CN116116462A - 一种引入官能化烯烃的含膦聚合物负载钯催化剂及其制备和在硅-碳偶联反应中的应用 - Google Patents
一种引入官能化烯烃的含膦聚合物负载钯催化剂及其制备和在硅-碳偶联反应中的应用 Download PDFInfo
- Publication number
- CN116116462A CN116116462A CN202310095483.7A CN202310095483A CN116116462A CN 116116462 A CN116116462 A CN 116116462A CN 202310095483 A CN202310095483 A CN 202310095483A CN 116116462 A CN116116462 A CN 116116462A
- Authority
- CN
- China
- Prior art keywords
- phosphine
- containing porous
- functionalized olefin
- palladium catalyst
- catalyst
- 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.)
- Granted
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 152
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 76
- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 36
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 14
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229920000620 organic polymer Polymers 0.000 claims abstract description 27
- -1 aryl silane Chemical compound 0.000 claims abstract description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- WXKCRCGKCOKJEF-UHFFFAOYSA-N prop-2-enyl 2-cyanoacetate Chemical compound C=CCOC(=O)CC#N WXKCRCGKCOKJEF-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 13
- 150000003254 radicals Chemical class 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000002940 palladium Chemical class 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 claims description 2
- DJLBVUYUIACDIU-UHFFFAOYSA-N tris(4-ethenylphenyl)phosphane Chemical compound C1=CC(C=C)=CC=C1P(C=1C=CC(C=C)=CC=1)C1=CC=C(C=C)C=C1 DJLBVUYUIACDIU-UHFFFAOYSA-N 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 229910000077 silane Inorganic materials 0.000 abstract description 3
- 150000004696 coordination complex Chemical class 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000006884 silylation reaction Methods 0.000 abstract description 2
- UOYOTHRZSRWQNP-UHFFFAOYSA-N (2-ethenylphenyl)-diphenylphosphane Chemical compound C=CC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UOYOTHRZSRWQNP-UHFFFAOYSA-N 0.000 abstract 1
- 125000003700 epoxy group Chemical group 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000012876 carrier material Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 208000012839 conversion disease Diseases 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 125000004093 cyano group Chemical group *C#N 0.000 description 7
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 7
- 230000000379 polymerizing effect Effects 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZTKQNUFYTXZWBV-UHFFFAOYSA-N (4-tert-butylphenyl)-triethylsilane Chemical compound CC[Si](CC)(CC)c1ccc(cc1)C(C)(C)C ZTKQNUFYTXZWBV-UHFFFAOYSA-N 0.000 description 1
- WQVIVQDHNKQWTM-UHFFFAOYSA-N 1-tert-butyl-4-iodobenzene Chemical compound CC(C)(C)C1=CC=C(I)C=C1 WQVIVQDHNKQWTM-UHFFFAOYSA-N 0.000 description 1
- VLVCDUSVTXIWGW-UHFFFAOYSA-N 4-iodoaniline Chemical group NC1=CC=C(I)C=C1 VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical group CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- QXTIBZLKQPJVII-UHFFFAOYSA-N triethylsilicon Chemical compound CC[Si](CC)CC QXTIBZLKQPJVII-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/22—Esters containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Polymerization Catalysts (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种引入官能化烯烃的含膦聚合物负载钯催化剂及其制备和在硅‑碳偶联反应中的应用，所述催化剂中以Pd金属络合物作为活性组分，以由乙烯基三苯基膦及官能化烯烃聚合而成的含膦多孔有机聚合物为载体。本发明所提供的催化剂在卤代芳烃与氢硅烷的硅烷基化反应中具有很好的表现，能很好地抑制还原产物的生成，具有化学选择性高、易于分离、可多次回收再利用的特点，为芳基硅烷的生产提供了新的工业化技术。
Description
技术领域
本发明属于多相催化领域，涉及一种引入官能化烯烃的含膦聚合物负载钯催化剂及其制备和在硅-碳偶联反应中的应用。
背景技术
芳基硅烷是一类具有重要应用价值的有机硅化合物，不仅可作为芳基化试剂应用于交叉偶联反应中，还是一些新型有机光电材料的重要结构单元，已经在有机合成、新药研制和先进材料合成等多个领域得到应用。开发芳基硅烷的绿色化合成方法具有重要应用价值。相较于传统金属有机试剂法，过渡金属催化的硅-碳偶联反应具原子经济性高、生产工艺绿化环保的特点。目前，基于钯、铂、铑等贵金属已开发出多类均相催化体系，但仍存在化学选择性差、底物适用范围窄和催化剂难以回收的缺陷。
近年来，多孔含膦有机聚合物在不仅热稳定性高和孔隙率大，而且易于从分子结构层次对其组成和性能进行调控。同时由于聚合物本身的柔性，固定于聚合物中的有机配体与均相催化体系类似具有一定流动性，将有机金属配合物负载到这类多孔含膦有机聚合物上所形成的催化剂兼具均相和非均相催化剂的特征。
人们基于此类多孔含膦有机聚合物开发出了多类非均相过渡金属催化剂，并成功应用于加氢甲酰化、氢化、碳-碳偶联、碳-氮偶联、碳-卤偶联、硅氢加成和氧化羰基等有机转化反应中。但目前此类多孔含膦有机聚合物在过渡金属催化的硅-碳偶联反应中的应用尚未见著报道。
发明内容
本发明的第一个目的是针对现有技术的不足，提供一种引入官能化烯烃的含膦聚合物负载钯催化剂的制备方法。
一种引入官能化烯烃的含膦聚合物负载钯催化剂的制备方法，采用如下技术方案：
步骤(1)、惰性气氛下，在有机溶剂中加入三(4-乙烯基苯)基膦、官能化烯烃单体和自由基引发剂，室温下搅拌一定时间后得到混合液；
步骤(2)、将步骤(1)制得的混合液转移至合成高压釜中，在40～120℃下、惰性气氛中反应2～48小时，静置降温后除去有机溶剂得到含膦多孔有机聚合物；
步骤(3)、惰性气氛下，将钯盐和含膦多孔有机聚合物加入有机溶剂，室温搅拌一定时间后将混合液升温到40～120℃下加热0.5～4小时，减压蒸馏除去有机溶剂，真空干燥制得含膦多孔有机聚合物负载钯催化剂。
作为优选，步骤(1)中所述的有机溶剂为四氢呋喃、苯、甲苯、甲醇、乙醇、二氯甲烷或三氯甲烷中一种或两种以上；所述的官能化烯烃单体为甲基丙烯酸缩水甘油酯(GMA)、氰乙酸烯丙酯(ACA)或八乙烯基-POSS(Vi-POSS)中的一种或两种以上；所述的自由基引发剂为过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈中的一种或两种以上；
作为优选，步骤(1)中所述三(4-乙烯基苯)基膦、官能化烯烃单体和自由基引发剂的摩尔比为1:(1～5):(0.01～1.0)；
作为优选，步骤(3)中所述的钯盐包括但不限于PdX2(X＝Cl,Br,I)、Pd(dba)2、Pd2(dba)3、Pd(CN)2Cl2、Pd(CH3CN)4(BF4)2，钯盐和含膦多孔有机聚合物的质量比为1：(15～30)，有机溶剂为四氢呋喃THF、N-甲基吡咯烷酮NMP、N,N-二甲基甲酰胺DMF、二甲基亚砜DMSO中的一种或两种以上。
本发明的第二个目的是提供一种引入官能化烯烃的含膦聚合物负载钯催化剂，由上述方法制备得到。
一种引入官能化烯烃的含膦聚合物负载钯催化剂，所述催化剂以钯作为活性组分，以含膦多孔有机聚合物为载体，催化剂中钯金属担载量范围为0.1～5wt％；
所述含膦多孔有机聚合物由三(4-乙烯基苯)基膦和官能化烯烃单体聚合而成，其中官能化烯烃单体选自甲基丙烯酸缩水甘油酯(GMA)、氰乙酸烯丙酯(ACA)或八乙烯基-POSS(Vi-POSS)中的一种或两种以上。
作为优选，所述含膦多孔有机聚合物具有多级孔结构，比表面积为200～500m2/g，孔径为2.0～5.0nm，孔容积为0.15～0.8cm3/g。
本发明的第三个目的是提供上述催化剂在催化硅-碳偶联反应中的应用。
与现有技术相比，本发明的有益效果为：
本发明创造性地将含环氧基或氰基的烯烃作为烯烃聚合物单体引入到含膦多孔有机聚合物的制备中。所制得的官能化含膦多孔有机聚合物材料与钯金属配位后可形成适用于硅-碳偶联反应的高性能非均相催化剂。利用环氧基团和氰基对Pd中心的协同辅助配位作用，通过空间位阻效应和电子效应，对钯催化的卤代芳烃与烷基氢硅烷或烷氧基氢硅烷的硅-碳偶联反应的化学选择性起到调控作用，很好地抑制了还原产物的生成。本发明所保护的催化剂不仅化学选择性高，并且具有热稳定性好和易于从反应体系中分离出来的特点，适合于工业应用。
本发明所提供的催化剂在卤代芳烃与氢硅烷的硅烷基化反应中具有很好的表现，能很好地抑制还原产物的生成，具有化学选择性高、易于分离、可多次回收再利用的特点，为芳基硅烷的生产提供了新的工业化技术。
附图说明
图1是实施例1所制得含膦多孔有机聚合物的扫描电镜图。
图2是实施例2所制得含膦多孔有机聚合物的扫描电镜图。
图3是实施例3所制得含膦多孔有机聚合物的扫描电镜图。
图4是实施例4所制得含膦多孔有机聚合物的扫描电镜图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
本发明公开一种官能化含膦多孔有机聚合物负载催化剂的制备及应用，具体实施方案如下：
实施例1
环氧基功能化含膦多孔聚合物载体材料的制备(GMA-PPOP-1)：在室温和N2保护氛围下，取三(4-乙烯基苯)基膦(Vi-PPh3)10.0g和8.3g甲基丙烯酸缩水甘油酯(GMA)作为单体溶于100mLTHF中，向上述溶液中加入3.3g作为自由基引发剂偶氮二异丁腈(AIBN)，机械搅拌2h后将溶液移至水热釜中于353K和N2保护下聚合24h，冷却至室温，抽真空除溶剂后得到环氧基功能化的含膦多孔聚合物载体材料(GMA-PPOP-1)。
环氧基功能化含膦多孔聚合物负载钯催化剂的制备(Pd@GMA-PPOP-1)：在N2保护下，将0.01g Pd(CH3CN)4(BF4)2溶于50mL THF，搅拌30min后加入0.25g含膦多孔聚合物载体材料(GMA-PPOP)，室温下搅拌24h，过滤，用THF洗涤数次后在338K下真空干燥得到环氧基功能化含膦多孔聚合物负载钯催化剂(Pd@GMA-PPOP-1)。
实施例2
环氧基功能化含膦多孔聚合物载体材料的制备(GMA-PPOP-2)：在室温和N2保护氛围下，取三(4-乙烯基苯)基膦(Vi-PPh3)10.0g和13.5g甲基丙烯酸缩水甘油酯(GMA)作为单体溶于100mLTHF中，向上述溶液中加入0.1g作为自由基引发剂偶氮二异丁腈(AIBN)，机械搅拌2h后将溶液移至水热釜中于353K和N2保护下聚合24h，冷却至室温，抽真空除溶剂后得到环氧基功能化的含膦多孔聚合物载体材料(GMA-PPOP-2)。
环氧基功能化含膦多孔聚合物负载钯催化剂的制备(Pd@GMA-PPOP-2)：在N2保护下，将0.01g Pd(CH3CN)4(BF4)2溶于50mL THF，搅拌30min后加入0.5g含膦多孔聚合物载体材料(GMA-PPOP)，室温下搅拌24h，过滤，用THF洗涤数次后在338K下真空干燥得到环氧基功能化含膦多孔聚合物负载钯催化剂(Pd@GMA-PPOP-2)。
实施例3
氰基功能化含膦多孔聚合物载体材料的制备(ACA-PPOP-1)：在室温和N2保护氛围下，取三(4-乙烯基苯)基膦(Vi-PPh3)10.0g和15g氰乙酸烯丙酯(ACA)作为单体溶于100mLTHF中，向上述溶液中加入3.3g作为自由基引发剂偶氮二异丁腈(AIBN)，机械搅拌2h后将溶液移至水热釜中于353K和N2保护下聚合24h，冷却至室温，抽真空除溶剂后得到环氧基功能化的含膦多孔聚合物载体材料。
氰基基功能化含膦多孔聚合物负载钯催化剂的制备(Pd@ACA-PPOP-1)：在N2保护下，将0.01g PdCl2溶于50mLTHF，搅拌30min后加入5g含膦多孔聚合物载体材料(GMA-PPOP)，室温下搅拌24h，过滤、并用THF洗涤数次后在338K下真空干燥，得到氰基功能化含膦多孔聚合物负载钯催化剂(Pd@ACA-PPOP-1)。
实施例4
氰基功能化含膦多孔聚合物载体材料的制备(ACA-PPOP-2)：在室温和N2保护氛围下，取三(4-乙烯基苯)基膦(Vi-PPh3)10.0g和22g氰乙酸烯丙酯(ACA)作为单体溶于100mLTHF中，向上述溶液中加入0.3g作为自由基引发剂偶氮二异丁腈(AIBN)，机械搅拌2h后将溶液移至水热釜中于353K和N2保护下聚合24h，冷却至室温，抽真空除溶剂后得到环氧基功能化的含膦多孔聚合物载体材料。
氰基基功能化含膦多孔聚合物负载钯催化剂的制备(Pd@ACA-PPOP-2)：在N2保护下，将0.01g Pd(dba)2溶于50mL THF，搅拌30min后加入5g含膦多孔聚合物载体材料(GMA-PPOP)，室温下搅拌24h，过滤、并用THF洗涤数次后在338K下真空干燥，得到氰基功能化含膦多孔聚合物负载钯催化剂(Pd@ACA-PPOP-2)。
实施例5
氰基功能化含膦多孔聚合物载体材料的制备(ACA-POSS-PPOP)：在室温和N2保护氛围下，取三(4-乙烯基苯)基膦(Vi-PPh3)10.0g、15g氰乙酸烯丙酯(ACA)、1g八乙烯基POSS作为单体溶于100mL THF中，向上述溶液中加入5.0g作为自由基引发剂偶氮二异丁腈(AIBN)，机械搅拌2h后将溶液移至水热釜中于353K和N2保护下聚合24h，冷却至室温，抽真空除溶剂后得到环氧基功能化的含膦多孔聚合物载体材料。
氰基基功能化含膦多孔聚合物负载钯催化剂的制备(Pd@ACA-POSS-PPOP)：在N2保护下，将0.01g PdCl2溶于50mL THF，搅拌30min后加入0.15g含膦多孔聚合物载体材料(GMA-PPOP)，室温下搅拌24h，过滤、并用THF洗涤数次后在338K下真空干燥，得到氰基功能化含膦多孔聚合物负载钯催化剂(Pd@ACA-POSS-PPOP)。
实施例6
环氧基功能化含膦多孔聚合物载体材料的制备(GMA-POSS-PPOP)：在室温和N2保护氛围下，取三(4-乙烯基苯)基膦(Vi-PPh3)10.0g、16g甲基丙烯酸缩水甘油酯(GMA)和1g八乙烯基POSS作为单体溶于100mLTHF中，向上述溶液中加入1.5g作为自由基引发剂偶氮二异丁腈(AIBN)，机械搅拌2h后将溶液移至水热釜中于353K和N2保护下聚合24h，冷却至室温，抽真空除溶剂后得到环氧基功能化的含膦多孔聚合物载体材料(GMA-POSS-PPOP)。
环氧基功能化含膦多孔聚合物负载钯催化剂的制备(Pd@GMA-POSS-PPOP)：在N2保护下，将0.01g Pd(CH3CN)4(BF4)2溶于50mLTHF，搅拌30min后加入0.25g含膦多孔聚合物载体材料(GMA-POSS-PPOP)，室温下搅拌24h，过滤，用THF洗涤数次后在338K下真空干燥得到环氧基功能化含膦多孔聚合物负载钯催化剂(Pd@GMA-POSS-PPOP)。
实施例7：不添加官能化烯烃单体
含膦多孔聚合物载体材料的制备(PPOP)：在室温和N2保护氛围下，将三(4-乙烯基苯)基膦(Vi-PPh3)10.0g溶于100mL THF中，向上述溶液中加入1.5g作为自由基引发剂偶氮二异丁腈(AIBN)，机械搅拌2h后将溶液移至水热釜中于353K和N2保护下聚合24h，冷却至室温，抽真空除溶剂后未官能化的含膦多孔聚合物载体材料(PPOP)。
含膦多孔聚合物负载钯催化剂的制备(Pd@PPOP)：在N2保护下，将0.01g Pd(CH3CN)4(BF4)2溶于50mL THF，搅拌30min后加入0.25g含膦多孔聚合物载体材料(PPOP)，室温下搅拌24h，过滤，用THF洗涤数次后在338K下真空干燥得到未官能化的含膦多孔聚合物负载钯催化剂(Pd@PPOP)。
应用例1
在惰性气氛下，向三口烧瓶中加入4-叔丁基-碘苯(1.3g)、三乙基氢硅烷(0.87g)、二异丙胺(DIPA)(2.0g)和实施例1所制备的含膦多孔聚合物负载钯催化剂(Pd@GMA-PPOP-1)0.2g、20ml超干N-甲基吡咯烷酮(NMP)，机械搅拌下70℃反应2h，将混合物用石油醚萃取三次，合并上层有机相减压蒸馏除去溶剂，GC-MS检测所示反应转化率100％，产物4-(叔丁基)苯基三乙基硅烷收率达96％，偶联产物：还原产物＝96:4。
应用例2
在应用例2中，除了反应底物替代为对碘苯胺(1.1g)和二苯基甲基氢硅烷(1.5g)外，其余合成过程与应用例1相同，GC-MS检测所示反应转化率100％，反应化学选择性为偶联产物：还原产物＝92:8。
应用例3
在应用例3中，除了反应底物替代为三乙氧基氢硅烷(1.23g)外，其余合成过程与应用例1相同，GC-MS检测所示反应转化率100％，反应化学选择性为偶联产物：还原产物＝90:10。
应用例4
在应用例4中，除了催化剂替代为Pd@ACA-PPOP-1(0.2g)外，其余合成过程与应用例1相同，GC-MS检测所示反应转化率100％，反应化学选择性为偶联产物：还原产物＝92:8。
应用例5
在应用例5中，除了催化剂替代为Pd@ACA-POSS-PPOP(0.2g)外，其余合成过程与应用例1相同，GC-MS检测所示反应转化率100％，反应化学选择性为偶联产物：还原产物＝89:11。
应用例6
在应用例6中，除了催化剂替代为Pd@GMA-POSS-PPOP(0.2g)外，其余合成过程与应用例1相同，GC-MS检测所示反应转化率100％，反应化学选择性为偶联产物：还原产物＝96:4。
对比例1
在对比例1中，除了催化剂替代为Pd@PPOP(0.2g)外，其余合成过程与应用例1相同，GC-MS检测所示反应转化率100％，反应化学选择性为偶联产物：还原产物＝75:25。
由对比例1结果可知，在制备催化剂的过程中不添加官能化烯烃单体，所得的催化剂用于硅-碳偶联反应后，还原产物生成较多。而实施例所制备的含膦多孔聚合物负载钯催化剂利用环氧基团和氰基对Pd中心的协同辅助配位作用，很好地抑制了还原产物的生成。
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。
Claims (10)
1.一种引入官能化烯烃的含膦聚合物负载钯催化剂的制备方法，其特征在于，所述制备方法包括如下步骤：
步骤(1)、惰性气氛下，在有机溶剂中加入三(4-乙烯基苯)基膦、官能化烯烃单体和自由基引发剂，室温下搅拌一定时间后得到混合液；
步骤(2)、将步骤(1)制得的混合液转移至合成高压釜中，在40～120℃下、惰性气氛中反应2～48小时，静置降温后除去有机溶剂得到含膦多孔有机聚合物；
步骤(3)、惰性气氛下，将钯盐和含膦多孔有机聚合物加入有机溶剂，室温搅拌一定时间后将混合液升温到40～120℃下加热0.5～4小时，减压蒸馏除去有机溶剂，真空干燥制得含膦多孔有机聚合物负载钯催化剂。
2.根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述的有机溶剂为四氢呋喃、苯、甲苯、甲醇、乙醇、二氯甲烷或三氯甲烷中一种或两种以上。
3.根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述的官能化烯烃单体为甲基丙烯酸缩水甘油酯GMA、氰乙酸烯丙酯ACA或八乙烯基-POSS中的一种或两种以上。
4.根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述的自由基引发剂为过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈中的一种或两种以上。
5.根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述三(4-乙烯基苯)基膦、官能化烯烃单体和自由基引发剂的摩尔比为1:(1～5):(0.01～1.0)。
6.根据权利要求1所述的制备方法，其特征在于，步骤(3)中所述的钯盐为PdCl2、PdBr2、PdI2、Pd(dba)2、Pd2(dba)3、Pd(CN)2Cl2或Pd(CH3CN)4(BF4)2中的一种，钯盐和含膦多孔有机聚合物的质量比为1：(15～30)。
7.根据权利要求1所述的制备方法，其特征在于，步骤(3)中有机溶剂为四氢呋喃THF、N-甲基吡咯烷酮NMP、N,N-二甲基甲酰胺DMF、二甲基亚砜DMSO中的一种或两种以上。
8.一种引入官能化烯烃的含膦聚合物负载钯催化剂，采用权利要求1-6任一项所述方法制备得到，其特征在于，所述催化剂以钯作为活性组分，以含膦多孔有机聚合物为载体，催化剂中钯金属担载量范围为0.1～5wt％；
所述含膦多孔有机聚合物由三(4-乙烯基苯)基膦和官能化烯烃单体聚合而成，其中官能化烯烃单体为甲基丙烯酸缩水甘油酯GMA、氰乙酸烯丙酯ACA或八乙烯基-POSS中的一种或两种以上。
9.根据权利要求8所述的引入官能化烯烃的含膦聚合物负载钯催化剂，其特征在于，所述含膦多孔有机聚合物具有多级孔结构，比表面积为200～500m2/g，孔径为2.0～5.0nm，孔容积为0.15～0.8cm3/g。
10.权利要求8或9所述的引入官能化烯烃的含膦聚合物负载钯催化剂在催化硅-碳偶联反应中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310095483.7A CN116116462B (zh) | 2023-02-10 | 2023-02-10 | 一种引入官能化烯烃的含膦聚合物负载钯催化剂及其制备和在硅-碳偶联反应中的应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310095483.7A CN116116462B (zh) | 2023-02-10 | 2023-02-10 | 一种引入官能化烯烃的含膦聚合物负载钯催化剂及其制备和在硅-碳偶联反应中的应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116116462A true CN116116462A (zh) | 2023-05-16 |
| CN116116462B CN116116462B (zh) | 2024-06-04 |
Family
ID=86297085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310095483.7A Active CN116116462B (zh) | 2023-02-10 | 2023-02-10 | 一种引入官能化烯烃的含膦聚合物负载钯催化剂及其制备和在硅-碳偶联反应中的应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116116462B (zh) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260399A (en) * | 1992-06-08 | 1993-11-09 | General Electric Company | Regiospecific catalyst for the synthesis of epoxysiloxane monomers and polymers |
| WO2004030816A1 (en) * | 2002-10-04 | 2004-04-15 | Johnson Matthey Public Limited Company | Hydrosilation catalyst |
| US20160318009A1 (en) * | 2013-12-11 | 2016-11-03 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A solid heterogeneous catalyst for olefin hydroformylation reaction and production method and use thereof |
| CN106179505A (zh) * | 2016-07-18 | 2016-12-07 | 华东师范大学 | 含膦微孔有机纳米管骨架负载钯催化剂及其合成和应用 |
| CN109453815A (zh) * | 2017-09-06 | 2019-03-12 | 中国科学院大连化学物理研究所 | 有机含膦聚合物载体负载的铑基催化剂及其制备和应用 |
| CN111269577A (zh) * | 2020-02-17 | 2020-06-12 | 中山大学 | 纳米银负载poss聚合物复合材料及其制备方法与应用 |
-
2023
- 2023-02-10 CN CN202310095483.7A patent/CN116116462B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260399A (en) * | 1992-06-08 | 1993-11-09 | General Electric Company | Regiospecific catalyst for the synthesis of epoxysiloxane monomers and polymers |
| WO2004030816A1 (en) * | 2002-10-04 | 2004-04-15 | Johnson Matthey Public Limited Company | Hydrosilation catalyst |
