WO2022267991A1 - 硫醚基氧杂环丁烷硅烷偶联剂及其制备方法 - Google Patents
硫醚基氧杂环丁烷硅烷偶联剂及其制备方法 Download PDFInfo
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- WO2022267991A1 WO2022267991A1 PCT/CN2022/099402 CN2022099402W WO2022267991A1 WO 2022267991 A1 WO2022267991 A1 WO 2022267991A1 CN 2022099402 W CN2022099402 W CN 2022099402W WO 2022267991 A1 WO2022267991 A1 WO 2022267991A1
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- Prior art keywords
- compound
- formula
- alkylene
- alkyl
- alkyleneoxy
- Prior art date
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- 239000006087 Silane Coupling Agent Substances 0.000 title abstract description 19
- WIFJFQLSBXPWQQ-UHFFFAOYSA-N oxetane silane Chemical compound [SiH4].O1CCC1 WIFJFQLSBXPWQQ-UHFFFAOYSA-N 0.000 title abstract description 9
- 150000003568 thioethers Chemical class 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 170
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 229910052760 oxygen Inorganic materials 0.000 claims description 46
- 125000005842 heteroatom Chemical group 0.000 claims description 45
- 125000002947 alkylene group Chemical group 0.000 claims description 44
- 229910052717 sulfur Inorganic materials 0.000 claims description 43
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 28
- 229910052753 mercury Inorganic materials 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 19
- 150000002367 halogens Chemical class 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 125000005647 linker group Chemical group 0.000 claims description 12
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 125000004737 (C1-C6) haloalkoxy group Chemical group 0.000 claims description 8
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 8
- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 claims description 8
- 239000000976 ink Substances 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 229920002120 photoresistant polymer Polymers 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims description 4
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 4
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 238000000016 photochemical curing Methods 0.000 abstract description 6
- -1 1-methylpentyl Chemical group 0.000 description 84
- 229940125904 compound 1 Drugs 0.000 description 24
- 238000003756 stirring Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 2
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004438 haloalkoxy group Chemical group 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VQVGJEIVVJBMCV-UHFFFAOYSA-N (4-octoxyphenyl)-phenyliodanium Chemical compound C1=CC(OCCCCCCCC)=CC=C1[I+]C1=CC=CC=C1 VQVGJEIVVJBMCV-UHFFFAOYSA-N 0.000 description 1
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 1
- 125000004643 (C1-C12) haloalkoxy group Chemical group 0.000 description 1
- 125000004641 (C1-C12) haloalkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- SQAAXANYWPZYJI-UHFFFAOYSA-N 2-propan-2-yl-9h-thioxanthene Chemical compound C1=CC=C2CC3=CC(C(C)C)=CC=C3SC2=C1 SQAAXANYWPZYJI-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- LPNANKDXVBMDKE-UHFFFAOYSA-N 5-bromopent-1-ene Chemical group BrCCCC=C LPNANKDXVBMDKE-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- FMIBWXAWUDPQCZ-UHFFFAOYSA-N CC(CCCS)[Si](OC)(OC)OC Chemical compound CC(CCCS)[Si](OC)(OC)OC FMIBWXAWUDPQCZ-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000006003 dichloroethyl group Chemical group 0.000 description 1
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical class C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-O diphenylsulfanium Chemical compound C=1C=CC=CC=1[SH+]C1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-O 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SWYHWLFHDVMLHO-UHFFFAOYSA-N oxetan-3-ylmethanol Chemical compound OCC1COC1 SWYHWLFHDVMLHO-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000006000 trichloroethyl group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Images
Classifications
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- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
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- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Definitions
- the invention relates to the field of photocurable materials, in particular to a thioether-based oxetane silane coupling agent.
- the present invention also relates to a preparation method of the silane coupling agent, a photocurable composition containing the silane coupling agent and a photocurable material obtained from the photocurable composition.
- Photopolymerization technology is the process of using light to initiate the conversion of liquid oligomers or monomers with active substances into solid products. Compared with traditional thermal polymerization technology, photopolymerization can achieve efficient and pollution-free production without using volatile organic solvents, saving a lot of energy. It is estimated that energy costs can be reduced by 20-25% by switching from thermal to photopolymerization. Photopolymerization technology is regarded as a green process because of its unique low energy consumption requirements, fast curing, solvent-free formula, no pollution, room temperature treatment and environmental protection, so it is widely used in the fields of photocuring coatings, adhesives and ink printing. Wide range of applications.
- silane coupling agent can improve the performance of materials, but the silane coupling agent will be free in the photopolymerization system, affecting the overall performance of the product and causing environmental pollution. Therefore, people hope to develop a silane coupling agent with little or no free, so as to improve the overall performance of the product and reduce the environmental pollution of the product.
- the preparation process of silane coupling agents that can be industrially produced at present requires heating and the use of a large amount of solvents, and the reaction time is long, which leads to the disadvantages of high energy consumption, low production efficiency and pollution to the environment. With the increasing awareness of global environmental protection, the development of green chemical reactions and processes has become a major trend in the development of the modern chemical industry. Therefore, it is urgent to provide an environmentally friendly and efficient method for preparing silane coupling agents.
- the inventors of the present invention have conducted extensive and in-depth research on silane coupling agents in order to find a new type of oxetane silane coupling agent.
- the inventors found that the thioether-based oxetanylsilane coupling agent of the present invention will be fixed in the system after photocuring, with little or no dissociation, and it also has the advantages of good tensile properties and strong adhesion.
- an object of the present invention is to provide a thioether-based oxetane silane coupling agent.
- the thioether-based oxetane silane coupling agent will be fixed in the system after photocuring, with little or no dissociation, and it also has the advantages of good tensile performance and strong adhesion.
- Another object of the present invention is to provide a method for preparing a thioether-based oxetane silane coupling agent.
- the preparation method is simple, environmentally friendly, efficient, solvent-free, and high in yield.
- Another object of the present invention is to provide a photocurable composition comprising the thioether-based oxetane silane coupling agent according to the present invention.
- Another object of the present invention is to provide a photocurable material obtained from the photocurable composition of the present invention.
- Another object of the present invention is to provide the use of the compound of formula (I) of the present invention in photocurable coatings, adhesives, inks and photoresists.
- R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
- R 4 is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy;
- L is a direct bond or a divalent linking group with 1-20 carbon atoms
- L 2 is a direct bond or a divalent linking group having 1-30 carbon atoms.
- R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 3 alkyl or C 1 -C 3 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 - C 3 alkoxy.
- R 4 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkane Oxygen or C 1 -C 4 haloalkoxy.
- L 1 is a direct bond, C 1 -C 20 alkylene, C 1 -C 20 alkyleneoxy, one or more independently selected from C 2 -C 20 alkylene separated by non-adjacent heteroatoms of NR a , O, S, or C 2 - C 20 alkyleneoxy, wherein R a is H or C 1 -C 4 alkyl;
- L 2 is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 30 alkylene, or C 2 -C 30 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 15 alkylene and L 22 is a direct bond or C 1 -C 15 alkylene.
- R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
- R 4 is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy;
- L 1 is a direct bond, C 1 -C 11 alkylene, C 1 -C 11 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 11 alkylene, or C 2 -C 11 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; and
- L 2 is a direct bond, C 1 -C 8 alkylene, C 1 -C 8 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 8 alkylene, or C 2 -C 8 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 5 alkylene and L 22 is a direct bond or C 1 -C 3 alkylene;
- R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
- R 4 is H or C 1 -C 4 alkyl
- L 1 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 6 alkylene, or C 2 -C 6 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; and
- L 2 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 6 alkylene, or C 2 -C 6 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 4 alkylene and L 22 is a direct bond or C 1 -C 2 alkylene.
- R and L are as defined for any one of items 1-6 ;
- L 1 , R 1 , R 2 and R 3 are as defined for any one of items 1-6.
- L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 15 alkylene and L 22 is a direct bond or C 1 -C 15 alkylene, preferably L 21 is C 1 -C 5 alkylene and L 22 is a direct bond or C 1 -C 3 alkylene.
- L 21 is C 1 -C 15 alkylene, preferably C 1 -C 5 alkylene
- X is halogen, such as fluorine, chlorine, bromine or iodine
- L 22 is a direct bond or a C 1 -C 15 alkylene group, preferably a direct bond or a C 1 -C 3 alkylene group, and R 4 is as defined for item 7.
- reaction of the compound of formula (II) with the compound of formula (III) is carried out in the presence of a basic catalyst, preferably sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof, More preferably, the molar ratio of the compound of formula (II) to the basic catalyst is 1:1-1:3;
- reaction between the compound of formula (II) and the compound of formula (III) is carried out at 80-120°C, preferably at 100-120°C;
- reaction between the compound of formula (II) and the compound of formula (III) is carried out for 6-15 hours, preferably 8-12 hours.
- reaction of the compound of formula (IV) and the compound of formula (V) is under the mercury lamp of 50-500mw/cm -2 in light intensity;
- the molar ratio of the compound of formula (IV) to the compound of formula (V) is 1:0.7-1:1.5;
- reaction between the compound of formula (IV) and the compound of formula (V) is carried out at 0-40°C, preferably at 10-30°C;
- reaction between the compound of formula (IV) and the compound of formula (V) is carried out for 5-60 minutes, preferably 20-40 minutes.
- a photocurable composition comprising a compound of formula (I) according to any one of items 1-6 as a polymerizable monomer.
- FIG. 1 is a graph showing the conversion of E4221 in a system containing compound 1 prepared in Example 1 as a function of irradiation time.
- FIG. 2 is a curve diagram of the conversion rate of Compound 1 in the system containing Compound 1 prepared in Example 1 as a function of irradiation time.
- Fig. 3 is a graph showing the mechanical properties of a blank E4221 cured film and a cured film containing different amounts of compound 1 prepared in Example 1.
- a numerical range is used to indicate a range in which the numerical values described before and after are taken as the minimum value and the maximum value, respectively.
- R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
- R 4 is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy;
- L is a direct bond or a divalent linking group with 1-20 carbon atoms
- L 2 is a direct bond or a divalent linking group having 1-30 carbon atoms.
