CN107400144A - Acylphosphanes（Oxygen）Compound and its preparation method and application - Google Patents
Acylphosphanes（Oxygen）Compound and its preparation method and application Download PDFInfo
- Publication number
- CN107400144A CN107400144A CN201710667166.2A CN201710667166A CN107400144A CN 107400144 A CN107400144 A CN 107400144A CN 201710667166 A CN201710667166 A CN 201710667166A CN 107400144 A CN107400144 A CN 107400144A
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- China
- Prior art keywords
- compound
- acid
- oxygen
- logical formula
- acylphosphanes
- Prior art date
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- Granted
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 111
- 239000001301 oxygen Substances 0.000 title claims abstract description 38
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 title description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910001868 water Inorganic materials 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000005855 radiation Effects 0.000 claims abstract description 8
- 238000009472 formulation Methods 0.000 claims abstract description 7
- -1 amine salt Chemical class 0.000 claims description 95
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 53
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 40
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims description 24
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 claims description 22
- 239000000543 intermediate Substances 0.000 claims description 22
- 230000000694 effects Effects 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 19
- 239000002585 base Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 239000005864 Sulphur Substances 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 150000003384 small molecules Chemical group 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 10
- 150000002513 isocyanates Chemical class 0.000 claims description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 9
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007259 addition reaction Methods 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 8
- 150000004820 halides Chemical class 0.000 claims description 8
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 150000002431 hydrogen Chemical group 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 6
- 239000000123 paper Substances 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000007848 Bronsted acid Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000007641 inkjet printing Methods 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 5
- HIKRJHFHGKZKRI-UHFFFAOYSA-N 2,4,6-trimethylbenzaldehyde Chemical compound CC1=CC(C)=C(C=O)C(C)=C1 HIKRJHFHGKZKRI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- 238000010422 painting Methods 0.000 claims description 4
- 239000002952 polymeric resin Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- 125000004098 2,6-dichlorobenzoyl group Chemical group O=C([*])C1=C(Cl)C([H])=C([H])C([H])=C1Cl 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010464 Blanc reaction Methods 0.000 claims description 3
- 125000006519 CCH3 Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001350 alkyl halides Chemical class 0.000 claims description 3
- RMRFFCXPLWYOOY-UHFFFAOYSA-N allyl radical Chemical compound [CH2]C=C RMRFFCXPLWYOOY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000002587 enol group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 230000026030 halogenation Effects 0.000 claims description 3
- 238000005658 halogenation reaction Methods 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 239000005022 packaging material Substances 0.000 claims description 3
- 150000004965 peroxy acids Chemical class 0.000 claims description 3
- 238000007142 ring opening reaction Methods 0.000 claims description 3
- 125000006850 spacer group Chemical group 0.000 claims description 3
- 238000003786 synthesis reaction Methods 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
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000004035 construction material Substances 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 229920002313 fluoropolymer Polymers 0.000 claims description 2
- 239000004811 fluoropolymer Substances 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000003847 radiation curing Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 44
- 239000007788 liquid Substances 0.000 description 38
- 239000007787 solid Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 33
- 239000011734 sodium Substances 0.000 description 26
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 239000004814 polyurethane Substances 0.000 description 19
- 229920002635 polyurethane Polymers 0.000 description 19
- 238000010898 silica gel chromatography Methods 0.000 description 16
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 16
- 235000002639 sodium chloride Nutrition 0.000 description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 13
- 238000010828 elution Methods 0.000 description 13
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 13
- 239000012074 organic phase Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 12
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical class COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 11
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- 238000000016 photochemical curing Methods 0.000 description 11
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 10
- 235000011152 sodium sulphate Nutrition 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 0 CC1CCC(CC(CC2)CCC2C(C(OC*(*)*C(*(CCC2=CC3NC23)=C)=O)=O)=C)CC1 Chemical compound CC1CCC(CC(CC2)CCC2C(C(OC*(*)*C(*(CCC2=CC3NC23)=C)=O)=O)=C)CC1 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229960000583 acetic acid Drugs 0.000 description 6
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- 230000000269 nucleophilic effect Effects 0.000 description 6
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- 238000003860 storage Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
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- 239000003999 initiator Substances 0.000 description 5
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- 239000007983 Tris buffer Substances 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- UQRKXZOISAAYQQ-UHFFFAOYSA-N diphenylphosphorylformaldehyde Chemical compound C=1C=CC=CC=1P(=O)(C=O)C1=CC=CC=C1 UQRKXZOISAAYQQ-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 229940093499 ethyl acetate Drugs 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical class CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- UZFYJOPHCKOAKF-UHFFFAOYSA-N 2-hydroxy-1-[3-(hydroxymethyl)phenyl]-2-methylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC(CO)=C1 UZFYJOPHCKOAKF-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- APKFLZGRWMXNNV-UHFFFAOYSA-N 6-(carboxyamino)hexylcarbamic acid Chemical compound OC(=O)NCCCCCCNC(O)=O APKFLZGRWMXNNV-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- YYEMUGRCANSNQM-UHFFFAOYSA-N Br(=O)(=O)O.[O] Chemical compound Br(=O)(=O)O.[O] YYEMUGRCANSNQM-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BSPVXBAFDXGUEU-UHFFFAOYSA-N CC1=CC(C)=C(C(P(CCC(OCCCOC(CCP(C(C2=C(C)C=C(C)C=C2C)=O)(C2=CC=CC=C2)=O)=O)=O)(C2=CC=CC=C2)=O)=O)C(C)=C1 Chemical compound CC1=CC(C)=C(C(P(CCC(OCCCOC(CCP(C(C2=C(C)C=C(C)C=C2C)=O)(C2=CC=CC=C2)=O)=O)=O)(C2=CC=CC=C2)=O)=O)C(C)=C1 BSPVXBAFDXGUEU-UHFFFAOYSA-N 0.000 description 1
- SXNICUVVDOTUPD-UHFFFAOYSA-N CC1=CC(C)=CC(C)=C1C(=O)P(=O)C1=CC=CC=C1 Chemical class CC1=CC(C)=CC(C)=C1C(=O)P(=O)C1=CC=CC=C1 SXNICUVVDOTUPD-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NIXVMBBZNVOBHS-ASRKUVFVSA-N [(8r,9s,10r,13s,14s,17r)-17-acetyl-6,10,13-trimethyl-3-oxo-2,8,9,11,12,14,15,16-octahydro-1h-cyclopenta[a]phenanthren-17-yl] acetate;(8r,9s,13s,14s,17r)-17-ethynyl-13-methyl-7,8,9,11,12,14,15,16-octahydro-6h-cyclopenta[a]phenanthrene-3,17-diol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.C1=C(C)C2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(C)=O)(OC(=O)C)[C@@]1(C)CC2 NIXVMBBZNVOBHS-ASRKUVFVSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QMKYBPDZANOJGF-UHFFFAOYSA-K benzene-1,3,5-tricarboxylate(3-) Chemical compound [O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-K 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical group Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- AZLPEJUVWWGLHA-UHFFFAOYSA-N ethyl acetate;hexane;methanol Chemical compound OC.CCCCCC.CCOC(C)=O AZLPEJUVWWGLHA-UHFFFAOYSA-N 0.000 description 1
- HYKFUNUAQCOKEW-UHFFFAOYSA-N ethyl acetate;hexane;toluene Chemical compound CCCCCC.CCOC(C)=O.CC1=CC=CC=C1 HYKFUNUAQCOKEW-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000003811 finger Anatomy 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- WTDFFADXONGQOM-UHFFFAOYSA-N formaldehyde;hydrochloride Chemical compound Cl.O=C WTDFFADXONGQOM-UHFFFAOYSA-N 0.000 description 1
- ZEXYPISQISIGFV-UHFFFAOYSA-N formyl chloride 1,3,5-trimethylbenzene Chemical compound C(=O)Cl.CC1=CC(=CC(=C1)C)C ZEXYPISQISIGFV-UHFFFAOYSA-N 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- KQPBSBAEBKRAAU-UHFFFAOYSA-N hypochlorous acid;sodium Chemical compound [Na].ClO KQPBSBAEBKRAAU-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- DMKSVUSAATWOCU-HROMYWEYSA-N loteprednol etabonate Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)OCCl)(OC(=O)OCC)[C@@]1(C)C[C@@H]2O DMKSVUSAATWOCU-HROMYWEYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 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
- PXLABDTXHJPRRH-UHFFFAOYSA-N methyl 2,4,6-trimethylbenzoate Chemical compound COC(=O)C1=C(C)C=C(C)C=C1C PXLABDTXHJPRRH-UHFFFAOYSA-N 0.000 description 1
- DXASQZJWWGZNSF-UHFFFAOYSA-N n,n-dimethylmethanamine;sulfur trioxide Chemical group CN(C)C.O=S(=O)=O DXASQZJWWGZNSF-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000013035 waterborne resin Substances 0.000 description 1
- 229920006313 waterborne resin Polymers 0.000 description 1
- 239000002023 wood Substances 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
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5337—Phosphine oxides or thioxides containing the structure -C(=X)-P(=X) or NC-P(=X) (X = O, S, Se)
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6521—Six-membered rings
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
- C07F9/6533—Six-membered rings
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
- C07F9/65505—Phosphonic acids containing oxirane groups; esters thereof
-
- 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
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention relates to new material organic chemicals technical field, more particularly to formula（I）The noval chemical compound of shown acylphosphanes oxygen type structure, its chemical preparating process technology, its purposes as radiation curing photoinitiator, and it is in radiation curable formulation product, particularly water-based UV LED lights are coating material solidified or ink, wait the application purpose of many occasions.
Description
【Technical field】
The present invention relates to new material organic chemicals technical field, more particularly to a kind of new acylphosphanes oxygen type structure
Compound, its chemical preparating process technology, its purposes as radiation curing photoinitiator, and it matches somebody with somebody in radiation curing
Square product, particularly in water-based UV-LED photocureable coating or ink, wait the application purpose of many occasions.
【Background technology】
Photoinitiator compound is a kind of important Fine Organic Chemical product material.With ultraviolet light or visible (UV) light
Or the radiation curing technology field that LED (i.e. Light-Emitting Diode) is light source, it can be generated under light radiation parameter certainly
Photoinitiator compound by base active specy is to induce the crucial thing that the system of unsaturation containing alkene carries out efficient photopolymerization reaction
Kind, therefore be one of important radiation curable formulation component.In numerous light trigger products of business application have been obtained,
Phosphono class compound occupies prominent status, its mainstream product such as monoacyl phosphine oxide compound " 2,4,6- trimethylbenzene first
Acyl group diphenyl phosphine oxide " (trade name TPO) and " 2,4,6- trimethylbenzoyl ethoxyl phenenyl phosphine oxide " (TPO-L),
And double acylphosphine oxide " double (2,4,6- trimethylbenzoyl) phenyl phosphine oxides " (BAPO, or Irgacure
819), and 819 water-borne dispersions (BASF AG Irgacure 819-DW).This kind of compound is lived due to having high trigger concurrently
Property, photobleaching, long wavelength's absorbability, and UV-LED wide spectrums applicability and obtain increasingly extensive application, related patent example
Such as US4292154, US4737593, US6399805, EP495752 etc..It is in addition, also existing a considerable amount of in technical literature
Disclose the example of above-mentioned acylphosphanes oxygen light trigger and other types light trigger composite usage, for example, patent US8507726 and
US6777459。
On the other hand, the Water-borne modification of photocureable coating and ink product has met world's energy-conserving and environment-protective industry development
Strategic new trend, thus increasingly extensive attention and quickly development are obtained in recent years, particularly in the wide water of universality
Property sprayed on material, water-based ink-jet printing material, and other water-based UV-LED photo-curing materials fields, due in work progress
Completely avoid environmental pollution and artificial health protection problem with latter two stage of photocuring, and LED light curing technology should
Generated with energy resource consumption and ozone is considerably reduced, industry sustainable growth powerful.Technically consider, water-based light is consolidated
Changing the compounding of coating or ink needs water borne UV curing resin (waterborne resins) and water-soluble photoinitiator
(waterborne photo- initiators) two kinds of critical materials；Solidify for water-based LED systems, it is also desirable to be both directed to
LED longwave transmissions wavelength (365-420 nanometers, particularly 395-405 nanometers) has the light trigger of sensitive absorption, and requiring again should
Light trigger possesses good water solubility or water dispersible.Therefore, the new water solubility of design, research and development, and industrialization or moisture
Property photoinitiator compound is dissipated, is the key technique challenge that current this area faces.Known acylphosphanes oxygen type chemical combination
Thing, including above-mentioned the oil-soluble TPO, TPO-L, 819 referred to, or 819-DW products, due to the hydrophobic property of height, none tool
Enough water solubilitys or water dispersing characteristic are prepared enough, thus is difficult to compound the coating or oil to form stable storing with water-base resin system
Graphite product.
【The content of the invention】
For above-mentioned technical problem, the invention provides it is a kind of it is new there is preferably water-soluble or water dispersible, can
Acylphosphanes effectively compatible with water borne UV curing resin and that the water-based UV-curalble ink or coating that form storage stabilization can be compounded
(oxygen) compound and its preparation method and application.
First purpose of the present invention is to provide acylphosphanes (oxygen) compound shown in a kind of logical formula (I)：
In logical formula (I)：
R0It is containing R3、R4、R5、R6、R7Substituted aryl, or R8、R9、R10Substituted tertiary alkyl, wherein R3、R4、R5、
R6、R7Independent of each other is hydrogen, halogen atom, R, OR, NRR ', CH2OH、CH2OR or CH2NRR ', wherein R or R ' are independent of one another
The alkyl selected from the straight or branched containing 1-24 carbon atom ,-C6-C12Aryl, contain the individual discrete element As of 1-6
The alkyl of straight or branched containing 1-24 the carbon atom ,-C containing 1-6 discrete element As6-C12One in aryl
Kind, wherein, one or more of the element A in oxygen, nitrogen, element sulphur；R and R ' individualisms or connection form a 3-6
The ring system structure of member；R8、R9、R10Independent of each other is R, R8、R9、 R10Individualism or the two any connection form a 3-
6 yuan of carbocyclic ring structure；
X is oxygen or sulphur, or X is not present：
Integer between n values 1-1000；R1It is R or-C (O)-R0；
As n=1, R2- Q is selected from hydrogen, the C containing 0-4 substituent6-C24Aryl, CH2OH、 CH2OR、CH2OC(O)R、
CH2NRR’、CHR(OH)、CRR’(OH)、CCH3(CH2OH)OH、 C(CH2OH)2OH、CH2CH2OH、CH2CHMeOH、
CHMeCH2OH、CH2CHPhOH、 CH2C(O)R、CH2CO2H or its metal salt or amine salt, CH2CH2CO2H or its metal salt or amine
Salt, CH2CH2C(O)OCH2CH2OH、CH2CHMeC(O)OCH2CH2OH、 CH2CH2C(O)OCH2CH2OCH2CH2OH、CH2CH2C
(O)OY、CH2OC(O)-NHY、 CH2CH2One kind in OC (O) NHY, Y are one containing 2-6 C=C double bonds-C2-C36Base
Group,
When n values 2 or the integer more than 2 ,-R2- Q is a n member spacer group；-R2- it is selected from-CH2-、-
CH2CH2-、-CH2CH(OH)CH2-、-CH2CH(OR)CH2-、- CH2CH(OC(O)R)CH2-、-CH2CH2C(O)OCH2CH2-、-
CH2CH(Me)C(O)OCH2CH2-、 -CH2CH2C(O)OCH2CH2OCH2CH2-、-CH2CH2C(O)OCH2CH2CH2-、- CH2CH2C
(O)OCH2CH2CH2CH2- in one kind；Q is a small molecule or polymer matrix with 2 or more-NHC (O) O- units
Group；Or Q is a small molecule or polymeric groups with 2 or more-C (O) O- units；
Or when n values 2 or the integer more than 2 and work as R1When being R ,-R2- Q is one and contains n members-CH2CH2C(O)
O-、-CH2CH(Me)C(O)O-、-CH2CH2C(O)C(O)O-、- CH2CH(Me)C(O)C(O)O-、-CH2CH2C(O)C(O)-、-
CH2CH(Me)C(O)C(O)-、- CH2CH2C(O)C(O)NH-、-CH2CH(Me)C(O)C(O)NH-、-CH2CH2C(O)-、-
CH2CH(Me)C(O)-、-CH2CH2C(O)NH-、-CH2CH(Me)C(O)NH-、- CH2CH2C(O)NR-、-CH2CH(Me)C(O)
NR-、-CH2CH28O2-、-CH2CH(Me)SO2-、- CH2CH2S (O) R- or-CH2The small molecule of CH (Me) S (O) R- units is poly-
Compound group,
Or when n values 2 or the integer more than 2 ,-R2- Q is one and contains n members-CH2CH (OH)-or-CH2CH
(OR) small molecule or polymeric groups of-unit.
It is preferred that R3=R5=R7=CH3And R4=R6=H；Or R3=R7=Cl and R4=R5=R6=H；Or R3=R7=
OCH3And R4=R5=R6=H；Or R3=R5=R7=CH3And R4=R6=CH2OH；Or R3=R5=R7=CH3And R4=R6=
CH2OC(O)R；Or R3=R5=R7=CH3And R4=CH2OH and R6=H；Or R3=R5=R7=CH3And R4=R6=CH2OR；Or
R3=R5=R7=CH3And R4=R6=CH2NRR’；Or R3=R5=R7=CH3And R4=CH2OH and R6=CH2NRR’。
It is preferred that R8=R9=R10=CH3；Or R8=R9=R10=CH2CH3；Or R8=CH3、R9- R10It is cyclohexane structure.
It is preferred that the integer between n values 1-100；Further preferably, the integer between n values 1-10.
It is preferred that R1Selected from C6H5、p-CH3OC6H4、CH3、CH2CH3、CH2CH=CH2、CH2Ph、 C(O)CEt3、C(O)CMe3、
Xenyl, 2, one kind in 4,6- trimethylbenzoyls, 2,6- Dimethoxybenzoyls or 2,6- dichloro-benzoyl base.
It is preferred that C6-C24The one kind of aryl in phenyl, xenyl, naphthyl.
It is preferred that Y is one containing 2-6 acrylic ester unit-C2-C36Group, it is preferable that Y be it is following shown in group it
One：
It is preferred that when n values 2 or the integer more than 2, Q is one of following shown group：
Or Q is one of following shown group：
Wherein, R11It is hydrogen or R.
Or preferably, when n values 2 or the integer more than 2 and work as R1When being R, Q is one of following shown group：
Or preferably, when n values 2 or the integer more than 2 ,-R2- Q structures are one and contain n members-CH2CH (OH)-or-
CH2The small molecule or polymeric groups of CH (OR)-unit, Q are one of following shown groups：
Second object of the present invention is to provide the method that one kind prepares the compound of acylphosphanes (oxygen) shown in logical formula (I)：From
Organic halogenation phosphine R1PHal2Set out, organic phosphine hydrogen R is made1PH2, organic phosphine hydrogen R1PH2Alkali effect under and carboxylic acid halides R0C(O)Hal
Or acid anhydrides R0C(O)OC(O)R0Reaction, obtain under the intermediate that form is A or B, the intermediate and formaldehyde and oxidant effect,
Acylphosphanes (oxygen) compound shown in logical formula (I) is obtained, wherein, Hal is halogen；Or representated by intermediate A or B and formula C
Material the first reaction is carried out in oxidant presence, obtain acylphosphanes (oxygen) compound shown in logical formula (I)；Wherein, Q is represented
The structure of one Q chemistry speciality description, contain polynary epoxy, multicomponent isocyanate, polynary unsaturated carbonyl compound, more for one
First carboxylic acid, the micromolecular compound of polynary carboxylic acid halides or multi-anhydride functional group or fluoropolymer resin compound；Alkali is inorganic
Metal hydroxides or alkoxide or carbonate or carboxylate compounds, or trimethylamine type compound；Oxidant is selected from oxygen
Gas, air, air-metal salt composite, metal hypochlorite salt, oxygen-metal salt complex, hydrogen peroxide, form are ROOH's
One kind in peroxide, peroxy acid or sulphur；Integer of the q values between 1-n；Material representated by formula C is selected from polynary
In epoxy C1, multicomponent isocyanate C2, polynary unsaturated carbonyl compound C3, polybasic carboxylic acid C4, polynary carboxylic acid halides C5, multi-anhydride C6
One kind；
Or intermediate A or B and alkyl halide or alkyl pseudohalogen compound labeled as R-Hal occur, the
In the presence of two alkali, nucleophilic substitution, acylphosphanes (oxygen) compound shown in logical formula (I) is prepared,
Or, the phosphono raw material D via a starting, Blanc reactions occur under acid and formaldehyde collective effect, obtain halogen
Compound intermediate E, wherein, r values 1 or 2, the acid is Louis or Bronsted acid, and Hal represents halogen atom；Intermediate E exists
Nucleopilic reagent HNu effects are lower to occur nucleophilic substitution, and the compound of acylphosphanes (oxygen) shown in logical formula (I) is prepared,
Or, double acylphosphine oxides (BAPO) are in acid and electrophilic reagent E+Under effect, single phosphono group occurs to E+'s
Addition reaction, the compound of acylphosphanes (oxygen) shown in logical formula (I) is prepared；The acid is lewis acid or Bronsted acid；Electrophilic examination
Agent E+It is C1-C48Side chain or straight chain aliphatic or aromatic series aldehydes or ketones, or α, beta-unsaturated aldehyde, ketone, ester, nitrile or acyl
Amine, or nitro compds, or alkenyl sulfone or sulfoxide,
Or, structure F phosphonos intermediate sodium bis (2,4,6-trimethylbenzoyl) phosphanide or structure
G phosphinediylbis (mesitylmethanone), or the resonant isomers of their enol forms with formaldehyde or C
Reagent reacts and passes through oxidant effect, obtains acylphosphanes (oxygen) compound shown in logical formula (I)；C reagents are selected from polynary
In epoxy C1, multicomponent isocyanate C2, polynary unsaturated carbonyl compound C3, polybasic carboxylic acid C4, polynary carboxylic acid halides C5, multi-anhydride C6
One kind,
It is preferred that the first reaction is selected from epoxy ring opening reaction, isocyanates addition reaction, Michael's conjugate addition reaction, ester
Change one kind in reaction.
It is preferred that the second alkali is inorganic metal hydroxide or alkoxide or carbonate or carboxylate compounds, or it is organic
Tertiary amine-type compound.
It is preferred that the acid is in alchlor, zinc chloride, ferric trichloride, alchlor, hydrochloric acid, hydrobromic acid, acetic acid
One or more；Further preferably, the acid is alchlor or hydrochloric acid.
It is preferred that the Hal is chlorine.
It is preferred that the nucleopilic reagent HNu is the material containing aerobic, nitrogen, sulphur or phosphorus atoms, and further preferably, the HNu
It is water, NR3、HNRR’、H2NR, HSR, RSSR ', HP (O) RR ' or the heterocycle containing aerobic, nitrogen, sulphur or phosphorus atoms.
It is preferred that the electrophilic reagent E+Be formaldehyde, acrylic acid, methacrylaldehyde or unitary or polynary acrylate monomer or
Acrylate polymer resin；Further preferably, the acid is alchlor or hydrochloric acid, the electrophilic reagent E+It is formaldehyde.
Third object of the present invention is to provide acylphosphanes (oxygen) compound shown in a kind of logical formula (I) in photocurable formulation
Purposes in system as light trigger or other functional additive compositions；Or intermediate or original are used as in chemical synthesis
The purposes of material or reagent.
Fourth object of the present invention is to provide a kind of containing above-mentioned logical formula (I) compound, can solidify via light radiation
Mixture.
It is preferred that mixture contains at least one logical formula (I) compound as one of light trigger or light trigger component；
And contain at least one unsaturated compound containing ethylene linkage.
It is preferred that calculated with the every 100 parts of weight of the total amount of unsaturated compound containing ethylene linkage, the amount of the logical formula (I) compound contained
It is 0.01-30 parts by weight；It is preferred that calculated with the every 100 parts of weight of the total amount of unsaturated compound containing ethylene linkage, the logical formula (I) contained
The amount of compound is 0.5-10 parts by weight.
It is preferred that unsaturated compound containing ethylene linkage is the compound or mixed being crosslinked by the Raolical polymerizable of double bond
Compound, the unsaturated compound containing ethylene linkage are monomer, oligomer or prepolymer or their mixture or copolymer, or
Their water-borne dispersions.
The 5th purpose of the present invention is to provide said mixture and is used as photocureable coating or ink.
It is preferred that above-mentioned photocureable coating or ink apply in inkjet printing, paper printing, adhesive, woodwork coating, plastic cement
Dress, painting dressing automobiles, packaging material, Display Technique, construction material, the application in flexible electronic or photovoltaic material field.
The present invention via what synthetic method of the present invention obtained it has been unexpectedly discovered that contain appropriate polar functional group
Acylphosphanes (oxygen) compound of group, possesses suitable water-soluble or water dispersible.We further demonstrate that the new type water of this bar
Property light trigger can be effectively compatible with water borne UV curing resin and compound to form the stable water-based UV-curalble ink of storage or painting
Material, particularly, such water-soluble photoinitiator causes water-based energy-saving environment-friendly LED photocuring technology to be achieved first, such
Technology possesses far-reaching influence to fields such as woodenware green application, environmental printing, inkjet printing, energy-saving materials.
【Brief description of the drawings】
Fig. 1 is UV-Vis absorption spectrums (ultra-violet absorption spectrum) figure of compound prepared by the embodiment of the present invention one；
Fig. 2 is UV-Vis absorption spectrums (ultra-violet absorption spectrum) figure of compound prepared by the embodiment of the present invention 13.
【Embodiment】
This item application discloses new acylphosphanes (oxygen) compound shown in below formula (I)：
In above-mentioned logical formula (I) compound structure：
R0It is containing R3、R4、R5、R6、R7Substituted aryl, or R8、R9、R10Substituted tertiary alkyl (as shown in the figure), its
Middle R3、R4、R5、R6、R7Independent of each other is hydrogen, halogen atom, R, OR, NRR ', CH2OH、CH2OR or CH2NRR ', wherein R or
R ' independent of each other is (to be labeled as-C containing 1-24 carbon atom1-C24, similarly hereinafter) straight or branched alkyl or-C6-C12
Can contain in aryl, R or R ' structures 1-6 discrete oxygen, nitrogen, or element sulphur, R and R ' and meanwhile in the presence of also may be used therebetween
To form the ring system structure of a 3-6 member.R8, R9, R10Independent of each other is R, among three it is any the two can also be formed
The carbocyclic ring structure of one 3-6 member.Preferably, R3=R5=R7=CH3And R4=R6=H, or R3=R7=Cl and R4=R5=R6=
H, or R3=R7=OCH3And R4=R5=R6=H, or R3=R5=R7=CH3And R4=R6=CH2OH, or R3=R5=R7=CH3
And R4=R6=CH2OC (O) R, or R3=R5=R7=CH3And R4=CH2OH and R6=H, or R3=R5=R7=CH3And R4=
R6=CH2OR, or R3=R5=R7=CH3And R4=R6=CH2NRR ', or R3=R5=R7=CH3And R4=CH2OH and R6=
CH2NRR’.Preferably, R8=R9=R10=CH3, or R8=R9=R10=CH2CH3, or R8=CH3And R9-R10It is hexamethylene knot
Structure：
X is oxygen or sulphur, or (i.e. compound of formula I is trivalent phosphine alkane) is not present in X；
Integer between n values 1-1000, it is preferred that the integer between n values 1-100, it is furthermore preferred that n values 1-10
Between integer；
R1It is R or-C (O)-R0, preferable R1It is C6H5, p-CH3OC6H4, CH3, CH2CH3, CH2CH=CH2, CH2Ph, C
(O)CEt3, C (O) CMe3, xenyl, 2,4,6- trimethylbenzoyls, 2,6- Dimethoxybenzoyls, or 2,6- dichloro
Benzoyl；
As n=1, R2- Q structures are hydrogen, the C containing 0-4 substituent6-C24Aryl (preferably phenyl, biphenyl
Base, naphthyl), CH2OH, CH2OR, CH2OC (O) R, CH2NRR ', CHR (OH), CRR ' (OH), CCH3(CH2OH) OH, C (CH2OH)2OH, CH2CH2OH, CH2CHMeOH, CHMeCH2OH, CH2CHPhOH, CH2C (O) R, CH2CO2H or its metal salt or amine salt,
CH2CH2CO2H or its metal salt or amine salt, CH2CH2C(O)OCH2CH2OH, CH2CHMeC(O)OCH2CH2OH, CH2CH2C(O)
OCH2CH2OCH2CH2OH, CH2CH2C (O) OY, CH2OC (O)-NHY, or CH2CH2OC (O) NHY, here Y be one and contain 2-6
- the C of individual C=C double bonds2-C36Group, preferably Y are one containing 2-6 acrylic ester unit-C2-C36Group, more preferably
Y be it is following shown in one of group：
When n values 2 or the integer more than 2 ,-R2- Q structures are a n member spacer groups；-R2- preferably-
CH2- ,-CH2CH2- ,-CH2CH(OH)CH2- ,-CH2CH(OR)CH2- ,-CH2CH(OC(O)R)CH2- ,-CH2CH2C(O)
OCH2CH2- ,-CH2CH(Me)C(O)OCH2CH2- ,-CH2CH2C(O)OCH2CH2OCH2CH2- ,-CH2CH2C(O)
OCH2CH2CH2- ,-CH2CH2C(O)OCH2CH2CH2CH2-, and Q is one has the small of 2 or more-NHC (O) O- units
Molecule or polymeric groups, and Q is preferably following groups：
Or Q is a small molecule or polymeric groups with 2 or more-C (O) O- units, and Q is preferably
Following groups (wherein R11It is hydrogen or R)：
It is apparent that for this specialty obtains employment technical staff, it will therefore be readily appreciated that the polynary isocyanic acid in above-mentioned Q structures
Ester【-NHC(O)O-】Unit or polyester【-C(O)O-】Unit is derived from R2Hydroxyl OH and corresponding polynary poly- ammonia in structure
Ester NCO group or polyacid or multi-anhydride or polynary carboxylic acid halides carry out esterification and got, therefore above-mentioned preferably Q structures are only
It is exemplary and non-restrictive structure, every Q structures for meeting above-mentioned chemical reaction essence main idea belong to present disclosure model
Enclose.
Or when n values 2 or the integer more than 2 and work as R1When being R ,-R2- Q structures be one containing n member-
CH2CH2C (O) O- ,-CH2CH (Me) C (O) O- ,-CH2CH2C (O) C (O) O- ,-CH2CH (Me) C (O) C (O) O- ,-CH2CH2C
(O) C (O)-,-CH2CH (Me) C (O) C (O)-,-CH2CH2C (O) C (O) NH- ,-CH2CH (Me) C (O) C (O) NH- ,-CH2CH2C
(O)-,-CH2CH (Me) C (O)-,-CH2CH2C (O) NH- ,-CH2CH (Me) C (O) NH- ,-CH2CH2C (O) NR- ,-CH2CH
(Me) C (O) NR- ,-CH2CH2SO2- ,-CH2CH(Me)SO2- ,-CH2CH2S (O) R-, or-CH2CH (Me) S (O) R- units it is small
Molecule or polymeric groups, it is preferred that Q is following groups：
It is apparent that for this specialty obtains employment technical staff, it will therefore be readily appreciated that-the CH in above-mentioned Q structures2CH2C(O)
O- ,-CH2CH (Me) C (O) O- ,-CH2CH2C (O) C (O) O- ,-CH2CH (Me) C (O) C (O) O- ,-CH2CH2C (O) C (O)-,-
CH2CH (Me) C (O) C (O)-,-CH2CH2C (O) C (O) NH- ,-CH2CH (Me) C (O) C (O) NH- ,-CH2CH2C (O)-,-
CH2CH (Me) C (O)-,-CH2CH2C (O) NH- ,-CH2CH (Me) C (O) NH- ,-CH2CH2C (O) NR- ,-CH2CH(Me)C(O)
NR- ,-CH2CH2SO2- ,-CH2CH(Me)SO2- ,-CH2CH2S (O) R-, or-CH2CH (Me) S (O) R- units are derived from changing as follows
(wherein Metal represents a metal cation or silane to the intermediate of nucleophilic (nucleophilic) characteristic of one of structure
Group, preferable Metal are sodium, potassium, lithium, SiR3Deng) to corresponding beta-unsaturated esters, unsaturated amides, unsaturated sulfone or sulfoxide
Deng Michael addition reaction prepare.Therefore above-mentioned preferably-R2- Q structures are merely illustrative and non-restrictive structure, every symbol
Close the small molecule or polymer-type-R for stating the substantive main idea that chemically reacts2- Q structures belong to present disclosure scope.
Or when n values 2 or the integer more than 2 ,-R2- Q structures are one and contain n members-CH2CH (OH)-, or-
CH2The small molecule or polymeric groups of CH (OR)-unit, it is preferred that Q is following groups：
It is apparent that for this specialty obtains employment technical staff, it will therefore be readily appreciated that-the CH in above-mentioned Q structures2CH
(OH)-or-CH2CH (OR)-unit is derived from the intermediate of nucleophilic (nucleophilic) characteristic of one of following chemical constitution
It is prepared by the ring-opening reaction of corresponding epoxide.Therefore above-mentioned preferably-R2- Q structures are merely illustrative and non-limiting knot
Structure, every small molecule or polymer-type-R for meeting above-mentioned chemical reaction essence main idea2- Q structures belong to present disclosure model
Enclose.
One of universality preparation method of logical formula (I) compound is as shown in following equation, from organic halogenation phosphine R1PHal2
(Hal is halogen) sets out, via known references method【CN201510020417.9】In situ it can prepare or isolate and purify to obtain
Organic phosphine hydrogen R1PH2, organic phosphine hydrogen R1PH2Carboxylic acid halides R under appropriate alkali Base effects with equivalent0C (O) Hal or acid anhydrides R0C
(O)OC(O)R0Reaction, you can obtain the intermediate that form is A or B, the intermediate and formaldehyde and oxidant【O】Under effect, i.e.,
Obtain formula partial Formula (I) product；
Or intermediate A or B and the polynary epoxy C1 representated by formula C, multicomponent isocyanate C2, polynary unsaturated carbonyl
Compound C3, polybasic carboxylic acid C4, polynary carboxylic acid halides C5, multi-anhydride C6 etc. are in oxidant【O】Participate in the lower corresponding epoxy addition of progress
Reaction, isocyanates addition reaction (esterification), Michael's conjugate addition reaction, esterification etc., obtain another part and lead to
Formula (I) product：Here net circle Q represents the structure of a Q chemistry speciality description, i.e., one contains polynary epoxy, polynary isocyanic acid
Ester, polynary unsaturated carbonyl compound, polybasic carboxylic acid, polynary carboxylic acid halides, or the micromolecular compound of multi-anhydride functional group are poly-
Polymer resin compound.
Oxidant【O】Represent oxygen, air, air-metal salt composite, metal hypochlorite salt's (preferably hypochlorous acid
Sodium), oxygen-metal salt complex, hydrogen peroxide, form is ROOH peroxide, peroxy acid, or sulphur；Q values are between 1-n
Integer.
Meanwhile in view of intermediate A or B nucleophilic (Nucleophilic) species chemistry speciality, associated, A or B can
To mark the alkyl halide (chloride, bromide, or iodide) for being or alkyl pseudohalogen compound with a series of
(sulfonate radical etc.) occurs, it is preferred that in the presence of suitable alkali, nucleophilic substitution, prepares the logical formula (I) targeted of a part
Compound.Alkali Base is inorganic metal oxygen oxide or alkoxide or carbonate or carboxylate compounds, or trimethylamine type
Compound.
The preparation method of above-mentioned logical formula (I) compound we will do further exemplary illustration by son in conjunction with the embodiments.
