TW202340331A - 聚矽氧可溶性醯基膦氧化物光起始劑 - Google Patents
聚矽氧可溶性醯基膦氧化物光起始劑 Download PDFInfo
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- TW202340331A TW202340331A TW112111387A TW112111387A TW202340331A TW 202340331 A TW202340331 A TW 202340331A TW 112111387 A TW112111387 A TW 112111387A TW 112111387 A TW112111387 A TW 112111387A TW 202340331 A TW202340331 A TW 202340331A
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- Prior art keywords
- compound
- mixture
- phenyl
- photoinitiator
- alkyl
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- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- JPRPJUMQRZTTED-UHFFFAOYSA-N 1,3-dioxolanyl Chemical group [CH]1OCCO1 JPRPJUMQRZTTED-UHFFFAOYSA-N 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- -1 polysiloxane Polymers 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229940126062 Compound A Drugs 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
- 239000012230 colorless oil Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000013058 crude material Substances 0.000 description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 4
- 239000003039 volatile agent Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 229910010082 LiAlH Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 2
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 2
- UKRQMDIFLKHCRO-UHFFFAOYSA-N 2,4,6-trimethylbenzoyl chloride Chemical compound CC1=CC(C)=C(C(Cl)=O)C(C)=C1 UKRQMDIFLKHCRO-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XSDCTSITJJJDPY-UHFFFAOYSA-N chloro-ethenyl-dimethylsilane Chemical compound C[Si](C)(Cl)C=C XSDCTSITJJJDPY-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000005499 phosphonyl group Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YHWDXZIPQAWTPU-UHFFFAOYSA-N (4-bromophenyl)-ethenyl-dimethylsilane Chemical compound C=C[Si](C)(C)C1=CC=C(Br)C=C1 YHWDXZIPQAWTPU-UHFFFAOYSA-N 0.000 description 1
- QDNBBDYPPSSRTB-UHFFFAOYSA-N 1-bromo-4-but-3-enylbenzene Chemical compound BrC1=CC=C(CCC=C)C=C1 QDNBBDYPPSSRTB-UHFFFAOYSA-N 0.000 description 1
- HIKRJHFHGKZKRI-UHFFFAOYSA-N 2,4,6-trimethylbenzaldehyde Chemical compound CC1=CC(C)=C(C=O)C(C)=C1 HIKRJHFHGKZKRI-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JVEHJSIFWIIFHM-UHFFFAOYSA-N n-[chloro(diethylamino)phosphanyl]-n-ethylethanamine Chemical compound CCN(CC)P(Cl)N(CC)CC JVEHJSIFWIIFHM-UHFFFAOYSA-N 0.000 description 1
- FEHUTHGOLLQBNW-UHFFFAOYSA-N n-[chloro-[di(propan-2-yl)amino]phosphanyl]-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C(C)C)P(Cl)N(C(C)C)C(C)C FEHUTHGOLLQBNW-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical group [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011179 visual inspection Methods 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
-
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/30—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen phosphorus-containing groups
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- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
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Abstract
本發明係式I化合物:
其中R
1-R
4、m、及n在本文中定義。本發明之化合物可用作可溶於烯系不飽和有機聚矽氧烷中之光起始劑。
Description
本發明係關於一種醯基膦氧化物光起始劑。在有機聚矽氧烷固化系統領域中之一個持續挑戰是設計與有機聚矽氧烷相容之光起始劑。相容性差之光起始劑作為固化劑是不合乎需要的,因為其在儲存期間與聚矽氧基質分離,導致固化產物出現嚴重霧度。
US 10,597,413 B2 (Tan)描述經-CH
2-O-Si(OR)
3基團取代之醯基膦氧化物,其典型實例為以下化合物:
儘管Tan揭露此等光起始劑解決了一個長期存在的溶解度問題,但顯然引入了另一個問題,亦即對矽醚鍵(CH
2-OSi)之酸裂解的敏感性,從而使光起始劑與聚矽氧基質不相容。因此,在聚矽氧系統中之光引發技術中,實現溶解度且維持穩定性將是有利的。
本發明藉由提供由式I表示之化合物來解決本領域需求:
I
其中m係0、1、2、或3;且n係0、1或2;
R
1係-苯基-(R
3)
n、-C(O)-苯基-(R
2)
m、-O-C
1-C
20烷基、或-O(CH
2CH
2O)
x-H,其中x係1至20;
各R
2獨立地係C
1-C
6烷基;C
1-C
6烷氧基;-OCH
2-苯基;或R
2與苯環上之相鄰R
2一起是1,3-二氧雜環戊烷基或1,4-二
烷基;
各R
3獨立地係C
1-C
6烷基或C
1-C
6烷氧基;
R
4係
i) -(Si(Me
2)
p(CH
2)
q(Si(R
5 2)O)
r(X)
s-Y;其中
p係0或1,其限制條件為當p係0時,q係3至12,且當p係1時,q係2至12;
r係3至300;
X係CH
2CH
2或CH(CH
3);
s係0或1,其限制條件為當s係0時,Y係SiMe
2H,且當s係1時,Y係Si(OMe)
3;SiMe
3;Si(OEt)
3;SiMe
2OMe;SiMe
2OEt;Si(OSiMe
3)
3;SiMe(OSiMe
3)
2;SiMe
2(OSiMe
3);或
;
其中虛線係Y至X之連接點;及
各R
5獨立地係C
1-C
6烷基或苯基;
或R
4係
ii) -(Si(Me
2)
p(CH
2)
t-Z;其中
p係0或1,其限制條件為當p係0時,t係4,且當p係1時,t係2;及
Z係:
其中虛線係Z至(CH
2)
t之連接點。
本發明係一種由式I表示之化合物:
I
其中m係0、1、2、或3;且n係0、1或2;
R
1係-苯基-(R
3)
n、-C(O)-苯基-(R
2)
m、-O-C
1-C
20烷基、或-O(CH
2CH
2O)
x-H,其中x係1至20;
各R
2獨立地係C
1-C
6烷基;C
1-C
6烷氧基;-OCH
2-苯基;或R
2與苯環上之相鄰R
2一起是1,3-二氧雜環戊烷基或1,4-二
烷基;
各R
3獨立地係C
1-C
6烷基或C
1-C
6烷氧基;
R
4係
i) -(Si(Me
2)
p(CH
2)
q(Si(R
5 2)O)
r(X)
s-Y;其中
p係0或1,其限制條件為當p係0時,q係3至12,且當p係1時,q係2至12;
r係3至300;
X係CH
2CH
2或CH(CH
3);
s係0或1,其限制條件為當s係0時,Y係SiMe
2H,且當s係1時,Y係Si(OMe)
3;SiMe
3;Si(OEt)
3;SiMe
2OMe;SiMe
2OEt;Si(OSiMe
3)
3;SiMe(OSiMe
3)
2;SiMe
2(OSiMe
3);或
;
其中虛線係Y至X之連接點;且
各R
5獨立地係C
1-C
6烷基或苯基;
或R
4係
ii) -(Si(Me
2)
p(CH
2)
t-Z;其中
p係0或1,其限制條件為當p係0時,t係4,且當p係1時,t係2;且
Z係:
其中虛線係Z至(CH
2)
t之連接點。
在一個態樣中,R
1係-C(O)-苯基-(R
2)
m。較佳R
1基團之一實例係由以下結構表示:
在一個態樣中,R
4係–(Si(Me
2)
p(CH
2)
q(Si(R
5 2)O)
r(X)
s-Y;在另一態樣中,各R
5係甲基。在一個態樣中,當p係0時,q係3或4;在另一態樣中,當p係1時,q係2;r係3或6或10至300或至200或至100或至50。
式I化合物可如方案1至3所述製備。當R
1係-C(O)-苯基-(R
2)
m,且R
4位於苯環之對位時,式I化合物可根據方案1製備。在實驗部分中描述各步驟之反應條件。
方案1
其中當p係0時,q'係1至10,且當p係1時,q'係0至10。
替代地,當R
1係-C(O)-苯基-(R
2)
m時,本發明化合物可藉由使最終中間物與化合物A或B反應而製備:
其中X係CH
2CH
2或CH(CH
3)。
當p係1時,方案1中之第一化合物可藉由在第一步驟中使二溴苯,特別是對二溴苯,與乙烯基二甲基矽烷基氯在正丁基鋰的存在下接觸以形成以下中間物來製備:
其中b係0至10。
當p係0時,第一化合物,尤其是當q'係2時,可如Li, Y.-L.;Song, D.-P.;Pan, L.;Ma, Z.;Li, Y.-S.
Polym. Chem. 2019,
10, 6368-6378中所述製備。
當R
1係-O-C
1-C
20烷基或-O(CH
2CH
2O)
x-H時,式I化合物可根據方案2製備。
方案2
其中R係HO-C
1-C
20烷基或HO(CH
2CH
2O)
x-H。
當R
1係-苯基-(R
3)
n時,式I化合物可根據方案3製備。
方案3
包含本發明化合物及烯系不飽和有機聚矽氧烷之均勻不混濁的組成物可藉由劇烈混合該化合物與有機聚矽氧烷來製備。適合的烯系不飽和聚有機矽氧烷之實例包括具有下式之二烯系不飽和化合物:
其中y係10至10,000,且R
5如先前定義。市售聚有機矽氧烷包括XIAMETER™ RBL-9119有機聚矽氧烷及XIAMETER™ RBL-9128有機聚矽氧烷(XIAMETER係陶氏化學公司或其附屬公司之商標)。
以組成物之重量計,光起始劑核心之濃度通常在0.1 wt.%或0.2 wt.%至4 wt.%或至2 wt.%之範圍內。如本文所用,「光起始劑核心(photoinitiator core)」係指本發明化合物之以下片段:
。
實例
中間物實例1 - (4-(丁-3-烯-1-基)苯基)二氯磷烷的製備
在手套箱中,向500 mL圓底燒瓶中裝入1-溴-4-(丁-3-烯-1-基)苯(17.1 g)、無水THF (118 mL)及無水乙醚(37 mL)。將燒瓶密封且轉移至通風櫥。將混合物在N
2下攪拌且冷卻至-78℃,接著將正丁基鋰(
n-BuLi,2.5 M於己烷中,34.0 mL)逐滴添加至混合物中。將混合物攪拌30分鐘,之後添加氯雙(二乙胺基)膦(17.9 mL,85.1 mmol)。將混合物攪拌20分鐘,且使其升溫至環境溫度。將溶液倒入含有乙醚及水之分液漏斗中。分離各相,且用數份二乙基乙醚萃取水相。合併之有機溶離份用鹽水洗滌,經MgSO
4乾燥且真空濃縮。
將粗製油狀物轉移至1000 mL圓底燒瓶中,置於手套箱中。將油狀物溶解於無水乙醚(100 mL)中。將混合物攪拌且用HCl(2.0 M於乙醚中,162 mL,324 mmol,4.00當量)逐滴處理,且沈澱白色固體。2小時後,過濾漿液且濃縮濾液。分離無色油狀物(15.9 g, 84%),其未經進一步純化即用於下一步驟中。
1H NMR (500 MHz, C
6D
6) δ 7.63 – 7.40 (m, 2H), 6.86 – 6.76 (m, 2H), 5.62 (ddt,
J= 18.1, 9.5, 6.6 Hz, 1H), 5.00 – 4.83 (m, 2H), 2.35 (dd,
J= 8.8, 6.7 Hz, 2H), 2.06 (tdt,
J= 7.8, 6.5, 1.5 Hz, 2H)。
13C NMR (126 MHz, C
6D
6) δ 146.99, 137.73 (d,
J= 51.8 Hz), 137.14, 130.12 (d,
J= 32.1 Hz), 128.85 (d,
J= 8.3 Hz), 115.16, 35.02, 34.73。
31P NMR (202 MHz, C
6D
6) δ 161.94。
中間物實例2 - (4-(丁-3-烯-1-基)苯基)磷烷的製備
在手套箱中,向500 mL廣口瓶中裝入乙醚(100 mL)及LiAlH
4(2.0 M於THF中,19.8 mL,39.6 mmol,0.60 eq.)。劇烈攪拌溶液,且經10分鐘將含中間物實例1 (15.4 g, 66.1 mmol, 1.00 eq.)之乙醚(65 mL)逐滴添加至溶液中。將混合物攪拌30分鐘,隨後小心地添加固體芒硝(25.5 g, 79.3 mmol, 1.20 eq.)。將混合物攪拌60分鐘,將液體傾析且經由0.45 µm注射器過濾器過濾且濃縮,得到無色油狀物(9.73 g, 90%),其未經進一步純化即用於下一步驟中。
1H NMR (500 MHz, C
6D
6) δ 7.33 – 7.22 (m, 2H), 6.88 – 6.79 (m, 2H), 5.70 (ddt,
J= 16.9, 10.2, 6.6 Hz, 1H), 5.02 – 4.89 (m, 2H), 3.87 (d,
J= 198.5 Hz, 2H), 2.44 (dd,
J= 8.8, 6.7 Hz, 2H), 2.16 (tdt,
J= 7.9, 6.6, 1.5 Hz, 2H)。
13C NMR (126 MHz, C
6D
6) δ 141.77, 137.65, 134.92 (d,
J= 15.7 Hz), 134.19 (dt,
J= 26.8, 9.8 Hz), 128.56 (d,
J= 6.2 Hz), 114.84, 35.26, 34.96。
31P NMR (202 MHz, C
6D
6) δ -125.28 (tt,
J= 197.6, 7.3 Hz)。
中間物實例3 - ((4-(丁-3-烯-1-基)苯基)膦醯基)雙(均三甲苯基甲酮)的製備
在手套箱中,中間物實例2 (9.73 g, 59.3 mmol, 1.00 eq.)於無水THF (300 mL)中之溶液用三級丁醇鈉(Na
t-OBu, 11.4 g, 118 mmol, 2.00 eq.)處理,隨後將2,4,6-三甲基苯甲醯氯(19.8 mL, 118 mmol, 2.00 eq.)逐滴添加至混合物中。將混合物攪拌隔夜。粗品
31P NMR光譜分析指示膦被部分消耗。將額外量之Na
t-OBu (3.99 g)及苯甲醯氯(6.9 mL)添加至反應混合物中。5小時後,將混合物過濾以移除氯化鈉,且自手套箱中移出濾液且真空濃縮。將粗殘餘物溶解於二氯甲烷(200 mL)中,且將溶液用過氧化氫(6.0 mL 30 wt.%)處理。將混合物在環境溫度下攪拌隔夜,接著用亞硫酸氫鈉水溶液(100 mL)處理且攪拌直至有機相對過氧化物帶測試呈陰性。分離各相且用矽藻土濃縮用於矽膠層析法(0至50% EtOAc/己烷)。分離含有產物及一些其他雜質之黃色油狀物(13 g)。進行第二次管柱純化,由此分離呈黃色油狀之中間物實例3 (11.3 g)。
1H NMR (500 MHz, CDCl
3) δ 7.78 (dd,
J= 10.1, 8.1 Hz, 2H), 7.23 (dd,
J= 8.3, 3.0 Hz, 2H), 6.78 (s, 4H), 5.77 (ddt,
J= 16.0, 10.7, 6.6 Hz, 1H), 5.20 – 4.61 (m, 2H), 2.74 (t,
J= 7.6 Hz, 2H), 2.39 – 2.32 (m, 2H), 2.25 (s, 6H), 2.14 (s, 12H)。
13C NMR (126 MHz, CDCl
3) δ 216.37 (d,
J= 59.9 Hz), 147.41 (d,
J= 2.9 Hz), 140.92, 137.12, 135.73 (d,
J= 41.8 Hz), 135.47, 132.19 (d,
J= 8.3 Hz), 128.93, 128.77 (d,
J= 11.6 Hz), 122.82 (d,
J= 78.0 Hz), 115.50, 35.32, 34.93, 21.18, 19.60。
中間物實例4 - (4-溴苯基)二甲基(乙烯基)矽烷的製備
在N
2氛圍下,向配備有加料漏斗之1000 mL 3頸圓底燒瓶中裝入無水THF (425 mL)及1,4-二溴苯(20.0 g, 84.8 mmol, 1.00 eq.)。將混合物在冷卻至-78℃下攪拌。將
n-BuLi溶液(2.5 M於己烷中,35.6 mL,89.0 mmol,1.05 eq.)經25分鐘逐滴添加至二溴苯溶液中。在
n-BuLi溶液添加完成後,再繼續攪拌50分鐘。
在攪拌下將氯二甲基乙烯基矽烷(12.9 mL,93.3 mmol,1.10當量)逐滴添加至反應混合物中。將混合物經1小時逐漸升溫至室溫,之後將混合物用氯化銨水溶液淬滅。用若干份乙酸乙酯萃取產物。合併之有機溶離份經硫酸鈉乾燥且濃縮。將粗製油狀物真空純化(450 mTorr, 52-60℃),得到呈無色油狀之中間物實例4 (18.75 g)。
1H NMR (400 MHz, CDCl
3) δ 7.53 – 7.44 (m, 2H), 7.40 – 7.33 (m, 2H), 6.25 (dd,
J= 20.2, 14.6 Hz, 1H), 6.06 (dd,
J= 14.6, 3.8 Hz, 1H), 5.74 (dd,
J= 20.2, 3.8 Hz, 1H), 0.33 (s, 6H)。
13C NMR (101 MHz, CDCl
3) δ 137.33, 137.22, 135.42, 133.26, 130.90, 123.83, -3.03。
中間物實例5 - ((4-(二甲基(乙烯基)矽烷基)苯基)磷醯基)雙(均三甲苯基甲酮)的製備
在手套箱中,向250 mL圓底燒瓶中裝入中間物實例4 (4.31 g, 17.9 mmol, 1.00 eq.)、無水THF (26 mL)及無水乙醚(8 mL)。將燒瓶密封且轉移至通風櫥。將混合物在氮氣下攪拌且冷卻至-78℃。隨後逐滴添加
n-BuLi(2.5 M於己烷中,7.51 mL,18.8 mmol,1.05 eq.)。將混合物攪拌30分鐘,之後將氯雙(二異丙基胺基)膦(5.01 g, 18.8 mmol, 1.05 eq.)以固體形式添加。攪拌混合物且經2小時使其升溫至環境溫度。將溶液倒入含有乙醚及水之分液漏斗中。分離各相,且用數份二乙基乙醚萃取水相。合併之有機溶離份用鹽水洗滌,用MgSO
4乾燥且藉由旋轉蒸發濃縮。
將粗製油狀物轉移至250 mL圓底燒瓶中,置於手套箱中。將油狀物溶解於無水乙醚(20 mL)中。將燒瓶密封且轉移至通風櫥。在N
2下攪拌混合物且冷卻至0℃。接著逐滴添加HCl(2.0 M於乙醚中,35.7 mL,71.5 mmol,4.00 eq.)且沈澱白色固體。繼續攪拌2小時後,過濾漿液且濃縮濾液。將粗殘餘物與乙醚及己烷混合且再次過濾。濃縮濾液,得到無色油狀物(4.59 g)。粗物質未經進一步純化即用於下一步驟中。
在手套箱中,在劇烈攪拌下向150 mL廣口瓶中裝入乙醚(44 mL)及LiAlH
4(2.0 M於THF中,5.23 mL,10.5 mmol,0.60 eq.)。將來自前一步驟之粗物質(4.59 g,17.4 mmol,1.00當量)經5分鐘逐滴添加至LiAlH
4溶液中。將混合物攪拌30分鐘,之後小心地添加固體芒硝(6.74 g, 20.9 mmol, 1.20 eq.)。繼續攪拌14小時,之後過濾溶液且濃縮濾液,得到2.71 g呈無色油狀之粗產物。粗物質未經進一步純化即用於下一步驟中。
將來自前一步驟之粗物質(2.71 g)於無水THF (70 mL)中之溶液用無水Na
t-OBu (2.68 g, 27.9 mmol, 2.00 eq.)處理,隨後逐滴添加2,4,6-三甲基苯甲醯氯(4.65 mL, 27.9 mmol, 2.00 eq.)。將混合物攪拌3小時且接著過濾混合物以移除氯化鈉。
自手套箱中移出濾液且真空濃縮。將粗殘餘物溶解於二氯甲烷(50 mL)中,且將溶液用過氧化氫(1.4 mL, 30 wt.%)處理。將混合物在環境溫度下攪拌隔夜,接著用亞硫酸氫鈉水溶液(30 mL)處理。分離各相,且在矽膠存在下濃縮有機相,以促進矽膠液相層析(0至50% EtOAc/己烷)。分離呈黃色油狀之中間物實例5 (1.98 g),其在靜置後固化。
1H NMR (500 MHz, CDCl
3) δ 7.90 – 7.79 (m, 2H), 7.56 (dd,
J= 8.0, 3.3 Hz, 2H), 6.78 (s, 4H), 6.24 (dd,
J= 20.2, 14.7 Hz, 1H), 6.07 (dd,
J= 14.6, 3.6 Hz, 1H), 5.71 (dd,
J= 20.3, 3.7 Hz, 1H), 2.25 (s, 6H), 2.14 (s, 12H), 0.35 (s, 6H)。
13C NMR (126 MHz, CDCl
3) δ 215.87 (d,
J= 58.9 Hz), 144.76 (d,
J= 2.5 Hz), 140.99, 136.91, 135.84, 135.52, 133.67 (d,
J= 10.8 Hz), 133.55, 131.01 (d,
J= 7.6 Hz), 128.95, 126.27 (d,
J= 75.6 Hz), 21.18, 19.64, -3.17。
31P NMR (202 MHz, CDCl
3) δ 7.19 (t,
J= 10.6 Hz)。
在以下實例中,M'D
rM'聚矽氧烷係指H-Si(Me
2)O[Si(Me
2)O]
r-Si(Me
2)-H。
實例1 - M'D
38M'聚矽氧烷取代之光起始劑的製備
在手套箱中將中間物實例3 (0.07 g)與無水己烷(3.0 mL)及M'D
38M'聚矽氧烷(1.72 g)混合。將混合物在50℃下攪拌直至固體溶解。添加卡斯泰德催化劑(Karstedt’s Catalyst,2 wt% Pt於二甲苯中,0.03 mL)且將混合物攪拌隔夜。藉由
1H NMR光譜法監測烯烴的消耗,且再添加數份卡斯泰德催化劑,直至殘留<5%之烯烴。添加乙烯基三甲氧基矽烷以與剩餘Si-H基團反應。
藉由真空泵移除揮發物,留下琥珀色油狀物。產物之混合物經計算包含4.0 wt%的光起始劑。
實例2 - M'D
7M'聚矽氧烷取代之光起始劑的製備
遵循實例1中所述之程序,不同之處在於使用M'D
7M'聚矽氧烷(0.55 g)。產物之混合物經計算包含15.3 wt%的光起始劑。
實例3 - M'D