- the raw materials for preparing the compound of formula (I) of the present invention are easy to obtain, and can be prepared by a green, simple, solvent-free and heating-free reaction, and the compound of formula (I) of the present invention will be fixed in the system after photocuring, and will not dissociate , does not pollute the environment, and has the advantages of good tensile properties and strong adhesion.
- the prefix "C n -C m " indicates in each case that the number of carbon atoms contained in the group is nm.
- Halogen refers to fluorine, chlorine, bromine and iodine. In the present invention, it is preferred that the halogen includes bromine, chlorine or a combination thereof.
- C n -C m alkyl refers to a branched or unbranched saturated hydrocarbon group having nm, such as 1-12, preferably 1-6, particularly preferably 1-4 carbon atoms, such as Methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methyl Butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2- Dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethyl Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,
- the C 1 -C 6 alkyl group may be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl and isomers thereof.
- C 1 -C 4 Alkyl can be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl groups and their isomers.
- C n -C m alkoxy refers to a C n -C m alkyl corresponding to any carbon atom of an open chain C n -C m alkane bonded with an oxygen atom as a linking group C n -C m alkyl, such as C 1 -C 12 alkoxy, more preferably C 1 -C 6 alkoxy, especially preferably C 1 -C 4 alkoxy.
- C 1 -C 6 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy group, hexyloxy group and its isomers.
- C 1 -C 4 alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and its isomers body.
- C n -C m haloalkyl refers to C n -C m alkyl substituted by one or more same or different halogen atoms, such as C 1 -C 12 haloalkyl, preferably C 1 -C 6 Haloalkyl, particularly preferably C 1 -C 4 haloalkyl.
- Cn- Cm haloalkyl groups mention may be made of monochloromethyl, monochloroethyl, dichloroethyl, trichloroethyl, monochloropropyl, 1-chloromethylethyl, monochlorobutyl Base, 1-chloromethylpropyl, 2-chloromethylpropyl, 1,1-dichloromethylethyl, 1-chloropentyl, 1-chloromethylbutyl, 2-chloromethylbutyl, 3-chloromethylbutyl, 2,2-dichloromethylpropyl, 1-chloroethylpropyl, monochlorohexyl, 1,1-dichloromethylpropyl, 1,2-dichloromethyl Propyl, 1-chloromethylpentyl, 2-chloromethylpentyl, 3-chloromethylpentyl, 4-chloromethylpentyl, 1,1-dichloromethylbutyl, 1,
- C n -C m haloalkoxy refers to C n -C m alkoxy substituted by one or more same or different halogen atoms, such as C 1 -C 12 haloalkoxy, more preferably C 1 -C 6 haloalkoxy, especially preferably C 1 -C 4 haloalkoxy.
- C n -C m haloalkoxy mention may be made of monochloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 2-chloroisopropoxy, 4-chloro-n-butoxy , 3-chloro-sec-butoxy, 2-chloro-tert-butoxy, 5-chloropentyloxy, 4-chloroisoamyloxy, 6-chlorohexyloxy and its isomers.
- C n -C m hydroxyalkyl refers to a C n -C m that has a hydroxyl group bonded to any carbon atom of an open chain C n -C m alkane corresponding to a C n -C m alkyl group.
- Alkyl such as C 1 -C 6 hydroxyalkyl, especially preferably C 1 -C 4 hydroxyalkyl, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxyisopropyl, hydroxybutyl, hydroxypentyl, Hydroxyhexyl and its isomers.
- C 1 -C 30 alkylene as used herein includes C 1 -C 26 alkylene, C 1 -C 18 alkylene, C 1 -C 12 alkylene, C 1 -C 6 alkylene, C 2 -C 26 alkylene, C 2 -C 18 alkylene, C 2 -C 12 alkylene, C 2 -C 6 alkylene, C 3 -C 26 alkylene, C 3 -C 18 alkylene Alkyl, C 3 -C 12 alkylene or C 3 -C 6 alkylene.
- C 1 -C 30 alkyleneoxy as used herein includes C 1 -C 26 alkyleneoxy, C 1 -C 18 alkyleneoxy, C 1 -C 12 alkyleneoxy, C 1 -C 6 alkylene Alkoxy, C 2 -C 26 Alkyleneoxy, C 2 -C 18 Alkyleneoxy, C 2 -C 12 Alkyleneoxy, C 2 -C 6 Alkyleneoxy, C 3 -C 26 Alkylene Alkoxy, C 3 -C 18 alkyleneoxy, C 3 -C 12 alkyleneoxy or C 3 -C 6 alkyleneoxy.
- R 1 , R 2 , and R 3 are the same or different, and are independently C 1 -C 6 alkyl, C 1 -C 6 alkoxy, and among R 1 , R 2 , and R 3 at least Two, preferably all, are C 1 -C 6 alkoxy.
- R 1 , R 2 , and R 3 are the same or different, and are independently C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and at least two of R 1 , R 2 , and R 3 , preferably all C 1 -C 4 alkoxy groups.
- R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 3 alkoxy, and at least two, preferably all, of R 1 , R 2 , and R 3 are C 1 -C 3 alkoxy base.
- R 1 , R 2 , and R 3 are the same or different, and are independently methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy, isopropoxy, and At least two, preferably all, of R 1 , R 2 and R 3 are independently methoxy, ethoxy, n-propoxy or isopropoxy.
- R 4 is usually H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy.
- R 4 is H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 hydroxyalkyl, C 1 -C 4 alkoxy or C 1 -C 4 Haloalkoxy. It is particularly preferred that R 4 is H or C 1 -C 4 alkyl.
- R4 can be H, chloro, bromo, methyl, ethyl, n - propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy , isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl or hydroxy tert-butyl.
- L is a direct bond or a divalent linking group with 1-20 carbon atoms, for example with 1-16, 1-11, 1-8, 1-6, 1-4 or 1- 3, or a divalent linking group of 2-16, 2-11, 2-8, 2-6 or 2-4 carbon atoms.
- L 1 is a direct bond, C 1 -C 20 alkylene, C 1 -C 20 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 20 alkylene group spaced by heteroatoms, or a C 2 -C 20 alkylene group spaced by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
- non-adjacent heteroatom means that there is a non-adjacent heteroatom between two carbon atoms, for example, two carbon atoms of the divalent linking group.
- an ethylene group interrupted by O can be represented as: -CH2 - O-CH2-.
- L 1 is a direct bond, C 1 -C 11 alkylene, C 1 -C 11 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 11 alkylene group interrupted by heteroatoms, or a C 2 -C 11 alkyleneoxy group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
- L 1 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 6 alkylene group interrupted by heteroatoms, or a C 2 -C 6 alkyleneoxy group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl.
- L is a direct bond or a divalent linking group with 1-30 carbon atoms, for example with 1-20, 1-16, 1-11, 1-8, 1-6, 1- 4 or 1-3, or 2-20, 2-16, 2-11, 2-8, 2-6 or 2-4 divalent linking groups of carbon atoms.
- L 2 is a direct bond, C 1 -C 30 alkylene, C 1 -C 30 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 30 alkylene group separated by heteroatoms, or a C 2 -C 30 alkylene group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 15 alkylene (eg C 1 -C 10 alkylene) and L 22 is a direct bond Or C 1 -C 15 alkylene (eg C 1 -C 10 alkylene).
- L 2 is a direct bond, -O-, C 1 -C 8 alkylene, C 1 -C 8 alkyleneoxy, one or more independently selected from NR a , O, S C 2 -C 8 alkylene separated by non-adjacent heteroatoms, or C 2 -C 8 alkyleneoxy separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S , wherein R a is H or C 1 -C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 5 alkylene and L 22 is a direct bond or C 1 -C 3 alkylene alkyl.
- L 2 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, non-adjacent by one or more independently selected from NR a , O, S A C 2 -C 6 alkylene group interrupted by heteroatoms, or a C 2 -C 6 alkyleneoxy group separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 4 alkylene and L 22 is a direct bond or C 1 -C 2 alkylene.
- each variable in the compound of formula (I) has the following definitions:
- R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
- R 4 is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy;
- L 1 is a direct bond, C 1 -C 11 alkylene, C 1 -C 11 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 11 alkylene, or C 2 -C 11 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; and
- L 2 is a direct bond, -O-, C 1 -C 8 alkylene, C 1 -C 8 alkyleneoxy, replaced by one or more non-adjacent heteroatoms independently selected from NR a , O, S Interrupted C 2 -C 8 alkylene, or C 2 -C 8 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 -C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 5 alkylene and L 22 is a direct bond or C 1 -C 3 alkylene;
- each variable in the compound of formula (I) has the following definitions:
- R 1 , R 2 , R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two of R 1 , R 2 , R 3 are C 1 -C 6 alkoxy;
- R 4 is H or C 1 -C 4 alkyl
- L 1 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 6 alkylene, or C 2 -C 6 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; and
- L 2 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, C 2 separated by one or more non-adjacent heteroatoms independently selected from NR a , O, S -C 6 alkylene, or C 2 -C 6 alkyleneoxy interrupted by one or more non-adjacent heteroatoms independently selected from NR a , O, S, wherein R a is H or C 1 - C 4 alkyl; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 4 alkylene and L 22 is a direct bond or C 1 -C 2 alkylene.
- each variable in the compound of formula (I) has the following definitions:
- R 1 , R 2 , and R 3 are the same or different, and are independently C 1 -C 6 alkyl or C 1 -C 6 alkoxy, and at least two, preferably all, of R 1 , R 2 , and R 3 is C 1 -C 6 alkoxy;
- R 4 is H or C 1 -C 4 alkyl
- L 1 is a direct bond, C 1 -C 6 alkylene or C 1 -C 6 alkyleneoxy
- L 2 is a direct bond, C 1 -C 6 alkylene, C 1 -C 6 alkyleneoxy, C 2 -C 6 alkylene interrupted by one or more non-adjacent oxygen atoms, or separated by one or C 2 -C 6 alkyleneoxy group separated by multiple non-adjacent oxygen atoms; preferably L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 4 alkylene and L 22 is a direct bond or C 1 -C 2 alkylene.
- the compound of formula (I) is one or more compounds selected from the group consisting of:
- R 4 and L 2 are as defined above for the compound of formula (I);
- L 2 is L 21 -OL 22 , wherein L 21 is C 1 -C 15 alkylene and L 22 is a direct bond or C 1 -C 15 alkylene, preferably L 21 is C 1 -C 5 alkylene and L 22 are direct bonds or C 1 -C 3 alkylene.
- the compound of formula (IV) is prepared as follows:
- L 21 is C 1 -C 15 alkylene, preferably C 1 -C 5 alkylene
- X is halogen, such as fluorine, chlorine, bromine or iodine
- L 22 is a direct bond or a C 1 -C 15 alkylene group, preferably a direct bond or a C 1 -C 3 alkylene group, and R 4 is as defined above for the compound of formula (I).
- the reaction of the terminal hydroxyl group in the compound of formula (III) with the halogen in the compound of formula (II) belongs to the type of reaction known in the art, and the reaction produces hydrogen halide.
- the reaction is carried out in the presence of a catalyst.
- suitable catalysts for this reaction mention may be made of basic catalysts such as sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine, potassium carbonate or any mixture thereof.
- the amount of catalyst used is also conventional.
- the molar ratio of the compound of formula (III) to the catalyst is 1:1-1:5, preferably 1:1-1:3.
- the reaction of the compound of formula (III) with the compound of formula (II) is usually carried out in a solvent.
- a solvent there is no special limitation, as long as the compound of formula (III), compound of formula (II) and corresponding catalyst can be dissolved and the reaction between the compound of formula (III) and compound of formula (II) can not be participated in, preferably
- the solvent also facilitates the precipitation of the product, the compound of formula (IV).
- an organic solvent is usually used, preferably toluene, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, cyclohexane, 1,4-dioxane, dichloromethane, acetonitrile or any mixture thereof.
- the amount of solvent used is also conventional, generally speaking, the amount of solvent used is 1.0-3 times the total weight of the compound of formula (III) and compound of formula (II).
- the compound of formula (III) and the compound of formula (II) are usually used in approximately equimolar amounts.
- the molar ratio of the compound of formula (III) to the compound of formula (II) is 1:0.7-1:1.5 or 1:1-1:1.5, or 1:1-1:1.2.
- the compound of formula (II) and compound of formula (III) and the catalyst are usually dissolved in a solvent, and then react at 50-150°C, preferably at 60-130°C for 8-24 hours, preferably react 9-15 Hour.
- the reaction is advantageously carried out with stirring.
- the compound of formula (IV) can be obtained through conventional post-treatment.
- the post-treatment usually includes extraction or washing (such as washing with water, after which water-absorbing compounds such as magnesium sulfate or sodium sulfate are advantageously used to remove water), filtration or centrifugation to remove solid impurities, rotary evaporation to remove solvents, and vacuum distillation to further remove solvents. If a higher purity product is to be obtained, impurities can also be separated by recrystallization or column chromatography.
- the mercapto group in the compound of formula (V) and the unsaturated carbon-carbon double bond in the compound of formula (IV) undergo Click reaction.
- the reaction is performed under irradiation with a mercury lamp.
- the reaction of the compound of formula (IV) with the compound of formula (V) can usually be carried out without solvent. This reaction can be done without a catalyst.
- the amount of the compound of formula (IV) and the compound of formula (V) is usually used in an approximately equimolar amount, for example, the molar ratio of the compound of formula (IV) to the compound of formula (V) can be 1:0.7-1:5 or 1:1- 1:5, preferably 1:1-1:3.
- the compound of formula (IV) and compound of formula (V) are usually mixed uniformly first, and then the mixture is exposed under a mercury lamp for a period of time to obtain the compound of formula (I).
- the intensity of the mercury lamp used for exposure is typically 50-500 mW/cm 2 . Exposure times are typically 10-60 minutes.
- the wavelength of the mercury lamp is usually 365nm.
- the reaction temperature between the compound of formula (IV) and the compound of formula (V) is usually 0-40°C, preferably 10-30°C.
- the holding time of the reaction between the compound of formula (IV) and the compound of formula (V) at the reaction temperature is usually 10-60 minutes, preferably 20-40 minutes. Of course, the reaction is advantageously carried out with stirring. After the reaction is completed, the product of the compound of formula (I) can be obtained through conventional post-treatment.
- the compound of formula (I) of the present invention is a cationic light-curable silane coupling agent, which can also be fixed in the system after cationic light-curing, with little or no freeing, and has good tensile properties and strong adhesion Etc.
- a photocurable composition comprising the compound of formula (I) of the present invention as a coupling agent.
- the photocurable composition may also include a cationic photoinitiator for ring-opening polymerization (a photoinitiator capable of initiating cationic polymerization) and optionally other photoinitiators containing cationic photocurable groups.
- a cationic photoinitiator for ring-opening polymerization a photoinitiator capable of initiating cationic polymerization
- optionally other photoinitiators containing cationic photocurable groups include cationic photoinitiator for ring-opening polymerization (a photoinitiator capable of initiating cationic polymerization) and optionally other photoinitiators containing cationic photocurable groups.
- Groups such as vinyl ether double bonds, alicyclic epoxy, oxiranyl or oxetanyl monomers, oligomers, such as 3,4-epoxycyclohe
- the amount of the compound of formula (I) of the present invention may be at least 0.5 mol%, at least 1 mol%, at least 2 mol%, for example 0.5-12 mol%, based on the total amount of polymerized monomers, Or 0.5-10mol%, or 1-10mol%.
- the photocurable composition of the present invention may be a photocurable coating composition, a photocurable ink composition, a photoresist composition, and the like. After the composition is cured, the obtained cured product has good tensile properties and strong adhesion.
- iodonium salts and sulfonium salts are commonly used.
- the iodonium salt photoinitiator and the sulfonium salt photoinitiator have the following general formulas (A) and (B) respectively
- R a , R b , R c , R d , R e are each independently unsubstituted C 6 -C 10 aryl, or are selected from halogen, nitro, carbonyl, C 1 -C 12 alkyl, C 1 C 6 -C 10 aryl substituted by substituents of -C 12 alkoxy, phenylthio, phenyl and substituted phenyl, preferably phenyl or naphthyl, or selected from halogen, nitro, C 1 - C 6 alkyl and substituted phenyl or naphthyl substituted by substituents of phenyl, wherein the substituted phenyl contains one or more substituents selected from halogen, nitro, C 1 -C 6 alkyl and C 1 -C 6 alkoxy radicals; and
- Y and Z are non-nucleophilic anions, such as trifluoromethanesulfonate, BF 4 - , ClO 4 - , PF 6 - , AsF 6 - , SbF 6 - .
- a photoinitiator one or more selected from the group consisting of 4-(phenylthio)phenyl diphenylsulfonium hexafluorophosphate, 4-(phenylthio)phenyl ⁇ Diphenylsulfonium hexafluoroantimonate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonium)phenyl)sulfide bishexafluorophosphate Fluoroantimonate, 10-(4-biphenyl)-2-isopropylthioxanthone-10-sulfonium hexafluorophosphate, 10-(4-biphenyl)-2-isopropylthioxanthone Keto-10-sulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate
- the photocurable composition of the present invention may also contain a sensitizer.
- a sensitizer mention may be made, for example, of 2-isopropylthioxanthone.
- the amount of photoinitiator used is conventional. Based on the total molar amount of polymerized monomers in the photocurable composition of the present invention, the content of the photoinitiator is generally 0.5-5 mol%, preferably 1-3 mol%.
- a photocurable material obtained from the photocurable composition of the present invention is obtained by photocuring the photocurable composition of the invention.
- the light-curing material has the advantages of good tensile performance and strong adhesion.
- the compounds of formula (I) according to the invention can also be used in photocurable coatings, adhesives, inks and photoresists. Accordingly, the present invention also relates to the use of compounds of formula (I) in photocurable coatings, adhesives, inks and photoresists.
- the purpose of this example is to illustrate the photopolymerizable properties of the compounds of the present invention.
- a mixture of photoinitiator diphenyliodonium hexafluorophosphate (810) and 2-isopropylthioxanthone (ITX, sensitizer) in a molar ratio of 2:1 was used as the photoinitiation system, and real-time infrared
- the method of (RT-IR) tested the photopolymerization kinetics of compound 1, and investigated the influence of different contents on the photopolymerization performance of E4221.
- the vibrational absorption peak of the COC of the three-membered oxygen heterocycle of the monomer E4221 used is located at 750 cm -1
- the vibration absorption peak of the COC of the four-membered oxygen heterocycle of compound 1 as a polymerized monomer is 980 cm - 1 .
- the photocurable liquid composed of the initiator is evenly spread on the potassium bromide salt sheet (use a narrow tube to dip a little photocurable liquid on the potassium bromide salt sheet, and then spread it evenly), and irradiate the liquid sample with a high-pressure mercury lamp 900s, in which the main emission wavelength of the mercury lamp is 365nm, and it has an optical fiber with a diameter of 5mm.
- the distance between one end of the optical fiber and the test sample is 10 cm, and the radiation intensity is 20 mW cm -2 .
- the purpose of this example is to illustrate that the compounds of the present invention can improve the tensile properties of photocured films.
- the films were cured and tested for tensile properties.
- the tensile properties are based on the international standard ISO 1184-1983 "Determination of tensile properties of plastic films", and passed the E44.304 electronic universal testing machine test. Test conditions: temperature 25°C, humidity 60%, test speed 1mm ⁇ min -1 . At the same time, use the same method to prepare a blank E4221 cured film as a reference. The results are shown in Figure 3 and Table 2.
- the purpose of this example is to illustrate that the compounds of the present invention can improve the adhesion of photocured films.
- Coat the photosensitive liquid on a 25mm ⁇ 25mm substrate (see Table 3), and after curing under a mercury lamp, cut the coating into a square of 10 ⁇ 10 with 100 grids, stick the adhesive tape on the cut-out area and tear it off Adhesive tape, detect the peeling off of the coating at the cross-cut.
