Cl, toluene, or its combination.
The temperature of described hydrolytic polymerization has no particular limits, it is preferred that carry out (such as, 20-160 DEG C) at 0~180 DEG C.Preferably, described reaction temperature can be optimized according to the difference of reactant, and such optimization can be made in conjunction with prior art by those skilled in the art.
The described hydrolytic-polymeric reaction time has no particular limits, and method (such as TLC etc.) generally in the art can be adopted to determine the terminal of reaction, it is preferred that, the described response time is 24~72 hours.
Those skilled in the art can in conjunction with state of the art, preferred reaction conditions for different raw materials is optimized, after the structure of compound of formula I and above-mentioned preparation method are revealed, such change is apparent to those skilled in the art.
In some currently preferred embodiments of the present invention, when each R is-OH, described method includes step: (ia), in polar solvent, reacts with Formulas I V compound with formula II compound, obtaining type I compound, described step (ia) carries out in presence of an acid;It is preferred that described acid is chosen from the acid of lower group: HCl, HBr, H2SO4、CH3SO3H、CF3SO3H, or its combination.
In described step (ia), formula II compound is preferably 1:0.1~1 with sour ratio.
The ratio of each raw material has no particular limits, it is preferable that in described step (ia), and the ratio of formula II compound and fortified phenol is 1:1.5~5, it is preferred that, ratio is 1:2.5~3.
Solvent in described step (ia) is preferably polar solvent;It is preferred that described polar solvent is selected from lower group: CH2Cl2, CHCl3, ClCH2CH2Cl, toluene, or its combination.
In described step (ia), the temperature of described reaction is preferably 0~80 DEG C (such as 10-40 DEG C, or under room temperature).In another preference, in described step (ia), the time of described reaction is 24~72 hours.
In other preferred embodiments of the present invention, when each R is-NH2Time, described method includes step:
(ib) in polar solvent, react with Formulas I V compound with formula II compound, obtain type I compound, and described step (ib) carries out in presence of an acid;It is preferred that described acid is selected from lower group: HCl, HBr, H2SO4、 CH3SO3H、CF3SO3H, or its combination.
In described step (ib), formula II compound is preferably 1:0.1~1 with sour ratio.
Preferred solvent in a kind of described step (ib) is Formulas I V compound, namely corresponding reactant aniline.In described reaction, it is possible to be added without solvent, directly Formula II compound is dissolved in corresponding Formulas I V compound, is subsequently adding suitable acid and reacts.
In described step (ib), the temperature of described reaction is preferably 100~180 DEG C (such as 120-160 DEG C).In another preference, in described step (ib), the time of described reaction is 24~72 hours.
Described can be used as existing commercialization bis-phenol, diamine substitute containing the bis-phenol of benzocyclobutene construction unit, diamine, prepares high-performance thermosetting material;Can be used as additive to make an addition to containing in commercialization bis-phenol, diamine goods, existing goods are modified or prepare new material;Can be used as preparing the raw material of new polymers intermediate.
The preparation of formula II compound
Present invention also offers the preparation method that a kind of compound of formula I prepares intermediate formula II compound, described method adopts acylation reaction to introduce acyl group in benzocyclobutene structure, and described method includes step:
(ii) in polar solvent, react with formula III compound (4-halo benzocyclobutene) and acylating reagent, obtain formula II compound;
Wherein, X is selected from lower group: halogen;Described in the literary composition as defined above of all the other each groups.
In another preference, described R2Selected from lower group: H ,-CH3、-CF3。
In another preference, described X is selected from lower group: Cl, Br.
Described acylating reagent can be acylating reagent commonly used in the art, such as corresponding acyl chlorides, anhydride, amide etc., it is however preferred to have the reagent of following structure:
Wherein, R2Definition such as described in first aspect present invention, R is selected from lower group :-N (R ')2,-OR ', wherein, the alkyl that described R ' is C1-C4.In another preference, described acylating reagent is selected from lower group: DMF, N,N-dimethylacetamide, ethyl acetate, propyl acetate, methyl acetate, Trifluoroacetic Acid Ethyl Ester, trifluoro-acetate.
