CN102924509A - 双膦酰膦酸酯化合物 - Google Patents
双膦酰膦酸酯化合物 Download PDFInfo
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- CN102924509A CN102924509A CN 201110227608 CN201110227608A CN102924509A CN 102924509 A CN102924509 A CN 102924509A CN 201110227608 CN201110227608 CN 201110227608 CN 201110227608 A CN201110227608 A CN 201110227608A CN 102924509 A CN102924509 A CN 102924509A
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- -1 phosphonate compound Chemical class 0.000 title claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 4
- 150000001336 alkenes Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000000016 photochemical curing Methods 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 239000011964 heteropoly acid Substances 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
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
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- 238000003786 synthesis reaction Methods 0.000 claims description 3
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical class COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-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
- PEHQDSOLLVMPLB-UHFFFAOYSA-N OOP(O)=O Chemical compound OOP(O)=O PEHQDSOLLVMPLB-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N anhydrous trimethylamine Natural products CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 230000002255 enzymatic effect Effects 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000002739 metals Chemical class 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
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical group CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 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
- 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
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 2
- 238000012682 free radical photopolymerization Methods 0.000 abstract 2
- 238000005516 engineering process Methods 0.000 description 6
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PAXPHUUREDAUGV-UHFFFAOYSA-N OP(=O)OP(O)(O)=O Chemical class OP(=O)OP(O)(O)=O PAXPHUUREDAUGV-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
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 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
- NXHPIYRSMIFFBV-UHFFFAOYSA-N formaldehyde;1,3,5-trimethylbenzene Chemical compound O=C.CC1=CC(C)=CC(C)=C1 NXHPIYRSMIFFBV-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000003847 radiation curing Methods 0.000 description 2
- 239000011734 sodium 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 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
- 238000007792 addition Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000000977 initiatory effect 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
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 238000005502 peroxidation Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 239000000049 pigment Substances 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
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910052710 silicon Chemical group 0.000 description 1
- 239000010703 silicon Chemical group 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
本发明涉及UV光辐射自由基聚合新材料技术领域，特别涉及结构通式如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。
Description
【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。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WO2006/056541A1。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步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烷基，该烷基可以为不超过4个的非连续性氧原子，氮原子，硅原子，或硫原子所间断，或该烷基可以含有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烷基(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(烷氧基或芳氧基)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(hypophosphorous acid)为关键起始原料，经由R基酯化反应得到中间体次业磷酸酯A，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B。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A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。A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(O)H2胺盐，M优选NH4，PhNH3，HNEt3，下同]和原甲酸烷基酯反应，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的硅氧烷反应。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 theRelated 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ACS Medicinal Chemistry Letters，2(1)，11-16；2011；R是叔丁基，TetrahedronLetters，37(4)，425-8；1996；R是正丁基，Journal of Organic Chemistry，70(10)，4064-4072；2005和Journal 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iPr2NEt。
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，乙烯基吡咯烷酮，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，硅氧烷(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：
在氮气保护下将6.6克无水次亚磷酸置于50毫升的新鲜蒸馏四氢呋喃和甲苯混合溶剂(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Na2SO3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/己烷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：C21H25O4P，理论值：C％67.73％；H6.77％；实验值：C％67.87％；H6.81％。
其它实施例二至五化合物以如上类似的操作步骤制备，所不同处仅在于相应的次亚磷酸酯H2P(O)OR是参照如前所引文献步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：
依照下述的重量百分比配制光固化测试样品：
30份：环氧丙烯酸酯；
35份：聚酯丙烯酸酯；
5份：己二醇二丙烯酸酯；
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200W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 (4)
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烷基，该烷基可以为不超过4个的非连续性氧原子，氮原子，硅原子，或硫原子所间断，或该烷基可以含有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H3PO2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，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B。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A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。A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(O)H2胺盐，M优选NH4，PhNH3，HNEt3，下同]和原甲酸烷基酯反应，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)4的硅氧烷反应。
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iPr2NEt。
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，乙烯基吡咯烷酮，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，硅氧烷(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。
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| CN103333202A (zh) * | 2013-06-08 | 2013-10-02 | 广州市博兴化工科技有限公司 | 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 |
| CN104870456A (zh) * | 2012-12-19 | 2015-08-26 | 巴斯夫欧洲公司 | 双酰基次膦酸的衍生物、其制备及其作为光敏引发剂的用途 |
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