Meeting the preparation method of another part compound of above-mentioned logical formula (I) is, via one starting phosphono raw material D,
So-called Blanc reaction occurs under acid and formaldehyde collective effect, obtain corresponding halide intermediates E (wherein r values 1 or
2), acid is Louis or Bronsted acid here, and preferable acid is alchlor, zinc chloride, ferric trichloride, alchlor, hydrochloric acid,
Oxygen bromic acid, acetic acid, or above-mentioned sour appropriate mixture；Hal represents halogen atom, and preferable Hal is chlorine.Key intermediate E exists
Suitable nucleopilic reagent HNu effects are lower to occur nucleophilic substitution, that is, target compound (I) is prepared.Preferable nucleophilic
Reagent HNu is to contain aerobic, nitrogen, sulphur, or the species of phosphorus atoms, and particularly preferred HNu is water, NR3, HNRR ', H2NR, HSR,
RSSR ', HP (O) RR ', or the heterocycle containing aerobic, nitrogen, sulphur, or phosphorus atoms.Above-mentioned chemical preparation new technology in our early stages
Application for a patent for invention【CN103172770】In had a detailed disclosure, it is of the invention new unexpected beneficial to being the discovery that, lead to
Cross from appropriate HNu reagents, the new acyl with superior water dispersibility or water-soluble energy has been prepared using above-mentioned technology
Base phosphine oxide compound.
Preparing another method of partial Formula (I) compound is, as shown in following equation, allows double acylphosphanes to aoxidize
For example commercially available BAPO-819 of compound (bisacylphosphine oxide, abbreviation BAPO) is in acid and electrophilic reagent E+Effect
Under, single phosphono group occurs to E+Addition reaction, so as to easily prepare one or both of following products simultaneously coproduction.This
In sour definition with upper identical, electrophilic reagent E+It is C1-C48Side chain or straight chain aliphatic or aromatic series aldehydes or ketones, or α, β-
Unsaturated aldehyde, ketone, ester, nitrile, or acid amides, or nitro compds, or alkenyl sulfone or sulfoxide；Preferable electrophilic reagent E+It is formaldehyde, propylene
Acid, methacrylaldehyde, or unitary or polynary acrylate monomer or acrylate polymer resin；Particularly preferred acid is trichlorine
Change aluminium or hydrochloric acid, particularly preferred electrophilic reagent E+It is formaldehyde, under the effect of " alchlor or hydrochloric acid-formaldehyde " reagent, this
When following products in E=CH2OH or CH2Cl。
Preparing another method of partial Formula (I) compound is, as shown in following equation, according to Coenradus
The method synthetic mesophase of the record of page 124 in the rich upper papers of Johannes Hendrikus Hendriksen ETH-Z ü rich
Body sodiun bis (2,4,6-trimethylbenzoyl) phosphanide (i.e. structure F) or phosphinediylbis
(mesitylmethanone) (i.e. structure G), or the resonant isomers of their enol forms.Then, with foregoing intermediate
A or B are similar, and F or G react with formaldehyde or serial C reagents (foregoing C1-C6) and pass through oxidant【O】Effect
(definition of oxidant is as hereinbefore), obtain target compound.
The exemplary compounds for meeting logical formula (I) structure are listed below：
The present invention further disclose it is a kind of containing above-mentioned logical formula (I) compound, can via light (ultraviolet or visible ray or
LED light or equal lamp-house) radiation curing mixture, particularly aqueous photo-curing formula mixture system, and this kind of formula
Material system is flexible in inkjet printing, paper printing, adhesive, woodwork coating, plastic coating, painting dressing automobiles, packaging material
The application in the fields such as electronics, photovoltaic material.
This kind of light radiation curing formula system is characterized in：
(1) compound described by least one logical formula (I) is contained as one of light trigger or light trigger component；
(2) ethylene linkage (C=C) unsaturated compound is contained containing at least one.
Calculated with the every 100 parts of weight of the component of unsaturation containing ethylene linkage total amount in system, the conjunction of the logical formula (I) compound contained
Suitable amount is 0.01-30 parts by weight, preferably 0.5-10 parts by weight.What the appropriate radiation curing system that this item application discloses included
The polymerizable component of unsaturation containing ethylene linkage is the compound or mixing that can be crosslinked by the Raolical polymerizable of the double bond
Thing, this component of unsaturation containing ethylene linkage can be monomer, oligomer or prepolymer, or their mixture or copolymer, or
It is the water-borne dispersions of said components.
Appropriate radiation curing system described above, which can contain, with good grounds to be actually needed added inorganic or organic and fills out
Fill agent and/or colouring agent (such as pigment or dyestuff etc.), and other additives (such as ultra-violet absorber, light stabilizer,
Fire retardant, levelling agent, or defoamer etc.) and any condition such as solvent.
The monomer of suitable radical polymerization is such as polymerisable monomer containing ethylene linkage, includes but is not limited to (methyl) propylene
Acid esters, methacrylaldehyde, alkene, conjugated diolefin, styrene, maleic anhydride, fumaric acid anhydride, vinyl acetate, ethenyl pyrrolidone
Ketone, vinyl imidazole, (methyl) acrylic acid, (methyl) acrylic acid derivative such as (methyl) acrylamide, vinyl halides
Thing, vinylidene halide etc..
Suitable prepolymer containing ethylene linkage and oligomer include but is not limited to (methyl) propylene of (methyl) acryloyl functional group
Acid copolymer, polyurethane formic acid esters (methyl) acrylate, polyester (methyl) acrylate, unsaturated polyester (UP), polyethers (methyl)
Acrylate, siloxanes (methyl) acrylate, epoxy resin (methyl) acrylate etc., and the water solubility of above-mentioned substance
Or the analog of water dispersible.
It is above-mentioned either to contain alkene monomer or oligomer, prepolymer, or copolymer, to this specialty working technical staff
Speech, is all well known, is not particularly limited.
For idea of the invention, we will combine following series embodiments and further illustrate.
Embodiment zero：2- (phenyl (2,4,6-trimethylbenzoyl) phosphoryl) acetic acid
Under nitrogen protection, at room temperature to toluene-glycol dinitrate containing Phenylphosphine (12.5 grams, 114 mMs)
After adding sodium tert-butoxide (13.8 grams) in ether (300 milliliters, 1/1 volume ratio) solution, slowly it was added dropwise in 2 hours and adds 2,
4,6- mesitylene acyl chlorides (24.8 grams), continue to be slowly added into 16.2 grams of monoxones after stirring half an hour, stirred after adding in room temperature
Mix overnight.With the aqueous hydrogen peroxide solution (17 grams) that 30% is slowly added dropwise after 0.5N hydrochloric acid regulation reaction system pH~2-3, add
React at 40 degree or so after complete 1 hour, then toward 100 milliliters of water of addition in reaction system, stir, layering, 80 millis of organic phase
The sodium bicarbonate aqueous solution for rising full conjunction mixes 80 milliliters of washings twice, and weak brine is washed once, and sodium sulphate is dried, 60 degree of lower decompressions
Solvent is evaporated off, residue adds 100 milliliters of normal heptanes and beats oar, filters to obtain 24.7 grams of flaxen solids, takes this solid of part to exist
On silica gel column chromatography analysis pure sample product are afforded with ethyl acetate-hexane gradient.HRMS(M+H)for C18H20O4P：
331.1099 (calculated), 331.1017 (experimental)； (M+Na)for C18H19NaO4P：353.0919
(calculated), 353.0922 (experimental).
Embodiment one：((hydroxymethyl)(phenyl)phosphoryl)(mesityl)methanone
Under nitrogen protection, add at room temperature into toluene (300 milliliters) solution containing Phenylphosphine (114 mMs)
After entering sodium tert-butoxide (13.8 grams), slowly it was added dropwise in 2 hours and adds 2,4,6- mesitylene acyl chlorides (24.8 grams), finished
The concentrated sulfuric acid (5.7 grams) was added dropwise under cold bath cooling in reaction in 30 minutes, after being stirred 30 minutes after adding, was added dropwise more than 37%
The polyformaldehyde aqueous solution (11.0 grams), is stirred at room temperature 3 hours after adding.30% aqueous hydrogen peroxide solution (17 is slowly added dropwise
Gram), react at 40 degree or so after adding 1 hour, then toward 50 milliliters of water of addition in reaction system, stir, layering, organic phase
40 milliliters of washings are mixed with 20 milliliters of full Sodium bicarbonate aqueous solution closed twice, and weak brine is washed once, and sodium sulphate is dried, 60 degree
Under remove solvent under reduced pressure, add 70 milliliters of normal heptanes and beat oar, filter to obtain 26.5 grams of flaxen solid powder products.1H-NMR
(CDCl3)：δ=7.87-7.84 (m, 2H), 7.60-7.57 (m, 1H), 7.52-7.48 (m, 2H), 6.75 (s, 2H), 5.55
(br, 1H), 4.55 (dd, 1H), 4.10 (dd, 1H), 2.24 (s, 3H), 2.05 (s, 6H)；13C-NMR(CDCl3)：δ=＞ 220
(C=Osignal), 140.7,135.7,135.4,135.2,132.7,131.4,128.9,128.8,126.9,126.3,608
(d), 21.1,19.4ppm；31P-NMR(CDCl3)：δ=23.5ppm.HRMS(M+H)for C17H20O3P：303.1150
(calculated), 303.1140 (experimental)；(M+Na)for C17H19NaO3P：325.0970
(calculated), 325.0948 (experimental).
The UV-Vis abosrption spectrograms of the compound as shown in Figure 1 (solvent be acetonitrile, mass percentage concentration), can from figure
To find out that the compound has notable absorption in UV-LED launch wavelengths region：
Embodiment two：(phenyl (2,4,6-trimethylbenzoyl) phosphoryl) methyl 2,4,6-
trimethyl- benzoate
In the synthesis of above-described embodiment one, while the isolated compound of embodiment two.1H-NMR (CDCl3)：δ
=7.96-7.92 (m, 2H), 7.62-7.60 (m, 1H), 7.55-7.27 (m, 2H), 6.81 (s, 2H), 6.78 (s, 2H), 5.15
(d, 2H), 2.27 (s, 3H), 2.24 (s, 3H), 2.20 (s, 6H), 2.02 (s, 6H)；13C- NMR(CDCl3)：(the C of δ=＞ 220
=O signal), 139.7,135.7,135.3,133.1,131.6,131.5,129.1,128.9,128.3ppm；31P-NMR
(CDCl3)：δ=18.1ppm.HRMS(M+H)for C27H30O4P：(449.1882 calculated), 449.1890
(experimental)；(M+Na)for C27H29NaO4P：(471.1701 calculated), 471.1714
(experimental)。
Embodiment three：((chloromethyl)(phenyl)phosphoryl)(mesityl)methanone
Under nitrogen protection, by 418 milligrams of light triggers of Irgacure 819,142 milligrams of aluminum trichloride (anhydrous)s, 72 millis
Gram paraformaldehyde is placed in 10 milliliters of chloroforms, and system is heated to 75 degrees Celsius and reacted 45 minutes, pours the mixture into frozen water,
Liquid separation, dry, filtering, residue uses ethyl acetate gradient on silica gel column chromatography after concentration, obtains 112 milligrams of implementations
The compound of example one and 92 milligrams of the present embodiment target product.1H-NMR(CDCl3)：δ=7.92-7.88 (m, 2H), 7.62-
7.60 (m, 1H), 7.54-7.51 (m, 2H), 6.82 (s, 2H), 4.98 (dd, 1H), 4.81 (dd, 1H), 2.26 (s, 3H),
2.10 (s, 6H)；HRMS(M+H) for C17H19ClO2P：(321.0811 calculated), 321.0809
(experiental)；(M+Na)for C17H18NaClO2P：(343.0631 calculated), 343.0644
(experimental)。
Example IV：((2-hydroxyethyl)(phenyl)phosphoryl)(mesityl)methanone
Under nitrogen protection, add at room temperature into toluene (20 milliliters) solution containing Phenylphosphine (2.36 mMs)
After entering sodium tert-butoxide (464 milligrams), slowly it was added dropwise in 40 minutes and adds 2,4,6- mesitylene acyl chlorides (431 milligrams), added
Complete reaction system is transferred to a pressure-resistant tube sealing (Sealed tube) after continuing stirring 2 hours, and oxirane is passed through into tube sealing
After continue stirring 2 hours, reaction solution is with 0.86 milliliter of 28% concentration hydrogen peroxide under the conditions of being adjusted with sulfuric acid to pH=2-3
Processing 1 hour.Organic phase is dried with 1% sodium bicarbonate aqueous solution and saturated common salt water washing, liquid separation, sodium sulphate successively, mistake
Filter, residual solution uses hexane-ethylacetate gradient elution on silica gel column chromatography after obtained clear liquid concentration removes toluene, obtains
The target compound of 402 milligrams of faint yellow sticky wax.HRMS(M+H)for Ci8H22O3P：(317.1307 calculated),
317.1326(experimental)；(M+Na)for C18H21NaO3P：(339.1126 calculated), 339.1141
(experimental)。
Embodiment five：3- (phenyl (2,4,6-trimethylbenzoyl) phosphoryl) propanoic acid
Under nitrogen protection, add at room temperature into toluene (20 milliliters) solution containing Phenylphosphine (2.19 mMs)
After entering sodium tert-butoxide (214 milligrams), slowly it was added dropwise in 40 minutes and adds 2,4,6- mesitylene acyl chlorides (400 milligrams), added
After complete reaction system continues stirring 2 hours, acrylic acid (205 milligrams) is added, reaction system is transferred to a pressure-resistant tube sealing
(Sealed tube) continues stirring 1 hour in the heating of 60-70 degree.Reaction solution with 0.52 milliliter of 28% concentration hydrogen peroxide with
Sulfuric acid is handled 1 hour under the conditions of adjusting to pH=2-3.Organic phase is washed with 1% aqueous ammonium chloride solution and saturated common salt successively
Wash, liquid separation, sodium sulphate dry, filtering, obtain clear liquid concentration remove toluene after residual solution on silica gel column chromatography with hexane-
Ethyl acetate gradient, obtain 286 milligrams of faint yellow solid powder target compounds.HRMS(M+H)for C19H22O4P：
345.1256 (calculated), 345.1277 (experimental)；(M+Na)for C19H21NaO4P：367.1075
(calculated), 367.1082 (experimental).
Embodiment six：
Double isocyanates IPDI of 160 milligrams of the compound of embodiment one and 222 milligrams are placed in 8 under nitrogen protection
In the dry toluene solvent of milliliter, heated instead at 80 degree after 6 milligrams of dibutyltin dilaurate catalyst is added into system
Answer 1 hour, residual solution uses hexane-ethylacetate gradient elution on silica gel column chromatography after reaction system concentration removes toluene, obtains
To 334 milligrams of faint yellow sticky wax target compounds. HRMS(M+H)for C46H57N2O8P2：827.3590
(calculated), 827.358 (experimental)； (M+Na)for C46H56N2O8NaP2：849.3410
(calculated), 849.3423 (experimental).
Embodiment seven：Tris ((phenyl (2,4,6-trimethylbenzoyl) phosphoryl) methyl)
Benzene- 1,3,5-tricarboxylate
Under nitrogen protection, by 302 milligrams of the compound of embodiment one, 88 milligrams of mesitylene formyl chloride, 138 milliliters
Triethylamine, and 12 milligrams of 4- dimethylamino pyridines (DMAP) are placed in 25 milliliters of dry dichloroethane solvents, are stirred at room temperature
Reaction is overnight.Mixture isometric semi-saturation brine It 3 times, organic phase sodium sulphate is dried, and filtering, concentration removes molten
Residual solution uses hexane-ethylacetate gradient elution on silica gel column chromatography after agent, obtains 267 milligrams of faint yellow solid targeteds
Compound.HRMS(M+H)for C60H58O12P3：1063.3141 (calculated), 1063.3166 (experimental)；(M+
Na)for C60H57O12NaP3：1085.2961 (calculated), 1085.2961 (experimental).
Embodiment eight：2- ((acryloyloxy) methyl) -2-ethylpropane-1,3-diyl bis (3-
(phenyl (2,4,6-trimethylbenzoyl) phosphoryl) propanoate)
Under nitrogen protection, add at room temperature into toluene (20 milliliters) solution containing Phenylphosphine (2.36 mMs)
After entering sodium tert-butoxide (464 milligrams), slowly it was added dropwise in 40 minutes and adds 2,4,6- mesitylene acyl chlorides (431 milligrams), added
After complete reaction system continues stirring 2 hours, 219 milligrams of 351 monomers of Sartomer SR are slowly added into, this backward reaction system drop
0.90 milliliter of 28% concentration hydrogen peroxide (arriving pH=2-3 with sulfuric acid regulation in advance) is added, continues stirring reaction after 1 hour
Organic phase is dried with 1% sodium bicarbonate aqueous solution and saturated common salt water washing, liquid separation, sodium sulphate successively, and filtering, what is obtained is clear
Liquid concentration remove toluene after residual solution hexane-ethylacetate gradient elution is used on silica gel column chromatography, obtain 417 milligrams it is yellowish
Color thick liquid target compound.HRMS(M+H)for C63H72O12P3：(1113.4237 calculated), 1113.4256
(experimental)；(M+Na)for C63H71NaO12P3：(1135.4056 calculated), 1135.4063
(experimental)。
Embodiment nine：2,2-bis (((3- (phenyl (2,4,6- trimethylbenzoyl) phosphoryl)
Propanoyl) oxy) methyl) propane-1,3-diyl bis (3- (phenyl (2,4,6-trimethylbenzoyl)
phosphoryl)propanoate)
To be quite analogous to the operation of embodiment eight, under nitrogen protection, to Phenylphosphine is contained, (2.36 in the least at room temperature
Mole) toluene (20 milliliters) solution in add sodium tert-butoxide (464 milligrams) after, be slowly added dropwise in 40 minutes and add 2,
4,6- mesitylene acyl chlorides (431 milligrams), finish reaction system and continue after stirring 2 hours, be slowly added into pentaerythrite tetrapropylene
207 milligrams of acid ester monomer, the 28% concentration hydrogen peroxide that 0.95 milliliter of addition is added dropwise in this backward reaction system (are adjusted with sulfuric acid in advance
Save pH=2-3), continue stirring reaction after 1 hour organic phase successively with 1% sodium bicarbonate aqueous solution and saturated common salt washing
Wash, liquid separation, sodium sulphate dry, filtering, obtain clear liquid concentration remove toluene after residual solution on silica gel column chromatography with hexane-
Ethyl acetate gradient, obtain 466 milligrams of light yellow viscous liquid target compounds.HRMS(M+H) for C81H89O16P4：
1441.5101 (calculated), 1441.5129 (experimental)；(M+Na)for C81H88NaO16P4：1463.4921
(calculated), 1463.4954 (experimental).
Embodiment ten：(((dimethylamino)methyl)(phenyl)phosphoryl)(mesityl)
methanone
Under nitrogen protection, add at room temperature into toluene (30 milliliters) solution containing Phenylphosphine (2.83 mMs)
After entering sodium tert-butoxide (557 milligrams), slowly it was added dropwise in 40 minutes and adds 2,4,6- mesitylene acyl chlorides (520 milligrams), added
Complete reaction system is transferred to a pressure-resistant tube sealing (Sealed tube) after continuing stirring 2 hours, is added into tube sealing
Eschenmoser Salt CH2=NMe2Continue stirring 1 hour after I (524 milligrams), reaction solution is dense with the 28% of 0.34 milliliter
Degree hydrogen peroxide handles half an hour under the conditions of with sulfuric acid regulation to pH=2-3.Organic phase is successively with 1% sodium bicarbonate aqueous solution
With saturated common salt water washing, liquid separation, sodium sulphate is dried, filtering, and residual solution is in silicagel column after obtained clear liquid concentration removes toluene
Hexane-ethylacetate gradient elution is used in chromatogram, obtains the target compound of 484 milligrams of faint yellow sticky wax.HRMS (M+
H)for C19H25NO2P：330.1623 (calculated), 330.1629 (experimental)；(M+Na) for
C19H24NaNO2P：352.1442 (calculated), 352.1459 (experimental).
Embodiment 11：1,3,5-tris (2-hydroxy-3- (phenyl (2,4,6- trimethylbenzoyl)
Phosphoryl) propyl) -1,3,5-triazinane-2,4,6-trione
Under nitrogen protection, add at room temperature into toluene (20 milliliters) solution containing Phenylphosphine (2.36 mMs)
After entering sodium tert-butoxide (464 milligrams), slowly it was added dropwise in 40 minutes and adds 2,4,6- mesitylene acyl chlorides (431 milligrams), added
Complete reaction system is transferred to a pressure-resistant tube sealing (Sealed tube) after continuing stirring 2 hours, and 233 milligram three is added into tube sealing
First epoxy (NRC (O))3(R is expoxy propane here) continues to be stirred overnight, 1.12 milliliters of 28% concentration dioxygen of reaction solution
Water is handled 5 hours under the conditions of with sulfuric acid regulation to pH=2-3.Organic phase is eaten with 1% sodium bicarbonate aqueous solution and saturation successively
Salt water washing, liquid separation, sodium sulphate are dried, filtering, and residual solution is on silica gel column chromatography after obtained clear liquid concentration removes toluene
With hexane-ethylacetate-methanol elution gradient, the target compound of 276 milligrams of faint yellow sticky wax is obtained. HRMS(M+H)
for C60H67N3O2P3：1114.3938 (calculated), 1114.3948 (experimental)； (M+Na)for
C60H66N3NaO12P3：1136.3757 (calculated), 1136.3762 (experimental).
Embodiment 12：(3,5-bis (chloromethyl) -2,4,6- trimethylphenyl)
(diphenylphosphoryl)methanone
Protected in nitrogen and at room temperature, 1.5 grams of paraformaldehyde solids and 5.65 grams of alchlor powder are dispersed in 120
In the dichloroethanes that milliliter is dried, 3.48 grams of light trigger TPO are slowly added dropwise when system is warming up to 45 degree thereto at 80 milliliters
Solution in dichloroethanes, maintenance reaction are less than reflux temperature, drip and reaction solution is poured on frozen water after finishing half an hour, liquid separation, do
It is dry, concentration, solid re-crystallizing in ethyl acetate, 3.43 grams of flaxen target products are obtained, it is anti-to be used directly for lower step
Should.
Embodiment 13：(3,5-bis ((bis (2-hydroxyethyl) amino) methyl) -2,4,6-
trimethylphenyl)(diphenylphosphoryl)methanone
In nitrogen protection and at room temperature, by 2.28 grams of compounds of embodiment 12,1.24 grams of diethanol amine HN
(CH2CH2OH)2, and 1.32 grams of triethylamines are dispersed in the in the mixed solvent of 120 milliliters (volume ratio 1 to 6) of DMF and acetonitrile, body
Tie up under 80 degree and react 4 hours, be concentrated under reduced pressure after removing most of acetonitrile, residue pours into 100 milliliters of water under fast stirring
In, suction filtration obtains 2.66 grams of flaxen solid powder target products.1H-NMR(CDCl3)：δ=8.00-7.96 (m, 4H),
7.59-7.57 (m, 2H), 7.54-7.50 (m, 4H), 3.73 (s, 4H), 3.50 (s, 8H), 2.60 (s, 8H), 2.52 (s, 4H),
2.04 (s, 3H), 2.00 (s, 6H)；13C-NMR(CDCl3)：δ=＞ 220 (C=Osignal), 132.6,131.7,131.6,
128.9,128.8,59.7,55.7,53.4,17.8,16.7ppm；HRMS(M+H)for C32H44N2O6P：583.2937
(calculated), 583.2951 (experimental)；(M+Na)for C32H43NaN2O6P：605.2756
(calculated), 605.2774 (experimental).
The UV-Vis abosrption spectrograms of the compound as shown in Figure 2 (solvent be acetonitrile, mass percentage concentration), can from figure
To find out that the compound has notable absorption in UV-LED launch wavelengths region：
Embodiment 14：(3,5-bis (hydroxymethyl) -2,4,6- trimethylphenyl)
(diphenylphosphoryl)methanone
Nitrogen protect and at room temperature, by 1.7 grams of compounds of embodiment 12 be placed in 10 milliliters of DMF and 10 milliliter of acetic acid-
In sodium acetate buffer (pH~8), reaction is poured on frozen water after being stirred at room temperature overnight, liquid separation, is dried, concentration, solid
With ethylacetate-hexane, gradient elution obtains 0.68 gram of faint yellow solid target product on silica gel column chromatography.HRMS(M+H)
for C24H26O4P：409.1569 (calculated), 409.1571 (experimental)；(M+Na)for
C24H25NaO4P：431.1388 (calculated), 431.1395 (experimental).
Embodiment 15：((3- (hydroxymethyl) -2,4,6- trimethylbenzoyl) (phenyl)
phosphoryl)(mesityl)methanone
Under nitrogen protection, 2 grams of paraformaldehydes and 2.67 grams of alchlors are dissolved in the chloroform of minimum and heated
Reacted 45 minutes to 75 degree, add saturated solution of 8.4 grams of light triggers of Irgacure 819 in chloroform thereafter, finish after
Continuous reaction 35 minutes, then adds 2.67 grams of alchlors, continues to react 10 minutes (attention hexane-ethylacetate volume ratios
2 to 1 mixed solvent does solvent TLC tracking reaction process), reaction solution is poured into frozen water, liquid separation, extracted, dried, mistake
Filter, residue uses hexane-dichloromethane eluent gradient elution on silica gel column chromatography after concentration, obtains 2.9 grams of yellow powders
Solid target compound (while obtaining 1.7 grams of compounds of embodiment one).1H-NMR(CDCl3)：δ=7.97-7.91 (m, 2H),
7.59-7.62 (m, 1H), 7.56-7.26 (m, 2H), 6.81 (s, 2H), 6.78 (s, 2H), 5.15 (s, 2H), 2.30 (s, 1H),
2.26 (s, 3H), 2.24 (s, 3H), 2.20 (s, 6H), 2.02 (s, 6H)；13C-NMR(CDCl3)：δ=218.8,217.9,
169.1,169.0,141.0,139.7,135.7,135.4,135.2,134.9,133.1,131.7,131.6,131.5,
129.3,129.2,128.9,128.3,126.8,125.7,73.4,61.3,60.2,21.1,21.0,19.8,19.4ppm；31P-NMR(CDCl3)：δ=18.2ppm.HRMS(M+H)for C27H30O4P：(449.1882 calculated), 449.1888
(experimental)；(M+Na)for C27H29NaO4P：(471.1701 calculated), 471.1644
(experimental)。
Embodiment 16：2- (2-hydroxyethoxy) ethyl 3- (bis (2,4,6- trimethylbenzoyl)
phosphoryl)propanoate
In nitrogen protection and at room temperature, according to Coenradus Johannes Hendrikus Hendriksen ETH-
The method synthetic intermediate sodium bis (2,4,6- of the record of page 124 in Z ü rich thesis for the doctorate
Trimethylbenzoyl) phosphanide, faint yellow solid powder.3.48 grams of compounds are taken to be placed in 100 milliliter 50: 50
THF- water mixed solvents in, sequentially add 0.062 gram of glacial acetic acid and 1.65 grams of acrylate monomer CH2=CHC (O)
OCH2CH2OCH2CH2Reaction system is reacted 30 minutes under microwave irradiation after OH, and without isolation, the 28% of 1.6 milliliters of addition is dense
Degree hydrogen peroxide continues stirring reaction and stayed overnight, and reaction solution is poured into ethyl acetate-saturated ammonium chloride mixed solution, organic phase separation,
Saturated ammonium chloride solution and saline solution washed once respectively, dry, and filter, and concentration, residue uses acetic acid on silica gel column chromatography
Ethyl ester-hexane agent gradient elution, obtains 2.03 grams of yellow solid target products.HRMS(M+H)for C27H36O7P：
503.2199 (calculated), 503.2207 (experimental)；(M+Na)for C27H35NaO7P： 525.2018
(calculated), 525.2034 (experimental).
Embodiment 17：((hydroxymethyl)phosphoryl)bis(mesitylmethanone)
In nitrogen protection and at room temperature, according to Coenradus Johannes Hendrikus Hendriksen ETH-
The method synthetic intermediate sodium bis (2,4,6- of the record of page 124 in Z ü rich thesis for the doctorate
Trimethylbenzoyl) phosphanide, faint yellow solid powder.3.48 grams of compounds are taken to be placed in 80 milliliter 50: 50
THF- water mixed solvents in, reaction system is in microwave after sequentially adding the formalin of 0.62 gram of glacial acetic acid and 5 times of equivalents
The lower reaction of irradiation 30 minutes, without isolation, add 1.4 milliliters of 28% concentration hydrogen peroxide continuation stirring reaction and stay overnight, reaction solution
Pour into 200 milliliters of ethyl acetate-saturated ammonium chloride mixed solution, organic phase separation, saturated ammonium chloride solution and salt moisture
It not washed once, dry, filter, concentration, residue uses ethylacetate-hexane eluent gradient elution on silica gel column chromatography,
Obtain 1.88 grams of wax-like target products of clear yellow viscous.HRMS(M+H)for C21H26O4P：(373.1569 calculated),
373.1574(experimental)；(M+Na)for C21H25NaO4P：(395.1388 calculated), 395.1392
(experimental)。
Embodiment 18：((2-hydroxyethyl)phosphoryl)bis(mesitylmethanone)
In nitrogen protection and at room temperature, according to Coenradus Johannes Hendrikus Hendriksen ETH-
The method synthetic intermediate sodiun bis (2,4,6- of the record of page 124 in Z ü rich thesis for the doctorate
Trimethylbenzoyl) phosphanide, faint yellow solid powder.3.48 grams of compounds are taken to be placed in 60 milliliters of THF,
Stirring reaction half an hour after 0.62 gram of glacial acetic acid of addition, the solid of generation is centrifuged, clear liquid is transferred in a pressure pipe, is led to
Enter the oxirane rear enclosed pressure pipe of 3 atmospheric pressure, reaction 4 hours is stirred at room temperature, add 1.4 milliliters of 28% concentration
Hydrogen peroxide continues stirring reaction and stayed overnight, and reaction solution is poured into 200 milliliters of ethyl acetate-saturated ammonium chloride mixed solution, organic phase
Separation, saturated ammonium chloride solution and saline solution washed once respectively, dry, and filter, and concentration, residue is on silica gel column chromatography
With ethyl acetate-hexane agent gradient elution, 1.42 grams of wax-like target products of clear yellow viscous are obtained.HRMS(M+H)for
C22H28O4P：387.1725 (calculated), 387.1740 (experimental)；(M+Na)for C22H27NaO4P：
409.1545 (calculated), 409.1566 (experimental).
Embodiment 19：Bis ((bis (2,4,6-trimethylbenzoyl) phosphoryl) methyl) hexane-
1,6- diyldicarbamate
The hexamethylene diisocyanate HDI of 227 milligrams of the compound of embodiment 17 and 51 milligrams is placed under nitrogen protection
In 20 milliliters of dry toluene solvent, added into system after 8 milligrams of dibutyltin dilaurate catalyst in 80 degree of heating
Reaction 1 hour, residual solution uses hexane-ethylacetate gradient elution on silica gel column chromatography after reaction system concentration removes toluene,
Obtain 203 milligrams of faint yellow sticky wax target compounds.HRMS(M+H)for C50H63N2O10P2：913.3958
(calculated), 913.3977 (experimental)； (M+Na)for C50H62N2O10NaP2：935.3777
(calculated), 935.3789 (experimental).
Embodiment 20：Bis ((bis (2,4,6-trimethylbenzoyl) phosphoryl) methyl)
terephthalate
Under nitrogen protection, by 740 milligrams of the compound of embodiment 17,202 milligrams of paraphthaloyl chloride, 245 millis
The triethylamine risen, and 24 milligrams of 4- dimethylamino pyridines (DMAP) are placed in 60 milliliters of dry dichloroethane solvents, and room temperature is stirred
Mix reaction overnight.Mixture isometric semi-saturation brine It 3 times, organic phase sodium sulphate is dried, and filtering, concentration removes
Residual solution uses hexane-ethylacetate gradient elution on silica gel column chromatography after solvent, obtains 604 milligrams of yellow target compounds.
HRMS(M+H)for C50H53O10P2：875.3114 (calculated), 875.3140 (experimental)；(M+Na)for
C50H52O10NaP2：897.2933 (calculated), 897.2928 (experimental).
Embodiment 21：UV photocurings are tested
Made (by weight percentage) by following formula containing ethylene linkage (acrylate) sample system：
Bisphenol A epoxy acrylate (Ebecryl 605)：30%；Amino acrylates (Ebecryl 7100)：8%；Third
Epoxide glycerol tri-acrylate：30%；Hexanediyl ester：24%；Silicone acrylates：0.5%；Ethoxy
Base tetramethylol methane tetraacrylate：3.5%；Light trigger：2% the present embodiment light trigger, and the promising chemistry in 2% Shenzhen
Company's APi-180 light triggers【Structure is 2- hydroxy-1- (3- (hydroxymethyl) phenyl) -2-
methylpropan-1-one】。
Comparative example system one：Be formulated it is same as described above, except light trigger used is 2% TPO and 2%
Irgacure 184。
Comparative example system two：Be formulated it is same as described above, except light trigger used is 4% Irgacure 184.
By above-mentioned preparation embodiment and comparative example mixture coated on the coating that about 30-35 microns are formed on cardboard, 2
80 watts of Central Asia mercury lamps of branch are light source, and Variable-speed conveyor belt is tested.Press to scrape at quarter repeatedly using nail and do not produce trace to be photopolymerization curing
The criterion of completion.
Remaining smell test separately evaluates smell rank with 5 people, and the standard of assessment is as follows with numeral sign：0
Level：There is no smell；1 grade：Very slight smell；2 grades：Slight smell；3 grades：Obvious smell；4 grades：Strong smell；
5 grades：Smell strongly.
As a result show containing embodiment compound zero to two, four to 11, and 13 to 20 formula system with
Speed Efficient solidification higher than 60 ms/min, and oder levels are 0 or 0-1 levels；In contrast, comparative example formula system one
Laser curing velocity be 45-50 ms/min, and oder levels are 3-4 or 4；The Light-Curing Efficiency of comparative example formula system two exists
Bottom is presented under speed higher than 30 ms/min and does (through cure) insufficient problem, and oder levels are 4.
It is above-mentioned test result indicates that these light triggers of the invention prepared have good UV Light-Curing Efficiencies performance and
Low odor characteristics.
Embodiment 22：LED light solidity test
Made (by weight percentage) by following formula containing ethylene linkage (acrylate) sample system：
Bisphenol A epoxy acrylate (Ebecryl 605)：25%；Amino acrylates (Ebecryl 7100)：8%；Third
Epoxide glycerol tri-acrylate：25%；Hexanediyl ester：22%；Silicone acrylates：0.5%；Ethoxy
Base tetramethylol methane tetraacrylate：3.5%；Light trigger：2% the present embodiment light trigger；Aided initiating：14% CYTEC
Company LED-01【The light-cured resin of sulfydryl modification】.
By above-mentioned preparation embodiment mixture coated on the coating that about 30-35 microns are formed on cardboard, 1 Shenzhen is simultaneously
The unit power of day scientific ＆ technical corporation production is 16W/cm2Launch wavelength be 395 nanometers LED light sources it is (3 centimetres wide and 80 lis
The long LED area light source of rice), Variable-speed conveyor belt experiment.Press to scrape at quarter repeatedly using nail and do not produce trace as photopolymerization curing completion
Criterion.
Remaining smell test separately evaluates smell rank with 5 people, and the standard of assessment is as follows with numeral sign：0
Level：There is no smell；1 grade：Very slight smell；2 grades：Slight smell；3 grades：Obvious smell；4 grades：Strong smell；
5 grades：Smell strongly.
As a result show containing embodiment compound one to 11, and 13 to 20 formula system with higher than 45
M/min Speed Efficient solidification, and oder levels are 0 or 0-1 levels.
It is above-mentioned test result indicates that these light triggers of the invention prepared while there is good LED light curing efficiency
Performance and (net) or low odor characteristics.
