CN102188996B - Supported hydrosilylation catalyst and preparation method thereof - Google Patents

Supported hydrosilylation catalyst and preparation method thereof Download PDF

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CN102188996B
CN102188996B CN2011100660262A CN201110066026A CN102188996B CN 102188996 B CN102188996 B CN 102188996B CN 2011100660262 A CN2011100660262 A CN 2011100660262A CN 201110066026 A CN201110066026 A CN 201110066026A CN 102188996 B CN102188996 B CN 102188996B
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carrier
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CN102188996A (en
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来国桥
白赢
彭家建
厉嘉云
蒋剑雄
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Hangzhou Normal University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/584—Recycling of catalysts

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Abstract

The invention relates to a supported hydrosilylation catalyst and a preparation method thereof, and aims to provide a heterogeneous catalyst suitable for hydrosilylation and a preparation method thereof. When the catalyst is used, the reaction conditions are mild; and the catalyst is safe and effective and conveniently separated from the product, and can be recycled. The catalyst provided by the invention has the structural formula shown in the specification. The preparation method provided by the invention comprises the following steps: 1) modifying the carrier surface with a coupling agent; 2) modifying the carrier surface with a functional group compound; and 3) preparing the catalyst through coordination complexing with a platinum compound.

Description

A kind of loaded type silicon catalyst for addition reaction of hydrogen and preparation method thereof
Technical field
The present invention relates to the Catalysts and its preparation method in the organic chemistry filed, specifically a kind of loaded type silicon catalyst for addition reaction of hydrogen and preparation method thereof.
Background technology
The catalyzed alkene hydrosilylation occupies an important position in Synthetic Organic Chemistry, is one of synthesizing organo-silicon coupling agent and function organo-silicon compound and the most important approach of polymer.Usually directly use chloroplatinic acid as catalyst, it is Speier ' s catalyst (isopropyl alcohol solution of chloroplatinic acid) and Karstedt ' s catalyst (chloroplatinic acid and contain silane or the siloxanes complexing of vinyl) that experiment and industrial production make with the most use.Though these two kinds of catalyst have greater activity, selectivity of product is not high; And as homogeneous catalyst, reaction finishes rear catalyst and is difficult to separate from reaction system, is undoubtedly a kind of waste concerning the use of precious metals pt.
The platinum catalyst of support type is used for hydrosilylation, and document is also reported to some extent.Utilize Al 2O 3, SiO 2, activated carbon, MgO-Supported Pt preparation catalyst be used for the silicon hydrogenation of alkene.The advantage of the Pt heterogeneous catalyst maximum of inorganic carrier load just is that it can separate with product easily.But these heterogeneous catalysts are used in the hydrosilylation, carry out under high temperature, condition of high voltage often, and platinum runs off easily in the course of reaction, the very fast inactivation of catalyst.In addition, the selectivity of product that obtains is not high yet, so the catalytic effect of these heterogeneous catalysts is also undesirable.Some researchers adopt coupling agent to SiO 2Carry out modification, then the complex of Supported Pt Nanoparticles and other element is used for hydrosilylation as catalyst, can obtain than simple SiO 2The better catalytic effect of Supported Pt Nanoparticles.In the situation that the platinum consumption improves, namely reduce under the active prerequisite of catalyst, can obtain the selective of silicon hydrogen addition compound product preferably.
Hydrosilylation is as the fundamental reaction in the field of organic silicon, and its core technology just is to be fit to the preparation of this catalysts.Therefore, catalyst for addition reaction of hydrogen and silicon with high activity, high selectivity of research and preparation has great importance and practical value.
Summary of the invention
The technical issues that need to address of the present invention have provided a kind of heterogeneous catalyst that is applicable to hydrosilylation and preparation method thereof, and reaction condition was gentle when this catalyst used, safety, effectively, and with convenient product separation, recyclable recycling.
