CN118027089A - Double-curable epoxy-terminated polysiloxane and preparation method thereof - Google Patents
Double-curable epoxy-terminated polysiloxane and preparation method thereof Download PDFInfo
- Publication number
- CN118027089A CN118027089A CN202211426821.2A CN202211426821A CN118027089A CN 118027089 A CN118027089 A CN 118027089A CN 202211426821 A CN202211426821 A CN 202211426821A CN 118027089 A CN118027089 A CN 118027089A
- Authority
- CN
- China
- Prior art keywords
- epoxy
- group
- terminated polysiloxane
- formula
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 polysiloxane Polymers 0.000 title claims abstract description 68
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004593 Epoxy Substances 0.000 claims description 46
- 125000003118 aryl group Chemical group 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 21
- 239000003822 epoxy resin Substances 0.000 claims description 20
- 229920000647 polyepoxide Polymers 0.000 claims description 20
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 16
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 238000006467 substitution reaction Methods 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 239000012442 inert solvent Substances 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000001033 ether group Chemical group 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 125000006585 (C6-C10) arylene group Chemical group 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000013466 adhesive and sealant Substances 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000003566 oxetanyl group Chemical group 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 150000004292 cyclic ethers Chemical group 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 37
- 238000001723 curing Methods 0.000 description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 229940125904 compound 1 Drugs 0.000 description 26
- 229920002635 polyurethane Polymers 0.000 description 15
- 239000004814 polyurethane Substances 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 125000002091 cationic group Chemical group 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 6
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 4
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 4
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 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 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LBDSQNRQXIKAGX-UHFFFAOYSA-N (2-methyl-3-prop-2-enoyloxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(C)COC(=O)C=C LBDSQNRQXIKAGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 239000002519 antifouling agent Substances 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- BYOIQYHAYWYSCZ-UHFFFAOYSA-N prop-2-enoxysilane Chemical compound [SiH3]OCC=C BYOIQYHAYWYSCZ-UHFFFAOYSA-N 0.000 description 3
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical group [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 2
- OWDBMKZHFCSOOL-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)propoxy]propoxy]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(C)COC(C)COC(=O)C(C)=C OWDBMKZHFCSOOL-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- PAJMOXXWTLYTRV-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.NC(=O)OCC Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.NC(=O)OCC PAJMOXXWTLYTRV-UHFFFAOYSA-N 0.000 description 2
- TXURCWMDHWRYAG-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.NC(=O)OCC Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.NC(=O)OCC TXURCWMDHWRYAG-UHFFFAOYSA-N 0.000 description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- MMJKMQNOUIUZOJ-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.Nc1nc(N)nc(N)n1 Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.Nc1nc(N)nc(N)n1 MMJKMQNOUIUZOJ-UHFFFAOYSA-N 0.000 description 2
- BTMIECIFLDYMQD-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(N)=O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCOC(N)=O BTMIECIFLDYMQD-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 2
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical group C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-M pentadecanoate Chemical compound CCCCCCCCCCCCCCC([O-])=O WQEPLUUGTLDZJY-UHFFFAOYSA-M 0.000 description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- ICCCRCJXHNMZPJ-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) 2,2-dimethyl-3-prop-2-enoyloxypropanoate Chemical compound C=CC(=O)OCC(C)(C)COC(=O)C(C)(C)COC(=O)C=C ICCCRCJXHNMZPJ-UHFFFAOYSA-N 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- 125000006570 (C5-C6) heteroaryl group Chemical group 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AZOWOQZGIRYDQP-UHFFFAOYSA-N 2-methylidenepentanedioic acid 3-prop-2-enoyloxypropanoic acid Chemical compound C(=O)(O)CCC(C(=O)O)=C.C(C=C)(=O)OCCC(=O)O AZOWOQZGIRYDQP-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical class C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- AYHYUFMTBQUNJY-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate 8-methyl-2-methylidenenonanoic acid Chemical compound C(CCCCC(C)C)C(C(=O)O)=C.C(C=C)(=O)OCCCCCC(C)C AYHYUFMTBQUNJY-UHFFFAOYSA-N 0.000 description 1
- NWEXGPDHZMOVQY-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.OCC(C(=O)OC(C(CO)(C)C)=O)(C)C Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.OCC(C(=O)OC(C(CO)(C)C)=O)(C)C NWEXGPDHZMOVQY-UHFFFAOYSA-N 0.000 description 1
- HICDDSFDZHUQGX-UHFFFAOYSA-N C(CCCCCCC(C)C)C(C(=O)O)=C.C(C=C)(=O)OCCCCCCCC(C)C Chemical compound C(CCCCCCC(C)C)C(C(=O)O)=C.C(C=C)(=O)OCCCCCCCC(C)C HICDDSFDZHUQGX-UHFFFAOYSA-N 0.000 description 1
- ZPDOTKGATQLGNG-UHFFFAOYSA-N C(CCCCCCCCCCC)C=C(C(=O)O)C.C(C(=C)C)(=O)O.C(CCCCCCCCCCC)(=O)O Chemical compound C(CCCCCCCCCCC)C=C(C(=O)O)C.C(C(=C)C)(=O)O.C(CCCCCCCCCCC)(=O)O ZPDOTKGATQLGNG-UHFFFAOYSA-N 0.000 description 1
- WWQUWBYVGYUBNP-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)C=C(C(=O)O)C.C(CCCCCCCCCCCCCCCCC)(=O)O.C(C(=C)C)(=O)O Chemical compound C(CCCCCCCCCCCCCCCCC)C=C(C(=O)O)C.C(CCCCCCCCCCCCCCCCC)(=O)O.C(C(=C)C)(=O)O WWQUWBYVGYUBNP-UHFFFAOYSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- NACQHSBXBWRCAM-UHFFFAOYSA-N CCCCC(C)(COC(C=C)=O)COC(C=C)=O Chemical compound CCCCC(C)(COC(C=C)=O)COC(C=C)=O NACQHSBXBWRCAM-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- NFSAGZMETYAGKX-UHFFFAOYSA-N O(C1=CC=CC=C1)CCC(C(=O)O)=C.C(C=C)(=O)OCCOC1=CC=CC=C1 Chemical compound O(C1=CC=CC=C1)CCC(C(=O)O)=C.C(C=C)(=O)OCCOC1=CC=CC=C1 NFSAGZMETYAGKX-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- GVMYIWIPPADCPW-UHFFFAOYSA-N OC(=O)C(=C)Cc1ccccc1.C=CC(=O)OCc1ccccc1 Chemical compound OC(=O)C(=C)Cc1ccccc1.C=CC(=O)OCc1ccccc1 GVMYIWIPPADCPW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- VLVZXTNDRFWYLF-UHFFFAOYSA-N [2-ethyl-2-(prop-2-enoyloxymethyl)hexyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CC)(CCCC)COC(=O)C=C VLVZXTNDRFWYLF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N anhydrous methyl formate Natural products COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- BLMPUZAOLNGPQT-UHFFFAOYSA-N cyclohexylmethyl formate Chemical compound O=COCC1CCCCC1 BLMPUZAOLNGPQT-UHFFFAOYSA-N 0.000 description 1
- 230000001335 demethylating effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WTRRGIQUWPQIEA-UHFFFAOYSA-N methyl prop-2-enoate propane Chemical compound CCC.COC(C=C)=O WTRRGIQUWPQIEA-UHFFFAOYSA-N 0.000 description 1
- IQSHMXAZFHORGY-UHFFFAOYSA-N methyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound COC(=O)C=C.CC(=C)C(O)=O IQSHMXAZFHORGY-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000006120 scratch resistant coating Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin 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
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 125000005409 triarylsulfonium group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/089—Treatments not covered by a preceding group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a double-curable epoxy-terminated polysiloxane and a preparation method thereof. Specifically, the invention provides an epoxy-terminated polysiloxane which has a plurality of crosslinking groups, has strong cohesive force and can be widely applied to various fields; and the preparation method is simple and efficient.
