CN108137727A - 酰基锗光引发剂及其制备方法 - Google Patents
酰基锗光引发剂及其制备方法 Download PDFInfo
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- CN108137727A CN108137727A CN201680054564.0A CN201680054564A CN108137727A CN 108137727 A CN108137727 A CN 108137727A CN 201680054564 A CN201680054564 A CN 201680054564A CN 108137727 A CN108137727 A CN 108137727A
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- Prior art keywords
- alkyl
- formula
- group
- acyl group
- compound
- Prior art date
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- 125000002252 acyl group Chemical group 0.000 title claims description 46
- 238000002360 preparation method Methods 0.000 title abstract description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title description 11
- 229910052732 germanium Inorganic materials 0.000 title description 10
- -1 acyl group germanium compound Chemical class 0.000 claims abstract description 56
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 30
- 229910000078 germane Inorganic materials 0.000 claims description 28
- 239000002585 base Substances 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000945 filler Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 21
- 150000001266 acyl halides Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 230000006870 function Effects 0.000 claims description 7
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 125000005251 aryl acyl group Chemical group 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004665 trialkylsilyl group Chemical group 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- 238000006884 silylation reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 17
- 239000000654 additive Substances 0.000 description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- 238000007792 addition Methods 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000005548 dental material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 150000003254 radicals Chemical group 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 5
- 229930006711 bornane-2,3-dione Natural products 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000003479 dental cement Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000010437 gem Substances 0.000 description 3
- 150000002291 germanium compounds Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
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- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical class O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- AAMTXHVZOHPPQR-UHFFFAOYSA-N 2-(hydroxymethyl)prop-2-enoic acid Chemical compound OCC(=C)C(O)=O AAMTXHVZOHPPQR-UHFFFAOYSA-N 0.000 description 2
- UEKHZPDUBLCUHN-UHFFFAOYSA-N 2-[[3,5,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCOC(=O)C(C)=C UEKHZPDUBLCUHN-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
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- 229910003691 SiBr Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
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- 125000003302 alkenyloxy group Chemical group 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
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- PCNIYCRKELJPHT-UHFFFAOYSA-N trifluoroborane ytterbium Chemical compound [Yb].B(F)(F)F PCNIYCRKELJPHT-UHFFFAOYSA-N 0.000 description 2
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- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- SQAIGLXMIMWFEQ-UHFFFAOYSA-N tetrakis(prop-2-enyl) silicate Chemical compound C=CCO[Si](OCC=C)(OCC=C)OCC=C SQAIGLXMIMWFEQ-UHFFFAOYSA-N 0.000 description 1
- AKRQMTFHUVDMIL-UHFFFAOYSA-N tetrakis(prop-2-enyl)silane Chemical compound C=CC[Si](CC=C)(CC=C)CC=C AKRQMTFHUVDMIL-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- SXPUVBFQXJHYNS-UHFFFAOYSA-N α-furil Chemical compound C=1C=COC=1C(=O)C(=O)C1=CC=CO1 SXPUVBFQXJHYNS-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及通式为[RmAr‑(C=O)‑]4‑Ge的酰基锗化合物以及其制备方法。该化合物适合作为用于自由基聚合的引发剂。
Description
本发明涉及包含作为聚合引发剂的酰基锗化合物的可聚合组合物。该组合物特别适合制备粘合剂,涂料,粘固剂,复合材料,成形部件,如杆状物、板材、盘状物或透镜等,且特别是牙科材料。
使用的光引发剂对于光聚合反应性树脂的固化起着决定性的作用。在用UV或可见光照射时,其吸收光并形成引发聚合的物质。在自由基聚合的情况下,这些引发聚合的物质是自由基。根据自由基形成的化学机理将光引发剂分为两类。
Norrish I型光引发剂在照射时通过单分子键断裂形成自由基。在照射时,Norrish II型光引发剂经历双分子反应,其中处于激发态的光引发剂与第二分子,即共引发剂反应,并且通过电子和质子转移形成引发聚合的基团。I型和II型光引发剂用于UV光固化;迄今为止,除了双酰基二烷基锗化合物以外,II型光引发剂几乎仅用于可见光范围。
UV固化的特征在于高反应速率,并且经常用于不同基材例如木材、金属或玻璃的涂层。因此,例如在EP1247843A2中描述了UV-固化涂层材料,其中使用I型光引发剂如二乙氧基苯基苯乙酮、或酰基-或双酰基氧化膦。
WO01/51533A1描述了一种UV-固化木材涂层材料,其中酰基氧化膦、α-羟基苯烷基酮或α-二烷氧基苯乙酮也用作光引发剂。最重要的是,由于UV光的低波长,可以使用UV固化制备具有低层厚度的透明涂层。在具有明显的阴影或着色和更大的层厚度的情况下达到UV固化的极限。在UV光的情况下,这样的具有明显降低的透明度的光聚合反应性树脂仅不完全固化。
如果需要更大的贯穿固化深度,例如在光固化牙科填充材料的固化中,则使用可见光用于照射。最常用于此的光引发剂体系是如例如GB1408265中描述的α-二酮与胺共引发剂的组合。
其中使用这种光引发剂体系的牙科组合物公开于例如US4,457,818或US4,525,256中,其中樟脑醌优选地用作α-二酮。樟脑醌在468nm的波长处具有最大吸收。结果,樟脑醌显示强烈的黄色着色,缺点是由樟脑醌/胺引发的材料通常在固化后泛黄,因为引发剂体系没有被完全漂白(N.Moszner,R.Liska,Photoinitiators for direct adhesiverestorative materials,In:Basics and Applications of PhotopolymerizationReactions,Vol.1;Fouassier,J.-P.,Allonas,X.,Eds.,Research Signpost,Kerala,2010,93-114)。该漂白行为特别是在完全聚合的材料的亮白色色调的情况下是非常不利的。此外,当用于酸粘合剂中时,樟脑醌胺体系具有以下缺点,即形成自由基的胺组分质子化,并由此对于形成自由基部分失效。
锗化合物作为光引发剂的用途是已知的。双酰基二烷基锗化合物是用于在蓝光范围内固化的最有效的Norrish I型光引发剂(B.Ganster,U.K.Fischer,N.Moszner,R.Liska,New photocleavable structures,Diacylgerman-based photoinitiators forvisible light curing,Macromolecules 41(2008)2394-2400;N.Moszner,U.K.Fischer,B.Ganster,R.Liska,V.Rheinberger,Benzoyl germanium derivatives as novelvisible light photoinitiators for dental materials Dent.Mater.24(2008)901-907;N.Moszner,F.Zeuner,I.Lamparth,U.K.Fischer,Benzoylgermanium derivatives asnovel visible-light photoinitiators for dental composites,Macromol.Mater.Eng.294(2009)877-886)。
EP1905413A1和EP1905415A1公开了适合作为用于使用可见光固化牙科材料的光引发剂的单-、双-和三酰基锗化合物。它们的合成是昂贵的并且使用二噻烷保护基团技术由昂贵的二烷基锗二卤化物开始并且使用柱色谱纯化来进行。
根据EP2103297A1,适合的包含数个锗原子的酰基锗化合物作为光引发剂是已知的。
WO2015/067815A1公开了具有式R1R2R3Ge(CO)GeR4R5R6的双(甲锗烷基)酮及其制备方法。这些双(甲锗烷基)酮也旨在适合作为用于牙科材料的光引发剂。
本发明的目的是提供用于可见光范围的光引发剂,其特征在于改善的反应性和固化特征,并且其尤其可以通过长波范围内的可见光活化。本发明的另外的目的是提供用于制备酰基锗烷的简化方法。
该目的通过对应于通式(I)的四(tetra)-或四(tetrakis)-酰基锗烷来实现的:
[RmAr─(C=O)─]4─Ge (I)
其中,变量具有以下含义:
Ar为具有6至18个环碳原子的单环或多环烃基,其可以被R基团取代m次,并且其可以在环中包含一个或多个杂原子,其中
m是0至6的整数,并且不能大于Ar中可取代的氢原子的数目,
R为卤素,NR1 2,OH,OSiR2 3,(C=O)R3,CN,NO2,CF3,COOR4,C1至C20-烷基、-烯基、-烷氧基或-链烯氧基,所述C1至C20-烷基、-烯基、-烷氧基或-链烯氧基可以是直链的、支链的或环状的,其可以被一个或多个O原子中断,并且其可以具有可自由基聚合的基团,或=O,其中
R1至R3在每种情况下彼此独立地为H,或直链或支链C1-至C12-烷基,和
R4为H,直链或支链C1-至C12-烷基或SiR5 3,其中
R5为直链或支链C1至C10烷基。
如果存在数个R基团(m>1),则它们可以不同或优选是相同的。可以作为R基团中的取代基存在的优选的可自由基聚合的基团为乙烯基、苯乙烯基、丙烯酸酯基(CH2=CH-CO-O-)、甲基丙烯酸酯基(CH2=C(CH3)-CO-O-)、丙烯酰胺基(CH2=CH-CO-NR6-,其中R6=H或C1-C8-烷基)、甲基丙烯酰胺基(CH2=C(CH3)-CO-NH-),特别优选(甲基)丙烯酸酯基、甲基丙烯酰胺基和/或N-烷基丙烯酰胺基。R基团(多个R基团)优选地具有0至3,特别是0至1个可自由基聚合的基团。在非环状基团中,可聚合基团优选布置在末端。
根据化学命名规则,其中Ar为未取代基团的化合物称为四酰基锗烷(tetraacylgermane),而其中Ar被取代的化合物必须称为四(酰基)锗烷(tetrakis(acyl)germane)。为了简单起见,术语四酰基锗烷在本文用于这两种化合物基团。
Ar优选为包含至少一个芳族环的多环烃基,特别优选芳族烃基。优选的具有至少一个芳族环的多环烃基为蒽醌基和萘醌基。除了苯基以外,特别是稠合芳族基团,如萘基、蒽基、菲基和并四苯基优选作为芳族烃基。
Ar可以在环中包含一个或多个,优选1至2个杂原子。优选的杂原子为O、S和特别优选为N。特别优选的杂芳族基团为吡啶基、嘧啶基和喹啉基。
所有立体异构形式和各种立体异构形式的混合物,例如外消旋体被式(I)和本文所示的其他化学式涵盖。这些化学式仅涵盖那些符合化学价态理论的化合物。例如,m不能大于Ar基团中可取代的氢原子的数目。如果R通过两个键与Ar键合,则可能的R基团的最大数目相应较小。
基团可以被杂原子如O中断的表述应理解为是指O原子插入基团的碳链或碳环中,即两侧均与碳原子邻接。因此,杂原子的数目至少比碳原子的数目少1个,并且杂原子不能在末端。在包含碳原子和杂原子的烃基的情况下,杂原子的数目总是小于碳原子的数目,不考虑取代基。
卤素(缩写为Hal)优选表示F、Cl、Br或I,特别是F、Cl,非常特别优选Cl。
对应于通式(I)的四酰基锗烷是特别优选的,其中变量具有以下含义:
Ar为芳族C6-C10基团,其可以被R取代m次,其中
m为1至3的整数,和
R为Cl,NR1 2,OSiR2 3,(C=O)R3,CN,NO2,CF3,COOR4,或C1至C10-烷基、烯基、烷氧基或链烯氧基,所述C1至C10-烷基、烯基、烷氧基或链烯氧基可以是直链的、支链的或环状的,其可以被一个或多个O原子中断,并且其可以包含可自由基聚合的基团,优选乙烯基、甲基丙烯酸酯基、(甲基)丙烯酰胺基或N-烷基丙烯酰胺基,其中所述可自由基聚合的基团在非环状基团的情况下优选在末端,其中
R1至R3在每种情况下彼此独立地为H,或直链或支链C1-至C8-烷基,和
R4为H,直链或支链C1-至C8-烷基或SiR5 3,和
R5为直链或支链C1至C5烷基。
根据通式(I)的四酰基锗烷是进一步优选的,其中变量具有以下含义:
Ar为苯基、吡啶基、萘基、蒽基、蒽醌基,其可以被R取代m次,其中
m为1至3的整数,和
R为NR1 2、CN、NO2、CF3、C1-至C3-烷基或C1-至C3-烷氧基,所述C1-至C3-烷基或C1-至C3-烷氧基优选为直链的,并且其可以具有末端可自由基聚合的基团,优选乙烯基、丙烯酸酯基、甲基丙烯酸酯基,其中
R1为H或优选为直链C1-至C3-烷基。
如果Ar是苯基并且m=1,则R基团优选位于相对于该基团位置的对位,如果m=2或3,则R基团优选位于相对于该基团位置的邻位和对位。各个变量的优选和特别优选的含义可以在每种情况下彼此独立地选择。
非常特别优选的是式(I)的化合物,其中Ar是被R取代m次的苯基。m优选为1-3,特别优选1,并且R优选为电子给体基团,特别是烷氧基。
根据本发明,在400nm至700nm,特别优选400至550nm处具有最大吸收的式(I)的化合物是优选的,例如,四苯甲酰基锗或四(4-甲氧基苯甲酰基)锗。式(I)化合物的吸收光谱可以通过选择R基团以针对性的方式进行调整。例如,NO2或CN取代基引起吸收光谱的红移,即其中一个或多个R基团为CN的化合物吸收具有更长波长的光,结果是可以由在更长波长范围内的可见光引发聚合。
通式(I)的四酰基锗烷根据现有技术是未知的,并且不能用常规方法制备。这些化合物的特征在于高反应性,即在用可见光照射时优异的引发聚合的作用和良好的贯穿固化深度。这不仅在牙科材料的情况下,特别是在牙科填充复合材料的情况下是很有利的,而且在非牙科用途的情况下也是很有利的。
令人惊讶地发现式I'的(芳基酰基)k(烷基)4-k锗烷可以通过在碱的存在下使式(R'3Si)kGeR"4-k(II)的(三烷基甲硅烷基)锗烷与芳基酰基卤化物(III)反应来制备。
其中:
R'为具有1至6个,优选1至4个C原子的烷基,特别优选CH3,
R"为具有1至12个,优选1至6个,特别优选1至4个C原子的烷基,非常特别优选CH3、C2H5或C4H9,
X为F、Cl、Br或I,优选F或Cl,
k为1至4的整数,和
R具有以上给出的含义。
在R'和R"的情况下,直链烷基在所有情况下都是优选的。
优选使用碱金属醇盐,特别优选叔丁醇钾,碱金属氨化物,特别优选二异丙基氨基锂或碱金属有机化合物,特别优选正丁基锂作为碱。
式III的优选的芳基酰基卤化物直接根据Ar和R基团的优选和特别优选的定义衍生。以下化合物是这样的实例:
优选地,三甲基甲硅烷基锗烷(R'3Si)kGeR"4-k(II)首先与碱反应以形成(R'3Si)k- 1R"4-kGeM,其中M为金属离子,优选碱土金属离子,且特别是碱金属离子,并且(R'3Si)k-1R"4- kGeM随后用式(III)的酰基卤化物转化为式(R'3Si)k-1R"4-kGe(C=O)ArRm的化合物。以这种方式,式(II)的(R'3Si)-基团连续交换成-(C=O)ArRm基团。中间产物(R'3Si)k-1R"4-kGeM优选不分离。
采用根据本发明的方法,可以以高纯度和以高收率制备式(I')的酰基锗烷。特别的优点是可以避免使用利用含硫保护基团的昂贵的保护基团技术。含硫杂质很难从产物去除,并且即使微量的含硫基团也会导致最终产物的令人不愉快的气味。
式(I')的酰基锗烷的合成所需的起始原料(R'3Si)kGeR"4-k(II)可以优选通过使相应的锗氯化物ClkGeR"4-k(IV)与式R'3SiBr的三烷基甲硅烷基溴化物或优选的式R'3SiCl(V)的三烷基甲硅烷基氯化物反应来制备:
为此,R'3SiBr或优选的R'3SiCl(优选0.9至1.1k,特别优选0.99k当量)优选地首先被添加到细微分散的Li(优选1.7至2.2k,特别优选1.85k当量)在适合的溶剂中的悬浮液,然后缓慢加入锗氯化物(优选1当量)的溶液。在每种情况下优选使用醚,特别优选THF作为溶剂。使用的溶剂的量优选为20至40ml/g Li,非常特别优选30ml/g Li或1至5ml/g GeCl4,非常特别优选2.5ml/g GeCl4。反应温度优选为+30至-100℃,特别优选-78℃。产物混合物的处理(working up)优选通过以下进行:过滤,优选通过硅藻土过滤,酸水解,优选用H2SO4/冰的混合物酸水解,相分离,和随后去除溶剂,优选通过蒸馏去除溶剂。产物可以有利地通过结晶、升华或蒸馏来分离。
根据本发明的方法的特别优选的实施方案,式(I')的酰基锗烷可以通过使三甲基甲硅烷基锗烷(Me3Si)kGeR"4-k(II')与叔丁醇钾(KOtBu)反应,然后使中间体与酰基卤化物(III)(X=F或Cl)反应来制备:
为了形成(Me3Si)k-1R"4-kGeK,优选地首先将(Me3Si)kGeR"4-k(优选1当量)和KOtBu(优选0.9至4当量,特别优选1.1当量)溶解在适合的溶剂中并搅拌,直到反应完成。优选使用醚作为溶剂,特别优选使用DME(二甲氧基乙烷)作为溶剂。使用的溶剂的量优选为10至60ml/g KOtBu,特别优选20ml/g KOtBu。反应温度优选为+80至-30℃,特别优选为+25℃,反应时间优选为0.5至3小时,特别优选为1小时。
然后添加酰基卤化物(III)(优选1.0至1.5当量)并搅拌,直到反应完成,以获得式(I')的酰基锗烷。酰基卤化物(III)既可以原样使用也可以以溶液形式使用,其中溶剂的量优选为0至200ml,特别优选100ml/mmol酰基卤化物。优选醚,特别优选乙醚优选用作溶剂。反应温度优选为+30至-100℃,非常特别优选-78℃。反应时间优选为0.5至48小时,特别优选为24小时。产物混合物的处理优选通过以下进行:酸水解,优选用H2SO4/冰的混合物酸水解,相分离,和去除溶剂,例如通过蒸馏去除溶剂。产物可以通过柱色谱和通过结晶分离,优选仅通过结晶分离。
类似地,单酰基三烷基锗烷、双酰基二烷基锗烷和三酰基单烷基锗烷可以直接地且在没有保护基团技术的情况下通过使式(II)的单、双、三或四(三烷基甲硅烷基)锗烷与式(III)的酰基卤化物反应制备。
k=4的式(I')的四酰基锗烷首次可以通过该方法获得。为此,式(R'3Si)4Ge的三烷基甲硅烷基锗在碱的存在下与式(III)的芳族芳基卤化物以上述方式反应。三烷基甲硅烷基锗(R'3Si)4Ge可以如描述的通过使锗四氯化物与R'3SiCl和金属Li反应来制备。
通过使四(三甲基甲硅烷基)锗(Me3Si)4Ge与叔丁醇钾(KOtBu)反应,然后与式(III)的酰基卤化物(X=F或Cl)反应,可以特别有利地如上所述制备式(I)的四酰基锗烷:
酰基卤化物(III)优选以1.0至5当量,特别优选4.1当量的量添加,并搅拌直到反应完成。酰基卤化物如所述的既可以原样使用也可以以溶液形式使用。
通式(I)的四酰基锗烷和式(I')的(酰基)k(烷基)4-k锗烷特别适合作为用于聚合的光引发剂,特别是作为用于自由基聚合、光加成和硫醇-烯反应(加聚)的引发剂。已经发现,使用这些引发剂,在用光照射时,可以实现高贯穿固化深度,而引发剂不导致变色。这在许多技术和特别是医疗材料中是很大的优势。
通式(I)和(I')的化合物特别适合制备牙科材料、骨粘固剂,和非常特别地适合制备接触透镜、人工晶状体或其它医学成形部件,如耳罩(ear shell)、软骨植入物和人工组织部分。
用可见光波长范围内的光固化时,大的贯穿固化深度在技术应用中也是很大的优势。式(I)和(I')的引发剂因此也适合多种非医学用途,例如用于制备印刷油墨或油漆、清漆、粘合剂,用于制备印刷板、集成电路、光阻材料、焊接掩模,用于彩色印刷机的油墨,作为全息数据存储的材料,用于制备纳米级微机电元件、光波导、成形部件以及用于信息载体的光学制备。主要的应用领域是在技术成形部件,例如精密成形部件和陶瓷生坯体的立体光刻制备中用作光引发剂。
根据本发明的组合物优选包含相对于组合物的总质量0.001至5重量%,特别优选0.01至1.0重量%的式(I)或(I')的酰基锗化合物。除了式(I)或(I')的酰基锗化合物之外,组合物优选还包含可聚合的粘结剂。优选的粘结剂是可自由基聚合的和/或可阳离子聚合的单体和/或预聚物,特别优选可自由基聚合的单体,可自由基聚合的预聚物或其混合物。
单官能或多官能(甲基)丙烯酸酯或其混合物特别适合作为可自由基聚合的粘结剂。单官能(甲基)丙烯酸化合物是指具有一个可聚合基团的化合物,多官能(甲基)丙烯酸酯化合物是指具有两个或更多个,优选2至3个可聚合基团的化合物。
这方面的实例为(甲基)丙烯酸甲酯,(甲基)丙烯酸乙酯,(甲基)丙烯酸羟乙酯,(甲基)丙烯酸丁酯,(甲基)丙烯酸苄酯,(甲基)丙烯酸四氢糠酯或(甲基)丙烯酸异冰片酯,双酚A二(甲基)丙烯酸酯、双-GMA(甲基丙烯酸和双酚A二缩水甘油醚的加成产物),UDMA(甲基丙烯酸2-羟乙酯和2,2,4-三甲基六亚甲基二异氰酸酯的加成产物),二、三或四甘醇二(甲基)丙烯酸酯,三羟甲基丙烷三(甲基)丙烯酸酯,季戊四醇四(甲基)丙烯酸酯以及甘油二和三(甲基)丙烯酸酯,1,4-丁二醇二(甲基)丙烯酸酯,1,10-癸二醇二(甲基)丙烯酸酯或1,12-十二烷二醇二(甲基)丙烯酸酯。包含至少一种具有2个或更多个,优选2至3个可自由基聚合的基团的可自由基聚合的单体的组合物是特别优选的。多官能单体具有交联性质。
水解稳定的稀释单体,如水解稳定的单(甲基)丙烯酸酯也可用作可自由基聚合的粘结剂,例如,甲基丙烯酸三甲苯酯(mesitylmethacrylate)或2-(烷氧基甲基)丙烯酸,例如2-(乙氧基甲基)丙烯酸、2-(羟甲基)丙烯酸,N-单或二取代的丙烯酰胺,例如N-乙基丙烯酰胺、N,N-二甲基丙烯酰胺、N-(2-羟乙基)丙烯酰胺或N-甲基-N-(2-羟基乙基)丙烯酰胺,或N-单取代的甲基丙烯酰胺,例如N-乙基甲基丙烯酰胺或N-(2-羟基乙基)甲基丙烯酰胺,还有N-乙烯基吡咯烷酮或烯丙基醚。水解稳定的交联单体的优选实例为2-(羟基甲基)丙烯酸和二异氰酸酯的氨基甲酸酯,如2,2,4-三甲基六亚甲基二异氰酸酯或异佛尔酮二异氰酸酯;交联吡咯烷酮,例如1,6-双(3-乙烯基-2-吡咯烷酮基)己烷,或商业上可获得的双丙烯酰胺,如亚甲基或亚乙基双丙烯酰胺,或双(甲基)丙烯酰胺,例如N,N'-二乙基-1,3-双(丙烯酰胺基)丙烷、1,3-双(甲基丙烯酰胺基)丙烷、1,4-双(丙烯酰胺基)丁烷或1,4-双(丙烯酰基)哌嗪,其可以通过由相应的二胺与(甲基)丙烯酰氯的反应合成。
已知的低收缩自由基可开环聚合的单体,例如单官能或多官能乙烯基环丙烷或二环环丙烷衍生物(参见DE19616183C2或EP1413569A1)或环状烯丙基硫化物(参见US6,043,361或US6,344,556)也可用作可自由基聚合的粘结剂。这些单体也可以与上面列出的二(甲基)丙烯酸酯交联剂组合使用。适合的可开环聚合的单体是乙烯基环丙烷,如1,1-二(乙氧基羰基)-或1,1-二(甲氧基羰基)-2-乙烯基环丙烷,或1-乙氧基羰基-或1-甲氧基羰基-2-乙烯基环丙烷羧酸与乙二醇、1,1,1-三羟甲基丙烷、1,4-环己二醇或间苯二酚的酯。适合的双环环丙烷衍生物是2-(双环[3.1.0]己-1-基)丙烯酸甲酯或乙酯或其在3位双取代的衍生物,例如(3,3-双(乙氧基-羰基)-双环[3.1.0]己-1-基)丙烯酸甲酯或乙酯。适合的环状烯丙基硫化物是2-(羟甲基)-6-亚甲基-1,4-二硫杂环庚烷或7-羟基-3-亚甲基-1,5-二硫杂环辛烷与2,2,4-三甲基六亚甲基-1,6-二异氰酸酯或不对称六亚甲基二异氰酸酯三聚体(例如来自Bayer AG的VP LS 2294)的加成产物。
基于乙烯酯、碳酸乙烯酯和氨基甲酸乙烯酯的制剂也优选作为可自由基聚合的单体。此外,苯乙烯、苯乙烯衍生物或二乙烯基苯、不饱和聚酯树脂和烯丙基化合物或可自由基聚合的聚硅氧烷可以用作单体,所述可自由基聚合的聚硅氧烷可以由适合的甲基丙烯酸硅烷,例如3-(甲基丙烯酰氧基)丙基三甲氧基硅烷制备,并且其描述于例如DE19903177C2中。
此外,先前命名的单体与也可称为粘合剂单体的可自由基聚合的包含酸基团的单体的混合物也可以用作可自由基聚合的粘结剂。优选的包含酸基团的单体是可聚合的羧酸,如马来酸、丙烯酸、甲基丙烯酸、2-(羟甲基)丙烯酸、4-(甲基)丙烯酰氧基乙基偏苯三酸酐、10-甲基丙烯酰氧基癸基丙二酸、N-(2-羟基-3-甲基丙烯酰氧基丙基)-N-苯基甘氨酸或4-乙烯基苯甲酸。
可自由基聚合的膦酸单体,特别是乙烯基膦酸、4-乙烯基苯基膦酸、4-乙烯基苄基膦酸、2-甲基丙烯酰氧基乙基膦酸、2-甲基丙烯酰胺基乙基膦酸、4-甲基丙烯酰胺基-4-甲基-戊基-膦酸、2-[4-(二羟基-磷酰基)-2-氧杂-丁基]-丙烯酸或2-[2-二羟基磷酰基)-乙氧基甲基]-丙烯酸乙酯或2,4,6-三甲基苯酯也适合作为粘合剂单体。
此外,酸性可聚合磷酸酯,特别是2-甲基丙烯酰氧基丙基一氢磷酸酯或2-甲基丙烯酰氧基丙基二氢磷酸酯,2-甲基丙烯酰氧基乙基一氢磷酸酯或2-甲基丙烯酰氧基乙基二氢磷酸酯,2-甲基丙烯酰氧基乙基苯基氢磷酸酯,二季戊四醇-五甲基丙烯酰氧基磷酸酯,10-甲基丙烯酰氧基癸基-二氢磷酸酯,二季戊四醇-五甲基丙烯酰氧基磷酸酯,磷酸单(1-丙烯酰基-哌啶-4-基)酯,6-(甲基丙烯酰胺基)己基二氢磷酸酯和1,3-双(N-丙烯酰基-N-丙基-氨基)-丙烷-2-基二氢磷酸酯适合作为粘合剂单体。
另外,可聚合的磺酸适合作为粘合剂单体,特别是乙烯基磺酸、4-乙烯基苯基磺酸或3-(甲基丙烯酰胺基)丙基磺酸。
含有单官能或多官能巯基化合物和双官能或多官能不饱和单体,尤其是烯丙基或降冰片烯化合物的混合物的硫醇-烯树脂特别适合作为通过加聚可固化的粘结剂。
单或多官能巯基化合物的实例为邻、间或对二巯基苯,和硫甘醇或3-巯基丙酸与乙二醇、丙二醇或丁二醇、己二醇、甘油、三羟甲基丙烷或季戊四醇的酯。
双官能或多官能烯丙基化合物的实例是:烯丙醇与二羧酸或三羧酸的酯,所述二羧酸或三羧酸如丙二酸、马来酸、戊二酸、琥珀酸、己二酸、癸二酸、邻苯二甲酸、对苯二甲酸或没食子酸;和单官能或三官能烯丙基醚,例如二烯丙基醚、α,ω-双[烯丙氧基]烷烃、间苯二酚或对苯二酚二烯丙基醚和连苯三酚三烯丙基醚;或其它化合物,例如1,3,5-三烯丙基-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮、四烯丙基硅烷或四烯丙基原硅酸酯。
双官能或多官能降冰片烯化合物的实例是环戊二烯或呋喃与双官能或多官能(甲基)丙烯酸酯的Diels-Alder加成产物,以及5-降冰片烯-2-甲醇或5-降冰片烯-2-醇分别与二羧酸或多羧酸,二异氰酸酯或聚异氰酸酯的酯和氨基甲酸酯,所述二羧酸或多羧酸例如丙二酸、马来酸、戊二酸、琥珀酸、己二酸、癸二酸、邻苯二甲酸、对苯二甲酸或没食子酸;所述二异氰酸酯或聚异氰酸酯如六亚甲基二异氰酸酯或其环状三聚体,2,2,4-三甲基六亚甲基二异氰酸酯,甲代亚苯基二异氰酸酯或异佛尔酮二异氰酸酯。
除了通式(I)的酰基锗化合物之外,根据本发明的组合物还可以有利地包含用于UV或可见光范围的已知的光引发剂(参见J.P.Fouassier,J.F.Rabek(编辑)RadiationCuring in Polymer Science and Technology,Vol.II,Elsevier Applied Science,London and New York 1993),例如:安息香醚、二烷基苯偶酰缩酮、二烷氧基苯乙酮、酰基或双酰基氧化膦、α-二酮如9,10-菲醌、二乙酰、糠偶酰、联茴香酰,4,4'-二氯苯偶酰和4,4'-二烷氧基苯偶酰和樟脑醌。