| US20160318009A1 (en) * | 2013-12-11 | 2016-11-03 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | A solid heterogeneous catalyst for olefin hydroformylation reaction and production method and use thereof |
| CN106179505A (zh) * | 2016-07-18 | 2016-12-07 | 华东师范大学 | 含膦微孔有机纳米管骨架负载钯催化剂及其合成和应用 |
| CN109453815A (zh) * | 2017-09-06 | 2019-03-12 | 中国科学院大连化学物理研究所 | 有机含膦聚合物载体负载的铑基催化剂及其制备和应用 |
| CN111269577A (zh) * | 2020-02-17 | 2020-06-12 | 中山大学 | 纳米银负载poss聚合物复合材料及其制备方法与应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116116462B (zh) | 2024-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109453815B (zh) | 有机含膦聚合物载体负载的铑基催化剂及其制备和应用 | |
| CN107442177B (zh) | 5-羟甲基糠醛选择性加氢合成2,5-呋喃二甲醇的方法 | |
| EP1739104A1 (en) | Polymer-supported metal cluster compositions | |
| CN109453814B (zh) | 含磺酸基和膦配体多级孔聚合物固载铑催化剂及制备和应用 | |
| CN111995635A (zh) | 壳聚糖负载铜膜材料催化制备有机硅化合物的方法 | |
| CN111111775A (zh) | 有机含膦聚合物载体负载的Rh基催化剂及其制备和应用 | |
| CN114870901B (zh) | 用于烯烃氢甲酰化的双亚磷酸酯聚合物催化剂及其制备方法和应用 | |
| CN101850271B (zh) | 一种烯烃硅氢加成铂催化剂、制备方法及其应用 | |
| CN103408756A (zh) | 可回收利用的负载型一价铜催化剂催化的制备聚三唑的方法以及制得的聚三唑 | |
| CN109453812B (zh) | 有机含氮聚合物载体负载Rh基催化剂及其制备和应用 | |
| CN116116462B (zh) | 一种引入官能化烯烃的含膦聚合物负载钯催化剂及其制备和在硅-碳偶联反应中的应用 | |
| WO2022105047A1 (zh) | 催化剂以及制备方法、应用 | |
| CN112619705B (zh) | 环氧烷烃加成反应催化剂及其应用 | |
| Karimi et al. | Highly dispersed palladium nanoparticles supported on an imidazolium-based ionic liquid polymer: an efficient catalyst for oxidation of alcohols | |
| CN104759292A (zh) | 有机分子笼负载催化剂及其合成方法和用途 | |
| CN111111774A (zh) | 有机含膦聚合物载体负载铑和杂多酸催化剂及制备和应用 | |
| JP4568802B2 (ja) | 高分子固定化白金触媒及びその使用 | |
| Özdemir et al. | Syntheses and catalytic properties of alternating copolymers of poly [4-maleimidopyridyl (p-cymene) dichloro Ru (II)] with γ-methacryloxypropyl trimethoxysilane | |
| CN112756012B (zh) | 一种亲水性有机多孔聚合物负载钯催化剂及其制备方法和应用 | |
| CN109894148B (zh) | 一种多孔手性有机聚合物催化剂及其制备方法 | |
| CN114560964A (zh) | 一种羧基功能化聚离子液体的合成方法及其应用 | |
| CN109590029B (zh) | 离子交换树脂和其用途 | |
| CN109575162B (zh) | 离子交换树脂和用途 | |
| CN110694689A (zh) | 聚离子液体负载钌卡宾配合物催化剂及制备方法和其应用 | |
| CN101423565B (zh) | 一种负载型乙烯聚合催化剂及其应用方法 |
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 |