- Adhesion is divided into 6 grades according to the shedding of the coating at the position of the hundred grids. No shedding is 0, and the shedding ratio is within 5%, 5-15%, 15-35%, 35-65%, and 65% or more, respectively. Divided into 1 to 5 grades.
- the compounds of the present invention can improve the adhesion of photocured films.
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Abstract
本发明涉及一种硫醚基氧杂环丁烷硅烷偶联剂，其制备方法，包含其的可光固化组合物和由该可光固化组合物得到的光固化材料。本发明的硫醚基氧杂环丁烷硅烷偶联剂光固化后会固定在体系中，游离少，甚至不游离，还具有拉伸性能好，附着力强等优点。
Description
本发明涉及光固化材料领域，具体来说涉及一种硫醚基氧杂环丁烷硅烷偶联剂。本发明还涉及该硅烷偶联剂的制备方法，包含该硅烷偶联剂的可光固化组合物和由该可光固化组合物得到的光固化材料。
光聚合技术是利用光来引发带有活性物质的液态低聚物或单体转变为固态产物的过程。相比于传统的热聚合技术，光聚合无需使用挥发性有机溶剂即可实现高效的无污染生产，节省了大量能源。据估计，通过从热聚合转换为光聚合，能源成本可以降低20-25％。光聚合技术以其特有的低能耗要求、快速固化、无溶剂配方、无污染、室温处理和环保等特点而被视为一种绿色工艺，因而在光固化涂料、粘合剂和油墨印刷等领域应用广泛。
在光聚合领域，硅烷偶联剂的加入可以改善材料的性能，但是硅烷偶联剂会游离在光聚合体系中，影响产品的综合性能，并造成环境污染。因此，人们希望开发出一种游离少，甚至不游离的硅烷偶联剂，从而提高产品的综合性能并减少产品对环境的污染。另外，目前可工业化生产的硅烷偶联剂制备过程都需要加热和使用大量溶剂，并且反应时间长，这就导致了耗能大、生产效率低及对环境产生污染的弊病。而随着全球环保意识的不断增强，开发绿色化学反应及工艺已成为现代化学工业发展的大趋势。因此，迫切希望可以提供一种绿色环保、高效的制备硅烷偶联剂的方法。
发明内容
鉴于现有技术的上述状况，本发明的发明人在硅烷偶联剂方面进行了广泛而又深入的研究，以期发现一类新型的氧杂环丁烷硅烷偶联剂。本发明人发现，本发明的硫醚基氧杂环丁烷基硅烷偶联剂光固化后会固定在体系中，游离少，甚至不游离，还具有拉伸性能好，附着力强等优点。
因此，本发明的一个目的是提供一种硫醚基氧杂环丁烷硅烷偶联剂。所述硫醚基氧杂环丁烷硅烷偶联剂光固化后会固定在体系中，游离少，甚至不游离，还具有拉伸性能好，附着力强等优点。
本发明的另一目的是提供一种制备硫醚基氧杂环丁烷硅烷偶联剂的方法。该 制备方法简单易行，绿色环保，高效，无溶剂，产率高。
本发明的再一个目的是提供一种可光固化组合物，该组合物包含根据本发明的硫醚基氧杂环丁烷硅烷偶联剂。
本发明的再一个目的是提供一种由本发明的可光固化组合物得到的光固化材料。
本发明的再一个目的是提供本发明的式(I)化合物在光固化涂料、粘合剂、油墨和光致抗蚀剂中的用途。
实现本发明上述目的的技术方案可以概括如下：
1.下式(Ⅰ)化合物：
R
1、R
2、R
3相同或不同，并独立地为C
1-C
6烷基或C
1-C
6烷氧基，并且R
1，R
2，R
3中的至少两个为C
1-C
6烷氧基；
R
4为H、卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6羟烷基、C
1-C
6烷氧基或者C
1-C
6卤代烷氧基；
L
1为直接键或具有1-20个碳原子的二价连接基团；以及
L
2为直接键或具有1-30个碳原子的二价连接基团。
2.根据第1项的化合物，其中
R
1、R
2、R
3相同或不同，并独立地为C
1-C
3烷基或C
1-C
3烷氧基，并且R
1，R
2，R
3中至少两个为C
1-C
3烷氧基。
3.根据第1或2项的化合物，其中R
4为H、卤素、C
1-C
4烷基、C
1-C
4卤代烷基、C
1-C
4羟烷基、C
1-C
4烷氧基或者C
1-C
4卤代烷氧基。
4.根据第1-3项中任一项的化合物，其中L
1为直接键、C
1-C
20亚烷基、C
1-C
20亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
20亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
20亚烷氧基，其中R
a为H或C
1-C
4烷基；以及
L
2为直接键、C
1-C
30亚烷基、C
1-C
30亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
30亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
30亚烷氧基，其中R
a为H或C
1-C
4烷基；优选L
2为L
21-O-L
22，其中L
21为C
1-C
15亚烷基和L
22为直接键或C
1-C
15亚烷基。
5.根据第1-4项中任一项的化合物，其中
R
1、R
2、R
3相同或不同，并独立地为C
1-C
6烷基或C
1-C
6烷氧基，并且R
1，R
2，R
3中的至少两个为C
1-C
6烷氧基；
R
4为H、卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6羟烷基、C
1-C
6烷氧基或者C
1-C
6卤代烷氧基；
L
1为直接键、C
1-C
11亚烷基、C
1-C
11亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
11亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
11亚烷氧基，其中R
a为H或C
1-C
4烷基；以及
L
2为直接键、C
1-C
8亚烷基、C
1-C
8亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
8亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
8亚烷氧基，其中R
a为H或C
1-C
4烷基；优选L
2为L
21-O-L
22，其中L
21为C
1-C
5亚烷基和L
22为直接键或C
1-C
3亚烷基；
优选的是，
R
1、R
2、R
3相同或不同，并独立地为C
1-C
6烷基或C
1-C
6烷氧基，并且R
1，R
2，R
3中的至少两个为C
1-C
6烷氧基；
R
4为H或C
1-C
4烷基；
L
1为直接键、C
1-C
6亚烷基、C
1-C
6亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷氧基，其中R
a为H或C
1-C
4烷基；以及
L
2为直接键、C
1-C
6亚烷基、C
1-C
6亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷氧基，其中R
a为H或C
1-C
4烷基；优选L
2为L
21-O-L
22，其中L
21为C
1-C
4亚烷基和L
22为直接键或C
1-C
2亚烷基。
6.根据第1-5项中任一项的化合物，其为一种或多种选自下组的化合物：
7.一种制备根据第1-6项中任一项的式(Ⅰ)化合物的方法，包括：
使式(Ⅳ)化合物
其中R
4和L
2如对第1-6项中任一项所定义；
与式(Ⅴ)化合物反应，得到式(I)化合物，
其中L
1、R
1、R
2和R
3如对第1-6项中任一项所定义。
8.根据第7项的方法，其中L
2为L
21-O-L
22，其中L
21为C
1-C
15亚烷基和L
22为直接键或C
1-C
15亚烷基，优选L
21为C
1-C
5亚烷基和L
22为直接键或C
1-C
3亚烷基。
9.根据第7或8项的方法，其中式(IV)化合物如下制备：
使式(Ⅱ)化合物：
其中L
21为C
1-C
15亚烷基，优选C
1-C
5亚烷基，X为卤素，例如氟、氯、溴或碘，
与式(Ⅲ)化合物反应，得到式(IV)化合物，
其中L
22为直接键或C
1-C
15亚烷基，优选直接键或C
1-C
3亚烷基，R
4如对第7项所定义。
10.根据第9项的方法，其中式(Ⅱ)化合物与式(Ⅲ)化合物的反应满足下述条件中的至少一个：
-式(Ⅱ)化合物与式(Ⅲ)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选为氢化钠、氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(Ⅱ)化合物与碱性催化剂的摩尔用量比为1:1-1:3；
-式(Ⅱ)化合物与式(Ⅲ)化合物摩尔比为1:0.7-1:1.2；
-式(Ⅱ)化合物与式(Ⅲ)化合物之间的反应在80-120℃，优选100-120℃下进行；
-式(Ⅱ)化合物与式(Ⅲ)化合物之间的反应进行6-15小时，优选8-12小时。
11.根据第7-10项中任一项的方法，其中式(Ⅳ)化合物与式(Ⅴ)化合物的反应满足下述条件中的至少一个：
式(Ⅳ)化合物与式(Ⅴ)化合物的反应在光强为50-500mw/cm
-2的汞灯下反应；
式(Ⅳ)化合物与式(Ⅴ)化合物的用量摩尔比为1:0.7-1:1.5；
式(Ⅳ)化合物与式(Ⅴ)化合物之间的反应在0-40℃，优选10-30℃下进行；
式(Ⅳ)化合物与式(Ⅴ)化合物之间的反应进行5-60分钟，优选20-40分钟。
12.一种可光固化组合物，包含根据第1-6项中任一项的式(Ⅰ)化合物作为聚合单体。
13.一种由第12项的可光固化组合物得到的光固化材料。
14.根据第1-6项中任一项的式(I)化合物在光固化涂料、粘合剂、油墨和光致抗蚀剂中的用途。
图1是包含实施例1所制备的化合物1的体系中的E4221的转化率随辐照时间的变化曲线图。
图2是包含实施例1所制备的化合物1的体系中的化合物1的转化率随辐照时间的变化曲线图。
图3是空白E4221固化膜和包含不同量的实施例1制备的化合物1的固化膜的力学性能曲线图。
以下对本发明的实施方式进行说明。但是，本发明不限于以下的实施方式。
本文中，使用数值范围表示前后所记载的数值分别作为最小值和最大值的范围。