In the present invention, it is possible to according to required Formula II compound structure, select suitable acylating reagent.Such as, in the preference of the present invention, work as R2During for H, described acylating reagent is preferably DMF;Work as R2For CH3Time, described acylating reagent is preferably selected from the reagent of lower group: N,N-dimethylacetamide, ethyl acetate, propyl acetate, methyl acetate, or its combination;Work as R2For CF3Time, described acylating reagent is preferably selected from the reagent of lower group: Trifluoroacetic Acid Ethyl Ester, trifluoro-acetate, or its combination.
In described step (ii), described solvent is not particularly limited, it is therefore preferable to the solvent selected from lower group: oxolane, ether, methyltetrahydrofuran, methylcyclohexyl ether, or its combination.
In described step (ii), the ratio of each reactant has no particular limits, it is preferable that the ratio of described formula III compound and acylating reagent is 1:1~1.5.
In described step (ii), the temperature of described reaction preferably carries out at a lower temperature, and in a preference of the present invention, described reaction temperature is-100~40 DEG C.
In described step (ii), the time of described reaction has no particular limits, and method (such as TLC etc.) generally in the art can be adopted to determine the terminal of reaction, it is preferred that, the response time is 1~10 hour.
In the present invention, it is preferred to described step (ii) including: in polar solvent, with 4-halo benzocyclobutene and alkali reaction, prepare aryl anion, then react with acylating reagent again, obtain formula II compound.Described prepare the method for aryl anion with 4-halo benzocyclobutene and be preferably chosen from lower group:
(1) carry out lithium halogen exchange with formula III compound and n-BuLi, obtain aryl lithium salts;Preferably, when preparing aryl anion by described method (1), described X is Br;Or
(2) react with formula III compound and magnesium metal, obtain aryl grignard reagent;Preferably, when preparing aryl anion by described method (2), described X is Cl or Br.
In another preference, in described method (1), described method carries out (-78 DEG C~-30 DEG C) at low temperatures.In a preference of the present invention, described method (1) carries out at-78 ± 5 DEG C.
In another preference, in described method (2), described method at room temperature carries out, and especially, benzocyclobutene group will not be produced impact by described reaction.
Compared with prior art, the major advantage of the present invention includes:
(1) curable groups is introduced in bis-phenol, diamine side chain by simple method by the inventive method, simple to operate, good yields, and does not use the catalyst such as precious metal, creates advantage for large-scale industrial production.
(2) conventional and the bis-phenol of function admirable, diamine raw material have been carried out structural modification by the inventive method so that it is can be used to elevated cure, by the crosslinking of benzocyclobutene, can greatly improve the thermostability of material and rigidity;Meanwhile, performance under the room temperature of above-mentioned raw materials is not impacted.
(3) the inventive method may be used for preparing novel containing the bis-phenol of benzocyclobutene unit, diamine base polymer monomer, it is greatly enriched the kind of bisphenols, diamine base polymer monomeric compound, the development of high performance material is significant, meanwhile, also a kind of new thinking is provided for development high performance material monomeric compound.
(4) the inventive method technique is simple, easy and simple to handle, and good yields is adapted to large-scale industrial production.Products therefrom has curable groups, as replaced existing commercialization bis-phenol, diamine raw material with it or being added in existing bis-phenol, diamine goods by the mode such as copolymerization, doping, thermoplastic can be changed into thermosets, and then the heat-resisting and solvent resistance of raising material, Development of Novel high-performance organic material is significant.
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally conventionally condition, or according to manufacturer it is proposed that condition.Unless otherwise indicated, otherwise percentage ratio and number are calculated by weight.
The preparation of embodiment 14-acetyl group benzocyclobutene
At-78 DEG C, hexane solution (the 2.5M of butyl lithium it is slowly added dropwise in THF (150mL) solution of 4-bromine benzocyclobutene (10g), 26mL), after-78 DEG C of stirring 30min, it is slowly added dropwise DMAc (6.66g) wherein, stir 4h after being slowly increased to room temperature, be added thereto to saturated NaHCO3Solution (100mL) cancellation is reacted, extraction into ethyl acetate (100mLx3), saturated nacl aqueous solution washing organic facies, anhydrous MgSO4Dry, it is spin-dried for, column chromatography, petrol ether/ethyl acetate mixed solvent eluting, obtains white solid 5.92g, productivity 74%.