Description
Technical Field
The invention belongs to the field of epoxy organopolysiloxane, and in particular relates to double-curable terminal epoxy polysiloxane and a preparation method thereof.
Background
Epoxy resins are high molecular polymers, which are a generic term for a class of polymers that contain more than two epoxy groups in the molecule. The paint containing a large amount of epoxy groups in the composition is generally called an epoxy paint. Epoxy resins are an important thermosetting resin. After the pure epoxy resin is cured, the chemical crosslinking density is high, the molecular chain flexibility is low, the internal stress is large, the brittleness of the epoxy resin cured substance is large, the impact resistance and fatigue resistance durability are poor, and therefore the application range of the epoxy resin cured substance is limited.
In view of the above, it is needed to find a polymer material with high mechanical strength, toughness and high and low temperature resistance, which overcomes the defects of epoxy resin.
Disclosure of Invention
The invention aims to provide a double-curable epoxy-terminated polysiloxane and a preparation method thereof.
In a first aspect of the present invention, there is provided an epoxy-terminated polysiloxane having the structure of formula (0):
Y-X-Y formula (0);
Wherein X has at least four groups of structures of formula (III):
- { [ OSi (R) 2-]k -L } -formula (iii);
Wherein each R is independently R 1、R2、R3, k is a positive integer from 1 to 100, and k in each group is the same or different; wherein each R 1、R2、R3 is independently a substituted or unsubstituted group selected from the group consisting of: linear or branched C 1-25 alkyl, linear or branched C 1-25 alkoxy, C 3-25 cycloalkyl, C 6-22 aryl, 5-to 20-membered heteroaryl, C 6-25 aryloxy, C 2-25 cyclic ether group; the substitution means substitution with a group selected from the group consisting of: halogen, hydroxy, C 1-8 alkyl, C 2-8 alkenyl, C 6-10 aryl;
L is- (L 1)n -; and each L 1 is independently selected from the group consisting of substituted or unsubstituted C 1-10 alkylene, substituted or unsubstituted C 2-30 acyl, substituted or unsubstituted C 2-30 ester, and each group between each L 1 is optionally interrupted by oxygen and C 6-10 arylene, n is selected from the group consisting of 1,2,3,4,5,6,7,8,9, 10;
Y is selected from the group consisting of: (CH 2OCH)-C2-16 straight-chain or branched-chain alkyl, (CH 2OCH)-C2-16 straight-chain or branched-chain alkoxy, C 3-25 epoxy ether group and C 3-25 epoxy cycloalkyl, wherein the epoxy cycloalkyl is epoxy and cycloalkyl.
In another preferred embodiment, the epoxy-terminated polysiloxane has the structure of formula (I):
r 1、R2、R3, L, Y are as defined in the first aspect of the invention;
s is 0 or a positive integer from 1 to 100;
q and t are each independently positive integers of 1-100.
In another preferred embodiment, each R 1、R2、R3 is independently a substituted or unsubstituted group selected from the group consisting of: linear or branched C 1-16 alkyl, linear or branched C 1-16 alkoxy, C6-10 aryl, C 6-10 aryloxy; the substitution means substitution with a group selected from the group consisting of: halogen, hydroxy, C 1-8 alkyl, C 2-8 alkenyl, C 6-10 aryl;
L is- (L 1)n -; and each L 1 is independently selected from the group consisting of substituted or unsubstituted C 1-10 alkylene, and each of the groups between each L is optionally interrupted by oxygen and C 6-10 arylene, n is selected from the group consisting of 1,2,3, 4,5, 6,7, 8,9, 10;
Y is selected from the group consisting of: (CH 2OCH)-C2-10 straight or branched alkyl, (CH 2OCH)-C2-10 straight or branched alkoxy, C 3-16 epoxy ether group, C 3-16 epoxy cycloalkyl).
In another preferred embodiment, each R 1、R2、R3 is independently a substituted or unsubstituted group selected from the group consisting of: linear or branched C 1-8 alkyl, linear or branched C 1-8 alkoxy, C 6-10 aryl, C 6-10 aryloxy; the substitution means substitution with a group selected from the group consisting of: halogen, hydroxy, C 1-8 alkyl, C 2-8 alkenyl, C 6-10 aryl;
L is- (L 1)n -; and each L 1 is independently selected from the group consisting of substituted or unsubstituted C 1-4 alkylene, and each of the groups between each L is optionally interrupted by oxygen and C 6-10 arylene, n is selected from the group consisting of 1,2,3, 4,5, 6,7, 8,9, 10;
Y is selected from the group consisting of: (CH 2OCH)-C2-8 alkyl, (CH 2OCH)-C2-8 epoxy, C 3-8 epoxy ether, C 3-8 epoxy cycloalkyl).
In another preferred embodiment, L is-CH 2CH2 -.
In another preferred embodiment, s is a positive integer from 0 to 50; q and t are each independently positive integers of 1 to 50.
In another preferred embodiment, s is a positive integer from 0 to 10; q and t are each independently positive integers of 1 to 10.
In another preferred embodiment, s is a positive integer from 0 to 2; q and t are each independently positive integers of 1-2.
In another preferred embodiment, the epoxy-terminated polysiloxane has the structure of formula (II):
wherein Y is selected from 2- (3, 4-Epoxycyclohexyl), and oxetanyl (oxetane group).
