WO2013020469A1 - 双膦酰膦酸酯化合物 - Google Patents
双膦酰膦酸酯化合物 Download PDFInfo
- Publication number
- WO2013020469A1 WO2013020469A1 PCT/CN2012/079445 CN2012079445W WO2013020469A1 WO 2013020469 A1 WO2013020469 A1 WO 2013020469A1 CN 2012079445 W CN2012079445 W CN 2012079445W WO 2013020469 A1 WO2013020469 A1 WO 2013020469A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- compound
- meth
- formula
- reaction
- ethylenically unsaturated
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 150000003254 radicals Chemical class 0.000 claims abstract description 7
- -1 n-octyl Chemical group 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 238000003848 UV Light-Curing Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- NXHPIYRSMIFFBV-UHFFFAOYSA-N formaldehyde;1,3,5-trimethylbenzene Chemical compound O=C.CC1=CC(C)=CC(C)=C1 NXHPIYRSMIFFBV-UHFFFAOYSA-N 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- FDWNORQBNLVBQI-UHFFFAOYSA-N decoxymethanediol Chemical compound CCCCCCCCCCOC(O)O FDWNORQBNLVBQI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 125000003136 n-heptyl 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])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 230000005855 radiation Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 2
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000003847 radiation curing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- KNZSPKGFNVVCLS-UHFFFAOYSA-N 1,3,5-trimethylcyclohexa-2,4-diene-1-carbaldehyde Chemical compound CC1=CC(C)=CC(C)(C=O)C1 KNZSPKGFNVVCLS-UHFFFAOYSA-N 0.000 description 1
- 229940122361 Bisphosphonate Drugs 0.000 description 1
- 0 Cc1cc(C)c(C(O)P(C(c2c(C)cc(C)cc2C)O)(O*)=O)c(C)c1 Chemical compound Cc1cc(C)c(C(O)P(C(c2c(C)cc(C)cc2C)O)(O*)=O)c(C)c1 0.000 description 1
- HIKRJHFHGKZKRI-UHFFFAOYSA-N Cc1cc(C)c(C=O)c(C)c1 Chemical compound Cc1cc(C)c(C=O)c(C)c1 HIKRJHFHGKZKRI-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RMNRDBFBZMUPHB-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.CCCCCC Chemical compound OC(=O)C=C.OC(=O)C=C.CCCCCC RMNRDBFBZMUPHB-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000006612 decyloxy group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- XKCQASMZNPBLKI-UHFFFAOYSA-N phosphorosooxymethane Chemical compound COP=O XKCQASMZNPBLKI-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3247—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se)
- C07F9/3252—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se) containing the structure -C(=X)-P(=X)(R)(XR), (X = O, S, Se)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
Definitions
- the invention relates to the technical field of new materials for UV light radiation radical polymerization, in particular to a structural formula such as
- phosphono-type structural compounds are important photoinitiators in the field of UV ultraviolet radiation curing due to their long-wavelength light absorption and photobleaching properties, and have been widely disclosed in the patent literature, such as US 5,218,009, EP 0 615 980 A2, and CN 1 659 175 A. New preparation processes for some phosphono-type structural compounds have also been the focus of recent research. Representative patent documents such as WO2006/056541 Al o However, the cost and price of phosphono-type photoinitiator compounds are often significantly higher than other photoinitiator compounds.
- the disclosed preparation process inevitably uses highly air-sensitive alkali metals (sodium, potassium, or lithium metal) to undergo lengthy reaction times and operational steps to prepare corresponding
- the metal phosphine compound the yield is low (for example, the final product obtained in the above-mentioned latest process WO2006/056541A1 often has a yield of less than 30%), and the production safety hazard is large, which severely limits the economic and environmentally friendly promotion of the compound. . Therefore, the identification of new and more economical phosphono-type structural compounds, as well as the development of its new preparation process and application, is a very valuable application challenge in the field of new UV radiation curing materials.
- a bisphosphonophosphonate compound of the formula I is an effective ethylenically unsaturated compound system UV radical photopolymerization curing photoinitiator.
- Compound I (as defined in the following claims) is not only a new structure not reported, but equally important they must be prepared in a new economical process that is completely different from the literature disclosure method.
- R is a linear or branched fluorenyl group having 1 to 24 carbon atoms, and the fluorenyl group may be no more than 4 non-continuous oxygen atoms, nitrogen atoms, silicon atoms, or sulfur atoms.
- the fluorenyl group may have 1 to 40 fluorine atoms; or R is a phenyl group having 6 to 24 carbon atoms or a substituted phenyl group having 1 to 4 substituents, and these substituents may also be no more than Four discontinuous oxygen atoms, nitrogen atoms, silicon atoms, or sulfur atoms are interrupted.
- R methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, phenyl, tolyl.
- the bisphosphono-type compound manufacturing method disclosed in the literature can prepare a series of structures containing a fluorenyl group (branched or linear) or an aryl group (multiple substituents) on a phosphorus atom, such as a patented technology.
- WO2006/056541A1 and CN1659175A but their phosphorus-carbon bond formation chemical reaction characteristics determine that it is not possible to prepare phosphorus-containing structures of the formula I containing an OR group (decyloxy or aryloxy) on a phosphorus atom. Oxygen bond compound.
- the present application has now found that compounds of formula I can be conveniently produced economically via the following reaction formula.
- the industrially inexpensive and safe H 3 PO 2 iypophosphorous acid is the key starting material, and the intermediate hypophosphite is obtained via the R-based esterification reaction, followed by the homo-xylene formaldehyde.
- the carbonyl nucleophilic addition reaction gives a higher intermediate.
- the target compound I can be obtained by catalytic oxidation of B by a hydroxyl group.
- the core feature of this process is the preparation of a hydroxyphosphonate higher intermediate of the general formula B by a bis-carbonyl nucleophilic addition reaction using a hypophosphite of the formula ⁇ and a mesitylene formaldehyde.
- the reaction may be carried out as a pure compound, or may be carried out in an in situ mixture after completion of the hypophosphite reaction under suitable conditions.
- Suitable esterification conditions may be the reaction of hypophosphorous acid [or its corresponding form as MOP C H2 amine salt, hydrazine preferably N3 ⁇ 4, PhNH 3 , HNEt 3 , the same below] and the decyl orthoformate, or hypophosphorous acid. (or the corresponding amine salt) and the alcohol ROH and the acid chloride to promote the reaction, or inferior race phosphorous acid (or the corresponding amine salt) with the form of SI oR;) 4 the reaction of silicone embankment.
- R is methyl, Phosphorus, Sulfur and Silicon and the Related Elements, 177(6-7), 1793-1796; 2002; R is ethyl , Tetrahedron Letters, 42(30), 5033-5036; 2001; R is isopropyl, Chemistry Letters, 33(2), 116-117; 2004 and Medicinal Chemistry Letters, 2(1), 11-16; 2011; R is tert-butyl, Tetrahedron Letters, 37(4), 425-8; 1996; R is n-butyl, Journal of Organic Chemistry, 70(10), 4064-4072; 2005 and JOMrwa/of Organometallic Chemistry, 643-644, 154-163; 2002; R is phenyl, Journal of Organometallic Chemistry, 643-644, 154-163; 2002.
- the condensation of the hypophosphite and the aldehyde may employ a suitable base promoter, and the preferred base is an organic tertiary amine compound such as Et 3 N, Bu 3 N, or ' Pr 2 NEt.
- Suitable oxidation catalysts are selected from metal salts containing Mo, W or V, such as vanadium oxyacetate, molybdates, molybdates, phosphomolybdates, tungstic anhydrides, tungstates, or heteropoly containing these metals.
- metal salts containing Mo, W or V such as vanadium oxyacetate, molybdates, molybdates, phosphomolybdates, tungstic anhydrides, tungstates, or heteropoly containing these metals.