Nuclear-magnetism characterizes1HNMR(500MHz,CDCl3):δ7.71–7.52(m,1H),7.43–7.30(m,1H),6.95–6.84(m,1H),2.97(s,4H),2.33(s,3H);13CNMR(126MHz,CDCl3):δ197.21,151.28,145.39,135.78,127.18,121.90,121.76,29.33,28.87,25.95ppm;HRMS(m/z):[M]+calcdfor146.0732,found146.0730。
The preparation of embodiment 24-acetyl group benzocyclobutene
In 250mL flask, it is sequentially added into Mg (2.6g), THF (100mL) under room temperature, then is added thereto to an iodine.Another addition 4-bromine benzocyclobutene (10g) and THF (20mL) in Dropping funnel, thermal booster reaction is added with hair-dryer after instilling 5mL4-bromine benzocyclobutene solution in flask, control to drip speed after the color of iodine disappears, reactant is slowly dropped in flask, 30min is reacted after dropwising, it is slowly added dropwise DMAc (6.57g) wherein, after reaction 4h, is added thereto to saturated NaHCO3Solution (100mL), extraction into ethyl acetate (100mLx3), saturated nacl aqueous solution washing organic facies, anhydrous MgSO4Dry, it is spin-dried for, column chromatography, petrol ether/ethyl acetate mixed solvent eluting, obtains white solid 5.73g, productivity 72%.
Nuclear-magnetism characterizes1HNMR(500MHz,CDCl3):δ7.71–7.52(m,1H),7.43–7.30(m,1H),6.95–6.84(m,1H),2.97(s,4H),2.33(s,3H);13CNMR(126MHz,CDCl3):δ197.21,151.28,145.39,135.78,127.18,121.90,121.76,29.33,28.87,25.95ppm;HRMS(m/z):[M]+calcdfor146.0732,found146.0730。
The preparation of embodiment 34-trifluoroacetyl group benzocyclobutene
Adopt with method identical in embodiment 1 or embodiment 2, but DMAc Trifluoroacetic Acid Ethyl Ester substitutes, and can obtain 4-trifluoroacetyl group benzocyclobutene, colourless liquid.Yield, 76%.
Nuclear-magnetism characterizes1HNMR(400MHz,CDCl3): δ 7.97 (d, J=7.8Hz, 1H), 7.73 (s, 1H), 7.22 (d, J=7.9Hz, 1H), 3.27 (s, 4H);13CNMR(126MHz,CDCl3): δ 180.44 (q, J=34.26Hz), 155.27,146.68,129.71,128.91,123.73,123.13,117.00 (q, J=291.67Hz), 30.13,29.32;19FNMR(376MHz,CDCl3):δ-70.93.HRMS(m/z):[M]+calcdfor200.0449,found200.0448。
The preparation of embodiment 4 trifluoromethyl benzo cyclobutane bis-phenol
To the CHCl of 4-trifluoroacetyl group benzocyclobutene (400mg) under room temperature3(4mL) solution adds phenol (500mg), under stirring, drip CF wherein3SO3H (0.1mL), room temperature reaction overnight after, sucking filtration remove filtrate, filtering residue CHCl3Washing, then carry out column chromatography, petrol ether/ethyl acetate eluting, obtain white solid 530mg, productivity 72%.
Nuclear-magnetism characterizes1HNMR(500MHz,CD3: δ 6.93 (d, J=8.7Hz, 5H), OD) 6.83 (d, J=7.9Hz, 1H), 6.80 (s, 1H), 6.70 (d, J=8.9Hz, 4H), 4.90 (s, 2H), 3.03 (dd, J=15.7,4.3Hz, 4H);13CNMR(126MHz,CD3OD): δ 157.57,146.33,146.11,140.97,133.07,132.30,129.85,129.80 (q, J=285.92Hz), 125.12,122.87,115.63,65.57 (q, J=23.48Hz), 30.10,29.92;19FNMR(376MHz,acetone):δ-59.06.HRMS(m/z):[M]+calcdfor370.1181,found370.1179。
The preparation of embodiment 5 methyl benzocyclobutene bis-phenol
Adopt same procedure in embodiment 4 can obtain methyl benzocyclobutene bis-phenol, white solid.