In another preferred embodiment, R 1 is C 6-10 aryloxy, preferably benzyloxy.
In another preferred embodiment, R 2 is a straight or branched C1-8 alkoxy group.
In another preferred embodiment, R 3 is a straight or branched C1-8 alkyl group.
In another preferred embodiment Y is
In another preferred embodiment, the epoxy-terminated polysiloxane is polymerized from monomers selected from the group consisting of:
(a) At least a group 2a of hydrosilylation (poly) siloxane molecules;
(b) At least 2a group of terminal alkenyl epoxy molecules Y-ch=ch 2;
And (c) at least a group a of bis-alkenyl (poly) siloxane molecules;
Wherein,
R 1、R2、R3, Y, s, q and t are as defined in the first aspect of the invention;
a is a positive integer of 1-100.
In a further preferred embodiment of the present invention,
(A) The hydrosilylation (poly) siloxane molecule has polymerized units:
(b) The dienyl (poly) siloxane molecule has a polymeric unit:
(c) The terminal alkenyl epoxy molecule Y is selected from the following groups: (CH 2OCH)-C2-16 straight or branched alkyl, (CH 2OCH)-C2-16 straight or branched alkoxy, C 3-25 epoxy ether group, C 3-25 epoxy cycloalkyl).
In another preferred embodiment, the epoxy-terminated polysiloxane is:
in a second aspect of the present invention, there is provided a method for preparing an epoxy-terminated polysiloxane according to the first aspect of the present invention, comprising the steps of:
(a) In an inert solvent, in the presence of a catalyst, performing a hydrosilylation reaction on the hydrosilylation (poly) siloxane molecules and the alkenyl-terminated epoxy molecules Y in equal proportion to generate (poly) siloxane molecules P with a hydrosilylation structure and epoxy groups;
(b) In an inert solvent, under the low-temperature ammonia gas atmosphere, performing hydrosilylation reaction on (poly) siloxane molecules P and dienyl (poly) siloxane molecules in equal proportion to generate a structure shown in a formula I; the dienyl (poly) siloxane molecule has a structure shown in the following formula:
In another preferred embodiment, the inert solvent is selected from the group consisting of C 2-8 ether solvents.
In another preferred embodiment, the inert solvent is tetrahydrofuran.
In another preferred embodiment, the catalyst is tris (triphenylphosphine) rhodium (I) chloride.
In a third aspect of the invention, there is provided a composition a comprising:
(i) The epoxy-terminated polysiloxane of the first aspect of the present invention; and
(Ii) At least one cationically curable resin.
In another preferred embodiment, the content of the epoxy-terminated polysiloxane in the composition A is 0.1 to 50wt%, preferably 0.1 to 30wt%, based on the total weight of the composition A; more preferably 1 to 10wt%.
In a fourth aspect of the invention, there is provided a composition B comprising:
(a) At least one epoxy or acrylic resin;
(b) At least one cationically curable resin or UV photo radical curing agent; and
(C) The epoxy-terminated polysiloxane of the first aspect of the present invention.
In another preferred embodiment, the epoxy resin is selected from the group consisting of: alcohol glycidyl ether epoxy resins, glycidyl type epoxy resins, glycidyl amine type epoxy resins, melamine epoxy resins, cycloaliphatic epoxy resins, or combinations thereof.
In another preferred embodiment, the epoxy resin is selected from the group consisting of: epoxy E54, epoxy E44, epoxy E51, or a combination thereof.
The acrylic resin is selected from the following group: urethane acrylate (urethane (meth) acrylate), epoxy (meth) acrylate, alcohol acrylate, polyepoxy acrylate, polyester acrylate, or combinations thereof.
In another preferred embodiment, the urethane acrylate (urethane (meth) acrylate) is selected from the group consisting of: aliphatic polyurethane (meth) acrylate (ALIPHATIC URETHANE (meth) acrylate), aromatic polyurethane (meth) acrylate (aromatic urethane (meth) acrylate), aliphatic polyurethane di (meth) acrylate (ALIPHATIC URETHANE DI (meth) acrylate), aromatic polyurethane di (meth) acrylate (aromatic urethane di (meth) acrylate), silicone polyurethane (meth) acrylate (siliconized urethane (meth) acrylate), aliphatic polyurethane hexa (meth) acrylate (ALIPHATIC URETHANE HEXA (meth) acrylate), aromatic polyurethane hexa (meth) acrylate (aromatic urethane hexa (meth) acrylate), aliphatic polyurethane octaacrylate (ALIPHATIC URETHANE OCTAACRYLATE), aromatic polyurethane octaacrylate (aromatic urethane octaacrylate), aliphatic polyurethane nonacrylate (ALIPHATIC URETHANE NONAACRYLATE), aromatic polyurethane nonacrylate (aromatic urethane nonaacrylate), aliphatic polyurethane pentadecanoate (ALIPHATIC URETHANE PENTADECACRYLATE), aromatic polyurethane pentadecanoate (aromatic urethane pentadecacrylate), or combinations thereof.
In another preferred embodiment, the epoxy (meth) acrylate is selected from the group consisting of: bisphenol a epoxy di (meth) acrylate (bisphenol-a epoxy di (meth) acrylate), novolac epoxy (meth) acrylate, or combinations thereof.
In another preferred embodiment, the polyester (meth) acrylate (polyester (meth) acrylate) is selected from the group consisting of: polyester di (meth) acrylate, (meth) acrylate oligomer, or a combination thereof.