本文对相关特征公开具体值(包括范围的端点)可以相互结合成一个新的范围。
根据本发明的一个方面，提供了一种下式(Ⅰ)化合物：
R
1、R
2、R
3相同或不同，并独立地为C
1-C
6烷基或C
1-C
6烷氧基，并且R
1，R
2，R
3中的至少两个为C
1-C
6烷氧基；
R
4为H、卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6羟烷基、C
1-C
6烷氧基或者C
1-C
6卤代烷氧基；
L
1为直接键或具有1-20个碳原子的二价连接基团；以及
L
2为直接键或具有1-30个碳原子的二价连接基团。
制备本发明的式(Ⅰ)化合物的原料易得、且可由绿色环保、简单、无溶剂及无需加热的反应制备，并且本发明的式(I)化合物光固化后会固定在体系中，不游离，不污染环境，并具有拉伸性能好，附着力强等优点。
在本发明中，前缀“C
n-C
m”在每种情况下表示该基团中包含的碳原子数为n-m个。
“卤素”是指氟、氯、溴和碘。在本发明中，优选的是，卤素包括溴、氯或其组合。
本文所用的术语“C
n-C
m烷基”是指具有n-m个，例如1-12个，优选1-6个，特别优选1-4个碳原子的支化或未支化饱和烃基，例如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、1-乙基丙基、己基、1,1-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、庚基、辛基、2-乙基己基、壬基、癸基、十一烷基、十二烷基及其异构体。C
1-C
6烷基可以是甲基、乙基、丙基、异丙基、正丁基、2-丁基、叔丁基、戊基、异戊基、己基及其异构体。C
1-C
4烷基可以是甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1,1-二甲基乙基及其异构体。
本文所用的术语“C
n-C
m烷氧基”是指在C
n-C
m烷基对应的开链C
n-C
m烷烃的任何碳原子上键合有一个氧原子作为连接基团的C
n-C
m烷基，例如C
1-C
12烷氧基，更优选C
1-C
6烷氧基，尤其优选C
1-C
4烷氧基。C
1-C
6烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、2-丁氧基、叔丁氧基、戊氧基、异戊氧基、己氧基及其异构体。C
1-C
4烷氧基可以是甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基及其异构体。
本文所用的术语“C
n-C
m卤代烷基”是指被一个或多个相同或不同卤素原子取代的C
n-C
m烷基，例如C
1-C
12卤代烷基，优选C
1-C
6卤代烷基，特别优选C
1-C
4卤代烷基。作为C
n-C
m卤代烷基的实例，可以提及一氯甲基、一氯乙基、二氯乙基、三氯乙基、一氯丙基、1-氯甲基乙基、一氯丁基、1-氯甲基丙基、2-氯甲基丙基、1,1-二氯甲基乙基、一氯戊基、1-氯甲基丁基、2-氯甲基丁基、3-氯甲基丁基、2,2-二氯甲基丙基、1-氯乙基丙基、一氯己基、1,1-二氯甲基丙基、1,2-二氯甲基丙基、1-氯甲基戊基、2-氯甲基戊基、3-氯甲基戊基、4-氯甲基戊基、1,1-二氯甲基丁基、1,2-二氯甲基丁基、1,3-二氯甲基丁基、2,2-二氯甲基丁基、2,3-二氯甲基丁基、3,3-二氯甲基丁基、1-氯乙基丁基、2-氯乙基丁基、1,1,2-三氯甲基丙基、1,2,2-三氯甲基丙基、1-氯乙基-1-甲基丙基、1-乙基-2-氯甲基丙基及其异 构体。
本文所用的术语“C
n-C
m卤代烷氧基”是指被一个或多个相同或不同卤素原子取代的C
n-C
m烷氧基，例如C
1-C
12卤代烷氧基，更优选C
1-C
6卤代烷氧基，尤其优选C
1-C
4卤代烷氧基。作为C
n-C
m卤代烷氧基的实例，可以提及一氯甲氧基、2-氯乙氧基、3-氯丙氧基、2-氯异丙氧基、4-氯正丁氧基、3-氯仲丁氧基、2-氯叔丁氧基、5-氯戊氧基、4-氯异戊氧基、6-氯己氧基及其异构体。
本文所用的术语“C
n-C
m羟烷基”是指在C
n-C
m烷基对应的开链C
n-C
m烷烃的任何碳原子上键合有一个羟基的C
n-C
m烷基，例如C
1-C
6羟烷基，尤其优选C
1-C
4羟烷基，例如羟甲基、羟乙基、羟丙基、羟异丙基、羟丁基、羟戊基、羟己基及其异构体。
本文所用的术语C
1-C
30亚烷基包括C
1-C
26亚烷基、C
1-C
18亚烷基、C
1-C
12亚烷基、C
1-C
6亚烷基、C
2-C
26亚烷基、C
2-C
18亚烷基、C
2-C
12亚烷基、C
2-C
6亚烷基、C
3-C
26亚烷基、C
3-C
18亚烷基、C
3-C
12亚烷基或C
3-C
6亚烷基。
本文所用的术语C
1-C
30亚烷氧基包括C
1-C
26亚烷氧基、C
1-C
18亚烷氧基、C
1-C
12亚烷氧基、C
1-C
6亚烷氧基、C
2-C
26亚烷氧基、C
2-C
18亚烷氧基、C
2-C
12亚烷氧基、C
2-C
6亚烷氧基、C
3-C
26亚烷氧基、C
3-C
18亚烷氧基、C
3-C
12亚烷氧基或C
3-C
6亚烷氧基。
在本发明化合物中，R
1、R
2、R
3相同或不同，并独立地为C
1-C
6烷基、C
1-C
6烷氧基，并且R
1，R
2，R
3中至少两个，优选全部为C
1-C
6烷氧基。优选的是，R
1、R
2、R
3相同或不同，并独立地为C
1-C
4烷基、C
1-C
4烷氧基，并且R
1，R
2，R
3中至少两个，优选全部为C
1-C
4烷氧基。尤其R
1、R
2、R
3相同或不同，并独立地为C
1-C
3烷氧基，并且R
1，R
2，R
3中至少两个，优选全部为C
1-C
3烷氧基。例如R
1、R
2、R
3相同或不同，并独立地为甲基、乙基、正丙基、异丙基、甲氧基、乙氧基、正丙氧基、异丙氧基，并且R
1，R
2，R
3中至少两个，优选全部独立地为甲氧基、乙氧基、正丙氧基或异丙氧基。
在本发明化合物中，R
4通常为H、卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6羟烷基、C
1-C
6烷氧基或者C
1-C
6卤代烷氧基。优选的是，R
4为H、卤素、C
1-C
4烷基、C
1-C
4卤代烷基、C
1-C
4羟烷基、C
1-C
4烷氧基或者C
1-C
4卤代烷氧基。特别优选的是，R
4为H或C
1-C
4烷基。例如，R
4可以为H、氯、溴、甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、羟甲基、羟乙基、羟正丙基、羟异丙基、羟正丁基、羟仲丁基或羟叔丁基。
在本发明化合物中，L
1为直接键或具有1-20个碳原子的二价连接基团，例如具有1-16，1-11，1-8，1-6，1-4或1-3，或2-16、2-11、2-8、2-6或2-4个碳原子的二价连接基团。
在一个实施方案中，L
1为直接键、C
1-C
20亚烷基、C
1-C
20亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
20亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
20亚烷氧基，其中R
a为H或C
1-C
4烷基。
本领域技术人员可以理解，被所述非相邻杂原子间隔是指，在两个碳原子，例如所述二价连接基团的两个碳原子中间存在非相邻杂原子。例如，被O间隔的亚乙基可以表示为：-CH
2-O-CH
2-。
在一个实施方案中，L
1为直接键、C
1-C
11亚烷基、C
1-C
11亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
11亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
11亚烷氧基，其中R
a为H或C
1-C
4烷基。
在一个实施方案中，L
1为直接键、C
1-C
6亚烷基、C
1-C
6亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷氧基，其中R
a为H或C
1-C
4烷基。
在本发明化合物中，L
2为直接键或具有1-30个碳原子的二价连接基团，例如具有1-20，1-16，1-11，1-8，1-6，1-4或1-3个，或2-20，2-16，2-11，2-8，2-6或2-4个碳原子的二价连接基团。
在一个实施方案中，L
2为直接键、C
1-C
30亚烷基、C
1-C
30亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
30亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
30亚烷氧基，其中R
a为H或C
1-C
4烷基；优选L
2为L
21-O-L
22，其中L
21为C
1-C
15亚烷基(例如C
1-C
10亚烷基)和L
22为直接键或C
1-C
15亚烷基(例如C
1-C
10亚烷基)。
在一个实施方案中，L
2为直接键、-O-、C
1-C
8亚烷基、C
1-C
8亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
8亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
8亚烷氧基，其中R
a为H或C
1-C
4烷基；优选L
2为L
21-O-L
22，其中L
21为C
1-C
5亚烷基和L
22为直接键或C
1-C
3亚烷基。
在一个实施方案中，L
2为直接键、C
1-C
6亚烷基、C
1-C
6亚烷氧基、被一个或 多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷氧基，其中R
a为H或C
1-C
4烷基；优选L
2为L
21-O-L
22，其中L
21为C
1-C
4亚烷基和L
22为直接键或C
1-C
2亚烷基。
在本发明的一个实施方案中，式(I)化合物中的各变量具有如下定义：
R
1、R
2、R
3相同或不同，并独立地为C
1-C
6烷基或C
1-C
6烷氧基，并且R
1，R
2，R
3中的至少两个为C
1-C
6烷氧基；
R
4为H、卤素、C
1-C
6烷基、C
1-C
6卤代烷基、C
1-C
6羟烷基、C
1-C
6烷氧基或者C
1-C
6卤代烷氧基；
L
1为直接键、C
1-C
11亚烷基、C
1-C
11亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
11亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
11亚烷氧基，其中R
a为H或C
1-C
4烷基；以及
L
2为直接键、-O-、C
1-C
8亚烷基、C
1-C
8亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
8亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
8亚烷氧基，其中R
a为H或C
1-C
4烷基；优选L
2为L
21-O-L
22，其中L
21为C
1-C
5亚烷基和L
22为直接键或C
1-C
3亚烷基；
在本发明的一个优选实施方案中，式(I)化合物中的各变量具有如下定义：
R
1、R
2、R
3相同或不同，并独立地为C
1-C
6烷基或C
1-C
6烷氧基，并且R
1，R
2，R
3中的至少两个为C
1-C
6烷氧基；
R
4为H或C
1-C
4烷基；
L
1为直接键、C
1-C
6亚烷基、C
1-C
6亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷氧基，其中R
a为H或C
1-C
4烷基；以及
L
2为直接键、C
1-C
6亚烷基、C
1-C
6亚烷氧基、被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷基、或者被一个或多个独立地选自NR
a、O、S的非相邻杂原子间隔的C
2-C
6亚烷氧基，其中R
a为H或C
1-C
4烷基；优选L
2为L
21-O-L
22，其中L
21为C
1-C
4亚烷基和L
22为直接键或C
1-C
2亚烷基。
在本发明的一个优选实施方案中，式(I)化合物中的各变量具有如下定义：
R
1、R
2、R
3相同或不同，并独立地为C
1-C
6烷基或C
1-C
6烷氧基，并且R
1，R
2，R
3中的至少两个，优选全部为C
1-C
6烷氧基；
R
4为H或C
1-C
4烷基；
L
1为直接键、C
1-C
6亚烷基或C
1-C
6亚烷氧基；以及
L
2为直接键、C
1-C
6亚烷基、C
1-C
6亚烷氧基、被一个或多个非相邻氧原子间隔的C
2-C
6亚烷基、或者被一个或多个非相邻氧原子间隔的C
2-C
6亚烷氧基；优选L
2为L
21-O-L
22，其中L
21为C
1-C
4亚烷基和L
22为直接键或C
1-C
2亚烷基。
在本发明的另一实施方案中，式(Ⅰ)化合物为一种或多种选自下组的化合物：
根据本发明的第二个方面，提供了一种制备本发明式(Ⅰ)化合物的方法，包括：
使式(Ⅳ)化合物
其中R
4和L
2如上对式(I)化合物所定义；
与式(Ⅴ)化合物反应，得到式(I)化合物，
其中L
1、R
1、R
2和R
3如上对式(I)化合物所定义。
根据本发明的一个优选实施方案，L
2为L
21-O-L
22，其中L
21为C
1-C
15亚烷基和L
22为直接键或C
1-C
15亚烷基，优选L
21为C
1-C
5亚烷基和L
22为直接键或C
1-C
3亚烷基。
根据本发明的一个实施方案，式(IV)化合物如下制备：
使式(Ⅱ)化合物：
其中L
21为C
1-C
15亚烷基，优选C
1-C
5亚烷基，X为卤素，例如氟、氯、溴或碘，
与式(Ⅲ)化合物反应，得到式(IV)化合物，
其中L
22为直接键或C
1-C
15亚烷基，优选直接键或C
1-C
3亚烷基，R
4如上对式(I)化合物所定义。
在式(II)化合物与式(III)化合物的反应中，式(Ⅲ)化合物中的端羟基与式(Ⅱ)化合物中的卤素的反应属于本领域已知的反应类型，反应产生卤化氢。通常而言，该反应在催化剂存在下进行。作为适合该反应的催化剂，可以提及碱性催化剂，如氢化钠、氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物。催化剂的用量也是常规的。通常而言，式(Ⅲ)化合物与催化剂的摩尔用量比为1:1-1:5，优选1:1-1:3。式(Ⅲ)化合物与式(Ⅱ)化合物的反应通常在溶剂中进行。作为溶剂的类型，没有特别的限制，只要能将式(Ⅲ)化合物、式(Ⅱ)化 合物和相应催化剂溶解并且不参与式(Ⅲ)化合物与式(Ⅱ)化合物之间的反应即可，优选该溶剂还有有利于产物，即式(IV)化合物析出。作为该溶剂，通常使用有机溶剂，优选使用甲苯、丙酮、丁酮、甲苯、四氢呋喃、环己烷、1,4-二氧六环、二氯甲烷、乙腈或其任意混合物。溶剂的用量也是常规的，通常而言，溶剂的用量为式(Ⅲ)化合物和式(Ⅱ)化合物总重量的1.0-3倍。式(Ⅲ)化合物和式(Ⅱ)化合物的用量通常以大致等摩尔量使用。有利的是，式(Ⅲ)化合物与式(Ⅱ)化合物的用量摩尔比为1:0.7-1:1.5或1:1-1:1.5，或1:1-1:1.2。为了实现上述反应，通常将式(II)化合物和式(Ⅲ)化合物、催化剂溶解在溶剂中，然后在50-150℃，优选在60-130℃下反应8-24小时，优选反应9-15小时。当然，反应有利地在搅拌下进行。反应完毕之后，通过常规后处理，即获得式(Ⅳ)化合物。该后处理通常包括萃取或洗涤(例如用水洗涤，水洗涤之后有利地采用吸水化合物比如硫酸镁或硫酸钠除水)、过滤或离心除去固体杂质，旋蒸除去溶剂，减压蒸馏进一步除去溶剂。如果要获得更高纯度的产物，还可重结晶或柱层析法分离杂质。
在式(IV)化合物与式(V)化合物的反应中，式(Ⅴ)化合物中的巯基与式(Ⅳ)化合物中的不饱和碳碳双键进行Click点击反应。通常而言，该反应在汞灯照射下进行。式(Ⅳ)化合物与式(Ⅴ)化合物的反应通常无溶剂即可进行。该反应可无需催化剂。式(Ⅳ)化合物和式(Ⅴ)化合物的用量通常以大致等摩尔量使用，例如式(Ⅳ)化合物和式(Ⅴ)化合物的摩尔比可以为1:0.7-1:5或1:1-1:5，优选1:1-1:3。为了实现上述反应，通常先将式(Ⅳ)化合物与式(Ⅴ)化合物混合均匀，然后再将其混合液置于汞灯下曝光一段时间，得到式(Ⅰ)化合物。用于曝光的汞灯光强通常为50-500mw/cm
2。曝光时间通常为10-60分钟。汞灯的波长通常为365nm。式(Ⅳ)化合物与式(Ⅴ)化合物之间的反应温度通常为0-40℃，优选10-30℃。式(Ⅳ)化合物与式(Ⅴ)化合物之间的反应在反应温度下的保持时间通常为10-60分钟，优选20-40分钟。当然，反应有利地在搅拌下进行。反应完毕之后，通过常规后处理，即获得式(Ⅰ)化合物产物。
本发明式(Ⅰ)化合物是一种可阳离子光固化硅烷偶联剂，该化合物还可以经阳离子光固化后固定在体系中，游离少，甚至不游离，并具有拉伸性能好，附着力强等优点。
根据本发明的第三个方面，提供了一种可光固化组合物，该组合物包含本发明的式(Ⅰ)化合物作为偶联剂。该可光固化组合物除了包含本发明的式(Ⅰ)化合物以外，还可包含开环聚合的阳离子光引发剂(可引发阳离子聚合的 光引发剂)以及任选地其它含有可阳离子光固化基团如乙烯基醚双键、脂环族环氧基、环氧乙烷基或者氧杂环丁烷基的单体、低聚物，例如3,4-环氧环己基甲基3,4-环氧环己基甲酸酯(E4221)。
在本发明的可光固化组合物中，基于聚合单体的总量，本发明的式(I)化合物的量可以为至少0.5mol％，至少1mol％，至少2mol％，例如0.5-12mol％，或0.5-10mol％，或1-10mol％。
本发明可光固化组合物可以为光固化涂料组合物、光固化油墨组合物、光致抗蚀组合物等。该组合物在固化后，所得固化产物拉伸性能好，附着力强。
作为开环聚合的光引发剂，常用的有碘鎓盐和硫鎓盐。有利的是，所述碘鎓盐光引发剂和硫鎓盐光引发剂分别具有如下通式(A)和(B)
其中
R
a、R
b、R
c、R
d、R
e各自独立地是未取代的C
6-C
10芳基，或者被选自卤素、硝基、羰基、C
1-C
12烷基、C
1-C
12烷氧基、苯硫基、苯基和取代苯基的取代基取代的C
6-C
10芳基，优选是苯基或萘基，或者被选自卤素、硝基、C
1-C
6烷基和取代苯基的取代基取代的苯基或萘基，其中所述取代苯基包含的取代基为一个或多个选自卤素、硝基、C
1-C
6烷基和C
1-C
6烷氧基的基团；以及
Y、Z是非亲核性阴离子，例如三氟甲磺酸根、BF
4
-、ClO
4
-、PF
6
-、AsF
6
-、SbF
6
-。
例如，作为光引发剂，可以使用选自下组中的一种或多种:4-(苯硫基)苯基·二苯基硫鎓六氟磷酸盐、4-(苯硫基)苯基·二苯基硫鎓六氟锑酸盐、双(4-(二苯基锍)苯基)硫醚双六氟磷酸盐、双(4-(二苯基锍)苯基)硫醚双六氟锑酸盐、10-(4-联苯基)-2-异丙基噻吨酮-10-硫鎓六氟磷酸盐、10-(4-联苯基)-2-异丙基噻吨酮-10-硫鎓六氟锑酸盐、六氟磷酸二苯基碘鎓盐(810)、4-辛氧基二苯碘鎓六氟磷酸盐、4-辛氧基二苯碘鎓六氟锑酸盐、4-异丁基苯基·4'-甲基苯基碘鎓六氟磷酸盐、4-异丁基苯基·4'-甲基苯基碘鎓六氟锑酸盐、双(4-十二烷基苯)碘鎓六氟锑酸盐、双(4-十二烷基苯)碘鎓六氟磷酸盐、双(4-叔丁基苯)碘鎓六氟磷酸盐、双(4-叔丁基苯)碘鎓六氟锑酸盐。
本发明可光固化组合物还可以包含增感剂。作为增感剂，例如可以提及2- 异丙基硫杂蒽酮。
对本发明而言，光引发剂的用量是常规的。基于本发明可光固化组合物中聚合单体的的总摩尔量，光引发剂的含量通常为0.5-5mol％，优选为1-3mol％。
根据本发明的一个方面，提供了一种由本发明的可光固化组合物得到的光固化材料。根据本发明，该材料通过将本发明的可光固化组合物光固化而获得。该光固化材料具有拉伸性能好，附着力强的优点。
根据本发明的式(I)化合物还可用于光固化涂料、粘合剂、油墨和光致抗蚀剂。因此，本发明还涉及式(I)化合物在光固化涂料、粘合剂、油墨和光致抗蚀剂中的用途。
实施例
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
在装有温度探头和回流冷凝管的三口烧瓶中，加入11.6g(0.1mol)3-羟甲基-3-乙基-氧杂环丁烷、14.40g(0.12mol)3-溴丙烯、30mL甲苯和11.2(0.2mol)氢氧化钾，升温至110℃，在500r/min的搅拌速率下反应10h，然后结束反应。将所得反应液用蒸馏水洗涤三次，取上层清液，离心除去固体杂质，后用旋转蒸发器于温度45℃和压力0.1MPa下旋蒸，再将所得溶液于300Pa和40℃下减压蒸馏，得到化合物1-a，产率为50％。
[1-a]：
1H NMR(400MHz,CDCl
3)δ0.82(t,J＝1.8Hz,3H),1.74(q,J＝7.5Hz,2H),3.54(s,2H),4.00(d,J＝5.6Hz,2H),4.48-4.32(m,4H),5.22(m,2H),5.92(m,1H).
