CN101850271B - Platinum catalyst for olefin hydrosilylation, preparation method and application thereof - Google Patents
Platinum catalyst for olefin hydrosilylation, preparation method and application thereof Download PDFInfo
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- CN101850271B CN101850271B CN201010183759XA CN201010183759A CN101850271B CN 101850271 B CN101850271 B CN 101850271B CN 201010183759X A CN201010183759X A CN 201010183759XA CN 201010183759 A CN201010183759 A CN 201010183759A CN 101850271 B CN101850271 B CN 101850271B
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Abstract
The invention belongs to the filed of synthesizing alkoxy silane monomers and relates to a platinum catalyst for olefin hydrosilylation and a preparation method and application thereof. The catalyst is a supported platinum catalyst which is formed by coordination complexing of carboxyl or carboxyl and ethylene together. The method for preparing the catalyst comprises the following steps of: preparing anhydride modified polyethylene glycol or polyethylene glycol monomethyl ether into carboxyl-containing or carboxyl and ethylene-containing polymer support; and performing support complexing on the polymer support and the chloroplatinic acid to obtain the platinum catalyst for olefin hydrosilylation. The anhydride modified polyethylene glycol serves as a catalyst support for performing support complexing on the platinum, and the obtained catalyst is suitable for hydrosilylation of the olefin and hydrosilane. The catalyst has the advantages of convenient use, safety, effectiveness and convenient separation from the products, can be recycled, and solves the problem that the conventional catalyst is difficult to recover and has high cost.
Description
Technical field
The invention belongs to the synthetic field of alkoxy silane monomer, relate to a kind of platinum catalyst, especially relate to a kind of platinum catalyst for hydrosilylation, preparation method and application thereof.
Background technology
As everyone knows, hydrosilylation of olefins 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 organosilicon macromolecule polymer.The addition of alkene silicon hydrogen directly uses chloroplatinic acid as catalyst usually.Speier catalyst (isopropyl alcohol solution of chloroplatinic acid) and Karstedt catalyst ([(ViMe
2Si)
2O] PtCl
2) have certain catalytic activity, in organosilicon production, obtained extensive use.Though these platinum catalyst system and catalyzings have greater activity, reaction is often carried out under high-temperature and high-pressure conditions, and after the reaction end, catalyst is difficult to reclaim, and the catalyst cost is higher.
Though the loaded catalyst catalytic activity is not as homogeneous catalyst, loaded catalyst can solve catalytic erosion equipment to a certain extent, with the product separation difficulty, can't reclaim, problem that can not recycle.Inorganic carrier is (like C, SiO
2, Al
2O
3, molecular sieve etc.) then there is shortcomings such as being prone to inactivation in the heterogeneous catalyst of platinum.Li Fengyi etc. utilize SiO
2, C, Al
2O
3Be used for styrene and methyl dichloro hydrogen silane asymmetrical siloxy hydrogenation with the molecular sieve carried polyethylene glycol complexing of 4-A platinum catalyst, obtained catalytic effect preferably.Catalyzed alkene and triethoxysilane reaction also have higher activity, but though such activity of such catalysts is good, but selectivity is not high.In addition, also have some macromolecular compounds also can both obtain catalytic effect preferably, but these catalyst preparation process are comparatively complicated, are difficult for repetition as carrier loaded complexing platinum catalyst.Publication number is that the Chinese invention patent of CN101322946A provides a kind of catalyst, and this catalyst is the mixture of platinum and carboxy-containing acid group's amino-compound, but this catalyst can not recycling, has increased the production cost of catalyst article greatly.Use the research situation of catalyst to present hydrosilylation of olefins, prepare novel, efficiently, callable catalyst is used for hydrosilylation of olefins and has important application prospects and ten minutes major and immediate significance.
Summary of the invention
The present invention mainly is the technical problem to existing in prior technology etc., and a kind of platinum catalyst for hydrosilylation is provided, and this catalyst is easy to use, and is safe and effective, with convenient product separation, recyclablely utilizes again.
The present invention also provides the preparation method and the application thereof of above-mentioned platinum catalyst for hydrosilylation.
Above-mentioned technical problem of the present invention mainly is able to solve through following technical proposals:
A kind of platinum catalyst for hydrosilylation; It is characterized in that: obtain containing carboxyl or contain carboxyl and the macromolecule carrier of ethylene linkage with anhydride modified polyethylene glycol or poly glycol monomethyl ether; Again this macromolecule carrier and chloroplatinic acid complexing are obtained described platinum catalyst for hydrosilylation, the load capacity of platinum is 0.002wt%～5wt% in the wherein said platinum catalyst for hydrosilylation; Described molecular weight polyethylene glycol is 1000～20000, and the poly glycol monomethyl ether molecular weight is 1000～15000; The mol ratio of described polyethylene glycol or poly glycol monomethyl ether and acid anhydrides is 0.25～2: 1.Catalyst amount is less, and the substrate minimum dosage is 5 * 10 relatively
-6The characteristics of utilizing polyethylene glycol under the normal temperature (molecular weight was greater than 1000 o'clock) to exist with solid-state form, reaction finish rear catalyst and can separate with product easily and recycle.
The preparation method of platinum catalyst for hydrosilylation of the present invention; Comprise with anhydride modified polyethylene glycol or poly glycol monomethyl ether obtaining containing carboxyl or containing carboxyl and the macromolecule carrier of ethylene linkage that this macromolecule carrier obtains described platinum catalyst for hydrosilylation with chloroplatinic acid load complexing again.This method makes anhydride modified polyethylene glycol as catalyst carrier load complexing platinum, and the catalyst that obtains is applicable to alkene and hydrogen silane hydrosilylation.
As preferably, acid anhydrides is succinic anhydride, maleic anhydride or phthalic anhydride; Described molecular weight polyethylene glycol is 1000～20000, and the poly glycol monomethyl ether molecular weight is 1000～15000.The preferred maleic anhydride of acid anhydrides; Described polyethylene glycol can be selected cetomacrogol 1000, Macrogol 2000, Macrogol 4000, Macrogol 6000, cetomacrogol 1000 0, preferred Macrogol 2000; Described poly glycol monomethyl ether can be selected poly glycol monomethyl ether 1900.
The method of said anhydride modified polyethylene glycol or poly glycol monomethyl ether is: polyethylene glycol or poly glycol monomethyl ether mix the back and under 60～140 ℃, are stirred to fusing fully with acid anhydrides, and reaction 2～12h adds solvent and constantly stirs 30min, under 0～30 ℃, leaves standstill 2～12h; Generate solid, filter, washing; The solid that obtains is dissolved in the carrene, uses the ether solvents reprecipitation, filter; Washing 20～60 ℃ of following vacuum drying, obtains containing carboxyl or contains carboxyl and the macromolecule carrier of ethylene linkage.
As preferably, the mol ratio of described polyethylene glycol or poly glycol monomethyl ether and acid anhydrides is 0.25～2: 1; Described solvent is pentane, n-hexane, normal heptane, normal octane, n-decane; Ether solvents is ether, butyl ether.The preferred n-hexane of solvent; The preferred ether of ether solvents.
The method of described macromolecule carrier and chloroplatinic acid complexing is: be solvent with the oxolane, with chloroplatinic acid and oxolane complexing macromolecule carrier, obtain described platinum catalyst for hydrosilylation except that after desolvating.As preferably, the mass ratio of described macromolecule carrier and oxolane is 1: 10～50, and the mass ratio of chloroplatinic acid and macromolecule carrier is 1: 20～50000, and reaction temperature is 20～80 ℃, and the reaction time is 8～24h.
The present invention also provides the application of platinum catalyst for hydrosilylation, and the platinum catalyst for hydrosilylation that in the hydrosilylation of alkene and silane containing hydrogen, adds effective dose makes this hydrosilylation of its catalysis.As preferably, described alkene is amylene, hexene, heptene, octene, certain herbaceous plants with big flowers alkene, hendecene, laurylene, tetradecene, hexadecylene, octadecylene, styrene, p-methylstyrene, to chlorostyrene or p-chloromethyl styrene; Described silane containing hydrogen is triethoxy hydrogen silane, trimethoxy hydrogen silane, methyl dichloro hydrogen silane, dimethyl chloride hydrogen silane or 3,5-dimethylphenyl hydrogen silane.
Compare with existing catalyst, the present invention has the following advantages:
1, because the catalyst of the present invention's preparation is a load solvay-type catalyst; Have efficient catalytic (the catalyst use amount can reach the ppm level), post catalyst reaction from product, separate easily, recyclable, characteristics such as recycle, also increased new varieties simultaneously for being used for the synthetic catalyst of organic silicon monomer.
2, the hydrosilylation of the catalyst aims alkene of the present invention preparation has good catalytic effect, and active high, good product selectivity can catalyzed alkene and the addition reaction of multiple silane containing hydrogen.
3, method for preparing catalyst provided by the invention is simple, is easy to control, and favorable reproducibility has the certain economic social benefit.
Description of drawings
Fig. 1 is the nuclear magnetic spectrum of the catalyst that makes of the embodiment of the invention 2.
Fig. 2 is the nuclear magnetic spectrum of the catalyst that makes of the embodiment of the invention 4.
Fig. 3 is the nuclear magnetic spectrum of the catalyst that makes of the embodiment of the invention 6.
Fig. 4 is the nuclear magnetic spectrum of the catalyst that makes of the embodiment of the invention 7.
The specific embodiment
Catalyst preparation process of the present invention comprises anhydride modified polyethylene glycol or poly glycol monomethyl ether and chloroplatinic acid load complexing two big steps.The method of said anhydride modified polyethylene glycol or poly glycol monomethyl ether is: polyethylene glycol or poly glycol monomethyl ether mix back control temperature and in 60～140 ℃ of scopes, are stirred to fusing fully with acid anhydrides, and reaction 2～12h adds solvent and constantly stirs 30min; The control temperature leaves standstill 2～12h in 0～30 ℃ of scope, generate solid, filters; Washing is dissolved in the solid that obtains in the carrene, uses the ether solvents reprecipitation; Filter; Washing, vacuum drying in 20～60 ℃ of scopes obtains containing carboxyl or contains ethylene linkage and the macromolecule carrier of carboxyl.Adopt maleic anhydride modified to obtain containing the macromolecule carrier of ethylene linkage and carboxyl; Adopt other acid anhydrides to obtain only carboxylic macromolecule carrier.The method of described macromolecule carrier and chloroplatinic acid complexing is: be solvent with the oxolane, with chloroplatinic acid and oxolane complexing macromolecule carrier, obtain described platinum catalyst for hydrosilylation except that after desolvating.
Through embodiment, do further bright specifically below to technical scheme of the present invention.
Embodiment 1: Macrogol 2000 modification (an end modification) load complexing platinum catalyst
Take by weighing 10.0g (0.005mol) Macrogol 2000, maleic anhydride 0.54g (0.0055mol) puts into the flask that has magnetic agitation son, and heat temperature raising to 80 ℃ stirs it is melted fully; Continue to stir 5h, add n-hexane, stir 30min, room temperature held 6h; Generate solid, shift out n-hexane, add the 20ml carrene and be stirred to dissolving fully; Sedimentation in the 400ml ether, suction filtration, washing; The deposition of collecting is put in the vacuum drying chamber, and 40 ℃ of dry 24h obtain modified poly (ethylene glycol).