In another preferred embodiment, the alcohol acrylate is selected from the group consisting of: dipentaerythritol pentaacrylate (dipentaerythritol pentacrylate), dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate), sorbitol hexaacrylate (Sorbitol hexaacrylate), caprolactone modified pentaerythritol hexaacrylate (caprolactone modified dipentaerythritol hexaacrylate), 3-hydroxy-2, 2-dimethylpropyl 3-hydroxy-2, 2-dimethylpropionate diacrylate (hydroxypivalyl hydroxypivalate diacrylate), ethoxylated1,6-hexanediol diacrylate (ethoxylated, 6-hexanediol diacrylate), dipropylene glycol diacrylate (dipropylene glycol diacrylate), tricyclodecane dimethanol diacrylate (Tricyclodecane dimethanol diacrylate), ethoxylated dipropylene glycol diacrylate (ethoxylated dipropylene glycol diacrylate), neopentyl glycol diacrylate (neopentyl glycol diacrylate), propoxylated neopentyl glycol diacrylate (propoxylated neopentyl glycol diacrylate), ethoxylated bisphenol A dimethacrylate (ethoxylated bisphenol-A DIMETHACRYLATE), 2-methyl-1,3-propanediol diacrylate (2-methyl-1, 3-propanediol diacrylate), ethoxylated 2-methyl-1,3-propanediol diacrylate (ethoxylated-2-methyl-1, 3-propanediol diacrylate), 2-butyl-2-ethyl-1,3-propanediol diacrylate (2-butyl-2-methyl-1, 3-propanediol diacrylate), diethylene glycol dimethacrylate (6558), diethylene glycol dimethacrylate (DIETHYLENE GLYCOL DIMETHACRYLATE), tris (2-hydroxyethyl) isocyanurate triacrylate (Tris (2-hydroxy ethyl) isocyanurate triacrylate), pentaerythritol triacrylate (pentaerythritol triacrylate), ethoxylated trimethylolpropane triacrylate (ethoxylated trimethylolpropane triacrylate), propoxylated trimethylolpropane triacrylate (propoxylated trimethylolpropane triacrylate), trimethylolpropane trimethacrylate (trimethylolpropane trimethacrylate), pentaerythritol tetraacrylate (pentaerythritol tetraacrylate), ethoxylated pentaerythritol tetraacrylate (ethoxylated pentaerythritol tetraacrylate), bis-trimethylolpropane tetraacrylate (ditrimethylolpropane tetraacrylate), propoxylated pentaerythritol tetraacrylate (propoxylated pentaerythritol tetraacrylate), dipentaerythritol hexaacrylate (dipentaerythritol hexaacrylate), tripropylene glycol dimethacrylate (tripropylene glycol dimethacrylate), 1,4-butanediol dimethacrylate (1, 4-butanediol dimethacrylate), 1,6-hexanediol dimethacrylate (1, 6-hexanediol dimethacrylate), allylated cyclohexyl dimethacrylate (ALLYLATED CYCLOHEXYL DIMETHACRYLATE), dimethacrylate isocyanurate (isocyanurate dimethacrylate), ethoxylated trimethylolpropane trimethacrylate- (ethoxylated trimethylolpropane trimethacrylate), propoxylated glycerol trimethacrylate (propoxylated glycerol trimethacrylate), tris (propenoethyl) isocyanurate (Tris (acryloxyethyl) isocyanurate), trimethylolpropane triacrylate (trimethylolpropane triacrylate), or combinations thereof.
In another preferred embodiment, the polyepoxy acrylate is selected from the group consisting of: a poly bisphenol a epoxy hexaacrylate (bisphenol-A epoxy hexaacrylate), a poly novolac epoxy hexaacrylate (novolac epoxy hexaacrylate), or a combination thereof.
In another preferred embodiment, the polyester acrylate is selected from the group consisting of: polyester hexaacrylate (polyester hexaacrylate), aliphatic modified polyester hexaacrylate (FATTY ACID modified polyester hexaacrylate), polyester polyol-based acrylate (polyester polyol based acrylate); melamine hexaacrylate (melamine hexaacrylate), or a combination thereof.
In another preferred embodiment, the acrylate is selected from the group consisting of: methyl acrylate (METHYL ACRYLATE), methyl methacrylate (METHYL METHACRYLATE; MMA), ethyl acrylate, butyl methacrylate, 2-phenoxyethyl acrylate (2-phenoxy ETHYL ACRYLATE), ethoxylated 2-phenoxyethyl acrylate (ethoxylated-phenoxy ETHYL ACRYLATE), 2- (2-ethoxyethoxy) ethyl acrylate (2- (2-ethoxyethoxy) ETHYL ACRYLATE), cyclotrimethylol propane methylacrylate (cyclic trimethylolpropane formal acrylate), beta-carboxyethyl acrylate (beta-carboxyethyl acrylate), lauric acid methacrylate (lauryl methacrylate), isooctyl acrylate (isooctyl acrylate), stearic acid methacrylate (STEARYL METHACRYLATE), isodecyl acrylate (isodecyl acrylate), isobornyl methacrylate (isoborny methacrylate), benzyl acrylate (benzyl acrylate), 2-hydroxyethyl methacrylate phosphate (2-hydroxyethyl metharcrylate phosphate), hydroxyethyl acrylate (hydroxyethyl acrylate, HEA), 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate, HEMA), acryloylmorpholine, or combinations thereof.
In another preferred embodiment, the acrylic resin is selected from the group consisting of: aliphatic urethane acrylates, dipentaerythritol hexaacrylate, acryloylmorpholine, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, or combinations thereof.
In another preferred embodiment, the cationic curable resin is selected from the group consisting of: 3, 4-epoxycyclohexylcarboxylic acid 3',4' -epoxycyclohexylmethyl ester, oxetane ring, triethylene glycol divinyl ether, or combinations thereof.
In another preferred embodiment, the oxetane ring is a commercially available TCM201.
In another preferred embodiment, the UV photo-radical curing agent is selected from the group consisting of: diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate, triarylsulfonium salts, or combinations thereof.
In another preferred embodiment, the epoxy-terminated polysiloxane is present in the composition B in an amount of 0.1 to 50wt%, preferably 1 to 30wt%, more preferably 5 to 20wt% based on the total weight of the components (a) and (B).
In a fifth aspect of the present invention there is provided the use of an epoxy-terminated polysiloxane according to the first aspect of the present invention for the preparation of coatings, adhesives and sealants.
In a sixth aspect of the invention there is provided the use of composition a according to the third aspect of the invention for the preparation of coatings, adhesives and sealants.
In a seventh aspect of the invention there is provided the use of composition B according to the fourth aspect of the invention for the preparation of coatings, adhesives and sealants.
It is understood that within the scope of the present invention, the above-described technical features of the present invention and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.
Drawings
Fig. 1: 1 H NMR of hydrogen-containing single head intermediate A;
Fig. 2: 1 H NMR chart of vinylmethoxy silane intermediate B;
Fig. 3: 1 H NMR of compound 1;
Fig. 4: FT-IR of Compound 1;
Fig. 5: 1 H NMR diagram of hydrogen-containing single-head intermediate C;
fig. 6: 1 H NMR of compound 2;
fig. 7: left: SEM of formulation a; right: SEM after compound 1/formulation a cured.
Detailed Description
The inventor of the present invention has studied extensively and intensively and provided a dual-curable epoxy-terminated polysiloxane and a preparation method thereof for the first time. The epoxy-terminated polysiloxane has a plurality of crosslinking groups, has strong cohesive force and can be widely applied to various fields; the preparation method is simple and efficient. On this basis, the present invention has been completed.
Terminology
As used herein, unless otherwise specified, the term "substituted" refers to the substitution of one or more hydrogen atoms on a group with a substituent selected from the group consisting of: C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, halogen, hydroxy, carboxyl (-COOH), C1-C10 aldehyde, C2-C10 acyl, C2-C10 ester, amino, phenyl; the phenyl group comprises unsubstituted phenyl or substituted phenyl with 1-3 substituents selected from the group consisting of: halogen, C1-C10 alkyl, cyano, hydroxy, nitro, C3-C10 cycloalkyl, C1-C10 alkoxy and amino.
As used herein, the term "C1-25 alkyl" refers to a straight or branched alkyl group having 1 to 25 carbon atoms, preferably a straight or branched alkyl group having 1 to 10 carbon atoms; such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, or the like.
As used herein, the term "C2-25 alkenyl" refers to a straight or branched alkenyl group having 2 to 25 carbon atoms, preferably a straight or branched alkenyl group having 2 to 10 carbon atoms; such as ethylene, propylene, isobutylene, butene, isobutylene, tertiary butene, or the like.
As used herein, the term "aryl" refers to an aromatic cyclic group that does not contain heteroatoms in the ring, which may be fused to a heteroaryl, heterocyclic or cycloalkyl ring, wherein the ring attached to the parent structure is an aryl ring. Such as phenyl (i.e., C6 aryl or six-membered aryl), naphthyl (i.e., C10 aryl or [6+6] aryl), and the like, wherein six-membered aryl is also intended to include six-membered aryl and 5-6 membered cycloalkyl and six-membered aryl and 5-6 membered heterocyclyl. The term "[5+6] aryl" refers to a fused 6, 5 bicyclic ring system. Aryl is preferably C6-C14 aryl, more preferably C6-C10 aryl. Examples of aryl groups include phenyl, naphthyl. Aryl groups may be optionally substituted or unsubstituted.
The term "heteroaryl" refers to a cyclic aromatic group having 1 to 3 atoms which are heteroatoms selected from the group consisting of N, S and O, which may be monocyclic or in the form of fused rings. In the present invention, the heteroaryl group is preferably a 5-6 membered heteroaryl group. Examples of heteroaryl groups include, but are not limited to: pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolyl, pyrazolyl, imidazolyl, (1, 2, 3) -triazolyl, (1, 2, 4) -triazolyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, oxazolyl, and the like. The heteroaryl ring may be fused to an aryl, heterocyclyl or cycloalkyl ring, wherein the ring attached to the parent structure is a heteroaryl ring. The term "[5+6] heteroaryl" refers to fused 6, 5 bicyclic ring systems such as benzothienyl, benzofuranyl, benzimidazolyl, benzotriazole, benzothiazolyl, benzothiadiazolyl, benzoxazolyl, and the like.
As used herein, the term "epoxy ether group" refers to a group in which one carbon atom on the epoxy group is attached to an alkyleneoxy group.
As used herein, the term "epoxycycloalkyl" refers to an epoxy group sharing two carbon atoms with a cycloalkyl group and linked to other groups through a cycloalkyl group.
The term "halogen" refers to F, cl, br and I.
Herein, "C1-10" is formed, meaning that the group may have 1 to 10 carbon atoms, e.g., 1, 2,3, 4, 5, 6, 7, 8, 9, 10.
Epoxy-terminated polysiloxanes
The epoxy-terminated polysiloxane can be used as a reinforcing and toughening agent of epoxy resin, has good compatibility through molecular design, can form epoxy organosilicon with a sea-island and IPN structure, can remarkably improve the strength and toughness, and solves the defect of hard and brittle epoxy resin. Compared with the traditional rubber particle toughening agent, the epoxy-terminated polysiloxane can remarkably improve the strength and toughness.
The double-curing end epoxy polysiloxane contains a plurality of active functional groups, has various curing modes, can be fully cured, and can obviously improve the adhesive force, such as the application of the compound 1 in the coil-rigid protective paint.
The dual-cure terminal epoxy polysiloxane of a special structure can be used as a special coupling agent, for example, compound 1 can be regarded as a reinforced version of KH560 as a substitute for it.
The double-cured epoxy polysiloxane has potential application prospect on a flexible scratch-resistant hard coating protective film of a flexible display screen.
Coating application of dual cure epoxy-terminated polysiloxanes: dual photo/thermal cationic, moisture cure is achieved to achieve good adhesion to a variety of substrates including, but not limited to: glass substrate, metal oxide substrate, metal substrate and polymer substrate, the adhesion force is obviously improved (the adhesion force of the cross-cut adhesion test can reach 4-5B, and the water boiling adhesion force reaches 4B); and a transparent bending-resistant scratch-resistant coating with excellent surface hardness can be obtained, and the potential application of the coating in the field of photoelectrons is shown.
The addition of the end-epoxy polysiloxanes according to the invention is exemplified by curing by photo cation-moisture means. The reason for improving the adhesion after curing is from: 1) The terminal epoxy groups in the MS710-4 molecule undergo photocationic curing crosslinking, and 2) the Si-OMe in the molecule undergoes demethylating post-condensation (moisture), producing Si-O-Si which continues to promote adhesion by 4B or more.
Compared with the prior art, the invention has the main advantages that:
(1) The epoxy-terminated polysiloxane combines the advantages of the organic silicon and the epoxy resin, and has the mechanical strength of the epoxy resin, and the toughness, high and low temperature resistance, weather resistance and hydrophobicity of the organic silicon resin;
(2) The preparation method is simple and efficient, and the prepared variable curing polysiloxane has a plurality of crosslinking groups and has strong binding power.
(3) The epoxy-terminated polysiloxanes of the present invention can be cured by various curing means such as photo cation-moisture, photo cation-thermal cation, moisture-thermal cation, etc.
(4) The epoxy-terminated polysiloxanes of the present invention may be used alone or as additives.
(5) The epoxy-terminated polysiloxane can be fully cured, can fully embody the characteristics of materials, expands the curing thickness and the application of the materials, and can be widely applied to various materials and fields.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are by weight unless otherwise indicated.
Example 1 Compound 1
(1) Synthesis of hydrogen-containing single-end socket intermediate A
Allyl glycidyl ether (114.14 g,1 mol) was dissolved in 60mL tetrahydrofuran for use. 0.03g of tris (triphenylphosphine) rhodium (I) chloride and 1, 3-tetramethyldisiloxane (171.98 g,1.2 mol) were charged into a multi-necked round bottom flask equipped with a condenser and a dropping funnel. Slowly dripping allyl glycidyl ether/tetrahydrofuran solution at 50 ℃ under the protection of dry nitrogen, and stirring and reacting for 8 hours. And after the reaction is finished, rotary steaming is carried out, tetrahydrofuran and unreacted 1, 3-tetramethyl disiloxane are steamed out (the reagent can be recovered and the cost is reduced in the step), a reddish brown hydrogen-containing single-end socket intermediate is obtained, and colorless transparent liquid A is obtained through activated carbon color removal treatment.