- Suitable terminal oxidizing agents can be organic peroxides such as t-butanol peroxide and the like.
- Such a system comprises at least one polymerizable ethylenically unsaturated component and comprises at least one compound of formula I as one of a photoinitiator or a photoinitiator component.
- a suitable amount of the compound of the formula I is contained in an amount of from 0.05 to 15 parts by weight, preferably from 0.5 to 8 parts by weight, per 100 parts by weight based on the total of the ethylenically unsaturated component in the system.
- the suitable UV-curable system disclosed in the present application comprises a polymerizable ethylenically unsaturated component which is a compound or mixture which can be crosslinked by free radical polymerization of the double bond, the ethylenically unsaturated component It may be a monomer, an oligomer or a prepolymer, or a mixture or copolymer thereof.
- Suitable free-radically polymerizable monomers are, for example, ethylenically-containing polymerizable monomers including, but not limited to, (meth) acrylates, acrolein, olefins, conjugated diolefins, styrene, maleic anhydride, fumaric anhydride, Vinyl acetate, vinylpyrrolidone, vinylimidazole, (meth)acrylic acid, (meth)acrylic acid derivatives such as (meth)acrylamide, vinyl halide, vinylidene halide, and the like.
- ethylenically-containing polymerizable monomers including, but not limited to, (meth) acrylates, acrolein, olefins, conjugated diolefins, styrene, maleic anhydride, fumaric anhydride, Vinyl acetate, vinylpyrrolidone, vinylimidazole, (meth)acrylic acid, (meth)acryl
- Suitable prepolymers and oligomers include, but are not limited to, (meth)acryloyl functional (meth)acrylic copolymers, urethane (meth) acrylates, polyester (meth) acrylates, Unsaturated polyester, polyether (meth) acrylate, siloxane (meth) acrylate, epoxy (meth) acrylate, etc.
- Suitable number average molecular weights thereof may vary, for example, from 500 to 10,000, preferably from 500 to 5,000.
- UV light curing application examples 30 parts: epoxy acrylate
- Example photoinitiator compound 4 parts: Example photoinitiator compound.
- the above components were sufficiently ground and sprayed on a white substrate to form a coating of about 5 ⁇ m.
- a 200 W high-pressure mercury lamp was used as a light source to irradiate at a distance of 12 cm from the sample.
- a finger-scratch method determines the complete cure of the coating.
- the above-mentioned examples of the compounds 1 to 5 all caused the film layer to be completely cured, showing good photoinitiation properties.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
本发明涉及UV光辐射自由基聚合新材料技术领域，特别涉及结构通式I所示的双膦酰膦酸酯化合物，其制备方法，其作为含烯不饱和化合物体系进行UV自由基光聚合固化的光引发剂的用途，以及含有该类化合物的UV自由基光聚合固化材料体系。
Description
双膦酰膦酸酯化合物
【技术领域】
本发明涉及 UV光辐射自由基聚合新材料技术领域，特别涉及结构式如 说
下所示的双膦酰膦酸酯化合物， 其制备方法， 其作为含烯不饱和化合物体系 进行 UV自由基光聚合固化的光引发剂的用途， 以及含有该类化合物的 UV 自由基光聚合固化材料体系。 【背景技术】
若干膦酰型结构化合物由于其长波光吸收和光漂白特性在 UV 紫外光 辐射固化领域是重要的光引发剂， 在专利文献中已经有相当丰富的披露， 例 如 US5218009, EP0615980A2, 和 CN1659175A等书。关于一些膦酰型结构化 合物的新的制备工艺也是近年来的研究重点， 代表性专利文献例如 WO2006/056541Al o 然而， 膦酰型光引发剂化合物成本和价格常常显著高 于其它品种光引发剂化合物 （例如胺基酮或羟基酮型光引发剂）， 已经披露 的制备工艺无可避免地使用高度空气敏感的碱金属 （钠， 钾， 或锂金属）经 历冗长的反应时间和操作歩骤制备相应的金属膦化合物， 产率低下（例如上 述最新的工艺 WO2006/056541A1得到的终产物收率常常小于 30%), 生产 安全隐患很大， 这严重限制了该类化合物的经济和环保友好型推广应用。 因 此， 鉴定发现新的更经济友好的膦酰型结构化合物， 同时开拓其全新的制备 工艺和应用用途，是当前 UV辐射固化新材料领域面临的极具应用价值的挑 战。
【发明内容】
本项申请现已意外地发现结构如通式 I所示的双膦酰膦酸酯化合物是有 效的含烯不饱和化合物体系 UV自由基光聚合固化光引发剂。 化合物 I (如 下权利要求所定义）不仅是未见报道的新结构， 同等重要的是它们必须以完 全不同于文献披露方法的经济性新工艺实现制备。
在通式 I中， R是含有 1-24个碳原子的直链或支链的垸基，该垸基可以 为不超过 4个的非连续性氧原子， 氮原子， 硅原子， 或硫原子所间断， 或该 垸基可以含有 1-40个氟原子； 或 R是含有 6-24个碳原子的苯基或含 1-4个 取代基的取代苯基， 这些取代基也可以为不超过 4个的非连续性氧原子， 氮 原子， 硅原子， 或硫原子所间断。优选的， R = 甲基， 乙基， 丙基， 异丙基， 丁基， 异丁基， 叔丁基， 正戊基， 正己基， 正庚基， 正辛基， 苯基， 甲苯基。
值得特别强调的是，经由文献披露的双膦酰型化合物制造方法虽然可以 制备一系列磷原子上含垸基 （支链或直链） 或芳基 （多种取代基） 的结构， 例如专利技术 WO2006/056541A1和 CN1659175A,但是其磷-碳键生成化学 反应特性决定了其不可能用于制备磷原子上含 OR基团 （垸氧基或芳氧基） 的通式 I结构描述的含磷-氧键化合物。
本申请现已发现通式 I 化合物可以经由下述反应通式经济而方便地制 造。 以工业上价廉易得且安全的次亚磷酸 H3PO2 iypophosphorous acid)为关 键起始原料， 经由 R基酯化反应得到中间体次亚磷酸酯 ^， ^接着和均三甲 苯甲醛进行双缩羰基亲核加成反应得到高级中间体^。 B经羟基催化氧化即 可得到目标化合物 I。此工艺过程的核心特征是使用了通式为^ 的次亚磷酸 酯和均三甲苯甲醛进行双缩羰基亲核加成反应制备通式为 B 的羟基膦酸酯 高级中间体。 ^可以以纯化合物形式参与反应， 也可以在合适条件下以次亚 磷酸酯化反应完成后的原位混合物形式参与反应。
合适的酯化条件可以是以次亚磷酸 [或其相应的形式为 MOP C H2胺盐， Μ优选 N¾， PhNH3， HNEt3 ,下同]和原甲酸垸基酯反应，或以次亚磷酸（或 其相应的胺盐） 和酰氯促进下和醇 ROH反应， 或以次亚磷酸 （或其相应的 胺盐） 与形式为 SI OR;)4的硅氧垸反应。 关于这些反应以及一些次亚磷酸酯 的合成文献已有报道，例如： R是甲基， Phosphorus, Sulfur and Silicon and the Related Elements, 177(6-7), 1793-1796; 2002； R是乙基， Tetrahedron Letters, 42(30), 5033-5036; 2001 ; R是异丙基， Chemistry Letters, 33(2), 116-117; 2004 和 Medicinal Chemistry Letters, 2(1), 11-16; 2011 ; R 是叔丁基，
Tetrahedron Letters, 37(4), 425-8; 1996； R 是正丁基， Journal of Organic Chemistry, 70(10), 4064-4072; 2005禾口 JOMrwa/ of Organometallic Chemistry, 643-644, 154-163; 2002； R 是苯基， Journal of Organometallic Chemistry, 643-644, 154-163; 2002。
次亚磷酸酯 ^ 和醛的缩合可以使用适当的碱促进剂， 优选的碱是有机 叔胺化合物例如 Et3N， Bu3N， 或' Pr2NEt。
合适的氧化催化剂是选自含 Mo， W或 V的金属盐， 例如双乙酰丙酮氧 化钒， 鉬酸酐， 鉬酸盐， 磷鉬酸盐， 钨酸酐， 钨酸盐， 或含有这些金 属的杂多酸或杂多酸盐的一种或多种。合适的终端氧化剂可以是有机过氧化 物例如过氧化叔丁醇等。
本项申请同时披露一类合适的 UV光固化体系。这样的体系包含至少一 种可聚合的含烯键不饱和组分， 且包含至少一种通式 I化合物为光引发剂或 光引发剂组分之一。 以体系中含烯键不饱和组分总量每 100份重量计算， 含 有的通式 I化合物的合适的量是 0.05-15重量份，优选 0.5-8重量份。本项申 请披露的合适 UV 光固化体系包含的可聚合的含烯键不饱和组分是可以通 过该双键的自由基聚合反应被交联的化合物或混合物，这种含烯键不饱和组 分可以是单体， 低聚物或预聚物， 或是它们的混合物或共聚物。合适的自由 基聚合的单体是例如含烯键可聚合单体， 包括但不限于 （甲基） 丙烯酸酯， 丙烯醛， 烯烃， 共轭双烯烃， 苯乙烯， 马来酸酐， 富马酸酐， 乙酸乙烯酯， 乙烯基吡咯垸酮， 乙烯基咪唑， （甲基） 丙烯酸， （甲基）丙烯酸衍生物例如 (甲基）丙烯酰胺， 乙烯基卤化物， 亚乙烯基卤化物等。 合适的预聚物和低 聚物包括但不限于（甲基）丙烯酰官能基的 （甲基）丙烯酸共聚物， 聚氨酯 甲酸酯 （甲基） 丙烯酸酯， 聚酯 （甲基） 丙烯酸酯， 不饱和聚酯， 聚醚（甲 基） 丙烯酸酯， 硅氧垸 （甲基） 丙烯酸酯， 环氧树脂 （甲基） 丙烯酸酯等。 其合适的数均分子量可在例如 500至 10000间变动， 优选 500-5000取值范 围。
【具体实施方式】 实施例一
和甲苯混合溶剂 （体积比 1/1 ) 中， 维持反应温度在 5摄氏度左右， 在搅拌 下向其徐徐加入 44毫升的原甲酸三甲酯。 反应 2小时后体系自然升温至室 温并继续搅拌反应 3 小时。 反应液用 200毫升甲醇稀释后向其加入 34克 1,3,5-三甲基苯甲醛， 混合体系回流反应直至 TLC检测显示次亚磷酸甲酯原 料消失。 反应液减压脱除溶剂和挥发性组分。 残余物和 300毫升氯苯混合， 依次加入 45毫升过氧化数丁醇， 20毫升水， 和 3.6克五氧化二钒络合物， 反应液搅拌过夜。 反应混合物用 2N氢氧化钠调节至若碱性， 弃去水相后有 机相用饱和食盐水和 Na2S03的 10%溶液分别洗涤一次，减压回收氯苯溶剂。 残余物通过一个 30厘米宽和 80厘米高的硅胶柱以乙酸乙酯 /己垸洗脱得到 目标化合物纯品 22 克， 总收率以起始次亚磷酸计约 60%。 元素分析： C21H2504P, 理论值： C% 67.73%； H 6.77%; 实验值： C% 67.87%； H 6.81%。
其它实施例二至五化合物以如上类似的操作歩骤制备，所不同处仅在于 相应的次亚磷酸酯 H2P O )R是参照如前所引文献歩骤单独制备和纯化后再 进行和 1,3,5-三甲基苯甲醛的加成和后续氧化反应。 收率和 C/H分析结果如 下：
UV光固化应用实施例:
30份： 环氧丙烯酸酯；
35份： 聚酯丙烯酸酯；
5份： 已二醇二丙烯酸酯；
3份： 季戊四醇三丙烯酸酯；
23份： 二氧化钛颜料；