Embodiment 23：Photocuring is tested
Made (by weight percentage) by following formula containing ethylene linkage (acrylate) sample system：
Prepare photocurable mixture system by following percentage by weights (amount to 100 parts), this mixture is dispersed with stirring or
(about 20-30 microns) is sprayed on aluminium sheet after dissolving, is triggered using 400 watts of high-pressure sodium lamps as radiation of light source and polymerize.Embodiment
Use the present embodiment acylphosphine oxide light trigger and the promising chemical APi-1173 in Shenzhen.Curing efficiency is with finger pressure
Method (i.e. it is not damaged to be wiped repeatedly coating for thumb nail press mold) judges that photocuring is completed.
White woodwork coating：77.2 parts of PEA, 5.9 parts of HDDA, 2.9 parts of TMPTA, 2.5 parts of light triggers of embodiment one,
1.5 parts of light trigger APi-1173【Structure is 2-hydroxy-2-methyl-1- phenylpropan-1-one】, 10 parts
TiO2。
Floor matt finish paint：14.78 parts of high glaze UP (VP LS2100), 14.78 parts of Tromox R KB6,7.39 parts
Banc-Fixe 1666,2.95 parts of TPGDA of N, 1.18 parts of Lancowax HM, mixed grinding is to adding after less than 10 microns
14.78 parts of high glaze UP (VP LS2100), 5.91 parts of Gasil EBN, 35.47 parts of TPGDA, 0.06 part of BYK, 300,1 part of implementation
The light trigger of example six, 1.7 parts of light trigger APi-1173.
CD ink：20 parts of PEA (EB525), 20 parts of EB1710,15 parts of EO-TMPTA, 10 parts of TPGDA, 25 parts of TiO2,
2.5 parts of light triggers of embodiment 15,2.5 parts of APi-1173 light triggers, 3.0 parts of SiO2, 2.0 parts of defoamer Airex
900。
Car paint：19.4 parts of urethane acrylates (Sartomer CN999), 19.4 parts of ethoxylated bisphenol A diacrylates
Ester (Sartomer SR601), 31 parts of Sartomer SR492,24 parts of Sartomer SR355,0.32 part of light trigger of embodiment 17,
2.60 parts of APi-180 light triggers, 3.28 parts of hydroxybenzotriazole light absorbers (pay attention to：The irradiation of this sample is protected in nitrogen
Carried out under atmosphere).
The above-mentioned formula system containing embodiment light trigger completes abundant solidification, presents excellent photopolymerization
Trigger activity.
Embodiment 24：Water-based UV-LED photocurings experiment
Made (by weight percentage) by following formula containing ethylene linkage (acrylate) sample system：
Embodiment 23A：The promising chemical company APi-313 aqueous polyurethane acrylates dispersion liquid (solid content in 78 parts of Shenzhen
43%wt), 15 parts of 75%TiO2Pigment, 2 parts of auxiliary agent propylene glycol monomethyl ethers, 1 part of deionized water, 2 parts of embodiments one are light-initiated
Agent, 2 parts of alcohol ketone photoinitiator APi-180.
Embodiment 23B：The promising chemical company APi-313 aqueous polyurethane acrylates dispersion liquid (solid content in 78 parts of Shenzhen
43%wt), 15 parts of 75%TiO2Pigment, 2 parts of auxiliary agent propylene glycol monomethyl ethers, 1 part of deionized water, 2 parts of embodiments six are light-initiated
Agent, 2 parts of alcohol ketone photoinitiator APi-180.
Embodiment 23C：The promising chemical company APi-313 aqueous polyurethane acrylates dispersion liquid (solid content in 96 parts of Shenzhen
43%wt), 2 parts of light triggers of embodiment one, 2 parts of alcohol ketone photoinitiator APi-180.
Embodiment 23D：96 parts of aqueous polyurethane acrylate dispersion liquids of cyanogen spy (existing ALLNEX) company UCECOAT 7699
(solid content 35%wt), 2 parts of light triggers of embodiment one, 2 parts of alcohol ketone photoinitiator APi-180.
Embodiment 23E：96 parts of aqueous polyurethane acrylate dispersion liquids of cyanogen spy (existing ALLNEX) company UCECOAT 7177
(solid content 35%wt), 2 parts of light triggers of embodiment 11,2 parts of alcohol ketone photoinitiator APi-180.
Embodiment 23F：94 parts of aqueous polyurethane acrylate dispersion liquids of cyanogen spy (existing ALLNEX) company UCECOAT 7856
(solid content 35%wt), 2 parts of auxiliary agent propylene glycol monomethyl ethers, 2 parts of light triggers of embodiment 13,2 parts of alcohol ketone photoinitiators
APi-180。
Embodiment 23G：96 parts of aqueous polyurethane acrylate dispersion liquids of cyanogen spy (existing ALLNEX) company UCECOAT 7856
(solid content 35%wt), 2 parts of light triggers of embodiment 15,2 parts of alcohol ketone photoinitiator APi-180.
Embodiment 23H：96 parts of aqueous polyurethane acrylate dispersion liquids of cyanogen spy (existing ALLNEX) company UCECOAT 7699
(solid content 35%wt), 1 part of auxiliary agent propylene glycol monomethyl ether, 2 parts of light triggers of embodiment 17.
Embodiment 23I：The promising chemical company APi-313 aqueous polyurethane acrylates dispersion liquid (solid content in 96 parts of Shenzhen
43%wt), 1 part of auxiliary agent propylene glycol monomethyl ether, 3 parts of light triggers of embodiment one.
Embodiment 23J：The promising chemical company APi-313 aqueous polyurethane acrylates dispersion liquid (solid content in 96 parts of Shenzhen
43%wt), 1 part of auxiliary agent propylene glycol monomethyl ether, 3 parts of light triggers of embodiment 17.
Embodiment 23K：The promising chemical company APi-313 aqueous polyurethane acrylates dispersion liquid (solid content in 96 parts of Shenzhen
43%wt), 1 part of auxiliary agent propylene glycol monomethyl ether, 3 parts of light triggers of embodiment 13.
Embodiment 23L：The promising chemical company APi-313 aqueous polyurethane acrylates dispersion liquid (solid content in 81 parts of Shenzhen
43%wt), 12 part of 50% charcoal blacks dispersion, 2 parts of auxiliary agent propylene glycol monomethyl ethers, 1 part of deionized water, 4 parts of light of embodiment one
Initiator.
Embodiment 23M：The promising chemical company APi-313 aqueous polyurethane acrylates dispersion liquid (solid content in 83 parts of Shenzhen
43%wt), 10 parts of water-based red pigment dispersions, 2 parts of auxiliary agent propylene glycol monomethyl ethers, 1 part of deionized water, 4 parts of embodiments 17
Light trigger.
Comparative example 23N：The promising chemical company APi-313 aqueous polyurethane acrylates dispersion liquid (solid content in 78 parts of Shenzhen
43%wt), 15 parts of 75%TiO2Pigment, 2 parts of auxiliary agent propylene glycol monomethyl ethers, 1 part of deionized water, 2 parts of TPO photoinitiators, 2 parts
Light trigger Irgacure 184.
Comparative example 23O：94 parts of aqueous polyurethane acrylate dispersion liquids of cyanogen spy (existing ALLNEX) company UCECOAT 7699
(solid content 35%wt), 2 parts of auxiliary agent propylene glycol monomethyl ethers, 2 parts of (50: 50 Irgacure of light trigger Irgacure 500
184 and benzophenone BP liquid mixtures).
Comparative example 23P：The promising chemical company APi-313 aqueous polyurethane acrylates dispersion liquid (solid content in 96 parts of Shenzhen
43%wt), 4 parts of Irgacure 819-DW initiators.
Comparative example 23Q：The promising chemical company APi-313 aqueous polyurethane acrylates dispersion liquid (solid content in 95 parts of Shenzhen
43%wt), 1 part of initiator of Irgacure 184,4 parts of Irgacure 819-DW initiators.
Photocuring method of testing：Above-mentioned formula system is sprayed on base material (glass, paper, plastic cement, or wood skin),
Moisture is removed under the conditions of 60 degree of heating and exhausting, the 10-20 microns film body of formation is in UV (400W high-pressure sodium lamps, base material and light source
Spacing is 18 centimetres) or LED (16W/cm2Unit power, 395 nano wave lengths, base material and light source spacing are 1 centimetre) under light source
Hardening with radiation.Various base materials are placed on belt feeder, and belt feeder linear velocity is arranged on 30 ms/min.It is hard to solidify hardness pencil
Scale shows.
Storage stability is investigated：Formulation stability (Formulation＆Storage Stability), which is investigated, passes through dynamic
Light scattering (UPA-EX150 instruments) and formula 60 degrees Celsius storage 10 days after viscosity rise percentage weigh (with it is new at room temperature
The formula initial viscosity of fresh preparation is compared, NDJ-5S Digital Viscometers).The method for expressing of formulation stability is：Viscosity rises
(the equal average grain diameter of dispersion number, unit are nanometer to percentage；If forming 10 microns or more particles, labeled as " heavy
Form sediment ").The room temperature initial average particle size representative value of aqueous resin dispersion is in 60-100 nanometers in above-mentioned formula.
Remaining Odor Evaluations：Smell rank is separately evaluated with 5 people, the standard of assessment is as follows with numeral sign：
0 grade：There is no smell；1 grade：Very slight smell；2 grades：Slight smell；3 grades：Obvious smell；4 grades：Strong gas
Taste；5 grades：Smell strongly.
Test result such as table 1.
Table 1
Above-described embodiment and comparative example experiment clearly prove, the new acylphosphanes oxygen light trigger of present disclosure without
By being oiliness or aqueous photo-curing system, either varnish still colored paint containing pigment, also either UV or LED light source are consolidated
Change, present outstanding and broad spectrum activity photocuring practical application performance, and prominent environmental protection and the friendly net taste of health etc.
Characteristic, this is particularly important to the industry such as green printing, furniture woodcare paint；Meanwhile further, due to being technically short of tool
There is light trigger water-soluble or water dispersing characteristic enough, the compounding and storage stability of water-based UV-LED formula systems are industry
The long-term puzzlement problem in boundary, the compound of present disclosure discloses the solution of maturation first, so as to efficiently solve
This key technology challenge.
Embodiment 25：Water-based UV-LED ink-jets (Ink-Jet) ink
Water-based UV-LED ink-jet inks sample is made (by weight percentage) by following formula：
The promising chemical company APi-313 aqueous polyurethane acrylate dispersion liquids (solid content 43%wt) in 81 parts of Shenzhen, 8
50% charcoal blacks dispersion of part, 2 parts of propylene glycol monobutyl ethers, 2 portions of anti-settling agents, 0.5 part of BYK-021 defoamer, 3 parts of deionizations
Water, 3.5 parts of embodiments one, or embodiment five, or embodiment six, or embodiment 11, or embodiment 15, or embodiment ten
Six, or the light trigger of embodiment 17.
Above-mentioned formula system is sprayed on copperplate paper base material, moisture is removed under the conditions of 60 degree of heating and exhausting, is formed
15 microns of film bodies in UV (400W high-pressure sodium lamps, base material and light source spacing are 18 centimetres) or LED (16W/cm2Unit power,
395 nano wave lengths, base material and light source spacing are 1 centimetre) hardening with radiation under light source, solidification linear velocity is arranged on 50 ms/min,
Nail scrapes that embrocation decision table is dry and inner dry degree, the results showed that above-mentioned all aqueous black ink-jet inks using no matter UV or
Energy-saving LED light source obtains satisfied solidification effect.
It is emphasized that the above-mentioned embodiment enumerated only is some exemplary tests, limited examination is not considered as
Test or condition.The innovation scope that the present patent application is covered should be recorded by claims and is defined.
