CN100378111C - Compound, synthetic method and application of organosilicon containing carbon-oxygen-ether linkage - Google Patents
Compound, synthetic method and application of organosilicon containing carbon-oxygen-ether linkage Download PDFInfo
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- CN100378111C CN100378111C CNB200510027452XA CN200510027452A CN100378111C CN 100378111 C CN100378111 C CN 100378111C CN B200510027452X A CNB200510027452X A CN B200510027452XA CN 200510027452 A CN200510027452 A CN 200510027452A CN 100378111 C CN100378111 C CN 100378111C
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 150000001875 compounds Chemical class 0.000 title claims abstract description 6
- 238000010189 synthetic method Methods 0.000 title abstract description 6
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 25
- 239000013335 mesoporous material Substances 0.000 claims abstract description 22
- 239000002210 silicon-based material Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 150000003377 silicon compounds Chemical class 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000003376 silicon Chemical class 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000006459 hydrosilylation reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 244000223014 Syzygium aromaticum Species 0.000 description 1
- 125000005466 alkylenyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229940006052 e.e.s. Drugs 0.000 description 1
- NSYZCCDSJNWWJL-YXOIYICCSA-N erythromycin ethylsuccinate Chemical compound O1[C@H](C)C[C@H](N(C)C)[C@@H](OC(=O)CCC(=O)OCC)[C@@H]1O[C@H]1[C@@](O)(C)C[C@@H](C)C(=O)[C@H](C)[C@@H](O)[C@](C)(O)[C@@H](CC)OC(=O)[C@H](C)[C@@H](O[C@@H]2O[C@@H](C)[C@H](O)[C@](C)(OC)C2)[C@@H]1C NSYZCCDSJNWWJL-YXOIYICCSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to an organosilicon compound containing a carbon-oxygen-ether linkage, a synthetic method thereof and an application of the organosilicon compound containing the carbon-oxygen-ether linkage in the surface modification of mesoporous silicon materials. The structural formula of the compound is disclosed in the figure I; the compound can be used for synthesizing the following organosilicon materials containing the carbon-oxygen-ether linkage, (which is disclosed in the figure II.), wherein R is hydrocarbyl of C1 to C6, and R1, R2 and R3 are alkyl groups of C1 to C6; mesoporous materials whose mesoporous pore canals are 2.0 to 50 nm have a bidimensional cubic syngony, a bidimensional hexagonal syngony, a tridimensional cubic syngony or a tridimensional hexagonal syngony, which is disclosed in the figure III. The method has the advantages of simplicity, high efficiency, easy obtainment of material, simple operation, convenient post-treatment, high reaction yield, simple reaction device and easy industrial production.
Description
Technical Field
The invention relates to a novel organic silicon compound containing carbon-oxygen ether bond, a synthetic method and application thereof. The synthesis method of the compound is to generate an organic silicon compound through olefin hydrosilation reaction. Organosilicon containing different numbers and types of carbon-oxygen ether bonds can be synthesized through different alkene substrates; or grafted to the surface of the silicon material, thereby changing the properties of the silicon material. The modified silicon material can be applied to a supported catalyst for synthesizing a noble metal catalyst. The modified silicon material is also potentially applied to metal adsorption, hydrophilic and hydrophobic regulation of the surface of the material, and phase transfer catalysis, and provides wide prospects for industrial production thereof.
Background
MCM-4 mesoporous silica materials previously reported by scientists of Mobil corporation in 1992 were popular among scientists of (a) C.T.Kresge, M.E.Leonowicz, W.J.Roth, J.C.Vartuli, J.S.Beck, Nature, 1992, 359, 710 (b) J.S.Beck, J.C.Vartuli, W.J.Roth, M.E.Leonowicz, C.T.Kresge, K.D.Schmitt, C.T-W.Chu, D.H.Olson, E.W.Sheppard, S.B.McCullen, J.B.Higgins, J.L.Schlenker, J.Am.Chem.1992.1992, 114, 10834 mesoporous silica materials. The silicon material has many advantages, such as very high specific surface area (500-2The/g), adjustable uniform regular mesoporous channels, high chemical stability and hydrothermal stability. [ (a) d.zhao, j.feng, q.huo, n.melosh, g.h.fredrickson, b.f.chmelka, g.d.stucky, Science1998, 279, 548.(b) y.liu, w.zhang, t.j.pinnavaia, j.am.chem.soc.2000, 122, 8791.(c) y.liu, w.zhang, t.j.pinnaavaia, angew.chem.int.ed.2001, 40, 1255.(d) y.han, f.s.xiao, s.wu, j.phys.chem.b.2001, 105, 7963.(e) y.han, d.li, l.zhao, f.zhao, s.zhao, s.yhu, j.phys.chem.2001, 7963, e.han, d.li, l.zhao, s.zhao, s.yhao, s.ihtmao, si.e.e.e.2003, si-via-oh, si-h.e.e, si-h, si-g. 33, h, si-si. These organosilicon modified mesoporous materials can be used in catalysis, as [ (a) d.e.de Vos, m.das, b.f.sels, p.a.jacobs, chem.rev.2002, 102, 3615.(b) r.raja, j.m.thomas, m.d.jones, b.f.g Johnson, d.e.w Vaughan, j.am.chem.soc.2003, 125, 14982.(c) s.huh, h-t.n, j.w.wich en, m.pruski, v.s. -y.lin, j.am.soc.2004, 126, 1010.(d) c.h.christen, john.133schenen, i.midt, c.h.christen, am.soc.2004, 126, 1010.(d) c.h.christen, john.133yan, i.midt, c.h.christen, am.m.m.2002, molve.h.m.m.m.h.m.2002, levam.g.p.r.r.70, levam.r.r.r.r.r.t.r.r.r.t.m.r.m.g; 4,4297. (f) m.jia,; seifert,; thiel, chem. mater.2003, 15, 2174.(g) m.jia, a.seifert, m.berger, h.giegengack, s.schulze, w.r.thiel, chem. mater.2004,16，877.(h)M.V.Vasylyev，R.Neumann，J.Am.Chem.Soc.2004，126，884.(i)K.Mukhopadhyay，A.B.Mandale，R.V.Chaudhari，Chem.Mater.2003，15，1766.(j)V.S.-Y.Lin，D.R.Radu，M.-K.Han，W.Deng，S.Kuroki，B.H.Shanks，M.Pruski，J.Am.Chem.Soc.2002，124，9040.(k)A.Vinu，T.Krithiga，V.Murugesan，M.Hartmann，Adv.Mater.2004，16，1817.(1)R.Becker，H.Parala，F.Hipler，O.P.Tkachenko，K.V.Klementiev，W.Grünert，H.Wilmer，O.Hinrichsen，M.Muhler，A.Birkner，C.Wöll，S.Sch*fer，R.A.Fischer，Angew.Chem.Inter.Ed.2004，43，2839.(m)M.Chatterjee，F.Y.Zhao，Y.Ikushima，Adv.Syn.&Catal.2004，346，459.(n)D.S.Shephard，T.Maschmeyer，B.F.G.Johnson，J.M.Thomas，G.Sankar，D.Ozkaya，W.Zhou，R.D.Oldroyd，R.G.Bell，Angew.Chem.Inter.Ed.1997，36，2242.(o)P.Sreekanth，S.-W.Kim，T.Hyeon，B.M.Kim，Adv.Syn.& Catal.2003，345，936.(p)J.H.Clark，A.J.Butterworth，S.J.Tavener，A.J.Teasdale，S.J.Barlow，T.W.Bastock，K.Martin，J.Chem.T ech.Biotechnol.1997，68，367.(q)J.D.Bass，S.L.Anderson，A.Katz，Angew.Chem.Int.Ed.2003，42，5219.(r)P.Ferreira，I.S.Gonc，F.E.Kühn，A.D.Lopes，M.A.Martins，Ma.Pillinger，A.Pina，J.Rocha，C.C.
santos, t.m.santos, a.a.valente.eur.j.inorg.chem.2000, 2263(s) k.mukhopadhyay, a.b.mandale, r.v.chaudhart, chem.mater.2003, 15, 1766. adsorption of metal ions,' (a) x.feng, g.e.fryxell, l.q.wang, a.y.kim, j.liu, k.m.mnner, Science, 1997, 276, 923.(b) l.mercier, t.j.pinnanvaia, adv.mater.1997, 9, 500.(C) j.liu, x.feng, g.e.frxe, l.q.wang.wang.m, a.y.wang.m, goarv.mater.161, gore.161, gore.15, chalce.r.t.j.j.j.n.p.neu, Science, r.r.r.t.m.wang.m.m.m.santos, gore.t.t.r.r.t.t.r.r.r.r.t.r.r.t.r.r.t.r.t.r.r.r.t.r.t.r.r.r.161, gore.e.e.e.15. e.r.Chem.Mater.2003，15，4181.(f)V.Antochshuk，Ok.Olkhovyk，Mi.Jaroniec，I.-S.ParkR.Ryoo, Langmuir, 2003, 19, 3031, for controlled release of drug or guest molecules, [ N.K.Mal, M.Fujiwara, Y.tanaka, Nature 2003, 421, 350 ] (b) N.K.Mal, M.Fujiwara, Y.tanaka, T.Taguchi, M.Matsukata, chem.Mater.2003, 15, 3385.(c) C.Y.Lai, B.G.Trewyn, D.M.Jettija, K.Jettiija, S.xu, S.Jettiijja, V.S.S.Lin, J.Am.C.Soc.125, 2003, 4451.(d) D.R.Radu, C.Lattinji, Largi.S.S.S.Lin, J.2004, J.S.S.S.Lin, J.S.S.S.S.S.Lin, J.S.S.S.S.S.S.S.S.D.D.D.D.D.D.D.R.D.D.R.D.R.D.E.E.E.D.E.E.E.S.S.S.S.S.S.S.S.S.S.S.S.S.S.J.S.S.S.S.S.J.S.S.S.S.S.S.S.S.S.S.S.S.S.J.S.S.S.S.S.S.S.S.S.J.S.S.S.S. [ (a) E.W.Hagaman, H.Zhu, S.H.Overbury, S.Dai, Langmir, 2004, 20, 9577 ] although documents [ (a) M.E.Havill, I.Joffe, H.W.post, J.org.Chem.1948, 2, 282.(b) A.Behr, F.Naendrup, D.Obst, adv.Sunth.Catal, 2002, 344, 1142 ] have reported the formation of organosilicon compounds by olefin hydrosilation using chloroplatinic acid as a catalyst, this novel carbon-bond-containing organosilicon has not been reported. Because the organosilicon has a structure similar to crown ether, the mesoporous material modified by the organosilicon has strong complexing ability to metal and hydrophilicity and lipophilicity. Here, the palladium catalyst supported by the mesoporous material modified by the organic silicon is reported for the first time. The catalyst shows extremely high catalytic activity in the reaction, is stable in air, is environment-friendly, and can be recycled and uses water as a solvent.
Disclosure of Invention
The invention aims to provide a novel compound, namely an organic silicon compound containing a carbon-oxygen-ether bond.
The invention also aims to provide a synthetic method of the organic silicon compound containing the carbon-oxygen ether bond.
The invention also provides the use of the organosilicon compounds described above, i.e. for the surface modification of silicon materials.
The organosilicon compound containing carbon-oxygen-ether bond is added with the following structural formula:
wherein n is 1 to 20, R1、R2、R3Is C1～6R is C1～6Of hydrocarbon radicals, e.g. C1～6Alkyl or phenyl of
The synthetic method of the organic silicon compound containing the carbon-oxygen ether bond can be synthesized by the following method, and the typical reaction formula is as follows:
the method comprises the following steps: neutralizing in an organic solvent at a temperature of-78-70 DEG C
And reacting with a catalyst for 0.5-48 hours to obtain the carbon-oxygen ether bond organic silicon compound. Wherein,
the molar ratio of the catalyst to the catalyst is 1: 2-100: 0.001-10.0. The recommended molar ratio is 1: 2.2-30: 0.20-0.001.
The catalysts used may be: chloroplatinic acid (H)2PtCl6) Or rhodium acetylacetonate (Rh (acac)3) And the like. The reaction solvent is a conventional organic solvent such as N-hexane, cyclohexane, toluene, tetrahydrofuran, dichloromethane, dimethyl sulfoxide, N-dimethylformamide, 1, 4-dioxane, acetone, diethyl ether or acetonitrile.