4份： 实施例光引发剂化合物。 将上述组分充分研磨均匀后喷涂在白色基板上， 形成约 5微米的涂层。 以 200 W高压汞灯为光源于距离样品 12厘米处辐照。 指压刮擦法判定涂层 完全固化情况。上述实施例化合物一至五均引发膜层固化完全， 显示了良好 的光敏引发性能。
Claims
1. 一种为结构通式 I描述化合物， 其中 R是含有 1-24个碳原子的直链 或支链的垸基， 该垸基可以为不超过 4个的非连续性氧原子， 氮原子， 硅原 子， 或硫原子所间断， 或该垸基可以含有 1-40个氟原子； 或 R是含有 6-24 个碳原子的苯基或含 1-4个取代基的取代苯基， 这些取代基也可以为不超过 4个的非连续性氧原子，氮原子，硅原子，或硫原子所间断。优选的， R = 甲 基， 乙基， 丙基， 异丙基， 丁基， 异丁基， 叔丁基， 正戊基， 正己基， 正庚 基， 正辛基， 苯基， 甲苯基。 
2. 通式 I化合物的制造方法。 如下反应通式所示， 以工业上价廉易得 且安全的次亚磷酸 ¾P02为关键起始原料， 经由 R基酯化反应得到中间体 次亚磷酸酯^ ， A接着和均三甲苯甲醛进行双缩羰基亲核加成反应得到高级 中间体 β。 β经羟基催化氧化即可得到目标化合物 I。 此工艺过程的核心特 征是使用了通式为 ^ 的次亚磷酸酯和均三甲苯甲醛进行双缩羰基亲核加成 反应制备通式为 Β的羟基膦酸酯高级中间体。 ^可以以纯化合物形式参与反 应，也可以在合适条件下以次亚磷酸酯化反应完成后的原位混合物形式参与 反应。
合适的酯化条件可以是以次亚磷酸 [或其相应的形式为 MOP C H2胺盐， M优选 N¾， PhNH3， HNEt3,下同]和原甲酸垸基酯反应，或以次亚磷酸（或 其相应的胺盐） 在酰氯促进下和醇 ROH反应， 或以次亚磷酸 （或其相应的 胺盐） 与形式为 Si OR^的硅氧垸反应。
次亚磷酸酯 A 和醛的缩合可以使用适当的碱促进剂， 优选的碱是有机 叔胺化合物例如 Et3N， Bu3N， 或' Pr2NEt。
合适的氧化催化剂是选自含 Mo， W或 V的金属盐， 例如双乙酰丙酮氧 化钒， 鉬酸酐， 鉬酸盐， 磷鉬酸盐， 钨酸酐， 钨酸盐， 或含有这些金 属的杂多酸或杂多酸盐的一种或多种。合适的终端氧化剂可以是有机过氧化 物例如过氧化叔丁醇等。
3. 通式 I化合物作为含烯键不饱和化合物或含有含烯键不饱和化合物 的混合物体系进行 UV光聚合自由基固化的光引发剂的用途。
4. 一类合适的 UV光固化体系。 这样的体系包含至少一种可聚合的含 烯键不饱和组分， 且包含至少一种通式 I化合物为光引发剂或光引发剂组分 之一。 以体系中含烯键不饱和组分总量每 100份重量计算， 含有的通式 I化 合物的合适的量是 0.05-15重量份， 优选 0.5-8重量份。 本项申请披露的合 适 UV 光固化体系包含的可聚合的含烯键不饱和组分是可以通过该双键的 自由基聚合反应被交联的化合物或混合物，这种含烯键不饱和组分可以是单 体， 低聚物或预聚物， 或是它们的混合物或共聚物。 合适的自由基聚合的单 体是例如含烯键可聚合单体， 包括但不限于（甲基）丙烯酸酯， 丙烯醛， 烯 烃， 共轭双烯烃， 苯乙烯， 马来酸酐， 富马酸酐， 乙酸乙烯酯， 乙烯基吡咯 垸酮， 乙烯基咪唑， （甲基） 丙烯酸， （甲基） 丙烯酸衍生物例如 （甲基） 丙 烯酰胺， 乙烯基 ¾化物， 亚乙烯基 ¾化物等。 合适的预聚物和低聚物包括但 不限于 （甲基） 丙烯酰官能基的 （甲基） 丙烯酸共聚物， 聚氨酯甲酸酯 （甲 基） 丙烯酸酯， 聚酯 （甲基） 丙烯酸酯， 不饱和聚酯， 聚醚（甲基） 丙烯酸 酯， 硅氧垸（甲基） 丙烯酸酯， 环氧树脂（甲基） 丙烯酸酯等。 其合适的数 均分子量可在例如 500至 10000间变动， 优选 500-5000取值范围。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110227608 CN102924509A (zh) | 2011-08-09 | 2011-08-09 | 双膦酰膦酸酯化合物 |
| CN201110227608.4 | 2011-08-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2013020469A1 true WO2013020469A1 (zh) | 2013-02-14 |
Family
ID=47639462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2012/079445 WO2013020469A1 (zh) | 2011-08-09 | 2012-07-31 | 双膦酰膦酸酯化合物 |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102924509A (zh) |
| WO (1) | WO2013020469A1 (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014095724A1 (en) * | 2012-12-19 | 2014-06-26 | Basf Se | Derivatives of bisacylphosphinic acid, their preparation and use as photoinitiators |
| US9644068B2 (en) | 2012-12-18 | 2017-05-09 | Basf Se | Semiconducting materials based on naphthalenediimide-vinylene-oligothiophene-vinylene polymers |
| US9796740B2 (en) | 2013-07-08 | 2017-10-24 | Basf Se | Liquid bisacylphosphine oxide photoinitiator |
| WO2018186822A1 (en) * | 2017-04-03 | 2018-10-11 | Hewlett-Packard Development Company, L.P. | Photo active agents |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333202B (zh) * | 2013-06-08 | 2016-09-07 | 广东博兴新材料科技有限公司 | 一种基于环氧化合物的含磷酸酯基的长波吸收光引发剂及其制备方法 |
| WO2017120743A1 (en) * | 2016-01-11 | 2017-07-20 | Henkel IP & Holding GmbH | Silicone-compatible compounds |
| CN109867693B (zh) * | 2019-01-08 | 2021-08-10 | 广东博兴新材料科技有限公司 | 一种氟碳链改性亚磷酸酯类丙烯酸酯化合物及其制备方法和应用 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5534559A (en) * | 1993-03-18 | 1996-07-09 | Ciba-Geigy Corporation | Daylight curing compositions containing bisacylphosphine oxide photoinitiators |
| CN101065388A (zh) * | 2004-11-23 | 2007-10-31 | 西巴特殊化学品控股有限公司 | 制备酰基磷烷及其衍生物的方法 |
| CN102471150A (zh) * | 2010-06-30 | 2012-05-23 | 帝斯曼知识产权资产管理有限公司 | D1492液体双酰基氧化膦光引发剂及其在可辐射固化组合物中的用途 |
-
2011
- 2011-08-09 CN CN 201110227608 patent/CN102924509A/zh active Pending
-
2012
- 2012-07-31 WO PCT/CN2012/079445 patent/WO2013020469A1/zh active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5534559A (en) * | 1993-03-18 | 1996-07-09 | Ciba-Geigy Corporation | Daylight curing compositions containing bisacylphosphine oxide photoinitiators |
| CN101065388A (zh) * | 2004-11-23 | 2007-10-31 | 西巴特殊化学品控股有限公司 | 制备酰基磷烷及其衍生物的方法 |
| CN102471150A (zh) * | 2010-06-30 | 2012-05-23 | 帝斯曼知识产权资产管理有限公司 | D1492液体双酰基氧化膦光引发剂及其在可辐射固化组合物中的用途 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9644068B2 (en) | 2012-12-18 | 2017-05-09 | Basf Se | Semiconducting materials based on naphthalenediimide-vinylene-oligothiophene-vinylene polymers |