为了双重固化,根据本发明的组合物除了通式(I)的四酰基锗烷和/或式I'的(酰基)k(烷基)4-k锗烷外,还可以含有偶氮化合物,如2,2'-偶氮双(异丁腈)(AIBN)或偶氮双-(4-氰基戊酸),或过氧化物,如过氧化二苯甲酰、过氧化二月桂酰、过辛酸叔丁酯、过苯甲酸叔丁酯或二-(叔丁基)-过氧化物。为了借助过氧化物加速引发,也可以使用与芳族胺的组合。已经证明有价值的氧化还原体系是:过氧化苯甲酰与胺,例如N,N-二甲基-对甲苯胺、N,N-二羟基乙基-对甲苯胺、对二甲基氨基苯甲酸乙酯或结构相关体系的组合。另外,由以下组成的氧化还原体系也适合双重固化:过氧化物和还原剂,例如,抗坏血酸、巴比妥酸盐或亚磺酸;或氢过氧化物与还原剂和催化金属离子的组合,例如氢过氧化枯烯、硫脲衍生物和乙酰基丙酮酸铜(II)的混合物。
根据本发明,含有一种或多种填料,优选有机或无机微粒填料的组合物是优选的。优选的无机微粒填料是基于氧化物的无定形球形纳米微粒填料,如热解硅酸或沉淀硅酸,ZrO2和TiO2或平均粒径为10至200nm的SiO2、ZrO2和/或TiO2的混合氧化物,微填料,如平均粒度为0.2至5μm的石英、玻璃陶瓷或玻璃粉末,和不透X-射线的填料,如三氟化镱或纳米颗粒氧化钽(V)或硫酸钡。另外,也可使用纤维填料,如纳米纤维、玻璃纤维、聚酰胺或碳纤维。
对于非牙科用途,除了上述材料之外,均聚物和/或共聚物,优选聚((甲基)丙烯酸酯),乙烯基聚合物,优选聚苯乙烯或聚乙酸乙烯酯或缩聚物,优选聚酯适合作为填料。这些填料优选作为平均粒度为0.5至100μm的粉末使用。它们部分可溶于单体中。
另外,如果必需,根据本发明的组合物可以包含另外的添加剂,例如,稳定剂,UV吸收剂,染料或颜料,和溶剂,例如,水、乙醇、丙酮和/或乙酸乙酯,或浆料添加剂。
根据本发明的材料优选包含:
(a)0.001至5重量%的通式(I)的四酰基锗烷(多种通式(I)的四酰基锗烷),
(b)10至99.9重量%的可自由基聚合的粘结剂,
(c)0至85重量%的填料,和任选地包含
(d)0至70重量%的添加剂(多种添加剂)。
除非另有指明,否则所有百分比都与材料的总质量有关。
特别适合作为牙科粘固剂的材料优选包含:
(a)0.001至5重量%的通式(I)的四酰基锗烷(多种通式(I)的四酰基锗烷),
(b)10至50重量%的可自由基聚合的粘结剂,
(c)40至70重量%的填料,和
(d)0至5重量%的添加剂。
特别适合作为牙科复合材料的材料优选包含:
(a)0.001至5重量%的通式(I)的四酰基锗烷(多种通式(I)的四酰基锗烷),
(b)10至40重量%的可自由基聚合的粘结剂,
(c)50至70重量%的填料,和
(d)0至5重量%的添加剂(多种添加剂)。
特别适合作为牙科涂层材料的材料优选包含:
(a)0.001至5重量%的通式(I)的四酰基锗烷(多种通式(I)的四酰基锗烷),
(b)20至99.9重量%的可自由基聚合的粘结剂,
(c)0至20重量%的纳米微粒填料,和
(d)0.01至2重量%的添加剂(多种添加剂),
(e)0至70重量%的溶剂。
特别适合作为牙科粘合剂的材料优选包含:
(a)0.001至5重量%的通式(I)的四酰基锗烷(多种通式(I)的四酰基锗烷),
(b)20至98.99重量%的可自由基聚合的粘结剂,
(c)0至20重量%的纳米微粒填料,
(d)0.01至2重量%的添加剂,
(e)0至50重量%的溶剂,和
(f)1至20重量%的可自由基聚合的粘合剂单体。
用于牙科假体或外科模塑体的材料优选包含:
(a)0.001至5重量%的通式(I)的四酰基锗烷(多种通式(I)的四酰基锗烷),
(b)30至99.9重量%的可自由基聚合的粘结剂,
(c)0至60重量%的填料(多种填料),和任选地包含
(d)0至3重量%的添加剂(多种添加剂)。
用于塑料成形部件的材料优选包含:
(a)0.001至5重量%的通式(I)的四酰基锗烷(多种通式(I)的四酰基锗烷),
(b)30至99.9重量%的可自由基聚合的粘结剂,
(c)0至60重量%的填料,和任选地包含
(d)0至15重量%的添加剂(多种添加剂)。
用于陶瓷生坯体的材料优选包含:
(a)0.001至5重量%的通式(I)的四酰基锗烷(多种通式(I)的四酰基锗烷),
(b)0至40重量%的可自由基聚合的粘结剂,
(c)40至90重量%的填料,和任选地包含
(d)0至20重量%的添加剂(多种添加剂)。
包含通式(I)的四酰基锗烷作为光引发剂的根据本发明的材料可以用于制备光聚合物、复合材料、粘固剂、涂层材料、底漆或粘合剂。它们特别适合医疗领域中的用途,尤其适合牙科材料,例如填充复合材料、固定粘固剂、粘合剂、假体材料、饰面材料、牙冠或嵌体或涂层的制备。
牙科材料主要适合由牙科医生进行的口腔内应用以恢复受损牙齿,即用于治疗应用,例如作为牙科粘固剂、填充复合材料和饰面材料。然而,它们也可以在口外使用,例如用于制造或修复牙科修复体,例如假体、义齿、嵌体、高嵌体、牙冠和牙桥。
此外,根据本发明的材料适合外科中的医学用途,例如,用于组织再生中,用于制备助听器或在眼科中用于制备人工晶状体或接触透镜。
在技术应用中,通式(I)的四酰基锗烷可在立体光刻中或在用于制备模塑体、原型或生坯体的3D打印中,在涂料领域中或在微电子,例如光刻胶技术中用作光引发剂。
下面参照实施例进一步详细描述本发明。
实施例1:
四苯甲酰基锗烷(TBGe)的合成
a)四(三甲基甲硅烷基)锗烷[(Me3Si)4Ge]的合成
将10.00g(1.4mol)锂置于具有滴液漏斗和压力平衡器的烧瓶中,并加入300mL干燥THF。快速滴加三甲基氯硅烷(95ml,0.75mol)并在-78℃下搅拌10min。然后在-78℃下非常缓慢地滴加锗四氯化物(21ml,0.19mol,在THF中1:5稀释)(约2h)。一旦结束加入,将反应溶液加热至室温并再搅拌12小时。为了处理,首先通过硅藻土过滤反应混合物,然后倒至1MH2SO4/冰上。在滴液漏斗中相分离后,水相用乙醚萃取3次,合并的有机相用无水Na2SO4干燥,过滤并在旋转蒸发仪中除去溶剂。为了纯化,将粗产物升华(p<5毫巴;T>150℃)。升华后的产量为26.8g(Me3Si)4Ge(42%)。
NMR光谱:1H(CDCl3)δ[ppm]=0.24(s,Si(CH3)3)。29Si(CDCl3):δ[ppm]=-5.33(SiMe3)。
b)四苯甲酰基锗烷(TBGe)的合成
将3.00g(8.21mmol;1.00当量)四三甲基甲硅烷基锗烷和1.01g KOtBu(9.03mmol;1.1当量)称量到Schlenk烧瓶中,并溶于20ml乙二醇二甲醚(DME)中。当反应溶液具有澄清的黄色至橙色时,反应完成。约1小时后,借助注射器添加4.18g(33.66mmol,4.1当量)的苯甲酰氟。反应溶液变黑,并且在添加完成后变成橙色。然后将反应溶液在室温下搅拌过夜。用3%H2SO4水溶液处理后,分离各相,并且水相用乙醚萃取3次。将合并的有机相用无水硫酸钠干燥,并在旋转蒸发仪中除去挥发性组分。获得的粗产物用丙酮重结晶,并且得到1.70g纯的四苯甲酰基锗烷(42%),为结晶的黄色固体(熔点:82.5-83.0℃)。
NMR光谱:1H(CDCl3):δ[ppm]=7.99-7.96(m,2H,芳基-H),6.84-6.82(m,3H,芳基-H)。13C(CDCl3):δ[ppm]=222.01(GeCOPh),140.57(芳基-C1),133.81(芳基-C2),129.15(芳基-C3),128.77(芳基-C4)。
UV-VIS光谱:λ[nm](ε[L mol-1cm-1])=403(1240),419sh(1050)。
IR光谱:ν[cm-1]=1639,1617(m,νC=O);1590,1574,1444(m,νC=C);880,762,673(s,δC-H)。
实施例2:
四(2,4,6-三甲基苯甲酰基)锗烷(TMGe)的合成
将2.77g(7.66mmol;1.00当量)(Me3Si)4Ge和0.94g KOtBu(8.4mmol;1.1当量)称量到Schlenk容器中并溶于15ml DME中。当反应溶液具有澄清的黄色至橙色时,反应完成。约1小时后,将得到的溶液缓慢滴加到冷却至-78℃的1.66g(0.91mmol,1.2当量)2,4,6-三甲基苯甲酰氯在80ml乙醚中的溶液,并且将得到的混合物在室温下搅拌过夜。用3%H2SO4水溶液处理后,分离各相,并且将水相用乙醚萃取3次。将合并的有机相用无水硫酸钠干燥,并在旋转蒸仪中除去挥发性组分。形成的质量为3.85g的粗产物含有36%的四酰基锗和64%的单酰基锗化合物,并通过硅胶柱色谱分离(梯度:庚烷,甲苯)。然后用丙酮进行重结晶,并且得到1.58g(24%)四(2,4,6-三甲基苯甲酰基)锗烷,为结晶的黄色固体(熔点:198-199℃)。
NMR光谱:1H(CDCl3):δ[ppm]=6.57(s,2H,芳基-H),2.24(s,3H,对-CH3),2.06(s,6H,邻-CH3)。13C(CDCl3):δ[ppm]=233.40(GeCOMes),141.60(芳基-C1),139.26(芳基-C2),132.88(芳基-C3),128.53(芳基-C4),21.15(对-CH3),19.13(邻-CH3)。
UV-VIS光谱:λ[nm](ε[L mol-1cm-1])=288(17428),376(1475)。
IR光谱:ν[cm-1]=2917(w,νasCH3);1639,1608(m,νC=O);1202(m,δasCH3);833,609(m,ρCH3)。
实施例3:
使用来自实施例1和2的四苯甲酰基锗烷(TBGe)或四(2,4,6-三甲基苯甲酰基)锗
烷(TMGe)制备光固化树脂
各种光固化树脂体系由二甲基丙烯酸酯双-GMA(甲基丙烯酸和双酚-A-二缩水甘油醚的加成产物)、UDMA(甲基丙烯酸2-羟乙酯和2,2,4-三甲基六亚甲基二异氰酸酯的加成产物)和D3MA(癸二醇-1,10-二甲基丙烯酸酯)的混合物(值以质量%给出),以及Ge引发剂四苯甲酰基锗烷(TBGe)、四(2,4,6-三甲基苯甲酰基)锗烷(TMGe)和二苯甲酰二乙基锗烷(DBEGe,作为参考)制备(表1)。树脂体系R1和R4(0.29mmol/100g)或R2、R3和R5(0.59mmol/100g)含有相同摩尔量的光引发剂。
表1:树脂R1至R5的组成
*比较例
由这些材料制备试样,用牙科光源(Ivoclar Vivadent AG)照射两次,持续3分钟并由此固化。试样在室温(RT)下储存24小时后或在37℃的水中(WS)储存24小时后,根据ISO标准ISO4049(牙科学-基于聚合物的填充、修复和粘接材料(Dentistry-Polymer-based filling,restorative and luting materials)测定挠曲强度和挠曲弹性模量(表2)。
表2:聚合树脂R1至R5的挠曲强度(FS,MPa)和挠曲弹性模量(FME,GPa)
R1 | R2 | R3 | R4* | R5* | |
FS,RT | 72.7±3.5 | 81.7±9.5 | 81.5±5.5 | 58.5±2.3 | 79.7±7.5 |
FS,WS | 98.2±8.7 | 115.2±11.2 | 101.8±6.1 | 75.3±3.0 | 96.4±8.1 |
FME,RT | 1.59±0.12 | 2.25±0.22 | 1.89±0.21 | 1.15±0.07 | 1.76±0.19 |
FME,WS | 1.15±0.20 | 2.48±0.10 | 2.37±0.12 | 1.54±0.11 | 2.19±0.20 |
*比较例
表2中的结果证明,与基于已知的具有相同摩尔浓度的光引发剂的二(苯甲酰基)锗烷DBEGe的参考树脂R4和R5相比(比较R1与R4,或R2与R5),具有根据本发明的四(苯甲酰基)锗烷TBGe作为光引发剂的树脂R1和R3产生具有改善的强度和较高的弹性模量的光聚合物。
实施例4:
使用来自实施例1和2的四苯甲酰基锗烷(TBGe)或四(2,4,6-三甲基苯甲酰基)锗
烷(TMGe)制备光固化树脂
借助辊式磨碎机(“Exakt”型,Exakt Apparatebau,Norderstedt)由来自实施例3的树脂R1至R5制备复合糊料K1至K5。在每种情况下,36.44重量%的树脂R1至R5填充有52.22重量%的硅烷化玻璃填料GM 27884(1.0μm,Schott)、4.02重量%的硅烷化玻璃填料GM G018-056(1.0μm,Schott)、4.02重量%的硅烷化SiO2-ZrO2混合氧化物Spherosil(Transparent Materials,USA)、0.80重量%的硅烷化热解硅酸OX-50(Degussa)和2.50重量%的三氟化镱YbF3(Sukgyung,South Korea)。与实施例3类似,由糊料制备试样,固化,并测定挠曲强度和弹性模量(表3)。
表3:聚合的复合糊料K1至K5的挠曲强度(FS,MPa)和挠曲弹性模量(FME,GPa)
K1 | K2 | K3 | K4* | K5* | |
FS,RT | 96.5±9.2 | 125.4±7.7 | 114.8±4.6 | 92.4±6.4 | 112±6.9 |
FS,WS | 117.4±8.7 | 129.7±9.9 | 133.8±4.8 | 101.9±9.0 | 123.3±3.5 |
FME,RT | 5.51±0.33 | 7.13±0.40 | 6.73±0.37 | 4.99±0.39 | 6.20±0.32 |
FME,WS | 6.16±0.46 | 7.68±0.87 | 7.36±0.62 | 5.45±0.64 | 6.59±0.34 |
*比较例
表3中的结果证明,与基于已知的具有相同摩尔浓度的光引发剂的二(苯甲酰基)锗烷DBEGe的参考糊剂K4和K5相比(比较K1与K4,或K2与K5),具有根据本发明的四(苯甲酰基)锗烷TBGe作为光引发剂的复合糊料K1和K3在固化后产生具有改善的强度和较高的弹性模量的复合材料。
Claims (15)
1.根据通式(I)的酰基锗化合物,
[RmAr─(C=O)─]4─Ge (I)
其中变量具有以下含义:
Ar为具有6至18个环碳原子的单环或多环烃基,其可以被R基团取代m次,并且其可以在环中包含一个或多个杂原子,其中
m是0至6的整数,并且不能大于Ar中可取代的氢原子的数目,
R为卤素,NR1 2,OH,OSiR2 3,(C=O)R3,CN,NO2,CF3,COOR4,或C1-至C20-烷基、-烯基、-烷氧基或-链烯氧基,所述C1-至C20-烷基、-烯基、-烷氧基或-链烯氧基可以是直链的、支链的或环状的,其可以被一个或多个O原子中断,并且其可以包含可自由基聚合的基团,或=O,其中
R1-R3在每种情况下彼此独立地为H,或直链或支链C1-至C12-烷基,和
R4为H,直链或支链C1-至C12-烷基或SiR5 3,其中
R5为直链或支链C1-至C10-烷基。
2.根据权利要求1所述的酰基锗化合物,其中所述变量具有以下含义:
Ar为芳族C6-C10基团,其可以被R取代m次,其中
m为1至3的整数,和
R为Cl,NR1 2,OSiR2 3,(C=O)R3,CN,NO2,CF3,COOR4,或C1-至C10-烷基、-烯基、-烷氧基或-链烯氧基,所述C1-至C10-烷基、-烯基、-烷氧基或-链烯氧基可以是直链的、支链的或环状的,其可以被一个或多个O原子中断,并且其可以包含可自由基聚合的基团,优选乙烯基、甲基丙烯酸酯基、(甲基)丙烯酰胺基或N-烷基丙烯酰胺基,其中所述可自由基聚合的基团在非环状基团的情况下优选在末端,其中
R1-R3在每种情况下彼此独立地为H,或直链或支链C1-至C8-烷基,和
R4为H,直链或支链C1-至C8-烷基或SiR10 3,和
R5为直链或支链C1至C5烷基。
3.根据权利要求1或2所述的酰基锗化合物,其中所述变量具有以下含义:
Ar为苯基、吡啶基、萘基、蒽基、蒽醌基,其可以被R取代m次,其中
m为1至3的整数,和
R为NR1 2、CN、NO2、CF3、C1-至C3-烷基或C1-至C3-烷氧基,所述C1-至C3-烷基或C1-至C3-烷氧基优选为直链的,并且其可以具有末端可自由基聚合的基团,优选乙烯基、丙烯酸酯基、甲基丙烯酸酯基,其中
R1为H或优选为直链C1-至C3-烷基。
4.一种组合物,其包含相对于其总质量0.001至5重量%的根据权利要求1至3中任一项所述的式(I)的酰基锗化合物和至少一种可聚合的粘结剂。
5.根据权利要求4所述的组合物,其包含作为可聚合的粘结剂的至少一种可自由基聚合的单体和/或预聚物。
6.根据权利要求5的组合物,其包含作为粘结剂的至少一种单官能或多官能(甲基)丙烯酸酯或其混合物。
7.根据权利要求4至6中的一项所述的组合物,其在每种情况下相对于组合物的总质量包含:
0.001-5重量%的式(I)的酰基锗化合物,
10至99.9重量%的可聚合的粘结剂,
0至85重量%的填料。
8.根据式(I)的酰基锗烷作为用于自由基聚合的引发剂的用途。
9.一种用于制备式I'的(芳基酰基)k(烷基)4-k锗烷(k=1至4)的方法,其中在碱的存在下使式(R'3Si)kGeR"4-k(II)的(三烷基甲硅烷基)锗烷与芳基酰基卤化物(III)反应以形成I',
其中:
R'为具有1至6个C原子的烷基,
R"为具有1至12个C原子的烷基,
X为F、Cl、Br或I,
k为1至4的整数,和
R具有权利要求1、2或3中给出的含义。
10.根据权利要求9所述的方法,其中使用碱金属醇盐、碱金属氨化物或碱金属有机化合物作为碱。
11.根据权利要求9或10所述的方法,其中使用以下化合物之一作为式III的芳基酰基卤化物:
12.根据权利要求9至11中的一项所述的方法,其中三甲基甲硅烷基锗烷(R'3Si)kGeR"4-k(II)首先与碱反应以形成(R'3Si)k-1R"4-kGeM,其中M为金属离子,并且(R'3Si)k- 1R"4-kGeM随后用式(III)的酰基卤化物转化为式(I)的化合物。
13.根据权利要求9至12中的一项所述的方法,其中通过使式ClkGeR"4-k(IV)的锗氯化物与式R'3SiCl(V)的三烷基甲硅烷基氯化物反应制备式(II)的化合物:
14.根据权利要求9至13中的一项所述的方法,其中式(Me3Si)kGeR"4-k(II')的三甲基甲硅烷基锗烷首先与叔丁醇钾(KOtBu)反应,然后与式(III)的酰基卤化物(X=F或Cl)反应。
15.根据权利要求9至14中的一项所述的方法,其中式(R'3Si)4Ge的四(三烷基甲硅烷基)锗烷在碱的存在下与式(III)的酰基卤化物反应,以获得式(I)的化合物。
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PCT/EP2016/072835 WO2017055209A1 (de) | 2015-09-29 | 2016-09-26 | Acylgermanium-photoinitiatoren und verfahren zu deren herstellung |
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EP (1) | EP3150641B1 (zh) |
JP (1) | JP6872535B2 (zh) |
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JP2018534249A (ja) | 2018-11-22 |
EP3150641B1 (de) | 2018-08-29 |
US20180265527A1 (en) | 2018-09-20 |
CN108137727B (zh) | 2020-07-24 |
WO2017055209A1 (de) | 2017-04-06 |
US10787468B2 (en) | 2020-09-29 |
JP6872535B2 (ja) | 2021-05-19 |
ES2695237T3 (es) | 2019-01-02 |
US10533025B2 (en) | 2020-01-14 |
EP3150641A1 (de) | 2017-04-05 |
US20200087329A1 (en) | 2020-03-19 |
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