Nuclear-magnetism characterizes1HNMR(400MHz,CD3OD):δ6.92–6.79(m,6H),6.71(s,1H),6.68–6.61(m,4H),4.86(s,2H),3.08(m,4H),2.03(s,3H);13CNMR(126MHz,CD3OD):δ156.31,150.45,146.07,144.10,142.41,130.93,128.63,124.03,122.55,115.43,52.71,31.74,30.11,29.85.HRMS(m/z):[M]+calcdfor316.1463,found316.1458。
The preparation of embodiment 6 trifluoromethyl benzo cyclobutane diamine
In aniline (4mL) solution of 4-trifluoroacetyl group benzocyclobutene (400mg), CF is added under stirring under room temperature3SO3H (0.1mL), after 140 DEG C of reaction 48h, is made directly column chromatography, petrol ether/ethyl acetate eluting, obtains yellow solid 612mg, productivity 83%.
Nuclear-magnetism characterizes1HNMR(500MHz,CD3OD): δ 6.94 (d, J=7.9Hz, 1H), 6.89 (d, J=7.9Hz, 1H), 6.85 6.79 (m, 4H), 6.61 (d, J=8.7Hz, 3H), 4.85 (s, 4H), 3.14 3.06 (m, 3H).13CNMR(126MHz,CD3OD): δ 146.53,144.81,144.55,140.00,130.46,130.10,128.58 (q, J=286.07), 128.54,123.78,121.29,114.21,64.13 (q, 22.95), 28.65,28.49;19FNMR(376MHz,acetone):δ-59.02;HRMS(m/z):[M]+calcdfor368.1500,found368.1501。
The preparation of embodiment 7 methyl benzocyclobutene diamine
Adopt same procedure in embodiment 6 can obtain methyl benzocyclobutene diamine, yellow solid.
Nuclear-magnetism characterizes1HNMR(400MHz,CD3OD): δ 6.88 (d, J=7.8Hz, 1H), 6.84 (d, J=7.8Hz, 1H), 6.80 (d, J=8.5Hz, 4H), 6.71 (s, 1H), 6.61 (d, J=8.5Hz, 4H), 4.86 (s, 4H), 3.09 (m, 4H), 2.00 (s, 3H);13CNMR(126MHz,CD3OD):δ150.64,145.93,145.92,143.90,141.47,130.57,128.61,124.06,122.48,116.14,52.60,31.61,30.11,29.86.HRMS(m/z):[M]+calcdfor314.1783,found314.1788。
The preparation of embodiment 7 trifluoromethyl benzo cyclobutane diamine
Adopt the method that embodiment 6 is identical, but trifluoromethanesulfonic acid anilinechloride is substituted, trifluoromethyl benzo cyclobutane diamine can be obtained.
Nuclear-magnetism characterizes1HNMR(500MHz,CD3OD): δ 6.94 (d, J=7.9Hz, 1H), 6.89 (d, J=7.9Hz, 1H), 6.85 6.79 (m, 4H), 6.61 (d, J=8.7Hz, 3H), 4.85 (s, 4H), 3.14 3.06 (m, 3H).13CNMR(126MHz,CD3OD): δ 146.53,144.81,144.55,140.00,130.46,130.10,128.58 (q, J=286.07), 128.54,123.78,121.29,114.21,64.13 (q, 22.95), 28.65,28.49;19FNMR(376MHz,acetone):δ-59.02;HRMS(m/z):[M]+calcdfor368.1500,found368.1501。
The preparation of embodiment 8 trifluoromethyl benzo cyclobutane diamine
Adopt the method that embodiment 6 is identical, but trifluoromethanesulfonic acid aniline sulfate is substituted, trifluoromethyl benzo cyclobutane diamine can be obtained.
