CN107857777B - Hydrosilylation reaction using recyclable platinum compound as catalyst - Google Patents

Hydrosilylation reaction using recyclable platinum compound as catalyst Download PDF

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CN107857777B
CN107857777B CN201711031885.1A CN201711031885A CN107857777B CN 107857777 B CN107857777 B CN 107857777B CN 201711031885 A CN201711031885 A CN 201711031885A CN 107857777 B CN107857777 B CN 107857777B
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厉嘉云
彭家建
白赢
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Zhejiang Xinshichen New Material Co.,Ltd.
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Hangzhou Normal University
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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Abstract

The invention relates to the field of organic chemistry, and aims to solve the problems of catalysts in the existing hydrosilylation reaction. The method has the advantages of mild and safe reaction conditions, high reaction conversion rate, strong selectivity of beta addition products, convenient separation of the products from the catalyst and recyclable catalyst.

Description

Hydrosilylation reaction using recyclable platinum compound as catalyst
Technical Field
The invention relates to the field of organic chemistry, in particular to a method for carrying out hydrosilylation reaction by taking 1-mPEG-3-alkyl-2-diphenylphosphine imidazole halide as a metal platinum organic ligand and preparing high-selectivity bis [ (1-mPEG-3-alkyl-2-diphenylphosphine imidazole halide) platinum dichloride ] as a catalyst.
Background
One of the most important ways to synthesize functional organosilicon compounds and organosilicon coupling agents and polymers is to catalyze the hydrosilylation reaction of olefins (Leslie D.field, Antony J.Ward, J.Organomet. chem, 2003, 681, 91-97), which plays an important role in organosilicon chemistry, and before the invention, chloroplatinic acid and a Karster catalyst are mostly used in industry, and although the catalyst system has higher activity, the catalyst system is difficult to separate and recover from the reaction system, and the reaction cost is higher (Chisso Corp. JP., 8204995, 1982). Later, through research on various transition metal complexes, transition metals (Pt, Rh and the like) are found to have certain catalytic activity on hydrosilylation. However, for certain types of hydrosilylation reactions, such as the hydrosilylation of olefins with alkoxysilanes, the catalytic activity is not high using transition metals (Pt, Rh, etc.) as catalysts (Bogdan Marciniec, and Jacek)
Figure GDA0002384908170000011
J.Organomet.Chem.,1983, 253, 349-362). Meanwhile, the catalytic system is difficult to separate, recycle and reuse from the reaction system. Chen Yuanyin et al (Ben Zhi, Coxiqing, Chen Yuanyin, applied chemistry, 1997, 14, 1, 107-.
Disclosure of Invention
In order to solve the problems of the catalyst in the existing hydrosilylation reaction, the invention provides a hydrosilylation reaction method which has the advantages of mild and safe reaction conditions, high reaction conversion rate, strong selectivity of beta addition products, convenient separation of the products from the catalyst and capability of recycling the catalyst.
The invention is realized by the following technical scheme: a hydrosilylation reaction method comprises the steps of taking olefin and triethoxyhydrosilane as raw materials, taking bis [ (1-mPEG-3-alkyl-2-diphenylphosphine imidazole halide) platinum dichloride ] as a catalyst, heating to 50-90 ℃, stirring, reacting for 4-6 hours, filtering, distilling, collecting fractions, preferably decompressing, distilling, collecting fractions, and obtaining a hydrosilylation product.
The reaction formula is shown as follows:
Figure GDA0002384908170000021
wherein R is selected from C5H9，C6H11，C7H13，C10H19，Ph，CH3One of Ph, namely the olefin is selected from one of hexene, heptene, octene, undecene, styrene and alpha-methyl styrene. The mol ratio of the olefin, the triethoxy hydrosilane and the catalyst is 10000: 11000-12000: 1-50, and the preferable mol ratio is 10000: 11000: 5.
The catalyst is bis [ (1-mPEG-3-alkyl-2-diphenylphosphine imidazole halide)Oxide) platinum dichloride]Wherein mPEG is methoxy polyethylene glycol with the structural formula
Figure GDA0002384908170000022
n-8, 12,17 and 43, and the alkyl is selected from one of methyl, ethyl, butyl and hexyl.