14M'聚矽氧烷取代之光起始劑的製備
遵循實例1中所述之程序,不同之處在於使用M'D
14M'聚矽氧烷(0.99 g)。產物之混合物經計算包含9.1 wt%的光起始劑。
實例1至3中鑑別出以下產物及副產物:
實例4 - M'D
38M'聚矽氧烷取代之光起始劑的製備
在手套箱中將中間物實例5 (0.10 g)與無水甲苯(1.5 mL)及M'D
38M'聚矽氧烷(0.60 g)混合。將混合物在80℃下攪拌直至固體溶解。將卡斯泰德催化劑(2 wt% Pt於二甲苯中,0.012 mL)添加至混合物中且繼續攪拌1小時。藉由
1H NMR光譜法監測烯烴的消耗,且再添加數份卡斯泰德催化劑,直至殘留<5%之烯烴。添加乙烯基三甲氧基矽烷以與剩餘Si-H基團反應。真空移除揮發物,留下琥珀色油狀物。產物之混合物經計算包含14.5 wt%的光起始劑。
實例5 - M'D
7M'聚矽氧烷取代之光起始劑的製備
遵循實例4中所述之程序,不同之處在於使用M'D
7M'聚矽氧烷(0.14 g)。產物之混合物經計算包含43.5 wt%的光起始劑。
實例6 - M'D
14M'聚矽氧烷取代之光起始劑的製備
遵循實例4中所述之程序,不同之處在於使用M'D
14M'聚矽氧烷(0.24 g)。產物之混合物經計算包含30.0 wt%的光起始劑。實例4至6中鑑別出以下產物及副產物:
實例7 -用化合物A取代之光起始劑的製備
在手套箱中將中間物實例5 (0.11 g)與無水甲苯(1.5 mL)在80℃下攪拌混合,直至固體溶解。將化合物A (0.19 mL)與卡斯泰德催化劑(2 wt.% Pt於二甲苯中,0.06 mL)一起添加至混合物中,且攪拌混合物1小時。藉由
1H NMR光譜法監測中間物實例5的消耗;添加額外催化劑直至殘留< 5 wt.%的起始材料。接著,添加過量的乙烯基三甲氧基矽烷且繼續攪拌,直至Si-H官能基完全消耗。真空移除揮發物,留下琥珀色油狀物。產物經計算包含18 wt%的光起始劑。鑑別出以下產物。
實例8 -用化合物B取代之光起始劑的製備
遵循實例7中所述之程序,不同之處在於使用化合物B (0.10 mL)。產物經計算包含20 wt%的光起始劑。鑑別出以下產物。
實例9 -用化合物A取代之光起始劑的製備
在手套箱中將中間物實例3 (0.14 g)與無水己烷(3.0 mL)及無水甲苯(1.5 mL)在50℃下攪拌混合,直至固體溶解。將化合物A (1.03 mL)與卡斯泰德催化劑(2 wt.% Pt於二甲苯中,0.06 mL)一起添加至混合物中,且攪拌混合物1小時。藉由
1H NMR光譜法監測中間物實例3的消耗;添加額外催化劑直至殘留< 5 wt.%的起始材料。接著,添加過量的乙烯基三甲氧基矽烷且繼續攪拌,直至Si-H官能基完全消耗。真空移除揮發物,留下琥珀色油狀物。產物經計算包含18 wt%的光起始劑。鑑別出以下產物。
光起始劑組成物製備
將實例1-9中製備之化合物之各者與足夠的XIAMETER™ RBL-9119有機聚矽氧烷混合以形成相對於光起始劑核心為0.5 wt.%的混合物。目視檢查組成物的均質性。未觀察到樣品含有固體粒子或相分離之油液滴;因此,全部發現是均質的。
在目視檢查均質性後,將各小瓶置於機械成像站中。在環境溫度下拍攝照片以量測相位清晰度。藉由減去影像背景、裁剪影像、使用Otsu閾值對像素強度進行閾值化、及計算剩餘像素之平均強度來判定相位清晰度;像素強度(相位清晰度)報告為0(透明)至255(不透明)之間的值。像素強度<120被視為合格的清晰度。
表1顯示光起始劑組成物之清晰度資料。
實例編號 | 光起始劑之Wt% | 最大相位清晰度(0-255) |
實例1 | 0.5% | 47 |
實例2 | 0.5% | 73 |
實例3 | 0.5% | 54 |
實例4 | 0.5% | 45 |
實例5 | 0.5% | 55 |
實例6 | 0.5% | 39 |
實例7 | 0.5% | 48 |
實例8 | 0.5% | 24 |
實例9 | 0.5% | 50 |
發現由光起始劑化合物及可光固化有機聚矽氧烷製備的組成物滿足均質性、清晰度及抗分解穩定性的準則。
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Claims (10)
- 一種化合物,其由式I表示: I 其中m係0、1、2、或3;且n係0、1或2; R 1係-苯基-(R 3) n、-C(O)-苯基-(R 2) m、-O-C 1-C 20烷基、或-O(CH 2CH 2O) x-H,其中x係1至20; 各R 2獨立地係C 1-C 6烷基;C 1-C 6烷氧基;-OCH 2-苯基;或R 2與苯環上之相鄰R 2一起是1,3-二氧雜環戊烷基或1,4-二 烷基; 各R 3獨立地係C 1-C 6烷基或C 1-C 6烷氧基; R 4係 i) -(Si(Me 2) p(CH 2) q(Si(R 5 2)O) r(X) s-Y;其中 p係0或1,其限制條件為當p係0時,q係3至12,且當p係1時,q係2至12; r係3至300; X係CH 2CH 2或CH(CH 3); s係0或1,其限制條件為當s係0時,Y係SiMe 2H,且當s係1時,Y係Si(OMe) 3;SiMe 3;Si(OEt) 3;SiMe 2OMe;SiMe 2OEt;Si(OSiMe 3) 3;SiMe(OSiMe 3) 2;SiMe 2(OSiMe 3);或 ; 其中虛線係Y至X之連接點;且 各R 5獨立地係C 1-C 6烷基或苯基; 或R 4係 ii) -(Si(Me 2) p(CH 2) t-Z;其中 p係0或1,其限制條件為當p係0時,t係4,且當p係1時,t係2;且 Z係: 其中虛線係Z至(CH 2) t之連接點。
- 如請求項1之化合物,其中各R 5係甲基。
- 如請求項2之化合物,其中R 1係-C(O)-苯基-(R 2) m;R 4係 -(Si(Me 2) p(CH 2) q(Si(Me 2)O) r(X) s-Y;其中r係6至200;且s係1。
- 如請求項3之化合物,其中n係0,p係1,q係2,r係6至50,且Y係Si(OMe) 3。
- 如請求項4之化合物,其中m係3,各R 2係甲基,且R 1由以下片段表示: 。
- 如請求項1之化合物,其中R 1係-C(O)-苯基-(R 2) m;且Z係 。
- 如請求項5之化合物,其中n係0,m係3,各R 2係甲基,且各R 5係甲基。
- 一種組成物,其包含如請求項1之式I化合物與烯系不飽和有機聚矽氧烷之溶液。
- 如請求項8之組成物,其中該烯系不飽和有機聚矽氧烷由以下結構表示: 其中y係10至10,000,且各R 5獨立地係C 1-C 6烷基或苯基。
- 如請求項9之組成物,其中各R 5係甲基。
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