Loaded type silicon catalyst for addition reaction of hydrogen of the present invention is a kind of supported Pt catalysts with following structural formula:
Figure 2011100660262100002DEST_PATH_IMAGE001
。
This loaded type silicon catalyst for addition reaction of hydrogen is realized by following method: take inorganic matter as catalyst carrier, by coupling agent and specific functional groups modifying and decorating carrier surface, then with the platinum compounds ligand complex, form the loaded platinum catalyst that is fit to efficiently hydrosilylation.
The preparation method of loaded type silicon catalyst for addition reaction of hydrogen of the present invention, as follows:
1) use coupling agent modified carrier surface: add carrier in solvent, the mass ratio of carrier and solvent is 1:30～50, and (5～60 min get final product) stirs; Add coupling agent, the mass ratio of coupling agent and carrier is 1:1 ~ 100, and (10～100 min get final product) stirs; Under the stirring, drip the mixed solution of water and ethanol, water and ethanol volume ratio are 1:5 ~ 5:1; Dropwise, be warming up to 50～150 ℃, continue to stir, the processing time is 2～24 h, filters, washs, dries, and gets modified support; Described carrier is silica or molecular sieve, and described solvent is toluene, benzene or dimethylbenzene, and described coupling agent is γ-aminopropyl alkoxy silane;
2) modify carrier surface with functional compounds: in solvent, with functional compounds and modified support reaction, modified support and solvent quality are than being 1:20～100, the mass ratio of functional compounds and modified support is 1:8 ~ 100, reaction temperature is 50～150 ℃, reaction time is 8～24h, filters, washs, dries, and gets twice-modified carrier; Described solvent is water, acetone or oxolane, and described functional compounds is undecenoic acid;
3) with the platinum compounds ligand complex: in solvent, add the reaction of twice-modified carrier and platinum compounds ligand complex, get product; Twice-modified carrier is 1:10 ~ 100 with the solvent quality ratio, and platinum compounds and twice-modified carrier mass ratio are 1:20 ~ 10000, and reaction temperature is 30～100 ℃, and the reaction time is 8～24 h, desolventizing, oven dry; Described platinum compounds is chloroplatinic acid, platinum chloride, potassium chloroplatinite or potassium chloroplatinate, and described solvent is oxolane, ethanol, methyl alcohol, acetone or water.
The beneficial effect that the present invention has is:
1, because the catalyst of the present invention preparation is modified inorganic thing carrier load type catalyst, have efficient catalytic, the recyclable characteristics such as recycle, also increased new varieties for catalyst for addition reaction of hydrogen and silicon simultaneously.
2, the catalyst aims unsaturated olefin hydrosilylation of the present invention preparation has good catalytic effect, can catalysis the addition reaction of itself and multiple silane containing hydrogen, applicability is comparatively extensive.
3, in the catalyst use procedure of the present invention's preparation, reaction condition is gentle, safety, and catalytic activity is high, and addition compound product is selectively high.
4, preparation method provided by the invention is simple, is easy to control, and reappearance is relatively good, has certain economic and social benefits.
Description of drawings
Fig. 1 is carrier, modified support and catalyst infrared spectrum thereof.(a) carrier silica wherein, (b) improved silica, (c) twice-modified silica, (d) Pt catalyst.
The specific embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
1) uses coupling agent modified carrier surface: in 500 mL reactors with charge door and agitating device, add 20.0 g silica gel and 250 mL toluene, stir 10 min under the room temperature, add 10.0 g gamma-aminopropyl-triethoxy-silanes, stir 20 min, drip the mixed solution of 10 mL water and 30 mL ethanol under the room temperature, stir 2h, heat 100 ℃ of return stirrings and react 2 h.Removing toluene and ethanol, obtain white powder, is dry 24 h under 80 ℃ of vacuum conditions in temperature, gets first improved silica.
2) modify carrier surface with functional compounds: in 250 mL there-necked flasks, add 2.0 g functional compounds undecenoic acids and 100 mL water, be heated to 80 ℃, stirring is dissolved undecenoic acid fully, adds the first improved silica of 6.0 g step 1), keep temperature to continue to stir 3 h, filter, washing obtains pale yellow powder, be dry 24 h under 80 ℃ of vacuum conditions in temperature, get twice-modified carrier.
3) prepare platinum catalyst with the platinum compounds ligand complex: twice-modified carrier adding 2.0 g steps 2 in 50 mL reaction bulbs), 2.7 mL chloroplatinic acid tetrahydrofuran solution (Pt content is 0.0037 g/mL), 20 mL oxolanes, stirring at room is reacted 24 h.Remove solvent, 60 ℃ of vacuum drying are to constant weight, and cooling gets pale yellow powder---and be product, platinum content is 0.5 wt%.(see figure 1)
Embodiment 2:
1) uses coupling agent modified carrier surface: in 500 mL reactors with charge door and agitating device, add 20.0 g silica gel and 250 mL toluene, stir 10 min under the room temperature, add 6.0 g gamma-aminopropyl-triethoxy-silanes, stir 20 min, drip the mixed solution of 10 mL water and 30 mL ethanol under the room temperature, stir 2 h, heat 100 ℃ of return stirring reaction 2h.Removing toluene and ethanol, obtain white powder, is dry 24 h under 80 ℃ of vacuum conditions in temperature, gets modified support.
2) use the modified with functional group carrier surface: in the 250mL there-necked flask, add 2.0 g undecenoic acids and 100 mL water, be heated to 80 ℃, stirring is dissolved undecenoic acid fully, adds products therefrom in the 6.0 g step 1), keep temperature to continue to stir 3 h, filter, washing obtains pale yellow powder, be dry 24 h under 80 ℃ of vacuum conditions in temperature, get twice-modified carrier.
3) prepare platinum catalyst with the platinum compounds ligand complex: in 50 mL reaction bulbs, add 2.0 g steps 2) the middle twice-modified carrier of gained, 2.7 mL chloroplatinic acid tetrahydrofuran solution (Pt content is 0.0037 g/mL), 20 mL oxolanes are warming up to 40 ℃ of stirring and refluxing and react 12 h.Remove solvent, 60 ℃ of vacuum drying are cooled off to get pale yellow powder to constant weight, and platinum content is 0.5 wt%.
Embodiment 3:
1) uses coupling agent modified carrier surface: in 500 mL reactors with charge door and agitating device, add 20.0 g silica gel and 250 mL toluene, stir 10 min under the room temperature, add 5.0 g γ-aminopropyltrimethoxysilanes, stir 20 min, drip the mixed solution of 10 mL water and 30 mL ethanol under the room temperature, stir 2h, heat 100 ℃ of return stirrings and react 2 h.Removing toluene and ethanol, obtain white powder, is dry 24 h under 80 ℃ of vacuum conditions in temperature, gets modified support.
2) use the modified with functional group carrier surface: in the 250mL there-necked flask, add 2.0 g undecenoic acids and 100 mL water, be heated to 80 ℃, stirring is dissolved undecenoic acid fully, adds products therefrom in the 6.0 g step 1), keep temperature to continue to stir 3 h, filter, washing obtains pale yellow powder, be dry 24 h under 80 ℃ of vacuum conditions in temperature, get twice-modified carrier.
3) prepare platinum catalyst with the platinum compounds ligand complex: in 50 mL reaction bulbs, add 2.0 g steps 2) the middle twice-modified carrier of gained, 2.7 mL chloroplatinic acid ethanolic solutions (Pt content is 0.0037 g/mL), 20 mL ethanol, stirring at room is reacted 12 h.Remove solvent, 60 ℃ of vacuum drying are cooled off to get pale yellow powder to constant weight, and platinum content is 0.5 wt%.
Embodiment 4:
1) uses coupling agent modified carrier surface: in 500 mL reactors with charge door and agitating device, add 20.0 g silica gel and 250 mL toluene, stir 10 min under the room temperature, add 3.5 g γ-aminopropyl ethyl dimethoxy silane, stir 20 min, drip the mixed solution of 10 mL water and 30 mL ethanol under the room temperature, stir 2h, heat 100 ℃ of return stirrings and react 2 h.Removing toluene and ethanol, obtain white powder, is dry 24 h under 80 ℃ of vacuum conditions in temperature, gets modified support.
2) use the modified with functional group carrier surface: in the 250mL there-necked flask, add 2.0 g undecenoic acids and 100 mL water, be heated to 90 ℃, stirring is dissolved undecenoic acid fully, adds products therefrom in the 6.0 g step 1), keep temperature to continue to stir 3 h, filter, washing obtains pale yellow powder, be dry 24 h under 80 ℃ of vacuum conditions in temperature, get twice-modified carrier.
3) prepare platinum catalyst with the platinum compounds ligand complex: in 50 mL reaction bulbs, add 2.0 g steps 2) the middle twice-modified carrier of gained, platinum chloride (containing Pt 0.02 g), 20 mL methyl alcohol are warming up to 40 ℃ of stirring reaction 12 h.Remove solvent, 60 ℃ of vacuum drying are cooled off to get pale yellow powder to constant weight, and platinum content is 1 wt%.
Embodiment 5:
1) uses coupling agent modified carrier surface: in 500 mL reactors with charge door and agitating device, add 20.0 g silica gel and 250 mL toluene, stir 10 min under the room temperature, add 8.0 g γ-aminopropyl methyldiethoxysilane, stir 20 min, drip the mixed solution of 10 mL water and 30 mL ethanol under the room temperature, stir 2h, heat 110 ℃ of return stirrings and react 2 h.Removing toluene and ethanol, obtain white powder, is dry 24 h under 80 ℃ of vacuum conditions in temperature, gets modified support.
2) use the modified with functional group carrier surface: in the 250mL there-necked flask, add 2.0 g undecenoic acids and 100 mL water, be heated to 80 ℃, stirring is dissolved undecenoic acid fully, adds products therefrom in the 6.0 g step 1), keep temperature to continue to stir 3 h, filter, washing obtains pale yellow powder, be dry 24 h under 80 ℃ of vacuum conditions in temperature, get twice-modified carrier.
3) prepare platinum catalyst with the platinum compounds ligand complex: in 50 mL reaction bulbs, add 2.0 g steps 2) the middle twice-modified carrier of gained, 2.7 mL potassium chloroplatinate tetrahydrofuran solution (containing Pt 0.01 g), 20 mL oxolanes are warming up to 60 ℃ of stirring and refluxing and react 12 h.Remove solvent, 60 ℃ of vacuum drying are cooled off to get pale yellow powder to constant weight, and platinum content is 0.5 wt%.
Embodiment 6:
1) uses coupling agent modified carrier surface: in 500 mL reactors with charge door and agitating device, add 20.0 g silica gel and 250 mL toluene, stir 10 min under the room temperature, add 6.0 g γ-aminopropyl methyldiethoxysilane, stir 20 min, drip the mixed solution of 10 mL water and 30 mL ethanol under the room temperature, stir 2h, heat 120 ℃ of return stirrings and react 2 h.Removing toluene and ethanol, obtain white powder, is dry 24 h under 80 ℃ of vacuum conditions in temperature, gets modified support.
2) use the modified with functional group carrier surface: in the 250mL there-necked flask, add 2.0 g undecenoic acids and 100 mL water, be heated to 80 ℃, stirring is dissolved undecenoic acid fully, adds products therefrom in the 6.0 g step 1), keep temperature to continue to stir 3 h, filter, washing obtains pale yellow powder, be dry 24 h under 80 ℃ of vacuum conditions in temperature, get twice-modified carrier.
3) prepare platinum catalyst with the platinum compounds ligand complex: in 50 mL reaction bulbs, add 2.0 g steps 2) the middle twice-modified carrier of gained, 2.7 mL chloroplatinous acid aqueous solutions of potassium (containing Pt 0.01 g), 20 mL water are warming up to 60 ℃ of stirring and refluxing and react 12 h.Remove solvent, 60 ℃ of vacuum drying are cooled off to get pale yellow powder to constant weight, and platinum content is 0.5 wt%.
Embodiment 7:
1) uses coupling agent modified carrier surface: in 500 mL reactors with charge door and agitating device, add 20.0 g 4A molecular sieves and 250 mL toluene, stir 10 min under the room temperature, add 6.0 g γ-aminopropyl methyldiethoxysilane, stir 20 min, drip the mixed solution of 10 mL water and 30 mL ethanol under the room temperature, stir 2h, heat 120 ℃ of return stirrings and react 2 h.Removing toluene and ethanol, obtain white powder, is dry 24 h under 80 ℃ of vacuum conditions in temperature, gets modified support.
2) use the modified with functional group carrier surface: in the 250mL there-necked flask, add 2.0 g undecenoic acids and 100 mL water, be heated to 80 ℃, stirring is dissolved undecenoic acid fully, adds products therefrom in the 6.0 g step 1), keep temperature to continue to stir 3 h, filter, washing obtains pale yellow powder, be dry 24 h under 80 ℃ of vacuum conditions in temperature, get twice-modified carrier.
3) prepare platinum catalyst with the platinum compounds ligand complex: in 50 mL reaction bulbs, add 2.0 g steps 2) the middle twice-modified carrier of gained, 2.7 mL chloroplatinous acid aqueous solutions of potassium (containing Pt 0.01 g), 20 mL water are warming up to 60 ℃ of stirring and refluxing and react 12 h.Remove solvent, 60 ℃ of vacuum drying are cooled off to get pale yellow powder to constant weight, and platinum content is 0.5 wt%.
Embodiment 8: styrene catalyzed hydrosilylation
Take by weighing catalyst 0.4 g among the embodiment 1,9.6 g (0.1 mol) styrene and 18.0 g (0.11 mol) triethoxy hydrogen silane place 100 milliliters single port flask, reaction 2 h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate to get product, product detects through GC-MS, the styrene conversion rate is that 99.8%, β-addition compound product productive rate is 92.7%.
Embodiment 9: styrene catalyzed hydrosilylation
Take by weighing catalyst 0.4 g among the embodiment 2,9.6 g (0.1 mol) styrene and 18.0 g (0.11 mol) triethoxy hydrogen silane place 100 milliliters single port flask, reaction 2 h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate to get product, product detects through GC-MS, the styrene conversion rate is 99.8%, β-addition compound product productive rate 91.5%.
Embodiment 10: styrene catalyzed hydrosilylation
Take by weighing catalyst 0.4 g among the embodiment 3,9.6 g (0.1 mol) styrene and 18.0 g (0.11 mol) triethoxy hydrogen silane place 100 milliliters single port flask, reaction 2 h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate to get product, product detects through GC-MS, the styrene conversion rate is 100%, β-addition compound product productive rate 89.5%.
Embodiment 11: styrene catalyzed hydrosilylation
Take by weighing catalyst 0.4 g among the embodiment 4,9.6 g (0.1 mol) styrene and 18.0 g (0.11 mol) triethoxy hydrogen silane place 100 milliliters single port flask, reaction 2 h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate to get product, product detects through GC-MS, the styrene conversion rate is 99.6%, β-addition compound product productive rate 91.5%.
Embodiment 12: styrene catalyzed hydrosilylation
Take by weighing catalyst 0.4 g among the embodiment 5,9.6 g (0.1 mol) styrene and 18.0 g (0.11 mol) triethoxy hydrogen silane place 100 milliliters single port flask, reaction 1 h in 70 ℃ of silicone oil baths, cooling, sedimentation, separate to get product, product detects through GC-MS, the styrene conversion rate is 95.6%, β-addition compound product productive rate 91.9%.