Nuclear-magnetism characterizes1HNMR(500MHz,CD3OD): δ 6.94 (d, J=7.9Hz, 1H), 6.89 (d, J=7.9Hz, 1H), 6.85 6.79 (m, 4H), 6.61 (d, J=8.7Hz, 3H), 4.85 (s, 4H), 3.14 3.06 (m, 3H).13CNMR(126MHz,CD3OD): δ 146.53,144.81,144.55,140.00,130.46,130.10,128.58 (q, J=286.07), 128.54,123.78,121.29,114.21,64.13 (q, 22.95), 28.65,28.49;19FNMR(376MHz,acetone):δ-59.02;HRMS(m/z):[M]+calcdfor368.1500,found368.1501。
The preparation of the embodiment 9 poly-aryl esters containing benzocyclobutene structure
To the CH of trifluoromethyl benzo cyclobutane bis-phenol (412mg) and paraphthaloyl chloride (226mg) under ice bath2Cl2(3mL), in solution, it is slowly added dropwise Et3N (1.5mL), dropwises recession deicing bath, reacts 2d, be added thereto to H2O (100mL), CH2Cl2Extract (50mLx3), the anhydrous MgSO of organic facies4Dry, rotation is dissolved in a small amount of (2mL) CH after solvent is evaporated off2Cl2In, sedimentation in MeOH (100mL), sucking filtration, anhydrous MeOH washs, and filtering residue is dissolved in CH again2Cl2In, and again settle, sucking filtration, obtain white solid 512mg, productivity 92% after 80 DEG C of vacuum drying 8h.
Nuclear-magnetism characterizes1HNMR(400MHz,CDCl3) δ 8.33 (d, J=3.7Hz, 4H), 7.31 7.16 (m, 8H), 7.01 (q, J=8.3Hz, 2H), 6.87 (s, 1H), 3.18 (d, J=2.0Hz, 4H).13CNMR(126MHz,CDCl3): δ 164.02,150.15,145.79,145.74,138.32,138.23,133.87,131.35,130.39,128.76,124.15,122.43,121.19,64.98 (q, J=23.48Hz), 29.65,29.47;19FNMR(376MHz,CDCl3)δ-58.37。
Embodiment 10 is containing the preparation of the Merlon of benzocyclobutene structure
To the Et of trifluoromethyl benzo cyclobutane bis-phenol (402mg) under ice bath3In N (1.5mL) solution, it is slowly added dropwise the CH of triphosgene (145mg)2Cl2(3mL) solution, dropwises recession deicing bath, reacts 2d, be added thereto to H2O (100mL), CH2Cl2Extract (50mLx3), the anhydrous MgSO of organic facies4Dry, rotation is dissolved in a small amount of (2mL) CH after solvent is evaporated off2Cl2In, sedimentation in MeOH (100mL), sucking filtration, anhydrous MeOH washs, and filtering residue is dissolved in CH again2Cl2In, and again settle, sucking filtration, obtain white solid 413mg, productivity 96% after 80 DEG C of vacuum drying 8h.
Nuclear-magnetism characterizes1HNMR(400MHz,CDCl3): δ 7.33 (dd, J=18.6,9.4Hz, 8H), 7.11 (d, J=7.8Hz, 1H), 7.04 (d, J=8.2Hz, 1H), 6.93 (s, 1H), 3.27 (d, J=4.0Hz, 1H);13CNMR(126MHz,CDCl3) δ 151.73,150.39,145.90,145.87,138.47,138.22,131.41,128.76,127.94 (q, J=286.9Hz) .124.14,122.52,120.56,64.98 (q, J=23.6Hz) .29.70,29.52;19FNMR(376MHz,CDCl3):δ-58.35。
The all documents mentioned in the present invention are incorporated as reference all in this application, are individually recited as reference such just as each section of document.In addition, it is to be understood that after the above-mentioned teachings having read the present invention, the present invention can be made various changes or modifications by those skilled in the art, these equivalent form of values fall within the application appended claims limited range equally.
Claims (10)
1. a class has the compound of structure as shown in following formula I:
In formula,
Each R is each independently selected from lower group :-OH ,-NH2;
Each R1It is each independently selected from lower group: the alkyl of H, C1-C4;
R2Selected from lower group: the alkyl of H, C1-C4, C1-C4 haloalkyl.
2. compound of formula I as claimed in claim 1, it is characterised in that each described R is each independently selected from lower group :-OH ,-NH2;
Each R1It is each independently selected from lower group: H ,-CH3;
R2Selected from lower group: H ,-CH3、-CF3。
3. the preparation method of compounds I as claimed in claim 1, it is characterised in that described method includes step:
I (), in atent solvent, with formula II compound and Formulas I V compound, or reactant salt formed by itself and acid, obtains type I compound;
Wherein, the definition of each group is as described in the appended claim 1;Preferably, in described step (i), the mol ratio of formula II compound and Formulas I V compound is 1:1.5~5, it is preferred that for 1:2.5~3.