将1.56g(10mmol)的化合物1-a与2.38g(10mmol)巯丙基三乙氧基硅烷放置于30mL的烧杯中混合搅拌10min至体系均匀，之后室温下将带有磁子的烧杯放在365nm的汞灯下垂直向下照射30min(照射过程中持续搅拌，烧杯与汞灯间距为10cm，汞灯光强100mW/cm
2)，得到化合物1，产率为99％。
[化合物1]：
1H NMR(400MHz,Chloroform-d)δ4.49-4.34(m,4H),3.82(qd,J＝7.0,1.4Hz,6H),3.54(d,J＝4.0Hz,4H),2.65-2.47(m,4H),1.86(dt,J＝7.7,6.3Hz,2H),1.77-1.67(m,4H),1.23(td,J＝7.0,1.4Hz,9H),0.92-0.85(m,3H),0.78-0.69(m,2H)。
实施例2
将1.56g(10mmol)的化合物1-a与1.96g(10mmol)巯丙基三甲氧基硅烷放置于30mL的烧杯中混合搅拌10min至体系均匀，之后室温下将带有磁子的烧杯放在波长为365nm的汞灯下垂直向下照射30min(照射过程中持续搅拌，烧杯与汞灯间距为10cm，汞灯光强100mW/cm
2)，得到化合物2，产率为99％。
[化合物2]：
1H NMR(400MHz,Chloroform-d)δ4.49-4.34(m,4H),3.82(qd,J＝7.0,1.4Hz,9H),3.54(d,J＝4.0Hz,4H),2.65-2.47(m,4H),1.86(dt,J＝7.7,6.3Hz,2H),1.77-1.67(m,4H),0.92-0.85(m,3H),0.78-0.69(m,2H)。
实施例3
将1.56g(10mmol)的化合物1-a与1.80g(10mmol)巯丙基甲基二甲氧基硅烷放置于30mL的烧杯中混合搅拌10min至体系均匀，之后室温下将带有磁子的烧杯放在波长为365nm的汞灯下垂直向下照射30min(照射过程中持续搅拌，烧杯与汞灯间距为10cm，汞灯光强100mW/cm
2)，得到化合物3，产率为99％。
[化合物3]：
1H NMR(400MHz,Chloroform-d)δ4.49-4.34(m,4H),3.82(qd,J＝7.0,1.4Hz,6H),3.54(d,J＝4.0Hz,4H),2.65-2.47(m,4H),1.86(dt,J＝7.7,6.3 Hz,2H),1.77-1.67(m,4H),0.92-0.85(m,3H),0.78-0.69(m,2H),0.16-0.08(m,3H)。
实施例4
将1.56g(10mmol)的化合物1-a与2.66g(10mmol)4-三甲氧基硅烷基戊烷-1-硫醇放置于30mL的烧杯中混合搅拌10min至体系均匀，之后室温下将带有磁子的烧杯放在365nm的汞灯下垂直向下照射30min(照射过程中持续搅拌，烧杯与汞灯间距为10cm，汞灯光强100mW/cm
2)，得到化合物4，产率为99％。
[化合物4]：
1H NMR(400MHz,Chloroform-d)δ4.49-4.34(m,4H),3.82(qd,J＝7.0,1.4Hz,9H),3.54(d,J＝4.0Hz,4H),2.65-2.47(m,4H),1.86(dt,J＝7.7,6.3Hz,2H),1.77-1.67(m,8H),0.92-0.85(m,3H),0.78-0.69(m,2H)。
实施例5
在装有温度探头和回流冷凝管的三口烧瓶中，加入11.6g(0.1mol)3-羟甲基-3-乙基-氧杂环丁烷、17.88g(0.12mol)5-溴-1-戊烯、30mL甲苯和11.2(0.2mol)氢氧化钾，升温至110℃，在500r/min的搅拌速率下反应10h，然后结束反应。将所得反应液用蒸馏水洗涤三次，取上层清液，离心除去固体杂质，后用旋转蒸发器于温度45℃和压力0.1MPa下旋蒸，再将所得溶液于300Pa和40℃下减压蒸馏，得到化合物5-a，产率为50％。
[5-a]：
1H NMR(400MHz,CDCl
3)δ0.82(t,J＝1.8Hz,3H),1.49-1.82(m,4H),2.2(q,J＝7.5Hz,2H),3.35(t,J＝2.0Hz,2H),4.00(d,J＝5.6Hz,2H),4.48-4.32(m,4H),5.22(m,2H),5.92(m,1H).
将1.84g(10mmol)的化合物5-a与2.66g(10mmol)4-三甲氧基硅烷基丙烷-1-硫醇放置于30mL的烧杯中混合搅拌10min至体系均匀，之后室温下将带有磁子的烧杯放在365nm的汞灯下垂直向下照射30min(照射过程中持续搅拌，烧杯与汞灯间距为10cm，汞灯光强100mW/cm
2)，得到化合物5，产率为99％。
[化合物5]：
1H NMR(400MHz,Chloroform-d)δ4.49-4.34(m,4H),3.82(qd,J＝7.0,1.4Hz,9H),3.54(d,J＝4.0Hz,4H),2.65-2.47(m,4H),1.86(dt,J＝7.7,6.3Hz,2H),1.77-1.67(m,4H),1.21-1.01(m,4H),0.92-0.85(m,3H),0.78-0.69(m,2H)。
实施例6
在装有温度探头和回流冷凝管的三口烧瓶中，加入8.8g(0.1mol)3-羟甲基氧杂环丁烷、14.40g(0.12mol)3-溴丙烯、30mL甲苯和11.2(0.2mol)氢氧化钾，升温至110℃，在500r/min的搅拌速率下反应10h，然后结束反应。将所得反应液用蒸馏水洗涤三次，取上层清液，离心除去固体杂质，后用旋转蒸发器于温度45℃和压力0.1MPa下旋蒸，再将所得溶液于300Pa和40℃下减压蒸馏，得到化合物6-a，产率为50％。
[6-a]：
1H NMR(400MHz,CDCl
3)δ2.81-3.03(m,1H),3.54(d,J＝4.0Hz,2H),4.00(d,J＝5.6Hz,2H),4.48-4.32(m,4H),5.22-5.40(m,2H),5.89-6.10(m,1H)。
将1.28g(10mmol)的化合物6-a与1.96g(10mmol)巯丙基三甲氧基硅烷放置于30mL的烧杯中混合搅拌10min至体系均匀，之后室温下将带有磁子的烧杯放在365nm的汞灯下垂直向下照射30min(照射过程中持续搅拌，烧杯与汞灯间距为10cm，汞灯光强100mW/cm
2)，得到化合物6，产率为99％。
[化合物6]：
1H NMR(400MHz,Chloroform-d)δ4.49-4.34(m,4H),3.82(qd,J＝7.0,1.4Hz,9H),3.54(d,J＝4.0Hz,4H),2.92-2.84(m,1H),2.65-2.47(m,4H),1.86(dt,J＝7.7,6.3Hz,2H),1.77-1.67(m,2H),0.78-0.69(m,2H)。
实施例7
本实施例的目的在于说明本发明化合物的光聚合性能。
称取适量X
1mol的上述化合物1，X
2mol的E4221(3,4-环氧环己基甲基3,4- 环氧环己基甲酸酯)，X
3mol的光引发剂六氟磷酸二苯基碘鎓盐(810)和X
4mol的光敏剂2-异丙基硫杂蒽酮(ITX)加入到棕色瓶中并搅拌均匀，避光保存。以光固化组合物“化合物1-0.5％”为例，其各组分摩尔比例为：化合物1(X
1):E4221(X
2):810(X
3):ITX(X
4)＝0.5:99.5:3:1.5(均为摩尔比),其中X
1+X
2＝100。各光组合物中本发明化合物1的摩尔百分数X
1如下表1所示，X
1+X
2＝100，X
3和X
4保持不变。
以光引发剂六氟磷酸二苯基碘鎓盐(810)与2-异丙基硫杂蒽酮(ITX，增感剂)以2:1摩尔比组成的混合物作为光引发体系，采用实时红外(RT-IR)的方法测试了化合物1光聚合动力学性能，并考察在不同含量下对E4221光聚合性能的影响。所使用单体E4221三元氧杂环的C-O-C的振动吸收峰位于750cm
-1位置，作为聚合单体的化合物1的四元氧杂环的C-O-C的振动吸收峰为980cm
-
1，将单体和光引发剂组成的可光固化液体均匀涂抹在溴化钾盐片上(用细管蘸取一点可光固化液体，在溴化钾盐片上点一下，然后平铺均匀)，用高压汞灯照射液体样品900s，其中汞灯主要发射波长为365nm，并且带有直径为5mm的光导纤维。光纤一端距离测试样品距离为10cm，辐照强度为20mW cm
-2。通过测量在750cm
-1和980cm
-1处C-O-C键峰面积的变化，表征了不同环氧基团，即单体的实时转化率和聚合速率。
其中包含化合物1的光固化组合物的结果如图1、2和表1所示。结果显示，化合物1的加入虽然会略微降低E4421单体的转化率和转化速率，但E4221的转化率依旧可在55％以上。并且由图2和表1可以看出化合物1的转化率也在56％以上，说明所制备的化合物1自身也具有良好的光聚合能力。
表1：使用化合物1的光固化组合物的900s时单体转化率
| 体系 | 化合物1含量X 1(mol％) | E4221转化率％ | 化合物1转化率％ |
| E4221 | 0 | 62.04 | - |
| 化合物1-0.5％ | 0.5％ | 58.90 | 56.07 |
| 化合物1-1.0％ | 1.0％ | 59.74 | 56.25 |
| 化合物1-1.5％ | 1.5％ | 60.40 | 57.65 |
| 化合物1-2.0％ | 2.0％ | 59.15 | 58.39 |