The organic silicon compound containing the carbon-oxygen-ether bond can be used for synthesizing modified silicon materials, and the organic silicon material containing the carbon-oxygen-ether bond has the following structural formula;
wherein n is 1-20, R is C1～6Of hydrocarbon radicals, e.g. C1～6The alkyl group or the phenyl group of (a),
the mesoporous material can be a mesoporous pore channel of 2.0-50 nm, and the crystal system of the mesoporous material can be a two-dimensional cube, a two-dimensional hexagon, a three-dimensional cube or a three-dimensional hexagon. Preferred is a mesoporous silica material satisfying the above conditions.
The typical reaction formula of the organic silicon compound containing the carbon-oxygen ether bond for synthesizing the organic silicon material containing the carbon-oxygen ether bond is as follows:
wherein n can be between 1 and 20, R is C1～6The hydrocarbon group of (2) may be an alkyl group such as a methyl group, an ethyl group, a propyl group, or a hexyl group, or a phenyl group, and the organosilicon compound containing a carbon-oxygen-ether bond is as described above. The mesoporous material can be a silicon material with a mesoporous pore channel of 2.0-50 nm, and the crystal system of the mesoporous material can be a two-dimensional cube, a two-dimensional hexagon, a three-dimensional cube or a three-dimensional hexagon. Preferred is a mesoporous silica material satisfying the above conditions.
The synthesis method of the organosilicon material containing carbon-oxygen-ether bond comprises the following steps: the mesoporous material and the organic silicon compound are reacted for 2-48 hours at the temperature of 20-200 ℃ in an organic solvent to obtain the silicon material modified by the organic silicon compound with carbon-oxygen ether bond. The molar ratio of silicon elements of the mesoporous material and the carbon-oxygen ether bond organic silicon compound is 10-10000: 1. The recommended molar ratio is 10-300: 1.
The reaction solvent used is a conventional organic solvent such as N-hexane, cyclohexane, toluene, tetrahydrofuran, dichloromethane, dimethyl sulfoxide, N-dimethylformamide, 1, 4-dioxane, acetone, diethyl ether, acetonitrile, etc.
The organosilicon material containing the carbon-oxygen-ether bond is expected to be capable of synthesizing a supported metal catalyst.
The invention generates organosilicon compounds by the hydrosilylation reaction of olefins. Silicones containing different numbers and types of carbon-oxygen bonds can be synthesized by different olefinic substrates. The method is simple and is a convenient and effective method. (1) The raw materials are convenient and easy to obtain, the operation is simple, and the post-treatment is convenient. (2) The reaction yield is high. (3) The reaction equipment is simple and easy for industrial production.
The organic silicon compound can be grafted on the surface of the silicon material, so that the property of the silicon material is changed. The modified silicon material is hopeful to be used for supporting the metal palladium catalyst.
Detailed Description
The following examples are helpful in understanding the present invention, but are not intended to limit the invention:
example 1
(1) Preparation of organosilicon Compound 1:
the operation is as follows: chloroplatinic acid (0.5 mol%) was dried under vacuum at 180 ℃ for 2 hours, and ethyl-allyl-tetraethyleneglycol ether (0.1mol) and triethoxysilylhydride (0.3mol) were added and stirred at room temperature for 1 day. Steaming to remove excessive triethoxysilicanhydride, vacuum pumping, and steaming at 178 deg.CA colored liquid to give 27.5g of product.1H NMR(300MHz，CDCl3)：δ3.79(q，J＝7.2Hz，6H)，3.64-3.43(m，18H)，3.39(t，J＝6.9Hz，2H)，1.71-1.61(m，2H)，1.19-1.14(m，12H)，0.59(t，J＝8.4Hz，2H)。13C NMR(75MHz，CDCl3)：δ73.4，70.9，70.6，70.1，63.0，51.3，17.9，15.5，14.7，8.0；MS m/z(％)337(100)，427(M+35.45); calculated value of elemental analysis, C19H42O8Si: c, 53.49; h, 9.92; measured value: c, 53.65; h, 9.70.
Example 2
(2) Preparation of organosilicon Compound 2:
the operation is as follows: the operation is as follows: chloroplatinic acid (0.5 mol%) was dried under vacuum at 180 ℃ for 2 hours, and methyl-allyl-tetraethyleneglycol ether (0.1mol) and triethoxysilylhydride (0.3mol) were added and stirred at room temperature for 1 day. Excess triethoxysilicane hydrogen was distilled off, the vacuum pump was used for pressure reduction, and colorless liquid was distilled off at 178 ℃ to obtain 27.3g of product.1H NMR(300MHz，CDCl3)：δ3.78(q，J＝7.2Hz，6H)，3.64-3.43(m，18H)，3.39(t，J＝6.9Hz，2H)，3.25(t，J＝8.4Hz，3H)，1.71-1.61(m，2H)，1.23(t，J＝8.2Hz，9H)，0.59(t，J＝8.4Hz，2H)。13C NMR(75MHz，CDCl3)：δ70.9，70.6，70.1，63.0，53.9，51.3，17.9，15.5，8.0；MS m/z(％)323(100)，413(M+22.23); calculated value of elemental analysis, C18H40O8Si: c, 52.40; h, 9.77; measured value: c, 52.62; h, 9.65.
Example 3
(3) Preparation of organosilicon Compound 3:
the operation is as follows: chloroplatinic acid (0.5 mol%) was dried under vacuum at 180 ℃ for 2 hours, and phenyl-allyl-tetraethyleneglycol ether (0.1mol) and triethoxysilylhydride (0.3mol) were added and stirred at room temperature for 1 day. Excess triethoxysilicane hydrogen was distilled off, the vacuum pump was used for pressure reduction, and colorless liquid was distilled off at 178 ℃ to obtain 32.8g of product.1H NMR(300MHz，CDCl3)：δ6.90-6.76(m，5H)，4.20(t，J＝6.9Hz，2H)，3.79(q，J＝7.2Hz，6H)，3.64-3.43(m，16H)，1.70-1.64(m，2H)，1.19-1.14((t，J＝7.2Hz，9H)，0.69(t，J＝8.4Hz，2H)。13C NMR(75MHz，CDCl3)：δ158.8，129.1，120.1，114.2，73.4，70.9，70.6，70.5，51.3，17.9，15.5，14.7，8.0；MS m/z(％)385(100)，475(M+22.54); calculated value of elemental analysis, C23H42O8Si: c, 58.20; h, 8.92; measured value: c, 58.45; h, 8.70.
Example 4
(4) Preparation of organosilicon Compound 4:
the operation is as follows: chloroplatinic acid (0.5 mol%) was dried under vacuum at 180 ℃ for 2 hours, and ethyl-allyl-triethylene glycol ether (0.1mol) and trimethoxysilylhydride (0.3mol) were added and stirred at room temperature for 1 day. Excess trimethoxysilylhydride was distilled off, the pressure was reduced by means of a vacuum pump, and a colorless liquid was distilled off at 169 ℃ to give 28.6g of a product.1H NMR(300MHz，CDCl3)：δ3.74(q，J＝7.2Hz，6H)，3.64-3.43(m，14H)，3.38(t，J＝6.9Hz，2H)，1.70-1.56(m，2H)，1.17-1.10(m，12H)，0.58(t，J＝8.4Hz，2H)。13C NMR(75MHz，CDCl3)：δ73.4，70.9，70.6，70.1，63.0，51.3，17.9，15.5，14.7，8.0；MS m/z(％)293(100)，383(M+53.21); elemental analysisCalculated value, C19H42O8Si: c, 53.37; h, 10.01; measured value: c, 53.55; h, 9.73.
Example 5
(5) Preparation of organosilicon Compound 5:
the operation is as follows: chloroplatinic acid (0.5 mol%) was dried under vacuum at 180 ℃ for 2 hours, and phenyl-allyl-triethylene glycol ether (0.1mol) and triethoxysilylhydride (0.3mol) were added and stirred at room temperature for 1 day. Excess triethoxysilicane hydrogen was distilled off, the vacuum pump was used for pressure reduction, and colorless liquid was distilled off at 178 ℃ to obtain 32.8g of product.1H NMR(300MHz，CDCl3)：δ6.90-6.76(m，5H)，4.20(t，J＝6.9Hz，2H)，3.79(q，J＝7.2Hz，6H)，3.64-3.43(m，12H)，1.70-1.64(m，2H)，1.19-1.14((t，J＝7.2Hz，9H)，0.69(t，J＝8.4Hz，2H)。13C NMR(75MHz，CDCl3)：δ158.8，129.1，120.1，114.2，73.4，70.9，70.6，70.5，51.3，17.9，15.5，14.7，8.0；MS m/z(％)341(100)，431(M+32.22); calculated value of elemental analysis, C23H42O8Si: c, 58.58; h, 8.89; measured value: c, 58.29; h, 8.92.
Example 6
(6) Preparing the mesoporous silicon material modified by the organic silicon 1:
the operation is as follows: 13.0g of the mesoporous material (SBA-15) treated with ethanol reflux was placed in a 100ml three-necked flask and vacuum-dried at 120 ℃ for 3 hours. After cooling, toluene (60ml) and silicone 1(9.6g) were added and refluxed at 110 ℃ for 6 hours. The solvent was spin dried and then dried under vacuum at 150 ℃ for 12 hours to give a white powder. Washing with ethanol for 3 times, and airing in the air to obtain the surface modified mesoporous material. Elemental analysis showed that C content was 15.42% and organosilicon content was 1.0 mmol/g.
Example 7
(7) Preparing the mesoporous silicon material modified by the organic silicon 2:
the operation is as follows: 10.0g of the mesoporous material (SBA-15) treated with ethanol reflux was placed in a 100ml three-necked flask and vacuum-dried at 120 ℃ for 3 hours. After cooling, toluene (60ml) and silicone 1(8.0g) were added and refluxed at 110 ℃ for 6 hours. The solvent was spin dried and then dried under vacuum at 150 ℃ for 12 hours to give a white powder. Washing with ethanol for 3 times, and airing in the air to obtain the surface modified mesoporous material. Elemental analysis showed C content 14.93% and organosilicon content 1.0 mmol/g.
Example 8
(8) Preparing the mesoporous silicon material modified by the organic silicon 2:
the operation is as follows: 13.0g of the mesoporous material (SBA-15) treated with ethanol reflux was placed in a 100ml three-necked flask and vacuum-dried at 120 ℃ for 3 hours. After cooling, toluene (60ml) and silicone 5(9.0g) were added and refluxed at 110 ℃ for 6 hours. The solvent was spin dried and then dried under vacuum at 150 ℃ for 12 hours to give a white powder. Washing with ethanol for 3 times, and airing in the air to obtain the surface modified mesoporous material. Element analysis shows that the C content is 16.23 percent and the organic silicon content is 0.9 mmol/g.
Claims (8)
1. An organosilicon compound containing a carbon-oxygen-ether bond, which has the following structural formula:
2. A process as claimed in claim 1The synthesis method of the organic silicon compound containing the carbon-oxygen-ether bond is characterized by comprising the following steps: neutralizing in an organic solvent at a temperature of-78-70 DEG C
HSiOR1OR2OR3Reacting with a catalyst for 0.5-48 hours to obtain a compound with a structural formula
The organosilicon compound containing a carbon-oxygen-ether bond of (a), wherein,
HSiOR1OR2OR3the molar ratio of the catalyst to the catalyst is 1: 2-100: 0.001-10.0; the catalyst is chloroplatinic acid or acetylacetonatorhodium.
3. A process for synthesizing an organosilicon compound containing a carbon-oxygen-ether bond, as claimed in claim 2, wherein
In the method described
HSiOR1OR2OR3The molar ratio of the catalyst to the catalyst is 1: 2.2-30: 0.001-0.20.
4. The application of the organosilicon compound containing carbon-oxygen ether bond as claimed in claim 1, wherein the organosilicon material is modified by grafting the organosilicon compound containing carbon-oxygen ether bond on the surface of the organosilicon material, wherein the organosilicon material is a mesoporous material with mesoporous pore channel of 2.0-50 nm and mesoporous material crystal system of two-dimensional cubic, two-dimensional hexagonal, three-dimensional cubic or three-dimensional hexagonal.
5. The use of organosilicon compounds containing carbon-oxygen ether linkages as claimed in claim 4, wherein the mesoporous material is a mesoporous silica material.
6. The application of the organosilicon compound containing carbon-oxygen ether bond as claimed in claim 4, wherein the grafting of the organosilicon compound containing carbon-oxygen ether bond to the surface of the organosilicon material is carried out by reacting the mesoporous material with the organosilicon compound containing carbon-oxygen ether bond at 20-200 ℃ for 2-48 hours in an organic solvent to obtain the organosilicon modified silicon material containing carbon-oxygen ether bond, wherein the mesoporous material is as claimed in claim 4, and the organosilicon compound containing carbon-oxygen ether bond is as claimed in claim 1.
7. The use of the organosilicon compound containing carbon-oxygen ether bond as claimed in claim 6, wherein the molar ratio of silicon element between the mesoporous material and the organosilicon compound containing carbon-oxygen ether bond is 10-300: 1.
8. The use of organosilicon compounds containing carbo-thioether bonds as claimed in claim 6, wherein the organic solvent is N-hexane, cyclohexane, toluene, tetrahydrofuran, dichloromethane, dimethyl sulfoxide, N-dimethylformamide, 1, 4-dioxane, acetone, diethyl ether or acetonitrile.
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| US8236915B2 (en) * | 2009-07-10 | 2012-08-07 | Momentive Performance Materials Inc. | Hydrosilylation catalysts |
| CN101766816B (en) * | 2009-12-30 | 2012-06-13 | 中国科学院上海硅酸盐研究所 | Dipolar molecule-modified mesoporous silicon material, preparation and application thereof |
| US9782763B2 (en) | 2011-12-14 | 2017-10-10 | Momentive Performance Materials Inc. | Non-precious metal-based hyrdosilylation catalysts exhibiting improved selectivity |
| US9371340B2 (en) | 2012-08-16 | 2016-06-21 | Momentive Performance Materials Inc. | Dehydrogenative silylation, hydrosilylation and crosslinking using cobalt catalysts |
| US9447125B2 (en) | 2012-08-16 | 2016-09-20 | Momentive Performance Materials Inc. | Reusable homogeneous cobalt pyridine diimine catalysts for dehydrogenative silylation and tandem dehydrogenative-silylation-hydrogenation |
| WO2014182670A2 (en) | 2013-05-06 | 2014-11-13 | Momentive Performance Materials Inc. | Selective 1,2-hydrosilylation of terminally unsaturated 1,3-dienes using iron catalysts |
| US9371339B2 (en) | 2013-05-06 | 2016-06-21 | Momentive Performance Materials Inc. | Saturated and unsaturated silahydrocarbons via iron and cobalt pyridine diimine catalyzed olefin silylation |
| JP2016520083A (en) | 2013-05-15 | 2016-07-11 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Activation of metal salts with silylhydrides and their use in hydrosilylation reactions. |
| WO2015077304A1 (en) | 2013-11-19 | 2015-05-28 | Momentive Performance Materials Inc. | Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation |
| EP3071552A1 (en) | 2013-11-19 | 2016-09-28 | The Trustees of Princeton University | Hydroboration and borylation with cobalt catalysts |
| JP6486925B2 (en) | 2013-11-19 | 2019-03-20 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Cobalt catalyst and its use for hydrosilylation and dehydrogenation silylation |
| CN105800703B (en) * | 2016-03-31 | 2018-12-21 | 任晓明 | A kind of silica modified nitrite removal material and its preparation regeneration method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1369497A (en) * | 2001-02-03 | 2002-09-18 | 德古萨股份公司 | Method for preparing 3-position functional propyl silane |
| JP2004175793A (en) * | 2002-11-15 | 2004-06-24 | Toyota Central Res & Dev Lab Inc | Method for combining organic modifying residue with inorganic solid |
-
2005
- 2005-07-01 CN CNB200510027452XA patent/CN100378111C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1369497A (en) * | 2001-02-03 | 2002-09-18 | 德古萨股份公司 | Method for preparing 3-position functional propyl silane |
| JP2004175793A (en) * | 2002-11-15 | 2004-06-24 | Toyota Central Res & Dev Lab Inc | Method for combining organic modifying residue with inorganic solid |
Non-Patent Citations (5)
| Title |
|---|
| SBA-15介孔分子筛表面的磺酸基改性及其催化性能. 袁兴东等.催化学报，第23卷,第5期. 2002 * |
| 介孔与介孔主客体材料在催化领域的应用. 李亮等.催化学报，第26卷，第2期. 2005 * |
| 氯铂酸催化剂在聚碳硅烷与二乙烯基苯交联中的应用. 陈曼华.硅酸盐学报，第32卷，第6期. 2004 * |
| 苯基改性的中孔分子筛SBA-15的合成及其磺化. 皇艳蕾等.催化学报，第25卷,第5期. 2004 * |
| 蛋白质芯片用表面改性剂的合成－蛋白质偶联剂与蛋白质非特异吸附抑制剂的合成. 曾冬冬等.化学试剂，第27卷，第6期. 2005 * |
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