Claims (10)
1. acylphosphanes (oxygen) compound shown in logical formula (I)：
In logical formula (I)：
R0It is containing R3、R4、R5、R6、R7Substituted aryl, or R8、R9、R10Substituted tertiary alkyl, wherein R3、R4、R5、R6、R7
Independent of each other is hydrogen, halogen atom, R, OR, NRR ', CH2OH、CH2OR or CH2NRR ', wherein R or R ' choosing independent of each other
From the alkyl of the straight or branched containing 1-24 carbon atom ,-C6-C12Aryl, contain containing for the individual discrete element As of 1-6
The alkyl of the straight or branched of 1-24 the carbon atom ,-C containing 1-6 discrete element As6-C12One kind in aryl, its
In, one or more of the element A in oxygen, nitrogen, element sulphur：R and R ' individualisms or connection form the ring of a 3-6 member
Architecture；R8、R9、R10Independent of each other is R, R8、R9、R10Individualism or the two any connection form the carbon of a 3-6 member
Ring structure；
X is oxygen or sulphur, or X is not present：
Integer between n values 1-1000：R1It is R or-C (O)-R0：
As n=1, R2- Q is selected from hydrogen, the C containing 0-4 substituent6-C24Aryl, CH2OH、CH2OR、CH2OC(O)R、
CH2NRR’、CHR(OH)、CRR’(OH)、CCH3(CH2OH)OH、C(CH2OH)2OH、CH2CH2OH、CH2CHMeOH、CHMeCH2OH、
CH2CHPhOH、CH2C(O)R、CH2CO2H or its metal salt or amine salt, CH2CH2CO2H or its metal salt or amine salt, CH2CH2C(O)
OCH2CH2OH、CH2CHMeC(O)OCH2CH2OH、CH2CH2C(O)OCH2CH2OCH2CH2OH、CH2CH2C(O)OY、CH2OC(O)-
NHY、CH2CH2One kind in OC (O) NHY, Y are one containing 2-6 C=C double bonds-C2-C36Group,
When n values 2 or the integer more than 2 ,-R2- Q is a n member spacer group；-R2- it is selected from-CH2-、-CH2CH2-、-
CH2CH(OH)CH2-、-CH2CH(OR)CH2-、-CH2CH(OC(O)R)CH2-、-CH2CH2C(O)OCH2CH2-、-CH2CH(Me)C
(O)OCH2CH2-、-CH2CH2C(O)OCH2CH2OCH2CH2-、-CH2CH2C(O)OCH2CH2CH2-、-CH2CH2C(O)
OCH2CH2CH2CH2- in one kind；Q is a small molecule or polymeric groups with 2 or more-NHC (O) O- units；
Or Q is a small molecule or polymeric groups with 2 or more-C (O) O- units；
Or when n values 2 or the integer more than 2 and work as R1When being R ,-R2- Q is one and contains n members-CH2CH2C(O)O-、-
CH2CH(Me)C(O)O-、-CH2CH2C(O)C(O)O-、-CH2CH(Me)C(O)C(O)O-、-CH2CH2C(O)C(O)-、-CH2CH
(Me)C(O)C(O)-、-CH2CH2C(O)C(O)NH-、-CH2CH(Me)C(O)C(O)NH-、-CH2CH2C(O)-、-CH2CH(Me)C
(O)-、-CH2CH2C(O)NH-、-CH2CH(Me)C(O)NH-、-CH2CH2C(O)NR-、-CH2CH(Me)C(O)NR-、-
CH2CH2SO2-、-CH2CH(Me)SO2-、-CH2CH2S (O) R- or-CH2The small molecule or polymer matrix of CH (Me) S (O) R- units
Group,
Or when n values 2 or the integer more than 2 ,-R2- Q is one and contains n members-CH2CH (OH)-or-CH2CH (OR)-mono-
The small molecule or polymeric groups of member.
2. acylphosphanes (oxygen) compound shown in logical formula (I) according to claim 1, it is characterised in that R3=R5=R7=CH3
And R4=R6=H；Or R3=R7=C1 and R4=R5=R6=H；Or R3=R7=OCH3And R4=R5=R6=H；Or R3=R5=R7
=CH3And R4=R6=CH2OH；Or R3=R5=R7=CH3And R4=R6=CH2OC(O)R；Or R3=R5=R7=CG3And R4=
CH2OH and R6=H；Or R3=R5=R7=CH3And R4=R6=CH2OR；Or R3=R5=R7=CH3And R4=R6=CH2NRR’；
Or R3=R5=R7=CH3And R4=CH2OH and R6=CH2NRR’；
And/or R8=R9=R10=CH3；Or R8=R9=R10=CH2CH3；Or R8=CH3、R9-R10It is cyclohexane structure；
And/or the integer between n values 1-100；It is preferred that the integer between n values 1-10.
3. acylphosphanes (oxygen) compound shown in logical formula (I) according to claim 1, it is characterised in that R1Selected from C6H5、p-
CH3OC6H4、CH3、CH2CH3、CH2CH=CH2、CH2Ph、C(O)CEt3、C(O)CMe3, xenyl, 2,4,6- trimethylbenzoyls
One kind in base, 2,6- Dimethoxybenzoyls or 2,6- dichloro-benzoyl base；
And/or C6-C24The one kind of aryl in phenyl, xenyl, naphthyl；
And/or Y is one containing 2-6 acrylic ester unit-C2-C36Group, it is preferable that Y is one of following shown group：
And/or
When n values 2 or the integer more than 2, Q is one of following shown group：
Or Q is one of following shown group：
Wherein, R11It is hydrogen or R；Or, when n values 2 or the integer more than 2 and work as R1When being R, Q is one of following shown group：
；Or, when n values 2 or the integer more than 2 ,-R2- Q structures are one and contain n members-CH2CH (OH)-or-CH2CH
(OR) small molecule or polymeric groups of-unit, Q are one of following shown groups：
4. prepare the method for acylphosphanes (oxygen) compound shown in logical formula (I)：
From organic halogenation phosphine R1PHal2Set out, organic phosphine hydrogen R is made1PH2, organic phosphine hydrogen R1PH2Alkali effect under and carboxylic acid halides R0C
(O) Hal or acid anhydrides R0C(O)OC(O)R0Reaction, obtains the intermediate that form is A or B, the intermediate and formaldehyde and oxidant is made
Under, acylphosphanes (oxygen) compound shown in logical formula (I) is obtained, wherein, Hal is halogen；Or intermediate A or B and formula C institutes
The material of representative carries out the first reaction in oxidant presence, obtains acylphosphanes (oxygen) compound shown in logical formula (I)；Wherein, Q generations
The structure of one Q chemistry speciality of table description, contain polynary epoxy, multicomponent isocyanate, polynary unsaturated carbonyl compound, more for one
First carboxylic acid, the micromolecular compound of polynary carboxylic acid halides or multi-anhydride functional group or fluoropolymer resin compound；Alkali is inorganic gold
Belong to hydroxide or alkoxide or carbonate or carboxylate compounds, or trimethylamine type compound；Oxidant be selected from oxygen,
Air, air-metal salt are answered, compound, metal hypochlorite salt, oxygen-metal salt complex, hydrogen peroxide, the mistake that form is ROOH
One kind in oxide, peroxy acid or sulphur；Integer of the q values between 1-n；Material representated by formula C is selected from polynary epoxy
One in C1, multicomponent isocyanate C2, polynary unsaturated carbonyl compound C3, polybasic carboxylic acid C4, polynary carboxylic acid halides C5, multi-anhydride C6
Kind；
Or intermediate A or B and alkyl halide or alkyl the pseudohalogen compound generation labeled as R-Hal, deposited in the second alkali
Under, nucleophilic substitution, acylphosphanes (oxygen) compound shown in logical formula (I) is prepared,
Or, the phosphono raw material D via a starting, Blanc reactions occur under acid and formaldehyde collective effect, obtain in halide
Mesosome E, wherein, r values 1 or 2, the acid is Louis or Bronsted acid, and Hal represents halogen atom；Intermediate E is in nucleopilic reagent
HNu effects are lower to occur nucleophilic substitution, and the compound of acylphosphanes (oxygen) shown in logical formula (I) is prepared,
Or, double acylphosphine oxides (BAPO) are in acid and electrophilic reagent E+Under effect, single phosphono group occurs to E+Addition it is anti-
Should, the compound of acylphosphanes (oxygen) shown in logical formula (I) is prepared；The acid is lewis acid or Bronsted acid；Electrophilic reagent E+It is
C1-C48Side chain or straight chain aliphatic or aromatic series aldehydes or ketones, or α, beta-unsaturated aldehyde, ketone, ester, nitrile or acid amides, or nitro
Alkene, or alkenyl sulfone or sulfoxide,
Or, structure F phosphonos intermediate sodium bis (2,4,6-trimethylbenzoyl) phosphanide or structure
Gphosphinediylbis (mesitylmethanone), or the resonant isomers of their enol forms with formaldehyde or C with trying
Agent reacts and passes through oxidant effect, obtains acylphosphanes (oxygen) compound shown in logical formula (I)；C reagents are selected from polynary epoxy
One in C1, multicomponent isocyanate C2, polynary unsaturated carbonyl compound C3, polybasic carboxylic acid C4, polynary carboxylic acid halides C5, multi-anhydride C6
Kind,
5. according to the method for claim 4, it is characterised in that first reaction is selected from epoxy ring opening reaction, isocyanic acid
One kind in ester addition reaction, Michael's conjugate addition reaction, esterification；
And/or second alkali be inorganic metal oxygen oxide or alkoxide or carbonate or carboxylate compounds, or trimethylamine
Type compound；
And/or the acid is in alchlor, zinc chloride, ferric trichloride, alchlor, hydrochloric acid, hydrobromic acid, acetic acid
It is one or more；It is preferred that the acid is alchlor or hydrochloric acid；
And/or the Hal is chlorine；
And/or the nucleopilic reagent HNu is the material containing aerobic, nitrogen, sulphur or phosphorus atoms, it is preferable that the HNu is water, NR3、
HNRR’、H2NR, HSR, RSSR ', HP (O) RR ' or the heterocycle containing aerobic, nitrogen, sulphur or phosphorus atoms；
And/or the electrophilic reagent E+It is formaldehyde, acrylic acid, methacrylaldehyde or unitary or polynary acrylate monomer or propylene
Acid ester polymer resin；It is preferred that the acid is alchlor or hydrochloric acid, the electrophilic reagent E+It is formaldehyde.
6. acylphosphanes (oxygen) compound shown in logical formula (I) adds in photocurable formulation system as light trigger or other features
Add the purposes of agent composition；Or the purposes in chemical synthesis as intermediate or raw material or reagent.
7. it is a kind of containing formula (I) compound is led to described in claim 1-3 any one, can be via the mixing of light radiation solidification
Thing.
8. mixture according to claim 7, it is characterised in that the mixture contains at least one logical formula (I) chemical combination
Thing is as one of light trigger or light trigger component；And contain at least one unsaturated compound containing ethylene linkage；
It is preferred that being calculated with the every 100 parts of weight of the total amount of unsaturated compound containing ethylene linkage, the amount of the logical formula (I) compound contained is
0.01-30 parts by weight；It is preferred that calculated with the every 100 parts of weight of the total amount of unsaturated compound containing ethylene linkage, the logical formula (I) chemical combination contained
The amount of thing is the 0.5-10 amount of holding parts；
And/or unsaturated compound containing ethylene linkage is the compound or mixture being crosslinked by the Raolical polymerizable of double bond,
The unsaturated compound containing ethylene linkage is monomer, oligomer or prepolymer or their mixture or copolymer, or they
Water-borne dispersions.
9. the mixture described in claim 7-8 any one is used as photocureable coating or ink.
10. the photocureable coating or ink described in claim 9 are in inkjet printing, paper printing, adhesive, woodwork coating, modeling
Glue application, painting dressing automobiles, packaging material, Display Technique, construction material, the application in flexible electronic or photovoltaic material field.
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| US10619065B2 (en) * | 2017-01-31 | 2020-04-14 | Hewlett-Packard Development Company, L.P. | Photo active agents |
| CN112334551A (en) * | 2018-06-19 | 2021-02-05 | 爱克发有限公司 | Acylphosphine oxide initiators |
| CN112724821A (en) * | 2021-01-19 | 2021-04-30 | 深圳有为技术控股集团有限公司 | Safety type long-wavelength LED photocureable coating for covering property, coating device and method thereof, and application of coating device and method to rail vehicles |
| JPWO2021095580A1 (en) * | 2019-11-11 | 2021-05-20 |
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