The catalyst is prepared by taking PEG imidazole salt containing organic phosphine ligand as metal platinum organic ligand. The preparation method of the catalyst comprises the following steps: under the protection of argon, a low-temperature constant-temperature reactor is used, the reaction temperature is controlled to be-78 ℃, and n-butyl lithium (A), (B), (C) and (C) is reacted for about 15 minutesnBuLi 3.0mmol, 15% n-hexane solution) was added dropwise to mPEG CnImCl (3.0mmol) in CH2Cl2(20mL) solution (previously with P)4O10Dried CH2Cl2) In (1). After the dropwise addition, the reaction temperature is kept at-78 ℃ and the stirring is continued for 45 minutes, and then the pH is added for about 20 minutes2And (3) dropwise adding PCl (3.0mmol) into the previous reaction solution, continuing stirring for 20 minutes after dropwise adding, slowly raising the reaction temperature to room temperature, and stirring overnight to finish the reaction. After washing the product three times with deoxygenated water (3 x 10mL), the organic phase was washed with Na2SO4Drying, spin-drying the solvent to obtain a solid product quantitatively in N2Under protection, in a 500ml flask, 4g K is put2PtCl4Dissolving in 10ml water, adding 12g of the solid product prepared above in 350ml methanol solution, heating and refluxing the reaction for 2h, collecting the solid, washing with diethyl ether to obtain bis [ 1-mPEG-3-alkyl-2-diphenylphosphinoimidazolium halide]The platinum dichloride compound was dried in vacuo and placed in a desiccator for use.
The hydrosilylation reaction comprises the following specific reaction steps: adding olefin and a bis [ (1-PEG-3-alkyl-2-diphenylphosphine imidazole halide platinum dichloride ] compound into a container, heating to 50-90 ℃ under the protection of nitrogen, stirring, dropwise adding triethoxysilane through a dropping funnel for less than or equal to 0.5 hour, keeping the reaction temperature, opening, condensing, refluxing, continuously stirring for 4-6 hours, standing, cooling to room temperature, filtering, distilling the filtrate to collect corresponding fractions, preferably distilling under reduced pressure to obtain a hydrosilylation product, performing purity analysis on a GC-MS (gas chromatography-mass spectrometry) combination instrument, calculating the conversion rate of the reaction and the selectivity of the hydrosilylation beta adduct, and washing the catalyst with ether for recycling.
The invention uses a series of bis [ (1-mPEG-3-alkyl-2-diphenylphosphine imidazole halide) platinum dichloride ] as a catalyst, so that the hydrosilylation reaction of olefin and triethoxy hydrosilane is easy to carry out, and the selectivity of a beta addition product in a product is improved.
After the reaction is finished, the product can be separated from a catalyst bis [ (1-mPEG-3-alkyl-2-diphenylphosphine imidazole halide) platinum dichloride ] system through cooling and filtration, wherein the catalyst bis [ (1-mPEG-3-alkyl-2-diphenylphosphine imidazole halide) platinum dichloride ] is recycled.
Compared with the prior art, the invention has the beneficial effects that:
(1) a series of bis [ (1-mPEG-3-alkyl-2-diphenylphosphine imidazole halide) platinum dichloride ] is used as a catalyst for hydrosilylation, the reaction condition is mild, the conversion rate is high, and the selectivity of beta addition products is high;
(2) the catalyst bis [ (1-mPEG-3-alkyl-2-diphenylphosphine imidazole halide) platinum dichloride ] and the product are simple to separate and can be recycled.
Detailed Description
The technical scheme of the invention is further specifically described by the following embodiments. The starting materials used in the examples are either commercially available or prepared by conventional methods.
Catalyst starting Material 1-methoxy polyethylene glycol-3-alkyl imidazole chloride salt (mPEG C) used in the examplesnimCl) preparation method: see literature (Bonhte, p.; Dias, a.p.; Papageorgiou, n.; Kalyanasundaram, k.;
Figure GDA0002384908170000032
M.Inorg.Chem.，1996，35，1168；Suarez，P.A.Z.；Einloft，S.；Dullius，J.E.；de Souza，R.F.；Dupont，J.Polyhedron1996，15，1217.)
Figure GDA0002384908170000031
example 1
Preparation of catalyst 1: under the protection of argon, a low-temperature constant-temperature reactor is used, the reaction temperature is controlled to be-78 ℃, and n-butyl lithium is reacted for about 15 minutes (nBuLi 3.0mmol, 15% n-hexane solution) was added dropwise to mPEG (350) MImCl (3.0mmol) in CH2Cl2(20mL) solution (previously with P)4O10Dried CH2Cl2) In (1). After the dropwise addition, the reaction temperature is kept at-78 ℃ and the stirring is continued for 45 minutes, and then the pH is added for about 20 minutes2And (3) dropwise adding PCl (3.0mmol) into the previous reaction solution, continuing stirring for 20 minutes after dropwise adding, slowly raising the reaction temperature to room temperature, and stirring overnight to finish the reaction. After washing the product three times with deoxygenated water (3 x 10mL), the organic phase was washed with Na2SO4Drying, spin-drying the solvent to obtain a solid product quantitatively in N2Under protection, in a 500ml flask, 4g K is put2PtCl4Dissolving in 10ml water, adding 12g of the above catalyst raw material in 350ml methanol, heating and refluxing the reaction for 2h, collecting the solid, washing with diethyl ether to obtain bis [ (1-mPEG (350) -3-methyl-2-diphenylphosphine imidazole halide) platinum dichloride]The compound was dried under vacuum and placed in a desiccator for use to give catalyst 1.
Adding styrene (1.25mol) and catalyst 1(1.25mmol) into a 500ml three-neck flask, slowly heating to 90 ℃ under the protection of nitrogen, stirring while adding triethoxy hydrosilane (1.5mol) dropwise through a dropping funnel, keeping the reaction temperature, continuously stirring for 5 hours, cooling to room temperature, distilling under reduced pressure, collecting corresponding fractions, measuring the conversion rate of the styrene to 93.9% by GC-MS (gas chromatography-mass spectrometry), and measuring the beta adduct 1-triethoxysilyl-2-phenyl ethane (PhCH)2CH2Si(OCH2CH3)3) The yield of (D) was 84.3%.
Example 2
Preparation of catalyst 2: under the protection of argon, a low-temperature constant-temperature reactor is used, the reaction temperature is controlled to be-78 ℃, and n-butyl lithium is reacted for about 15 minutes (nBuLi 3.0mmol, 15% n-hexane solution) was added dropwiseCH addition to mPEG (550) MImCl (3.0mmol)2Cl2(20mL) solution (previously with P)4O10Dried CH2Cl2) In (1). After the dropwise addition, the reaction temperature is kept at-78 ℃ and the stirring is continued for 45 minutes, and then the pH is added for about 20 minutes2And (3) dropwise adding PCl (3.0mmol) into the previous reaction solution, continuing stirring for 20 minutes after dropwise adding, slowly raising the reaction temperature to room temperature, and stirring overnight to finish the reaction. After washing the product three times with deoxygenated water (3 x 10mL), the organic phase was washed with Na2SO4Drying, spin-drying the solvent to obtain a solid product quantitatively in N2Under protection, in a 500ml flask, 4g K is put2PtCl4Dissolving in 10ml water, adding 12g above catalyst raw material 350ml methanol solution, heating and refluxing the reactant for 2h, collecting solid, washing with diethyl ether to obtain bis [ (1-mPEG (550) -3-methyl-2-diphenylphosphine imidazole halide) platinum dichloride]The compound was dried under vacuum and placed in a desiccator for use to give catalyst 2.
Adding styrene (1.25mol) and catalyst 2(1.25mmol) into a 500ml three-neck flask, slowly heating to 90 ℃ under the protection of nitrogen, stirring while dropwise adding triethoxysilane (1.5mol) through a dropping funnel for 20 minutes, keeping the reaction temperature, continuously stirring for 5 hours, cooling to room temperature, performing reduced pressure distillation, collecting corresponding fractions, determining the conversion rate of the styrene to be 99.1% through GC-MS, and determining the beta adduct 1-triethoxysilyl-2-phenyl ethane (PhCH)2CH2Si(OCH2CH3)3) The yield of (D) was 85.7%.
Example 3
Preparation of catalyst 3: under the protection of argon, a low-temperature constant-temperature reactor is used, the reaction temperature is controlled to be-78 ℃, and n-butyl lithium is reacted for about 15 minutes (nBuLi 3.0mmol, 15% n-hexane solution) was added dropwise to mPEG (750) MImCl (3.0mmol) in CH2Cl2(20mL) solution (previously with P)4O10Dried CH2Cl2) In (1). After the dropwise addition, the reaction temperature is kept at-78 ℃ and the stirring is continued for 45 minutes, and then the pH is added for about 20 minutes2PCl (3.0mmol) was added dropwise to the previous reactionAfter the dropwise addition, the mixture was stirred for 20 minutes, the reaction temperature was slowly raised to room temperature, and the mixture was stirred overnight to complete the reaction. After washing the product three times with deoxygenated water (3 x 10mL), the organic phase was washed with Na2SO4Drying, spin-drying the solvent to obtain a solid product quantitatively in N2Under protection, in a 500ml flask, 4g K is put2PtCl4Dissolving in 10ml water, adding 12g of the above catalyst raw material in 350ml methanol, heating and refluxing the reaction for 2h, collecting the solid, washing with diethyl ether to obtain bis [ (1-mPEG (750) -3-methyl-2-diphenylphosphine imidazole halide) platinum dichloride]The compound was dried under vacuum and placed in a desiccator for use to give catalyst 3.
Adding styrene (1.25mol) and a catalyst 3(1.25mmol) into a 500ml three-neck flask, slowly heating to 90 ℃ under the protection of nitrogen, stirring while dropwise adding triethoxysilane (1.5mol) through a dropping funnel for 25 minutes, keeping the reaction temperature, continuously stirring for 5 hours, cooling to room temperature, performing reduced pressure distillation, collecting corresponding fractions, determining the conversion rate of the styrene to be 98.9% through GC-MS, and determining a beta adduct 1-triethoxysilyl-2-phenylethane (PhCH)2CH2Si(OCH2CH3)3) The yield of (b) was 89.5%.
Example 4
Preparation of catalyst 4: under the protection of argon, a low-temperature constant-temperature reactor is used, the reaction temperature is controlled to be-78 ℃, and n-butyl lithium is reacted for about 15 minutes (nBuLi 3.0mmol, 15% n-hexane solution) was added dropwise to mPEG (1900) MImCl (3.0mmol) in CH2Cl2(20mL) solution (previously with P)4O10Dried CH2Cl2) In (1). After the dropwise addition, the reaction temperature is kept at-78 ℃ and the stirring is continued for 45 minutes, and then the pH is added for about 20 minutes2And (3) dropwise adding PCl (3.0mmol) into the previous reaction solution, continuing stirring for 20 minutes after dropwise adding, slowly raising the reaction temperature to room temperature, and stirring overnight to finish the reaction. After washing the product three times with deoxygenated water (3 x 10mL), the organic phase was washed with Na2SO4Drying, spin-drying the solvent to obtain a solid product quantitatively in N2Under protection, in a 500ml flask, 4g K is put2PtCl4Dissolving in 10ml water, adding 12g of the above catalyst raw material in 350ml methanol, heating and refluxing the reaction for 2h, collecting the solid, washing with diethyl ether to obtain bis [ (1-mPEG (1900) -3-methyl-2-diphenylphosphine imidazole halide) platinum dichloride]The compound was dried under vacuum and placed in a desiccator for use to give catalyst 4.
Adding styrene (1.25mol) and catalyst 4(1.25mmol) into a 500ml three-neck flask, slowly heating to 90 ℃ under the protection of nitrogen, stirring while dropwise adding triethoxysilane (1.5mol) through a dropping funnel for 0.5 h, keeping the reaction temperature, continuously stirring for 5 h, cooling to room temperature, performing reduced pressure distillation, collecting corresponding fractions, determining the conversion rate of styrene to be 99.7% by GC-MS, and determining the beta adduct 1-triethoxysilyl-2-phenylethane (PhCH)2CH2Si(OCH2CH3)3) The yield of (D) was 84.8%.
Example 5
Preparation of catalyst 5: under the protection of argon, a low-temperature constant-temperature reactor is used, the reaction temperature is controlled to be-78 ℃, and n-butyl lithium is reacted for about 15 minutes (nBuLi 3.0mmol, 15% n-hexane solution) was added dropwise to mPEG (550) EImCl (3.0mmol) in CH2Cl2(20mL) solution (previously with P)4Ol0Dried CH2Cl2) In (1). After the dropwise addition, the reaction temperature is kept at-78 ℃ and the stirring is continued for 45 minutes, and then the pH is added for about 20 minutes2And (3) dropwise adding PCl (3.0mmol) into the previous reaction solution, continuing stirring for 20 minutes after dropwise adding, slowly raising the reaction temperature to room temperature, and stirring overnight to finish the reaction. After washing the product three times with deoxygenated water (3 x 10mL), the organic phase was washed with Na2SO4Drying, spin-drying the solvent to obtain a solid product quantitatively in N2Under protection, in a 500ml flask, 4g K is put2PtCl4Dissolving in 10ml water, adding 12g of the above catalyst raw material in 350ml methanol, heating and refluxing the reaction for 2h, collecting the solid, washing with diethyl ether to obtain bis [ (1-mPEG (1900) -3-ethyl-2-diphenylphosphine imidazole halide) platinum dichloride]The compound was dried under vacuum and placed in a desiccator for use to give catalyst 5.
Adding styrene (1.25mol) and catalyst 5(1.25mmol) into a 500ml three-neck flask, slowly heating to 90 ℃ under the protection of nitrogen, stirring while dropwise adding triethoxysilane (1.5mol) through a dropping funnel for 20 minutes, keeping the reaction temperature, continuously stirring for 5 hours, cooling to room temperature, performing reduced pressure distillation, collecting corresponding fractions, determining the conversion rate of the styrene to be 95.8% through GC-MS, and determining the beta adduct 1-triethoxysilyl-2-phenylethane (PhCH)2CH2Si(OCH2CH3)3) The yield of (D) was 87.2%.
Example 6
Preparation of catalyst 6: under the protection of argon, a low-temperature constant-temperature reactor is used, the reaction temperature is controlled to be-78 ℃, and n-butyl lithium is reacted for about 15 minutes (nBuLi 3.0mmol, 15% n-hexane solution) was added dropwise to mPEG (550) C4ImCl (3.0mmol) in CH2Cl2(20mL) solution (previously with P)4O10Dried CH2Cl2) In (1). After the dropwise addition, the reaction temperature is kept at-78 ℃ and the stirring is continued for 45 minutes, and then the pH is added for about 20 minutes2And (3) dropwise adding PCl (3.0mmol) into the previous reaction solution, continuing stirring for 20 minutes after dropwise adding, slowly raising the reaction temperature to room temperature, and stirring overnight to finish the reaction. After washing the product three times with deoxygenated water (3 x 10mL), the organic phase was washed with Na2SO4Drying, spin-drying the solvent to obtain a solid product quantitatively in N2Under protection, in a 500ml flask, 4g K is put2PtCl4Dissolving in 10ml water, adding 12g of the above catalyst raw material in 350ml methanol, heating and refluxing the reaction for 2h, collecting the solid, washing with diethyl ether to obtain bis [ (1-mPEG (1900) -3-butyl-2-diphenylphosphine imidazole halide) platinum dichloride]The compound was dried under vacuum and placed in a desiccator for use to afford catalyst 6.
Adding styrene (1.25mol) and catalyst 6(1.25mmol) into a 500ml three-neck flask, slowly heating to 90 ℃ under the protection of nitrogen, dropwise adding triethoxysilane (1.5mol) through a dropping funnel while stirring, keeping the reaction temperature, and continuously stirring for 5 hoursCooling to room temperature, vacuum distilling, collecting corresponding fraction, and measuring conversion rate of styrene by GC-MS to be 95.1%, beta adduct 1-triethoxysilyl-2-phenylethane (PhCH)2CH2Si(OCH2CH3)3) The yield of (D) was 87.8%.
Example 7
Preparation of catalyst 7: under the protection of argon, a low-temperature constant-temperature reactor is used, the reaction temperature is controlled to be-78 ℃, and n-butyl lithium is reacted for about 15 minutes (nBuLi 3.0mmol, 15% n-hexane solution) was added dropwise to mPEG (550) C6ImCl (3.0mmol) in CH2Cl2(20mL) solution (previously with P)4O10Dried CH2Cl2) In (1). After the dropwise addition, the reaction temperature is kept at-78 ℃ and the stirring is continued for 45 minutes, and then the pH is added for about 20 minutes2And (3) dropwise adding PCl (3.0mmol) into the previous reaction solution, continuing stirring for 20 minutes after dropwise adding, slowly raising the reaction temperature to room temperature, and stirring overnight to finish the reaction. After washing the product three times with deoxygenated water (3 x 10mL), the organic phase was washed with Na2SO4Drying, spin-drying the solvent to obtain a solid product quantitatively in N2Under protection, in a 500ml flask, 4g K is put2PtCl4Dissolving in 10ml water, adding 12g of the above catalyst raw material in 350ml methanol, heating and refluxing the reaction for 2h, collecting the solid, washing with diethyl ether to obtain bis [ (1-mPEG (1900) -3-hexyl-2-diphenylphosphine imidazole halide) platinum dichloride]The compound was dried under vacuum and placed in a desiccator for use to afford catalyst 7.
Adding styrene (1.25mol) and a catalyst 7(1.25mmol) into a 500ml three-neck flask, slowly heating to 90 ℃ under the protection of nitrogen, stirring while dropwise adding triethoxysilane (1.5mol) through a dropping funnel for 0.5 h, keeping the reaction temperature, continuously stirring for 5 h, cooling to room temperature, performing reduced pressure distillation, collecting corresponding fractions, determining the conversion rate of the styrene to be 91.5% by GC-MS (gas chromatography-mass spectrometry), and obtaining a beta adduct 1-triethoxysilyl-2-phenyl ethane (PhCH)2CH2Si(OCH2CH3)3) The yield of (D) was 84.1%.
Example 8
Preparation of catalyst 8: under the protection of argon, a low-temperature constant-temperature reactor is used, the reaction temperature is controlled to be-78 ℃, and n-butyl lithium is reacted for about 15 minutes (nBuLi 3.0mmol, 15% n-hexane solution) was added dropwise to mPEG (550) C8ImCl (3.0mmol) in CH2Cl2(20mL) solution (previously with P)4O10Dried CH2Cl2) In (1). After the dropwise addition, the reaction temperature is kept at-78 ℃ and the stirring is continued for 45 minutes, and then the pH is added for about 20 minutes2And (3) dropwise adding PCl (3.0mmol) into the previous reaction solution, continuing stirring for 20 minutes after dropwise adding, slowly raising the reaction temperature to room temperature, and stirring overnight to finish the reaction. After washing the product three times with deoxygenated water (3 x 10mL), the organic phase was washed with Na2SO4Drying, spin-drying the solvent to obtain a solid product quantitatively in N2Under protection, in a 500ml flask, 4g K is put2PtCl4Dissolving in 10ml water, adding 12g of the above catalyst raw material in 350ml methanol, heating and refluxing the reaction for 2h, collecting the solid, washing with diethyl ether to obtain bis [ (1-mPEG (1900) -3-octyl-2-diphenylphosphine imidazole halide) platinum dichloride]The compound was dried under vacuum and placed in a desiccator for use to give catalyst 8.
Adding a quantity of hexene (1.25mol), a catalyst 8(1.25mmol) and nitrogen into a 500ml three-neck flask, slowly heating to 90 ℃, stirring while dropwise adding triethoxysilane (1.5mol) through a dropping funnel for 0.5 hour, keeping the reaction temperature, continuously stirring for 5 hours, cooling to room temperature, carrying out reduced pressure distillation to collect corresponding fractions, measuring the conversion rate of hexene to 90.1% through GC-MS, and measuring the conversion rate of beta adduct 1-triethoxysilyl-2-phenyl ethane (PhCH)2CH2Si(OCH2CH3)3) The yield of (D) was 83.8%.
Example 9
In a 500ml three-neck flask, hexene (1.25m0l) and catalyst 1(1.25mmol) are added, the temperature is slowly raised to 90 ℃ under the protection of nitrogen, triethoxysilane (1.5mol) is added dropwise through a dropping funnel while stirring, the reaction temperature is kept for 25 minutes, the reaction is continuously stirred for 5 hours, the temperature is cooled to room temperature, corresponding fractions are collected by reduced pressure distillation, the conversion rate of hexene is 95.1% by GC-MS, and the yield of the beta adduct 1-triethoxysilylhexane is 100%.
Example 10
In a 500ml three-necked flask, heptene (1.25mol), catalyst 1(1.25mmol) prepared in example 1, was added, the temperature was slowly raised to 90 ℃ under nitrogen protection, triethoxysilane (1.5mol) was added dropwise through a dropping funnel while stirring, the addition time was 0.5 hour, the reaction temperature was maintained, the reaction was continued for 5 hours while stirring, the reaction mixture was cooled to room temperature, the corresponding fraction was collected by reduced pressure distillation, the conversion of heptene was 94.3% by GC-MS, and the yield of β adduct 1-triethoxysilylheptane was 100%.
Example 11
In a 500ml three-necked flask, octene (1.25mol), catalyst 1(1.25mmol) prepared in example 1, was added, the temperature was slowly raised to 90 ℃ under nitrogen protection, triethoxysilane (1.5mol) was added dropwise through a dropping funnel while stirring, the reaction temperature was maintained, the reaction was continued for 5 hours while stirring, the reaction mixture was cooled to room temperature, the corresponding fraction was collected by vacuum distillation, and the conversion of octene was 94.3% and the yield of β -adduct 1-triethoxysilane was 100% as determined by GC-MS.
Example 12
In a 500ml three-neck flask, undecylene (1.25mol), catalyst 1(1.25mmol) prepared in example 1 was added, the temperature was slowly raised to 90 ℃ under the protection of nitrogen, triethoxysilane (1.5mol) was added dropwise through a dropping funnel while stirring, the dropping time was 0.5 hour, the reaction temperature was maintained, the reaction was continued for 5 hours while stirring, the reaction was cooled to room temperature, the corresponding fraction was collected by reduced pressure distillation, the conversion of undecylene was 92.7% as determined by GC-MS, and the yield of β adduct 1-triethoxysilylundecane was 100%.
Example 13
In a 500ml three-necked flask, 2-methylstyrene (1.25mol), catalyst 1(1.25mmol) prepared in example 1 was charged, the temperature was slowly raised to 90 ℃ under nitrogen protection, triethoxysilane (1.5mol) was added dropwise through a dropping funnel while stirring, the dropping time was 0.5 hour, the reaction temperature was maintained, the reaction was continued for 5 hours while stirring, the reaction was cooled to room temperature, the corresponding fraction was collected by reduced pressure distillation, the conversion of 2-methylstyrene was 87.5% as measured by GC-MS, and the yield of β -adduct 1-triethoxysilyl-2- (2-methylphenyl) ethane was 85.4%.
Example 14
In a 500ml three-necked flask, 3-methylstyrene (1.25mol), catalyst 1(1.25mmol) prepared in example 1 was charged, the temperature was slowly raised to 90 ℃ under nitrogen protection, triethoxysilane (1.5mol) was added dropwise through a dropping funnel while stirring, the dropping time was 0.5 hour, the reaction temperature was maintained, the reaction was continued for 5 hours, the mixture was cooled to room temperature, the corresponding fraction was collected by vacuum distillation, the conversion of 3-methylstyrene was 83.5% as measured by GC-MS, and the yield of β -adduct 1-triethoxysilyl-2- (3-methylphenyl) ethane was 85.7%.
Example 15
In a 500ml three-necked flask, 4-methylstyrene (1.25mmol), catalyst 1(1.25mmol) (1.25mmol) prepared in example 1 were charged, the temperature was slowly raised to 90 ℃ under nitrogen, triethoxysilane (1.5mol) was sequentially dropped through a dropping funnel while stirring, the dropping time was 0.5 hour, the reaction temperature was maintained, the reaction was continued to stir for 5 hours, the temperature was cooled to room temperature, the corresponding fraction was collected by reduced pressure distillation, the conversion of 4-methylstyrene was 84.8% as measured by GC-MS, and the yield of β -adduct 1-triethoxysilyl-2- (4-methylphenyl) ethane was 83.7%.
Example 16
In a 500ml three-neck flask, 4-methoxystyrene (1.25mol), catalyst 1(1.25mmol) prepared in example 1 was added, the temperature was slowly raised to 90 ℃ under nitrogen protection, and triethoxysilane (1.5mol) was added dropwise through a dropping funnel while stirring, the dropping time was 0.5 hour, the reaction temperature was maintained, the reaction was continued for 5 hours, the mixture was cooled to room temperature, the corresponding fraction was collected by reduced pressure distillation, the conversion of 4-methoxystyrene was 85.1% as measured by GC-MS, and the yield of β adduct 1-triethoxysilyl-2- (4-methoxyphenyl) ethane was 85.4%.
Example 17
In a 500ml three-necked flask, hexene (1.25mol), catalyst 1(1.25mmol) prepared in example 1 was added, the temperature was slowly raised to 90 ℃ under the protection of nitrogen, trimethoxyhydrosilane (1.5mol) was added dropwise through a dropping funnel while stirring, the reaction temperature was maintained, the reaction was continued for 5 hours while stirring, the mixture was cooled to room temperature, the corresponding fraction was collected by reduced pressure distillation, the conversion of hexene was 89.3% by GC-MS, and the yield of β -adduct 1-trimethoxysilylhexane was 100%.
Example 18
In a 500ml three-necked flask, hexene (1.25mol) and catalyst 1(1.25mmol) prepared in example 1 were charged, the temperature was slowly raised to 90 ℃ under nitrogen protection, triethylhydrosilane (1.5mol) was added dropwise through a dropping funnel while stirring for 0.5 hour, the reaction temperature was maintained, the reaction was continued for 5 hours while stirring, the reaction mixture was cooled to room temperature, the corresponding fraction was collected by vacuum distillation, the conversion of hexene was 94.2% as measured by GC-MS, and the β -adduct 1-triethylsilylhexane (CH) was added3(CH2)5Si(CH2CH3)3) The yield of (b) was 100%.
Example 19
In a 500ml three-neck flask, hexene (1.25mmol), catalyst 1(1.25mmol) prepared in example 1 were added, the temperature was slowly raised to 90 ℃ under the protection of nitrogen, trichlorosilane (1.5mol) was added dropwise through a dropping funnel while stirring, the reaction temperature was maintained, the reaction was continued for 5 hours while stirring, the reaction was cooled to room temperature, the corresponding fraction was collected by reduced pressure distillation, the conversion of hexene was 99.7% as measured by GC-MS, and β adduct 1-trichlorosilane (CH) was added3(CH2)5SiCl3) The yield of (b) was 100%.
Example 20
In a 500ml three-neck flask, hexene (1.25mmol), catalyst 1(1.25mmol) prepared in example 1 were added, the temperature was slowly raised to 90 ℃ under the protection of nitrogen, dichloromethylhydrogensilane (1.5mol) was added dropwise through a dropping funnel while stirring, the addition time was 0.5 hour, the reaction temperature was maintained, the reaction was continued for 5 hours while stirring, the mixture was cooled to room temperature, the corresponding fraction was collected by reduced pressure distillation, and the fraction was measured by GC-MSThe conversion of hexene to was 98.1%, and the beta adduct, 1-methyldichlorosilylhexane (CH)3(CH2)5SiCl2(CH3) ) was obtained in 100%.
Test example 1
In example 2, after the reaction, the lower catalyst system was washed with diethyl ether, dried, and then added again to a 250 ml reaction vessel, styrene (2.5mol) and triethoxysilane (2.75mol) were added, the temperature was slowly raised to 70 ℃ and the reaction was stirred for 5 hours, the product was collected under reduced pressure, the conversion of styrene was 99.9% by GC-MS, and the beta adduct, 1-triethoxysilyl-2-phenylethane (PhCH), was added2CH2Si(OCH2CH3)3) The yield of (D) was 87.7%.
Test example 2
In test example 1, after the reaction was completed, the lower catalyst system by the liquid-in-tank cooling decantation method was washed with diethyl ether, dried, and then charged again into a 250 ml reaction tank, styrene (2.5mol) and triethoxysilane (2.75mol) were added, the temperature was slowly raised to 70 ℃, the reaction was stirred for 5 hours, the product was collected under reduced pressure, the conversion of styrene was 99.9% by GC-MS, and the β -adduct 1-triethoxysilyl-2-phenylethane (PhCH) was added2CH2Si(OCH2CH3)3) The yield of (b) was 86.2%.

Claims (4)

1. The hydrosilylation reaction is characterized in that olefin and triethoxy hydrosilane are used as raw materials, bis [ (1-mPEG-3-alkyl 2-diphenylphosphine imidazole halide) platinum dichloride ] is used as a catalyst, the raw materials are heated to 50-90 ℃ and stirred for reaction for 4-6 hours, and the reaction product is filtered, distilled and collected to obtain fractions, so that a hydrosilylation product is obtained.
2. The hydrosilylation reaction of claim 1 catalyzed by a recyclable platinum compound of the general formula:
Figure FDA0002657832560000011
wherein R is selected from C5H9，C6H11，C7H13，C10H19，Ph，CH3One of Ph.
3. The hydrosilylation reaction of claim 1 or 2 using a recyclable platinum compound as a catalyst, wherein the molar ratio of the olefin to the triethoxysilane to the catalyst is 10000: 11000 to 12000: 1 to 50.
4. The hydrosilylation reaction as recited in claim 1 wherein said catalyst is a bis [ (1-mPEG-3-alkyl-2-diphenylphosphinoimidazole halide) dichloroplatinum prepared using PEG imidazole salt containing organophosphine ligand as metal platinum ligand]Wherein mPEG is
Figure FDA0002657832560000012
n-8, 12,17 and 43, and the alkyl is selected from one of methyl, ethyl, butyl and hexyl.
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CN103288863A (en) * 2013-04-07 2013-09-11 杭州师范大学 Method for hydrosilylation

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