Embodiment 13: styrene catalyzed hydrosilylation
Take by weighing catalyst 0.4 g among the embodiment 6,9.6 g (0.1 mol) styrene and 18.0 g (0.11 mol) triethoxy hydrogen silane place 100 milliliters single port flask, reaction 1 h in 80 ℃ of silicone oil baths, cooling, sedimentation, separate to get product, product detects through GC-MS, the styrene conversion rate is 97.6%, β-addition compound product productive rate 90.5%.
Embodiment 14: styrene catalyzed hydrosilylation
Take by weighing catalyst 0.4 g among the embodiment 7,9.6 g (0.1 mol) styrene and 18.0 g (0.11 mol) triethoxy hydrogen silane place 100 milliliters single port flask, reaction 1 h in 80 ℃ of silicone oil baths, cooling, sedimentation, separate to get product, product detects through GC-MS, the styrene conversion rate is 98.5%, β-addition compound product productive rate 91.2%.
Embodiment 15: catalyst is reused experiment 1
Product among the embodiment 8 is removed, catalyst stays in reactor, add 9.6 g (0.1 mol) styrene and 18.0 g (0.11 mol) triethoxy hydrogen silane, reaction 2 h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate to get product, product detects through GC-MS, and the styrene conversion rate is 99.5%, β-addition compound product yield 91.7%.
Embodiment 16: catalyst is reused experiment 2
Product among the embodiment 15 is removed, catalyst stays in reactor, add 9.6 g (0.1 mol) styrene and 18.0 g (0.11 mol) triethoxy hydrogen silane, reaction 2 h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate to get product, product detects through GC-MS, and the styrene conversion rate is 99.1%, β-addition compound product yield 91.4%.
Embodiment 17: catalyst is reused experiment 3
Product among the embodiment 16 is removed, catalyst stays in reactor, add 9.6 g (0.1 mol) styrene and 18.0 g (0.11 mol) triethoxy hydrogen silane, reaction 2 h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate to get product, product detects through GC-MS, and the styrene conversion rate is 99.2%, β-addition compound product yield 91.3%.
Embodiment 18: the addition reaction of catalysis different alkene and silane
Take by weighing embodiment 1 catalyst 0.4 g, 11.2 g (0.1 mol) octene and 18.0 g (0.11 mol) triethoxy hydrogen silane place 100 milliliters single port flask, react 2h in 60 ℃ of silicone oil baths, cooling, product detects through GC-MS, the octene conversion ratio is 100%, β-addition compound product yield 99.7%.
Take by weighing embodiment 1 catalyst 0.4 g, 16.8 g (0.1 mol) laurylene and 18.0 g (0.11 mol) triethoxy hydrogen silane place 100 milliliters single port flask, reaction 2 h in 70 ℃ of silicone oil baths, cooling, product detects through GC-MS, the laurylene conversion ratio is that 96.4%, β-addition compound product yield is 99.3%.
Take by weighing embodiment 1 catalyst 0.4 g, 19.6 g (0.1 mol) tetradecene and 18.0 g (0.11 mol) triethoxy hydrogen silane place 100 milliliters single port flask, reaction 3 h in 70 ℃ of silicone oil baths, cooling, product detects through GC-MS, the tetradecene conversion ratio is 92.1%, β-addition compound product yield 99.5%.
Take by weighing embodiment 1 catalyst 0.4g, 25.2 g (0.1 mol) octadecylene and 18.0 g (0.11 mol) triethoxy hydrogen silane place 100 milliliters single port flask, reaction 3 h in 90 ℃ of silicone oil baths, cooling, product detects through GC-MS, the octadecylene conversion ratio is 89.3%, β-addition compound product yield 98.1%.
Take by weighing embodiment 1 catalyst 0.4g, 11.2 g (0.1 mol) octene and 12.6 g (0.11 mol) dichloromethylsilane place 100 milliliters single port flask, reaction 2 h in 40 ℃ of silicone oil baths, cooling, product detects through GC-MS, the octene conversion ratio is 100%, β-addition compound product yield 99.2%.
Take by weighing embodiment 1 catalyst 0.4 g, 16.8 g (0.1 mol) laurylene and 12.6 g (0.11 mol) dichloromethylsilane place 100 milliliters single port flask, reaction 2 h in 40 ℃ of silicone oil baths, cooling, product detects through GC-MS, the laurylene conversion ratio is 98.2%, β-addition compound product yield 98.9%.
Take by weighing embodiment 1 catalyst 0.4 g, 19.6 g (0.1 mol) tetradecene and 12.6 g (0.11 mol) dichloromethylsilane place 100 milliliters single port flask, reaction 3 h in 40 ℃ of silicone oil baths, cooling, product detects through GC-MS, the tetradecene conversion ratio is 94.3%, β-addition compound product yield 92.0%.
Take by weighing embodiment 1 catalyst 0.4 g, 25.2 g (0.1 mol) octadecylene and 12.6 g (0.11 mol) dichloromethylsilane place 100 milliliters single port flask, reaction 3 h in 40 ℃ of silicone oil baths, cooling, product detects through GC-MS, the octadecylene conversion ratio is 90.6%, β-addition compound product yield 87.5%.
Take by weighing embodiment 1 catalyst 0.4 g, 11.2 g (0.1 mol) octene and 14.9 g (0.11 mol) 3,5-dimethylphenyl hydrogen silane place 100 milliliters single port flask, reaction 3 h in 60 ℃ of silicone oil baths, cooling, product detects through GC-MS, the octene conversion ratio is 100%, β-addition compound product yield 98.9%.
Take by weighing embodiment 1 catalyst 0.4 g, 16.8 g (0.1 mol) laurylene and 14.9 g (0.11 mol) 3,5-dimethylphenyl hydrogen silane place 100 milliliters single port flask, reaction 3 h in 60 ℃ of silicone oil baths, cooling, product detects through GC-MS, the laurylene conversion ratio is 96.5%, β-addition compound product yield 97.5%.
Take by weighing embodiment 1 catalyst 0.4g, 19.6 g (0.1 mol) tetradecene and 14.9 g (0.11 mol) 3,5-dimethylphenyl hydrogen silane place 100 milliliters single port flask, reaction 4 h in 90 ℃ of silicone oil baths, cooling, product detects through GC-MS, the tetradecene conversion ratio is 92.1%, β-addition compound product yield 90.7%.
Take by weighing embodiment 1 catalyst 0.4 g, 25.2 g (0.1 mol) octadecylene and 14.9 g (0.11 mol) 3,5-dimethylphenyl hydrogen silane place 100 milliliters single port flask, reaction 4 h in 90 ℃ of silicone oil baths, cooling, product detects through GC-MS, the octadecylene conversion ratio is 90.5%, β-addition compound product yield 82.8%.

Claims (2)

1. loaded type silicon catalyst for addition reaction of hydrogen is characterized in that: be a kind of loaded type silicon addition reaction of hydrogen Pt catalyst with following structural formula:
, wherein carrier is silica or molecular sieve.
2. the preparation method of a loaded type silicon catalyst for addition reaction of hydrogen as claimed in claim 1 is characterized in that as follows:
1) use coupling agent modified carrier surface: add carrier in solvent, the mass ratio of carrier and solvent is 1:30～50, stirs; Add coupling agent, the mass ratio of coupling agent and carrier is 1:1 ~ 100, stirs; Under the stirring, drip the mixed solution of water and ethanol, water and ethanol volume ratio are 1:5 ~ 5:1; Dropwise, be warming up to 50～150 ℃, continue to stir, the processing time is 2～24 h, filters, washs, dries, and gets modified support; Described carrier is silica or molecular sieve, and described solvent is toluene, benzene or dimethylbenzene, and described coupling agent is γ-aminopropyl alkoxy silane;
2) modify carrier surface with functional compounds: in solvent, with functional compounds and modified support reaction, modified support and solvent quality are than being 1:20～100, the mass ratio of functional compounds and modified support is 1:8 ~ 100, reaction temperature is 50～150 ℃, reaction time is 8～24h, filters, washs, dries, and gets twice-modified carrier; Described solvent is water, acetone or oxolane, and described functional compounds is undecenoic acid;
3) with the platinum compounds ligand complex: in solvent, add the reaction of twice-modified carrier and platinum compounds ligand complex, get product; Twice-modified carrier is 1:10 ~ 100 with the solvent quality ratio, and platinum compounds and twice-modified carrier mass ratio are 1:20 ~ 10000, and reaction temperature is 30～100 ℃, and the reaction time is 8～24 h, desolventizing, oven dry; Described platinum compounds is chloroplatinic acid, platinum chloride, potassium chloroplatinite or potassium chloroplatinate, and described solvent is oxolane, ethanol, methyl alcohol, acetone or water.
CN2011100660262A 2011-03-18 2011-03-18 Supported hydrosilylation catalyst and preparation method thereof Expired - Fee Related CN102188996B (en)

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CN105854934B (en) * 2016-03-31 2018-11-27 天津大学 A kind of preparation and application of environmentally protective solid-carrying type platinum catalyst
DE102016205526A1 (en) * 2016-04-04 2017-10-05 Wacker Chemie Ag Precious metal-free hydrosilylatable mixture
CN108467486B (en) * 2017-12-30 2021-01-26 深圳市安品有机硅材料有限公司 Sulfur poisoning resistant platinum catalyst and preparation method thereof
CN108892778B (en) * 2018-06-04 2021-03-19 榛硕（武汉）智能科技有限公司 Catalyst and preparation method thereof
CN112007634B (en) * 2019-05-28 2023-08-29 新特能源股份有限公司 Novel vinyl trichlorosilane catalyst, preparation method thereof and method for preparing vinyl trichlorosilane by catalysis of novel vinyl trichlorosilane catalyst
CN111303930B (en) * 2020-02-08 2022-02-08 河北工业大学 Method for hydrosilylation reaction of carbonyl compound in biological oil
CN115672401A (en) * 2022-11-01 2023-02-03 安徽壹石通材料科学研究院有限公司 Supported noble metal catalyst and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6166238A (en) * 2000-01-12 2000-12-26 Crompton Corporation High purity organofunctional alkyldialkoxysilanes
WO2004030816A1 (en) * 2002-10-04 2004-04-15 Johnson Matthey Public Limited Company Hydrosilation catalyst
CN101058077A (en) * 2007-05-22 2007-10-24 杭州师范大学 Addition reaction of silicon with hydrogen solid supported bimetallic catalyst and its preparation method
CN101322946A (en) * 2008-06-24 2008-12-17 杭州师范大学 Hydrosilylation catalyst, preparation method and uses thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6166238A (en) * 2000-01-12 2000-12-26 Crompton Corporation High purity organofunctional alkyldialkoxysilanes
WO2004030816A1 (en) * 2002-10-04 2004-04-15 Johnson Matthey Public Limited Company Hydrosilation catalyst
CN101058077A (en) * 2007-05-22 2007-10-24 杭州师范大学 Addition reaction of silicon with hydrogen solid supported bimetallic catalyst and its preparation method
CN101322946A (en) * 2008-06-24 2008-12-17 杭州师范大学 Hydrosilylation catalyst, preparation method and uses thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Qian Jiang Miao.Silica-supported Karstedt-type catalyst.《Catalysis Communications》.2003,第4卷 *
王玲治.聚-r-氨丙基硅氧烷-铂络合物对不饱和化合物的硅氢加成的催化活性和选择性.《催化学报》.1981,第2卷(第3期), *

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