| WO2014095724A1 (en) * | 2012-12-19 | 2014-06-26 | Basf Se | Derivatives of bisacylphosphinic acid, their preparation and use as photoinitiators |
| US9796740B2 (en) | 2013-07-08 | 2017-10-24 | Basf Se | Liquid bisacylphosphine oxide photoinitiator |
| WO2018186822A1 (en) * | 2017-04-03 | 2018-10-11 | Hewlett-Packard Development Company, L.P. | Photo active agents |
| US10858380B2 (en) | 2017-04-03 | 2020-12-08 | Hewlett-Packard Development Company, L.P. | Photo active agents |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102924509A (zh) | 2013-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2013020469A1 (zh) | 双膦酰膦酸酯化合物 | |
| EP0007508B1 (de) | Acylphosphinoxidverbindungen, ihre Herstellung und ihre Verwendung | |
| JPS60252443A (ja) | 重合体芳香族・脂肪族ケトン | |
| JP2000319524A (ja) | 硬化性組成物の製造方法およびその組成物 | |
| JP5007942B2 (ja) | 重合性組成物及びその重合物 | |
| CN112321823A (zh) | 低生物毒性的树枝状大分子光引发剂及其制备和应用 | |
| JP5435193B2 (ja) | １，４−ナフタレンジエーテル化合物及びその製造方法 | |
| CN110950977B (zh) | 酰基氧化膦类光引发剂及其合成方法 | |
| CN114230609A (zh) | 改性酰基氧化膦类光引发剂的制备方法及其在光固化材料中的应用 | |
| JP2007513069A (ja) | 粉末の形態での白色固体光開始剤およびその製造 | |
| WO2013091521A1 (zh) | 经由芳酰环系衍生的多官能团或聚合型酰基膦氧化合物 | |
| CN106349285B (zh) | 含羟基酰基膦氧化合物及其制备和应用 | |
| CN112694548A (zh) | 一种酰基膦氧化物光引发剂及其制备方法和用途 | |
| JP4158841B2 (ja) | 架橋性（メタ）アクリル基を有するホスフィン酸およびその製造方法 | |
| CN109705238B (zh) | 一种低丙酮释放低迁移性光引发剂及其制备方法和应用 | |
| JP6443741B2 (ja) | 光ラジカル重合開始剤 | |
| JP5470756B2 (ja) | １，４−ナフタレンジエーテル誘導体及びその製造方法並びに該１，４−ナフタレンジエーテル誘導体を含有する光重合性組成物 | |
| WO2000078709A1 (fr) | Alcoxyamine vinyle, son utilisation et son procede de preparation | |
| JPS63215720A (ja) | 末端に官能基を有するラクトン系重合体の製造方法 | |
| JP2009263441A (ja) | 分解性硬化樹脂 | |
| JPH03120263A (ja) | （メタ）アクリレート化合物の製造方法 | |
| JP2867644B2 (ja) | 反応性樹脂の製造方法 | |
| JPS6124588A (ja) | 重合性を有するクラウンエ−テル化合物 | |
| US5712411A (en) | N-vinylformamidopropionates and process for their synthesis | |
| Toneri et al. | Polymerization of epoxide with a fluorenyltriphenylphosphonium salt as a photo-latent initiator |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12821856 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 12821856 Country of ref document: EP Kind code of ref document: A1 |