As can be seen from the hydrogen spectrogram 1, si-H peaks are at 4-5 ppm; 3.4 to 3.8ppm is H peak adjacent to ether; 2.6 to 3.2ppm is H peak in the glycidyl ether group ternary ring; 1.6ppm of H peak of ether separated by one methylene; 0.5ppm is H peak converted from vinyl by hydrosilylation, and 0-0.3 ppm is H peak of Si-CH 3. Their integral corresponds to the molecular structure. Therefore, the hydrogen-containing single-end socket intermediate A is successfully synthesized.
(2) Synthesis of vinylmethoxy silane intermediate B
Vinyl trimethoxy (296.48 g,2 mol) was dissolved in 200mL of tetrahydrofuran and placed in a multi-necked round bottom flask equipped with a condenser and a dropping funnel. Diphenyldihydroxysilane (216.31 g,2 mol) was dissolved in 200mL of tetrahydrofuran and placed in a dropping funnel. Cooling to-20 ℃ under the protection of dry nitrogen, introducing ammonia gas into the vinyl trimethoxy/tetrahydrofuran solution, slowly dripping the diphenyl dihydroxysilane/tetrahydrofuran solution under the condition of stirring, and continuously reacting for 8 hours. After the reaction is finished, ammonia gas dissolved in the reaction liquid is pumped out in vacuum, and the reaction liquid is distilled in a rotary way, so that a clear and transparent liquid intermediate B is obtained.
Thin Layer Chromatography (TLC) of intermediate B showed only one spot, indicating it was pure. As can be seen from the hydrogen spectrum data of FIG. 2, the phenyl H peak is at 7-8 ppm; 5-6 ppm is vinyl H peak; 3 to 4ppm is H peak of methoxy.
(3) Synthesis of Compound 1
In a multi-necked round bottom flask equipped with a condenser and a dropping funnel, 1mol A, 0.5molB, 100mL of tetrahydrofuran and 20ppm of the card catalyst were placed. Under the protection of dry nitrogen, the temperature is raised to 65 ℃ and stirring is continued for 4 hours. And after the reaction is finished, performing rotary evaporation, performing activated carbon color removal treatment to obtain colorless transparent liquid, and drying to obtain the compound 1.
As can be seen from the hydrogen spectrum data of FIG. 3, the phenyl H peak is at 7-8 ppm; 3.4 to 3.8ppm is an ether adjacent H peak and a methoxy H peak; 2.6 to 3.2ppm is H peak in the glycidyl ether group ternary ring; 1.6ppm of H peak of ether separated by one methylene; 0.5ppm is H peak converted from vinyl by hydrosilylation, and 0-0.3 ppm is H peak of Si-CH 3.
As can be seen from the infrared data of FIG. 4, there was no Si-OH peak above 3100cm -1, a Si-OMe peak of 2850cm -1, a Si-Me peak of 910cm -1 epoxy characteristic peak of 1250cm -1, and Si-O-Si characteristic peak and benzene ring characteristic absorption peak (1600 cm -1、1450cm-1) of 1000 to 1200cm -1. In conclusion, compound 1 was successfully synthesized.
Example 2 Compound 2
(1) Synthesis of hydrogen-containing single-end socket intermediate C
1, 2-Epoxy-4-vinylcyclohexane (124.18 g,1 mol) was dissolved in 60mL of tetrahydrofuran for use. 0.03g of tris (triphenylphosphine) rhodium (I) chloride, and 1, 3-tetramethyldisiloxane (171.98 g,1.2 mol) were charged into a multi-necked round bottom flask equipped with a condenser and a dropping funnel. Under the protection of dry nitrogen, 1, 2-epoxy-4-vinylcyclohexane/tetrahydrofuran solution is slowly dripped at 50 ℃ and stirred for reaction for 8 hours. And after the reaction is finished, rotary steaming is carried out, tetrahydrofuran and unreacted 1, 3-tetramethyl disiloxane are steamed out (the reagent can be recovered and the cost is reduced in the step), a reddish brown hydrogen-containing single-end socket intermediate is obtained, and colorless transparent liquid C is obtained through activated carbon color removal treatment.
As can be seen from the hydrogen spectrum data of FIG. 5, si-H peaks are at 4 to 5 ppm; 3.1ppm is the epoxy H peak in the six-membered ring of epoxycyclohexane; 1-2 ppm is cyclohexane H peak; 0.5ppm is H peak converted from vinyl by hydrosilylation, and 0-0.3 ppm is H peak of Si-CH 3.
(2) The synthesis of vinylmethoxy silane intermediate B was as described in example 1.
(3) Synthesis of Compound 2
In a multi-necked round bottom flask equipped with a condenser and a dropping funnel, 1mol of intermediate C, 0.5mol of intermediate B, 100mL of tetrahydrofuran and 20ppm of the catalyst in the reaction system were placed. The temperature was raised to 65℃under the protection of dry nitrogen and the reaction was continued with stirring for 4 hours. And after the reaction is finished, performing rotary evaporation, performing activated carbon color removal treatment to obtain colorless transparent liquid, and drying to obtain the compound 2.
As can be seen from the hydrogen spectrum data of FIG. 6, the phenyl H peaks at 7 to 8 ppm; 3-4 ppm is epoxy H peak and methoxy H peak in the six-membered ring of the epoxy cyclohexane; 1-2 ppm is methylene H peak in cyclohexane six-membered ring; 0.5ppm is H peak converted from vinyl by hydrosilylation, and 0-0.3 ppm is H peak of Si-CH 3.
EXAMPLE 3 toughening Property
The compound 1 provided in the embodiment 1 is applied to the reinforcement and toughening of epoxy resin.
Preparing a bisphenol A epoxy adhesive formula A, wherein the main agent is: 80 parts of epoxy resin E54 (tin-free phoenix) and 15 parts of carboxyl-terminated nitrile rubber (Mars elastic Co., ltd., deep Co., ltd.) and 0.8 part of gamma-glycidoxy trimethoxysilane (Japanese Xinyue) and 5 parts of hydrophilic white carbon black AERSOIL parts (Yingchuang, germany); curing agent: 35 parts of polyamide curing agent (German winning machine 910), 35 parts of polyamide curing agent (German winning machine 350) and 30 parts of 800-mesh aluminum hydroxide powder (China aluminum industry).
After the main agent and the curing agent are respectively stirred evenly, the mixture is stood for standby, and the formula A is used as a control group.
Taking a formula A and a compound 1 as experimental groups, accurately weighing the compound 1, adding a main agent in the formula A, and uniformly stirring; adding the curing agent in the formula A, and uniformly stirring; wherein compound 1 represents 4.25% of the total mass.
Experimental procedure: and selecting a drawing die or a shearing die, respectively taking 10g of the same amount of formula A and formula A/compound 1, respectively coating the surfaces of the dies, spreading zirconium beads to fix the film thickness, fixing the dies by using a clamp after bonding, and measuring at 25 ℃ after curing at 40 ℃ for 24 hours in an oven.
Table 1: tensile strength of
Table 2: shear strength
The results show that by adding a small amount of compound 1 to formulation a, the tensile strength after curing is increased by 116%, the shear strength is increased by 36%, and the elongation, tensile and shear modulus are also increased. Compound 1 acts as a reinforcing and toughening additive therein.
As can be seen from fig. 7 of the scanning electron microscope, the formula a has almost no island structure, and the island structure with uniform size is formed after the compound 1 is introduced, so that the mechanical property is remarkably improved.
Example 4
This example 1 provides an example of the application of compound 1 as a UV cationic cure resin.
Compound 1 was introduced into a UV cationic cure evaluation base formulation and tested for adhesion to various substrates. The 3, 4-epoxy cyclohexyl methyl formate 3',4' -epoxy cyclohexyl methyl formate has the advantages of high curing speed, energy conservation, high production efficiency, good mechanical property after curing and the like in an ultraviolet curing system, and is widely applied to coatings, packaging materials and the like. 3, 4-epoxycyclohexylcarboxylic acid 3',4' -epoxycyclohexylmethyl ester was thus introduced as a comparative example.
According to the literature "preparation of 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate" (Feng Shaojing, song Yuwan, xiong Jianxi, shore, synthetic resins and plastics, 2018, 35 (6): 10) 3',4' -epoxycyclohexylmethyl 3, 4-epoxycyclohexylformate was synthesized in the laboratory with purities of 95% and 97% before and after purification of the product, designated C (unpurified) and D (purified), respectively.
The basic formula for UV cationic curing evaluation comprises the following components: 70 parts of compound 1 or C, D, 30 parts of TCM201, 5 parts of PAG201 and 0.5 part of sensitizer PSS 701. (oxetane) TCM201, (triarylsulfonium salt) PAG201, sensitizer PSS701 were purchased from Strong electronic New Material Co., ltd. After UV curing, the adhesion was evaluated by the hundred-cell method, with 0-5B as the standard, and the larger the data, the better the adhesion. The results are shown in Table 3.
TABLE 3 Table 3
The evaluation result of the basic formula of the UV cations shows that the compound 1 has short UV curing time as the UV cation curing resin, has excellent adhesive force on various base materials, and particularly has wide application range in the base materials with poor formula adhesion, such as polished tinplate, glass, PMMA and PET.
In the UV coil steel free radical protective paint system, the shrinkage is serious during curing, so that the UV coil steel free radical protective paint is difficult to adhere to a metal substrate. The free radical system is introduced with a low-shrinkage cationic curing system (such as a compound 1) to improve the paint film performance and improve the adhesive force.
The base formulation of the radical primer (about 15-20 μm) was evaluated by roll coating with a UV cationic cure containing 10wt% of Compound 1 on a galvanized coil steel substrate, followed by UV exposure, followed by roll coating with a topcoat (about 15-20 μm), and finally UV exposure curing.
Wherein the primer comprises the following formula: 60 parts of aliphatic polyurethane acrylate (DR-U315, changxing materials industry Co., ltd.), 11 parts of dipentaerythritol hexaacrylate (EM 265, changxing materials industry Co., ltd.), 17 parts of acryloylmorpholine (ACMO, jiangxi Lote chemical Co., ltd.), 3 parts of photoinitiator 184 (Shanghai Kaijin chemical Co., ltd.), 9 parts of TiO 2 (Changzhou full-open chemical Co., ltd.), and 10 parts of the basic formula for evaluating the UV cationic curing of the compound 1. Wherein, the basic formula of the UV cationic curing evaluation of the compound 1 comprises the following components: 70 parts of compound 1, 30 parts of TCM201, 5 parts of PAG201 and 0.5 part of sensitizer PSS 701.
The formula of the finishing paint is as follows: 60 parts of aliphatic polyurethane acrylate (DR-U315, changxing materials industry Co., ltd.), 15 parts of acryloylmorpholine (ACMO, jiangxi Lote chemical Co., ltd.), 5 parts of photoinitiator TPO (Jinan Weizhen chemical Co., ltd.), 1 part of photoinitiator 819 (Shanghai Kaiyan chemical Co., ltd.), 1 part of Pick leveling agent (BYK 333, shenzhen chemical Co., ltd.), and 30 parts of TiO 2 (Chang full-length chemical Co., ltd.).
Film thickness was measured after curing, and impact and bending properties were evaluated and collated in Table 4. The adhesive force is tested by adopting a hundred-grid method, and 0-5B is used as a standard. The larger the data, the better the adhesion. The adhesion after curing was evaluated and continued at 100 ℃/1h after curing.
TABLE 4 Table 4
| Testing | Free base paint formula | Primer formulation +10wt% cationic formulation |
| Film thickness (mum) | 17-20 | 15-18 |
| Adhesion force | 5B | 5B |
| Impact 9J | OK | OK |
| Bending 3T | OK | OK |
| Bending 2T | OK | OK |
| Boiling-resistant 100 ℃ for 1h | 0B | 4B |
The incorporation of the UV cationic formulation containing compound 1 into the primer had a significant improvement in water boiling. The larger the data, the better the adhesion. The primer formula is 0B in water boiling resistance after UV curing, and the formula is raised to 4B after curing by introducing the UV cation containing compound 1, which shows that the adhesive force of the primer to water boiling resistance is obviously improved. The cured sample is placed at room temperature for 7 days or is baked at 60 ℃ for 1 hour, and the adhesive force can be improved from original 4B to 5B through the hundred-lattice test. The reason why the post-curing can improve the adhesive force is derived from the fact that Si-OMe in the MS710-4 molecule is continuously condensed after methanol removal, and Si-O-Si is generated.
All documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (10)
1. An epoxy-terminated polysiloxane, characterized in that the epoxy-terminated polysiloxane has the structure of formula (0):
Y-X-Y formula (0);
Wherein X has at least four groups of structures of formula (III):
- { [ OSi (R) 2-]k -L } -formula (iii);
Wherein each R is independently R 1、R2、R3, k is a positive integer from 1 to 100, and k in each group is the same or different; wherein each R 1、R2、R3 is independently a substituted or unsubstituted group selected from the group consisting of: linear or branched C 1-25 alkyl, linear or branched C 1-25 alkoxy, C 3-25 cycloalkyl, C 6-22 aryl, 5-to 20-membered heteroaryl, C 6-25 aryloxy, C 2-25 cyclic ether group; the substitution means substitution with a group selected from the group consisting of: halogen, hydroxy, C 1-8 alkyl, C 2-8 alkenyl, C 6-10 aryl;
L is- (L 1)n -; and each L 1 is independently selected from the group consisting of substituted or unsubstituted C 1-10 alkylene, substituted or unsubstituted C 2-30 acyl, substituted or unsubstituted C 2-30 ester, and each group between each L 1 is optionally interrupted by oxygen and C 6-10 arylene, n is selected from the group consisting of 1,2,3,4,5,6,7,8,9, 10;
Y is selected from the group consisting of: (CH 2OCH)-C2-16 straight-chain or branched-chain alkyl, (CH 2OCH)-C2-16 straight-chain or branched-chain alkoxy, C 3-25 epoxy ether group and C 3-25 epoxy cycloalkyl, wherein the epoxy cycloalkyl is epoxy and cycloalkyl.
2. The epoxy-terminated polysiloxane of claim 1, wherein the epoxy-terminated polysiloxane has the structure of formula (I):
R 1、R2、R3, L, Y are as defined in claim 1;
s is 0 or a positive integer from 1 to 100;
q and t are each independently positive integers of 1-100.
3. The epoxy-terminated polysiloxane of claim 1, wherein the epoxy-terminated polysiloxane has the structure of formula (II):
wherein Y is selected from 2- (3, 4-Epoxycyclohexyl), and oxetanyl.
4. The epoxy-terminated polysiloxane of claim 1, wherein the epoxy-terminated polysiloxane is polymerized from monomers selected from the group consisting of:
(a) At least a group 2a of hydrosilylation (poly) siloxane molecules;
(b) At least 2a group of terminal alkenyl epoxy molecules Y-ch=ch 2;
And (c) at least a group a of bis-alkenyl (poly) siloxane molecules;
Wherein,
R 1、R2、R3, Y, s, q and t are as defined in claim 1;
a is a positive integer of 1-100.
5. The epoxy-terminated polysiloxane according to claim 1, wherein the epoxy-terminated polysiloxane is:
6. A process for the preparation of an epoxy-terminated polysiloxane according to any one of claims 1 to 5, comprising the steps of:
(a) In an inert solvent, in the presence of a catalyst, performing a hydrosilylation reaction on the hydrosilylation (poly) siloxane molecules and the alkenyl-terminated epoxy molecules Y in equal proportion to generate (poly) siloxane molecules P with a hydrosilylation structure and epoxy groups;
(b) In an inert solvent, under the low-temperature ammonia gas atmosphere, the (poly) siloxane molecules P and the dienyl (poly) siloxane molecules are subjected to hydrosilylation reaction in equal proportion to generate the epoxy-terminated polysiloxane; the dienyl (poly) siloxane molecule has a structure shown in the following formula:
7. a composition a comprising:
(i) The end-epoxy polysiloxane of any one of claims 1-5; and
(Ii) At least one cationically curable resin.
8. A composition B, characterized by comprising:
(a) At least one epoxy or acrylic resin;
(b) At least one cationically curable resin or UV photo radical curing agent; and
(C) The epoxy-terminated polysiloxane of any one of claims 1-5.
9. The composition B according to claim 8, wherein the epoxy-terminated polysiloxane is contained in the composition B in an amount of 0.1 to 50% by weight based on the total weight of the component (a) and the component (B).
10. Use of the epoxy-terminated polysiloxane according to claim 1 for the preparation of coatings, adhesives and sealants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211426821.2A CN118027089A (en) | 2022-11-14 | 2022-11-14 | Double-curable epoxy-terminated polysiloxane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211426821.2A CN118027089A (en) | 2022-11-14 | 2022-11-14 | Double-curable epoxy-terminated polysiloxane and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118027089A true CN118027089A (en) | 2024-05-14 |
Family
ID=90995651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211426821.2A Pending CN118027089A (en) | 2022-11-14 | 2022-11-14 | Double-curable epoxy-terminated polysiloxane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118027089A (en) |
-
2022
- 2022-11-14 CN CN202211426821.2A patent/CN118027089A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3591017B1 (en) | Resin composition for hard coating, and hard-coating film comprising cured form of same as coating layer | |
| CN108350314B (en) | Curable polymers | |
| CN112639038B (en) | Hard coat composition, polyimide film with hard coat layer, method for producing the same, and image display device | |
| JP3816112B2 (en) | Non-toxic initiators, resins containing cross-linkable organic functional groups including initiators, and their use to produce stable non-toxic polymers | |
| CN112239623B (en) | Polymer for display device | |
| TWI768347B (en) | Thermosetable composition, epoxy curable product prepared thereby and a method for degrading epoxy curable product | |
| KR101942006B1 (en) | Composition For Hard Coating and Hard Coating Film Including Cured Product Of The Same As The Coating Layer | |
| JP4998702B2 (en) | Articles coated or surface-treated with a coating agent composition | |
| CN112004838B (en) | Modifier, composition, hard coat film, article provided with hard coat film, and image display device | |
| CN107709400B (en) | Curable composition | |
| JP6994562B2 (en) | A coating film containing a coating resin composition and a cured product thereof as a coating layer. | |
| CN108250956B (en) | Coating composition and method for producing the same | |
| CN118027089A (en) | Double-curable epoxy-terminated polysiloxane and preparation method thereof | |
| GB2212163A (en) | Curable compositions and method of curing same | |
| JPH02232251A (en) | Resin composition, curable composition and paint composition | |
| TWI833458B (en) | Dual curable epoxy-terminated polysiloxane and preparation method and application thereof | |
| EP3636719B1 (en) | Resin composition for coating, and coating film comprising cured product thereof as coating layer | |
| JPH05239365A (en) | Curable resin composition and its cured product | |
| JP3839543B2 (en) | Active energy ray-curable resin composition | |
| JP2000212443A (en) | Photo-cationically curable resin composition | |
| JP3796906B2 (en) | Photocationically polymerizable organosilicon compound and method for producing the same, photocationically polymerizable coating composition, and film coating agent for peeling | |
| JP5339135B2 (en) | Polyester resin composition and cured product thereof | |
| JP5580118B2 (en) | RESIN COMPOSITION FOR AQUEOUS COATING LIQUID, AQUEOUS COATING LIQUID DISTRIBUTED AND COMPOSITE FILM WITH COATING LAYER WITH THE SAME | |
| CN111377817A (en) | Resin and ink | |
| JP3100440B2 (en) | Composite polycarbonate molded article having excellent surface properties and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |