CN115260225B - 一种过渡金属磷酸盐在催化烯烃硅氢加成反应上的应用及其工艺 - Google Patents
一种过渡金属磷酸盐在催化烯烃硅氢加成反应上的应用及其工艺 Download PDFInfo
- Publication number
- CN115260225B CN115260225B CN202210938900.5A CN202210938900A CN115260225B CN 115260225 B CN115260225 B CN 115260225B CN 202210938900 A CN202210938900 A CN 202210938900A CN 115260225 B CN115260225 B CN 115260225B
- Authority
- CN
- China
- Prior art keywords
- olefin
- silane
- transition metal
- metal phosphate
- hydrosilylation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 44
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000006459 hydrosilylation reaction Methods 0.000 title claims abstract description 30
- 229910000319 transition metal phosphate Inorganic materials 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000077 silane Inorganic materials 0.000 claims abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 aromatic olefins Chemical class 0.000 claims abstract description 12
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims abstract description 8
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000005048 methyldichlorosilane Substances 0.000 claims abstract description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000005055 methyl trichlorosilane Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000005052 trichlorosilane Substances 0.000 abstract description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 8
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 7
- 239000005955 Ferric phosphate Substances 0.000 description 5
- 229940032958 ferric phosphate Drugs 0.000 description 5
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- VBSUMMHIJNZMRM-UHFFFAOYSA-N triethoxy(2-phenylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC1=CC=CC=C1 VBSUMMHIJNZMRM-UHFFFAOYSA-N 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical class [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N isonitrile group Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- XDXCLOWYWRFTOS-UHFFFAOYSA-N octyl(diphenyl)silane Chemical compound C=1C=CC=CC=1[SiH](CCCCCCCC)C1=CC=CC=C1 XDXCLOWYWRFTOS-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 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
- 238000000926 separation method Methods 0.000 description 1
- 239000011995 wilkinson's catalyst Substances 0.000 description 1
- UTODFRQBVUVYOB-UHFFFAOYSA-P wilkinson's catalyst Chemical compound [Cl-].C1=CC=CC=C1P(C=1C=CC=CC=1)(C=1C=CC=CC=1)[Rh+](P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)P(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UTODFRQBVUVYOB-UHFFFAOYSA-P 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
-
- 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
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
- C07F7/0829—Hydrosilylation reactions
-
- 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
- C07F7/12—Organo silicon halides
- C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明涉及一种过渡金属磷酸盐在催化烯烃硅氢加成反应上的应用及其工艺。这类过渡金属磷酸盐和反应物不相溶，其催化烯烃和含氢硅烷加成为两相反应，反应结束后，可以通过沉降的方法，使得产物和催化剂分离，催化剂可以重复使用。反应物烯烃包括直链烯烃、功能化直链烯烃或芳香烯烃。含氢硅烷包括三甲氧基氢硅烷、三乙氧基氢硅烷、甲基二氯氢硅烷、三氯氢硅烷、苯基硅烷、二苯基硅烷等。该催化剂体系为非贵金属盐，制备简单，降低生产成本。
Description
技术领域
本发明属于烯烃硅氢加成反应技术领域，具体涉及一种过渡金属磷酸盐在催化烯烃硅氢加成反应上的应用及其工艺。
背景技术
烯烃催化硅氢加成反应催化剂研究是有机硅工业中重要的研究领域。烯烃硅氢加成反应通常使用贵金属铂、铑及其配合物等催化剂，如Karstedt催化剂、Speier催化剂、Wilkinson催化剂等。尽管这些贵金属催化剂具有较高活性，但存在价格昂贵，催化剂难以重复使用，且目标产物的选择性也较低，反应副产物较多等缺点(JP8204995,1982)。因此，研究工作者探索过渡金属(铁、钴、镍等)配合物对硅氢加成反应的催化性能并取得进展。A.M.Tondreau等合成铁氮配合物并应用于反马氏烯烃硅氢加成反应(A.M.Tondreau,et alScience,2012,335,567)；S.F.Zhu等合成邻菲啰啉铁配合物并用于催化硅氢加成反应(S.F.Zhu，et al Nat.Commun.,2018,9:221)；Z.Lu等利用钴配合物催化烯烃不对称硅氢加成(Z.Lu,et al J.Am.Chem.Soc.,2017,139,9439)；发明人之前报道端位为异腈基的直链脂肪羧酸的二价金属(亚铁、钴)配合物，在用量为0.05～0.5mol％条件下，对烯烃硅氢加成反应有较高的催化活性(彭家建等，CN106831850A)。上述报道的催化剂均为金属有机配合物，制备困难，并且配体对催化性能有较大影响，反应在均相条件下进行，催化剂不可重复使用。
发明内容
本发明的第一个目的在于针对现有技术的不足，提供一种过渡金属磷酸盐催化烯烃硅氢加成反应的方法，以烯烃与含氢硅烷为原料，在过渡金属磷酸盐催化剂作用下进行硅氢加成反应，得到加成产物。所述的过渡金属磷酸盐催化剂和反应物在反应过程中为两相体系，反应结束后通过沉降可以使得催化剂和反应产物分离，催化剂重复使用。
所述的过渡金属磷酸盐催化剂为不溶于烯烃及含氢硅烷的粉末状盐；其中过渡金属为铁、钴、镍中的一种。
所述的烯烃、含氢硅烷和过渡金属磷酸盐的摩尔比为100：110～120：0.03～5。
进一步地，所述的烯烃为直链烯烃、功能化直链烯烃或芳香烯烃；直链烯烃优选为1-己烯或1-辛烯，功能化直链烯烃优选为氯丙烯，芳香烯烃优选为未被取代或苯环上的氢被甲基或甲氧基取代的芳基乙烯化合物。
进一步地，所述的含氢硅烷为烷氧基硅烷、含氢聚硅氧烷或苯基硅烷，优选为三甲氧基氢硅烷、三乙氧基氢硅烷、甲基二氯氢硅烷、三氯氢硅烷、苯基硅烷、二苯基硅烷中的任意一种。
进一步地，硅氢加成的反应过程为：在氮气保护下，将催化剂和烯烃混合，升温至70～120℃，待混合均匀后加入含氢硅烷，反应5～10h，经过后处理得到加成产物。
进一步地，所述硅氢加成反应的反应温度为70～100℃，反应时间为5～10h。
进一步地，所述的烯烃、含氢硅烷和过渡金属磷酸盐的摩尔比优选为100：110：1.0。
本发明的第二个目的在于提供一种过渡金属磷酸盐在催化烯烃硅氢加成反应上的应用，所述过渡金属磷酸盐为不溶于烯烃及含氢硅烷的粉末状盐，其中过渡金属为铁、钴、镍中的一种。这类过渡金属磷酸盐催化剂反应结束后，通过简单沉降，即可将产物和催化剂分离，从而解决催化剂重复使用问题，降低生产成本。
与现有技术相比，本发明具有以下有益效果：
(1)本发明催化剂的廉价易得，反应条件温和，成本低，易于保存，底物普适性广；
(2)本发明催化剂用于催化烯烃硅氢加成反应，反应结束后简单沉降即可实现产物和催化剂分离，实现了催化剂的循环使用。
具体实施方式
下面通过具体例，对本发明的技术方案作进一步说明。
实施例1
在500毫升的三口烧瓶中，加入正辛烯140.25g(1.25mol)、磷酸铁1.89g(12.5mmol)，氮气保护下，缓慢升温至100℃，搅拌反应0.5小时，通过滴液漏斗滴加二苯基硅烷276.45g(1.5mol)，保持反应温度，继续搅拌反应6小时，冷却至室温，催化剂沉降，上层液体通过GC-MS测定苯乙烯的转化率，减压蒸馏上层液体，收集相应馏分，得到二苯基辛基硅烷。沉降出的催化剂重新加入正辛烯及二苯基硅烷进行催化硅氢加成反应，重复多次，所得结果列于表1。催化剂经过7次循环后，催化剂性能基本保持不变。
表1磷酸铁催化正辛烯与二苯基硅烷加成反应
实施例2
在500毫升的三口烧瓶中，加入苯乙烯130.19g(1.25mol)、磷酸铁1.89g(12.5mmol)，氮气保护下，缓慢升温至100℃，搅拌反应0.5小时，通过滴液漏斗滴加三乙氧基氢硅烷246.41g(1.5mol),保持反应温度，继续搅拌反应6小时，冷却至室温，催化剂沉降，上层液体通过GC-MS测定苯乙烯的转化率，减压蒸馏上层液体，收集相应馏分，得到1-三乙氧基硅基-2-苯基乙烷。上层液体通过GC-MS测定苯乙烯的转化率为76.8％，减压蒸馏上层液体，收集相应馏分β加成物1-三乙氧基硅基-2-苯基乙烷，收率72.4％。
实施例3
用磷酸钴1.53g(含钴12.5mmol)代替实施例2的磷酸铁，其余条件与实施例2相同，催化苯乙烯与三乙氧基硅烷硅氢加成。测定苯乙烯的转化率为79.2％，减压蒸馏上层液体，收集β加成物1-三乙氧基硅基-2-苯基乙烷收率74.8％。
实施例4
用磷酸镍1.53g(含镍12.5mmol)代替实施例2的磷酸铁，其余条件与实施例2相同，催化苯乙烯与三乙氧基硅烷硅氢加成。测定苯乙烯的转化率为72.4％，减压蒸馏上层液体，收集β加成物1-三乙氧基硅基-2-苯基乙烷收率68.5％。
实施例5～15
实施实施例1中的方法，通过改变催化剂种类以及反应底物，分别测试例5至例15金属磷酸盐催化烯烃硅氢加成反应的性能。所得结果列于表2。
表2过渡金属磷酸盐催化烯烃硅氢加成反应
实施例16
在500毫升的三口烧瓶中，加入正辛烯140.25g(1.25mol)、磷酸铁1.89g(12.5mmol)，氮气保护下，缓慢升温至70℃，搅拌反应0.5小时，通过滴液漏斗滴加二苯基硅烷253.41g(1.375mol)，保持反应温度，继续搅拌反应10小时，冷却至室温，催化剂沉降，减压蒸馏上层液体，收集相应馏分，得到最终产物。
实施例17
在500毫升的三口烧瓶中，加入正辛烯140.25g(1.25mol)、磷酸铁1.89g(12.5mmol)，氮气保护下，缓慢升温至120℃，搅拌反应0.5小时，通过滴液漏斗滴加二苯基硅烷276.45g(1.5mol)，保持反应温度，继续搅拌反应5小时，冷却至室温，催化剂沉降，减压蒸馏上层液体，收集相应馏分，得到最终产物。
Claims (5)
1.一种过渡金属磷酸盐催化烯烃硅氢加成反应的方法，其特征在于，以烯烃与含氢硅烷为原料，在过渡金属磷酸盐催化剂作用下进行硅氢加成反应，得到加成产物；
所述过渡金属磷酸盐为不溶于烯烃及含氢硅烷的粉末状盐；其中过渡金属为铁、钴、镍中的一种；
所述的烯烃、含氢硅烷和过渡金属磷酸盐的摩尔比为100：110：1.0；所述的烯烃为直链烯烃、功能化直链烯烃或芳香烯烃，其中功能化直链烯烃为氯丙烯；所述的含氢硅烷为烷氧基硅烷、含氢聚硅氧烷或苯基硅烷。
2.根据权利要求1所述的一种过渡金属磷酸盐催化烯烃硅氢加成反应的方法，其特征在于，所述的直链烯烃为1-己烯或1-辛烯，芳香烯烃为未被取代或苯环上的氢被甲基或甲氧基取代的芳基乙烯化合物。
3.根据权利要求1所述的一种过渡金属磷酸盐催化烯烃硅氢加成反应的方法，其特征在于，所述的含氢硅烷选自三甲氧基氢硅烷、三乙氧基氢硅烷、甲基二氯氢硅烷、三氯氢硅烷、二苯基硅烷中的任意一种。
4.根据权利要求1所述的一种过渡金属磷酸盐催化烯烃硅氢加成反应的方法，其特征在于该方法具体是：在氮气保护下，将过渡金属磷酸盐催化剂和烯烃混合，升温至70～120℃，待混合均匀后加入含氢硅烷，反应5～10h，经过后处理得到加成产物。
5.根据权利要求1所述的一种过渡金属磷酸盐催化烯烃硅氢加成反应的方法，其特征在于，所述硅氢加成反应的反应温度为70～100℃，反应时间为5～10 h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210938900.5A CN115260225B (zh) | 2022-08-05 | 2022-08-05 | 一种过渡金属磷酸盐在催化烯烃硅氢加成反应上的应用及其工艺 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210938900.5A CN115260225B (zh) | 2022-08-05 | 2022-08-05 | 一种过渡金属磷酸盐在催化烯烃硅氢加成反应上的应用及其工艺 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115260225A CN115260225A (zh) | 2022-11-01 |
| CN115260225B true CN115260225B (zh) | 2024-05-14 |
Family
ID=83749753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210938900.5A Active CN115260225B (zh) | 2022-08-05 | 2022-08-05 | 一种过渡金属磷酸盐在催化烯烃硅氢加成反应上的应用及其工艺 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115260225B (zh) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119371A (zh) * | 2014-03-26 | 2014-10-29 | 杭州师范大学 | 一种烯烃硅氢加成反应的方法 |
| CN107840856A (zh) * | 2017-10-27 | 2018-03-27 | 杭州师范大学 | 一种烯烃与含氢硅烷硅氢加成反应的方法 |
-
2022
- 2022-08-05 CN CN202210938900.5A patent/CN115260225B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119371A (zh) * | 2014-03-26 | 2014-10-29 | 杭州师范大学 | 一种烯烃硅氢加成反应的方法 |
| CN107840856A (zh) * | 2017-10-27 | 2018-03-27 | 杭州师范大学 | 一种烯烃与含氢硅烷硅氢加成反应的方法 |
Non-Patent Citations (2)
| Title |
|---|
| 多相硅氢加成催化剂的制备及应用;白赢 等;化学进展(第12期);2466-2477 * |
| 钴配合物催化硅氢加成反应研究进展;代自男 等;有机化学(第05期);1177-1187 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115260225A (zh) | 2022-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3071584B1 (en) | Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation | |
| US4424332A (en) | Polymeric metal-amine complex compounds, processes for their preparation and use | |
| TWI620752B (zh) | 經由鐵及鈷吡啶二亞胺催化烯烴矽烷化所得之飽和及不飽和矽代烴 | |
| EP3406616B1 (en) | Novel isocyanide compound and hydrosilylation reaction catalyst | |
| EP3195932B1 (en) | Hydrosilylation reaction catalyst | |
| EP3184172B1 (en) | Hydrosilylation iron catalyst | |
| Dash et al. | Diverse catalytic activity of the cationic actinide complex [(Et2N) 3U][BPh4] in the dimerization and hydrosilylation of terminal alkynes. Characterization of the first f-element alkyne π-complex [(Et2N) 2U (C CtBu)(η2-HC CtBu)][BPh4] | |
| EP3590596B1 (en) | Catalyst for hydrosilylation reaction, hydrogenation reaction, and hydrosilane reduction reaction | |
| EP3071585B1 (en) | Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation | |
| US20180334470A1 (en) | Dialkyl cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation | |
| CN109746048B (zh) | 一种多相铑基氢甲酰化催化剂及其制备方法和应用 | |
| Cullen et al. | Polymer supported ferrocene derivatives. Catalytic hydrosilylation of olefins by supported palladium and platinum complexes | |
| CN115260225B (zh) | 一种过渡金属磷酸盐在催化烯烃硅氢加成反应上的应用及其工艺 | |
| CN110117296B (zh) | 一种硅基修饰的异腈金属盐催化剂及其制备方法和应用 | |
| CN110605145B (zh) | 一种氢甲酯化反应催化剂及制备异壬酸的方法 | |
| Basato et al. | Cationic complexes of dirhodium (II) with 1, 8-naphthyridine: Catalysis of reactions involving silanes | |
| CN107840856B (zh) | 一种烯烃与含氢硅烷硅氢加成反应的方法 | |
| CN107857777B (zh) | 一种以可循环使用的铂化合物为催化剂的硅氢加成反应 | |
| TW201524604A (zh) | 使用鈷觸媒之脫氫甲矽烷化、矽氫化及交聯 | |
| CN113173859B (zh) | 一种合成手性α-胺基醇化合物的方法 | |
| CN114700116B (zh) | 一种可循环使用的树脂状硅氢加成催化剂及其制备和应用 | |
| CN113105494A (zh) | 一种3-氯丙基三氯硅烷的制备方法 | |
| JP6806299B2 (ja) | ヒドロシリル化鉄触媒の調製方法 | |
| JPH04124189A (ja) | 有機ケイ素化合物の製造方法 | |
| PL188754B1 (pl) | Sposób otrzymywania sililoetenów |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |