CN108129507B - 一种以钛酸酯为催化剂的硅氢加成反应与应用 - Google Patents
一种以钛酸酯为催化剂的硅氢加成反应与应用 Download PDFInfo
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- CN108129507B CN108129507B CN201711262129.XA CN201711262129A CN108129507B CN 108129507 B CN108129507 B CN 108129507B CN 201711262129 A CN201711262129 A CN 201711262129A CN 108129507 B CN108129507 B CN 108129507B
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- olefin
- hydrosilylation reaction
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 238000006459 hydrosilylation reaction Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 150000001336 alkenes Chemical class 0.000 claims description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 13
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 5
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- -1 alkoxy titanate Chemical compound 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及有机硅化学领域，为解决加成反应催化体系价格昂贵的问题，本发明提出了一种以钛酸酯为催化剂的硅氢加成反应，所述的钛酸酯的结构式为Ti(OR)4，其中R选自OMe,OEt,O i Pr,O n Bu,O t Bu,OPh中一种。反应条件温和，安全，有效。
Description
技术领域
本发明涉及有机硅化学领域，具体涉及一种适用于烯烃的以钛酸酯为催化剂的硅氢加成反应。
背景技术
催化硅氢加成反应在合成有机化学中占有重要的地位，是合成有机硅偶联剂和功能有机硅化合物及聚合物最重要的途径之一。通常直接使用铂、铑、铱等贵金属配合物作为硅氢加成反应的催化剂 (Ohtat T, Ito M, Tsuneto A ，J. Chem. Soc., Chem.Commun., 1994, 2525； Peng J, Bai Y, Li J, Lai G，Current Org. Chem.，2011, 15(16), 2802),虽然它们的催化活性比较好，但是这类催化体系价格昂贵的价格导致其工业应用受到限制，多数催化体系仅停留在研究层面。近年来，一些简单容易制备，成本低廉，低毒，环保，同时比较稳定催化体系得到广泛关注。
发明内容
为解决加成反应催化体系价格昂贵的问题，本发明提出了一种以钛酸酯为催化剂的硅氢加成反应与应用，反应条件温和，安全，有效。
本发明是通过以下技术方案实现的：一种以钛酸酯为催化剂的硅氢加成反应，所述的钛酸酯的结构式为Ti(R)4 ，其中R选自OMe, OEt, O i Pr, O n Bu, O t Bu, OPh中一种。
作为优选，钛酸酯选自烷氧基钛酸酯、芳氧基钛酸酯中一种。更优选为，钛酸酯选自钛酸四甲酯、钛酸四乙酯、钛酸四异丙酯、钛酸四丁酯、钛酸四叔丁酯、钛酸四苯酯中一种。催化剂钛酸酯是非贵金属催化剂，具有成本低、操作简单等特点。
以钛酸酯为催化剂的硅氢加成反应，烯烃与含氢硅烷比例为1：1.2，在80~100℃反应温度下，反应时间为5~20小时。
钛酸酯与烯烃的摩尔比为1:200~1:10，作为优选, 钛酸酯与烯烃的摩尔比为1:20。
以钛酸酯为催化剂的硅氢加成反应适用于烯烃硅氢加成反应。本发明针对烯烃的硅氢加成反应具有很好的催化效果，可以催化烯烃与多种含氢硅烷的加成反应，适用性较为广泛。
与现有技术相比，本发明的有益效果是：以钛酸酯为催化剂的硅氢加成反应，反应条件温和，安全，有效。
具体实施方式
下面通过实施例对本发明作进一步详细说明，实施例中所用原料均可市购或采用常规方法制备。
实施例1
将钛酸四甲酯（1.76 g，0.01 mol），己烯(16.8g，0.2 mol)，Ph2SiH2(44.2 g，0.24mol)加入100 mL烧瓶中，90 ℃下搅拌12 h，反应完成后，GC测得烯烃转化率为94.6%，β-加成产物选择性为96.5%。
实施例2
将钛酸四甲酯（1.76 g，0.01 mol），辛烯 (22.4g，0.2 mol)，Ph2SiH2(44.2 g，0.24mol)加入100 mL烧瓶中，80 ℃下搅拌12 h，反应完成后，GC测得烯烃转化率为92.5%，β-加成产物选择性为97.2%。
实施例3
将钛酸四甲酯（1.76 g，0.01 mol），苯乙烯 (20.8g，0.2 mol)，Ph2SiH2(44.2 g，0.24 mol)加入100 mL烧瓶中，90 ℃下搅拌12 h，反应完成后，GC测得烯烃转化率为82.5%，β-加成产物选择性为87.2%。
实施例4
将钛酸四甲酯（1.76 g，0.01 mol），辛烯 (22.4g，0.2 mol)， 三乙氧基硅烷（39.6g，0.24 mol)加入100 mL烧瓶中，95 ℃下搅拌12 h，反应完成后，GC测得烯烃转化率为90.3%，β-加成产物选择性为95.2%。
实施例5
将钛酸四甲酯（1.06 g，0.006 mol），己烯(16.8g，0.2 mol)，Ph2SiH2(44.2 g，0.24mol)加入100 mL烧瓶中，90 ℃下搅拌12 h，反应完成后，GC测得烯烃转化率为85.6%，β-加成产物选择性为96.8%。
实施例6
将钛酸四甲酯（1.06 g，0.006 mol），己烯(16.8g，0.2 mol)，Ph2SiH2(44.2 g，0.24mol)加入100 mL烧瓶中，100 ℃下搅拌12 h，反应完成后，GC测得烯烃转化率为92.4%，β-加成产物选择性为95.7%。
实施例7
实施例1中，钛酸四乙酯（2.28g，0.01 mol）代替钛酸四甲酯作催化剂，反应完成后，GC测得烯烃转化率为94.5%，β-加成产物选择性为96.2%。
实施例8
实施例1中，钛酸四异丙酯（2.84g，0.004 mol）代替钛酸四甲酯作催化剂，反应完成后，GC测得烯烃转化率为92.1%，β-加成产物选择性为97.2%。
实施例9
实施例1中，钛酸四丁酯（3.26g，0.002 mol）代替钛酸四甲酯作催化剂，反应完成后，GC测得烯烃转化率为90.3%，β-加成产物选择性为97.6%。
实施例10
实施例1中，钛酸四叔丁酯（3.26g，0.001 mol）代替钛酸四甲酯作催化剂，反应完成后，GC测得烯烃转化率为95.3%，β-加成产物选择性为97.6%。
实施例11
实施例1中，钛酸四苯酯（4.20g，0.02 mol）代替钛酸四甲酯作催化剂，反应完成后，GC测得烯烃转化率为98.1%，β-加成产物选择性为91.1%。
实施例12
实施例4中，钛酸四苯酯（4.20g，0.02 mol）代替钛酸四甲酯作催化剂，反应完成后，GC测得烯烃转化率为93.5%，β-加成产物选择性为94.2%。
实施例13
实施例2中，反应温度为100 ℃，反应完成后，GC测得烯烃转化率为94.7%，β-加成产物选择性为92.2%。
实施例14
实施例2中，反应时间为6小时，反应完成后，GC测得烯烃转化率为84.2%，β-加成产物选择性为95.2%。
应理解，该实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
Claims (2)
1.一种以钛酸酯为催化剂的硅氢加成反应，其特征在于，所述的硅氢加成反应为烯烃与含氢硅烷在以钛酸酯为催化剂, 80~100℃反应温度下进行反应,所述的钛酸酯的结构式为Ti(R)4 ，其中R选自OMe, OEt, O i Pr, O n Bu, O t Bu, OPh中一种。
2.根据权利要求1所述的一种以钛酸酯为催化剂的硅氢加成反应，其特征在于，钛酸酯与烯烃的摩尔比为1:200~1:10。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106029681A (zh) * | 2014-02-28 | 2016-10-12 | 瓦克化学股份公司 | 添加有机盐的氢化硅烷化方法 |
| CN106831850A (zh) * | 2016-12-02 | 2017-06-13 | 杭州师范大学 | 一种硅氢加成反应 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106029681A (zh) * | 2014-02-28 | 2016-10-12 | 瓦克化学股份公司 | 添加有机盐的氢化硅烷化方法 |
| CN106831850A (zh) * | 2016-12-02 | 2017-06-13 | 杭州师范大学 | 一种硅氢加成反应 |
Non-Patent Citations (3)
| Title |
|---|
| Platina-b-diketones as catalysts for hydrosilylation and their reactivity towards hydrosilanes;Sebastian Schwieger et al.,;《Journal of Organometallic Chemistry》;20090714;第694卷;第3548-3558页 * |
| Silicometallics and catalysis;Bogdan Marciniec;《Appl. Organometal. Chem.》;20001231;第14卷;第527-538页 * |
| 非贵金属催化酮的不对称硅氢加成反应的研究进展;刘帅等，;《有机化学》;20120521;第32卷;第1827-1835页 * |
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