| 化合物1-2.5％ | 2.5％ | 56.19 | 56.21 |
实施例8
本实施例的目的在于说明本发明化合物能够改善光固化膜的拉伸性能。
称取适量X
1mol的化合物1，X
2mol的E4221，X
3mol的光引发剂六氟磷酸二苯基碘鎓盐(810)和X
4mol的光敏剂2-异丙基硫杂蒽酮(ITX)加入到棕色瓶中并搅拌均匀，避光保存，配方各组分摩尔比例为：单体(X
1)：E4221(X
2):810(X
3):ITX(X
4)＝X
1:X
2:3:1.5(均为摩尔比)，其中X
1+X
2＝100。各光组合物中本发明化合物1的摩尔百分数X
1如下表2所示，X
1+X
2＝100，X
3和X
4保持不变。在6mm×8mm×70mm的聚四氟乙烯模具中加入搅拌均匀的光固化组合物，然后将模具放置于汞灯下照射(波长为365nm，光强为60mW cm
-2)，照射时间900s后取出固化膜，进行拉伸性能测试。
拉伸性能依据国际标准ISO 1184-1983《塑料薄膜拉伸性能的测定》，通过E44.304型电子万能试验机测试。测试条件：温度25℃，湿度60％，测试速度1mm·min
-1。同时，利用同样方法制备空白E4221固化膜作为参比。其结果见图3和表2。
表2
由图3和表2可见，当E4221聚合体系不添加本发明化合物时，固化膜的拉伸强度为6.1MPa，断裂伸长率为1.69％。而额外加入化合物1后，固化膜的断裂伸长率得到提高。因此，本发明化合物可以提高固化膜的拉伸性能。
实施例9
本实施例的目的在于说明本发明化合物能够改善光固化膜的附着力。
按照实施例8中所述完全相同的方法制得化合物1各自的固化膜，化合物1(X
1):E4221(X
2):810(X
3):ITX(X
4)＝X
1:X
2:3:1.5(均为摩尔比)，其中X
1+X
2＝100。各光组合物中X
1:X
2如下表3所示，X
3和X
4保持不变。按照国 标GB/T9286-1998《色漆和清漆漆膜的划格法试验》对材料附着力进行测定。将感光液涂敷在25mm×25mm的基材(见表3)上，在汞灯下固化后将涂层划成10×10的100格的正方形，将胶带粘附划格处后再撕开胶带，检测划格处涂层脱落情况。附着力根据百格位置处涂层的脱落情况分为6个等级，无脱落为0级，脱落比例在5％以内、5～15％、15～35％、35～65％、65％以上分别划分成1～5级。
如表3所示，化合物1在光聚合体系中含量的增加，薄膜在玻璃、铁和PVC三种基材上的附着力都有所增加，对于玻璃和PVC基材，附着力从3级增加至0级，在铁片板材上的附着力从4级增加至1级。因此，本发明化合物能够改善光固化膜的附着力。
表3
Claims (14)
- 下式(Ⅰ)化合物：
R 1、R 2、R 3相同或不同，并独立地为C 1-C 6烷基或C 1-C 6烷氧基，并且R 1，R 2，R 3中的至少两个为C 1-C 6烷氧基；R 4为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基；L 1为直接键或具有1-20个碳原子的二价连接基团；以及L 2为直接键或具有1-30个碳原子的二价连接基团。 - 根据权利要求1的化合物，其中R 1、R 2、R 3相同或不同，并独立地为C 1-C 3烷基或C 1-C 3烷氧基，并且R 1，R 2，R 3中至少两个为C 1-C 3烷氧基。
- 根据权利要求1或2的化合物，其中R 4为H、卤素、C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4羟烷基、C 1-C 4烷氧基或者C 1-C 4卤代烷氧基。
- 根据权利要求1-3中任一项的化合物，其中L 1为直接键、C 1-C 20亚烷基、C 1-C 20亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 20亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 20亚烷氧基，其中R a为H或C 1-C 4烷基；以及L 2为直接键、C 1-C 30亚烷基、C 1-C 30亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 30亚烷氧基，其中R a为H或C 1-C 4烷基；优选L 2为L 21-O-L 22，其中L 21为C 1-C 15亚烷基和L 22为直接键或C 1-C 15亚烷基。
- 根据权利要求1-4中任一项的化合物，其中R 1、R 2、R 3相同或不同，并独立地为C 1-C 6烷基或C 1-C 6烷氧基，并且R 1，R 2，R 3中的至少两个为C 1-C 6烷氧基；R 4为H、卤素、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6羟烷基、C 1-C 6烷氧基或者C 1-C 6卤代烷氧基；L 1为直接键、C 1-C 11亚烷基、C 1-C 11亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 11亚烷基、或者被一个或多个独立地选自NR a、 O、S的非相邻杂原子间隔的C 2-C 11亚烷氧基，其中R a为H或C 1-C 4烷基；以及L 2为直接键、C 1-C 8亚烷基、C 1-C 8亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 8亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 8亚烷氧基，其中R a为H或C 1-C 4烷基；优选L 2为L 21-O-L 22，其中L 21为C 1-C 5亚烷基和L 22为直接键或C 1-C 3亚烷基；优选的是，R 1、R 2、R 3相同或不同，并独立地为C 1-C 6烷基或C 1-C 6烷氧基，并且R 1，R 2，R 3中的至少两个为C 1-C 6烷氧基；R 4为H或C 1-C 4烷基；L 1为直接键、C 1-C 6亚烷基、C 1-C 6亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 6亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 6亚烷氧基，其中R a为H或C 1-C 4烷基；以及L 2为直接键、C 1-C 6亚烷基、C 1-C 6亚烷氧基、被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 6亚烷基、或者被一个或多个独立地选自NR a、O、S的非相邻杂原子间隔的C 2-C 6亚烷氧基，其中R a为H或C 1-C 4烷基；优选L 2为L 21-O-L 22，其中L 21为C 1-C 4亚烷基和L 22为直接键或C 1-C 2亚烷基。
- 根据权利要求1-5中任一项的化合物，其为一种或多种选自下组的化合物：
- 一种制备根据权利要求1-6中任一项的式(Ⅰ)化合物的方法，包括：使式(Ⅳ)化合物
其中R 4和L 2如对权利要求1-6中任一项所定义；与式(Ⅴ)化合物反应，得到式(I)化合物，
其中L 1、R 1、R 2和R 3如对权利要求1-6中任一项所定义。 - 根据权利要求7的方法，其中L 2为L 21-O-L 22，其中L 21为C 1-C 15亚烷基和L 22为直接键或C 1-C 15亚烷基，优选L 21为C 1-C 5亚烷基和L 22为直接键或C 1-C 3亚烷基。
- 根据权利要求7或8的方法，其中式(IV)化合物如下制备：使式(Ⅱ)化合物：
其中L 21为C 1-C 15亚烷基，优选C 1-C 5亚烷基，X为卤素，例如氟、氯、溴或碘，与式(Ⅲ)化合物反应，得到式(IV)化合物，
其中L 22为直接键或C 1-C 15亚烷基，优选直接键或C 1-C 3亚烷基，R 4如对权利要求7所定义。 - 根据权利要求9的方法，其中式(Ⅱ)化合物与式(Ⅲ)化合物的反应满足下述条件中的至少一个：-式(Ⅱ)化合物与式(Ⅲ)化合物的反应在碱性催化剂存在下进行，该碱性催化剂优选为氢化钠、氢氧化钠、氢氧化钾、三乙胺、碳酸钾或其任意混合物，更优选的是，式(Ⅱ)化合物与碱性催化剂的摩尔用量比为1:1-1:3；-式(Ⅱ)化合物与式(Ⅲ)化合物摩尔比为1:0.7-1:1.2；-式(Ⅱ)化合物与式(Ⅲ)化合物之间的反应在80-120℃，优选100-120℃下进行；-式(Ⅱ)化合物与式(Ⅲ)化合物之间的反应进行6-15小时，优选8-12小时。
- 根据权利要求7-10中任一项的方法，其中式(Ⅳ)化合物与式(Ⅴ)化合物的反应满足下述条件中的至少一个：式(Ⅳ)化合物与式(Ⅴ)化合物的反应在光强为50-500mw/cm -2的汞灯下反应；式(Ⅳ)化合物与式(Ⅴ)化合物的用量摩尔比为1:0.7-1:1.5；式(Ⅳ)化合物与式(Ⅴ)化合物之间的反应在0-40℃，优选10-30℃下进行；式(Ⅳ)化合物与式(Ⅴ)化合物之间的反应进行5-60分钟，优选20-40分钟。
- 一种可光固化组合物，包含根据权利要求1-6中任一项的式(Ⅰ)化合物作为聚合单体。
- 一种由权利要求12的可光固化组合物得到的光固化材料。
- 根据权利要求1-6中任一项的式(I)化合物在光固化涂料、粘合剂、油墨和光致抗蚀剂中的用途。
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