4. preparation method as claimed in claim 3, it is characterised in that when each R is-OH, described method includes step:
(ia) in polar solvent, react with Formulas I V compound with formula II compound, obtain type I compound, and described step (ia) carries out in presence of an acid;It is preferred that described acid is Bronsted acid, more preferably selected from lower group: HCl, HBr, H2SO4、CH3SO3H、CF3SO3H, or its combination.
5. preparation method as claimed in claim 3, it is characterised in that when each R is-NH2Time, described method includes step:
(ib) in polar solvent, with reactant salt formed by formula II compound and Formulas I V compound or itself and acid, type I compound is obtained;
Preferably, described step (ib) carries out in presence of an acid;It is preferred that described acid is selected from lower group: HCl, HBr, H2SO4、CH3SO3H、CF3SO3H, or its combination.
6. the preparation method of formula II compound as claimed in claim 1, it is characterised in that described method further comprises the steps of:
(ii) in polar solvent, react with formula III compound (4-halo benzocyclobutene) and acylating reagent, obtain formula II compound;
Wherein, X is selected from lower group: halogen;The definition of all the other each groups is as described in the appended claim 1.
7. method as claimed in claim 6, it is characterised in that described step (ii) also includes: in polar solvent, prepares aryl anion with 4-halo benzocyclobutene, then reacts with acylating reagent, obtains formula II compound;Preferably, in described step (ii), described prepares the method for aryl anion selected from lower group with 4-halo benzocyclobutene:
(1) carry out lithium halogen exchange with formula III compound and alkyl lithium reagents, obtain aryl lithium salts;Preferably, when preparing aryl anion by described method (1), described X is Br;Or
(2) react with formula III compound and magnesium metal, obtain aryl grignard reagent;Preferably, when preparing aryl anion by described method (2), described X is Cl or Br.
8. the compound as shown in Formula Il:
Wherein, described R2Haloalkyl (being preferably fluoro-alkyl) selected from lower group: C1-C4.
9. the purposes of compounds I as claimed in claim 1, it is characterised in that be used for:
A () prepares thermosets;
B existing goods are modified by () as the additive of bis-phenol or diamine goods, or prepare new material;
C () is used for preparing intermediate polymer.
10. a polymer, it is characterised in that described polymer carries out homopolymerization with compound I as claimed in claim 1 as monomer or prepared by copolymerization;Preferably, described polymer has the structure selected from lower group:
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CN110407713A (en) * | 2019-07-12 | 2019-11-05 | 中国林业科学研究院林产化学工业研究所 | A kind of binary abietyl benzocyclobutene monomer and its preparation method and application |
CN113683516A (en) * | 2021-08-25 | 2021-11-23 | 中国科学院过程工程研究所 | Diamine monomer and preparation method and application thereof |
CN118108661A (en) * | 2024-01-25 | 2024-05-31 | 波米科技有限公司 | Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof |
CN118125972A (en) * | 2024-01-25 | 2024-06-04 | 波米科技有限公司 | Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof |
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CN110407713A (en) * | 2019-07-12 | 2019-11-05 | 中国林业科学研究院林产化学工业研究所 | A kind of binary abietyl benzocyclobutene monomer and its preparation method and application |
CN113683516A (en) * | 2021-08-25 | 2021-11-23 | 中国科学院过程工程研究所 | Diamine monomer and preparation method and application thereof |
CN118108661A (en) * | 2024-01-25 | 2024-05-31 | 波米科技有限公司 | Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof |
CN118125972A (en) * | 2024-01-25 | 2024-06-04 | 波米科技有限公司 | Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof |
CN118108661B (en) * | 2024-01-25 | 2024-09-20 | 波米科技有限公司 | Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof |
CN118125972B (en) * | 2024-01-25 | 2024-09-20 | 波米科技有限公司 | Diamine monomer with nitrogen heterocycle and benzocyclobutene structure, and preparation method and application thereof |
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