Get the above-mentioned modified poly (ethylene glycol) of 1.0g, add the 10.0ml oxolane, add chloroplatinic acid 0.00026g, 40 ℃ of stirring reaction 24h remove solvent, obtain loaded platinum catalyst, and the platinum mass content that detects in the catalyst is 0.01%.
Take by weighing the loaded platinum catalyst 0.5g of present embodiment preparation; 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 2h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate product, product detects through GC-MS; The styrene conversion rate is 100%, and β-addition compound product selectivity is 99.2%.
Embodiment 2: Macrogol 2000 modification (both-end modification) load complexing platinum catalyst
Take by weighing 10.0g (0.005mol) Macrogol 2000, maleic anhydride 1.08g (0.011mol) puts into the flask that has magnetic agitation son, and heat temperature raising to 80 ℃ stirs it is melted fully; Continue to stir 5h, add n-hexane, stir 30min, room temperature held 6h; Generate solid, shift out n-hexane, add the 20ml carrene and be stirred to dissolving fully; Sedimentation in the 400ml ether, suction filtration, washing; The deposition of collecting is put in the vacuum drying chamber, and 40 ℃ of dry 24h obtain modified poly (ethylene glycol).The nuclear magnetic spectrum of modified poly (ethylene glycol) is seen Fig. 1, can find out that from this figure nuclear magnetic data is described as:
1H NMR (CDCl
3, 400MHz), δ: 6.43-6.39 (d, 2H; J=16, CHCHCOO), 6.24-6.21 (d, 2H, J=12; CHCHCOO), 3.83-3.46ppm (br, 192H;-CH
2CH
2O-).
Get the above-mentioned modified poly (ethylene glycol) of 1.0g, add the 10.0ml oxolane, add the 0.00026g chloroplatinic acid, 40 ℃ of stirring reaction 24h remove solvent, obtain loaded platinum catalyst, and the platinum mass content that detects in the catalyst is 0.01%.
Take by weighing the loaded platinum catalyst 0.5g of present embodiment preparation; 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask, reacts 2h in 60 ℃ of silicone oil baths; Cooling, sedimentation, separate product; Product detects through GC-MS, and the styrene conversion rate is 100%, and β-addition compound product selectivity is 98.9%.
Embodiment 3: Macrogol 4000 modification (an end modification) load complexing platinum catalyst
Take by weighing 20.0g (0.005mol) Macrogol 4000, maleic anhydride 0.54g (0.0055mol) puts into the flask that has magnetic agitation son, and heat temperature raising to 80 ℃ stirs it is melted fully; Continue to stir 4h, add n-hexane, stir 30min, room temperature held 6h; Generate solid, shift out n-hexane, add the 20ml carrene and be stirred to dissolving fully; Sedimentation in the 500ml ether, suction filtration, washing; The deposition of collecting is put in the vacuum drying chamber, and 40 ℃ of dry 24h obtain modified poly (ethylene glycol).
Get the above-mentioned modified poly (ethylene glycol) of 1.0g, add the 10.0ml oxolane, add chloroplatinic acid 0.00026g, 40 ℃ of stirring reaction 24h remove solvent, obtain loaded platinum catalyst, and the platinum mass content that detects in the catalyst is 0.01%.
Take by weighing the loaded platinum catalyst 0.5g of present embodiment preparation; 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 2h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate product, product detects through GC-MS; The styrene conversion rate is 97.3%, and β-addition compound product selectivity is 98.6%.
Embodiment 4: Macrogol 4000 modification (both-end modification) load complexing platinum catalyst
Take by weighing 20.0g (0.005mol) Macrogol 4000, maleic anhydride 1.08g (0.011mol) puts into the flask that has magnetic agitation son, and heat temperature raising to 80 ℃ stirs it is melted fully; Continue to stir 4h, add n-hexane, stir 30min, room temperature held 6h; Generate solid, shift out n-hexane, add the 20ml carrene and be stirred to dissolving fully, sedimentation in the 500ml ether; Suction filtration, washing, the deposition of collecting is put in the vacuum drying chamber, 40 ℃ of dry 24h; Obtain modified poly (ethylene glycol), the nuclear magnetic spectrum of modified poly (ethylene glycol) is seen Fig. 2, can find out that from this figure nuclear magnetic data is described as:
1H NMR (CDCl
3, 400MHz), δ: 6.42-6.39 (d, 2H; J=16, CHCHCOO), 6.25-6.22, (d, 2H, J=12; CHCHCOO), 3.74-3.65ppm (br, 356H;-CH
2CH
2O-).
Get the above-mentioned modified poly (ethylene glycol) of 1.0g, add the 10.0ml oxolane, add chloroplatinic acid 0.00026g, 40 ℃ of stirring reaction 24h remove solvent, obtain loaded platinum catalyst, and the platinum mass content that detects in the catalyst is 0.01%.
Take by weighing the loaded platinum catalyst 0.5g of present embodiment preparation; 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 2h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate product, product detects through GC-MS; The styrene conversion rate is 97.7%, and β-addition compound product selectivity is 97.9%.
Embodiment 5: Macrogol 6000 modification (an end modification) load complexing platinum catalyst
Take by weighing 20.0g (0.0033mol) Macrogol 6000, maleic anhydride 0.36g (0.0037mol) puts into the flask that has magnetic agitation son, and heat temperature raising to 80 ℃ stirs it is melted fully; Continue to stir 4h, add n-hexane, stir 30min, room temperature held 6h; Generate solid, shift out n-hexane, add the 20ml carrene and be stirred to dissolving fully, sedimentation in the 500ml ether; Suction filtration, washing, the deposition of collecting is put in the vacuum drying chamber, 40 ℃ of dry 24h.
Get the above-mentioned modified poly (ethylene glycol) of 1.0g, add the 10.0ml oxolane, add chloroplatinic acid 0.00026g, 40 ℃ of stirring reaction 24h remove solvent, obtain loaded platinum catalyst, and the platinum mass content that detects in the catalyst is 0.01%.
Take by weighing the loaded platinum catalyst 0.5g of present embodiment preparation; 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 2h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate product, product detects through GC-MS; The styrene conversion rate is 95.7%, and β-addition compound product selectivity is 97.5%.
Embodiment 6: Macrogol 6000 modification (both-end modification) load complexing platinum catalyst
Take by weighing 20.0g (0.0033mol) Macrogol 6000, maleic anhydride 0.72g (0.0073mol) puts into the flask that has magnetic agitation son, and heat temperature raising to 80 ℃ stirs it is melted fully; Continue to stir 4h, add n-hexane, stir 30min, room temperature held 6h; Generate solid, shift out n-hexane, add the 20ml carrene and be stirred to dissolving fully, sedimentation in the 500ml ether; Suction filtration, washing, the deposition of collecting is put in the vacuum drying chamber, 40 ℃ of dry 24h; Obtain modified poly (ethylene glycol), the nuclear magnetic spectrum of modified poly (ethylene glycol) is seen Fig. 3, can find out that from this figure nuclear magnetic data is described as:
1HNMR (CDCl
3, 400MHz), δ: 6.41-6.38 (d, 2H; J=12, CHCHCOO), 6.23-6.20, (d, 2H, J=12; CHCHCOO), 3.83-3.64ppm (br, 498H;-CH
2CH
2O-).
Get the above-mentioned modified poly (ethylene glycol) of 1.0g, add the 10.0ml oxolane, add chloroplatinic acid 0.00026g, 40 ℃ of stirring reaction 24h remove solvent, obtain loaded platinum catalyst, and the platinum mass content that detects in the catalyst is 0.01%.
Take by weighing the loaded platinum catalyst 0.5g of present embodiment preparation; 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 2h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate product, product detects through GC-MS; The styrene conversion rate is 96.3%, and β-addition compound product selectivity is 97.4%.
Embodiment 7: cetomacrogol 1000 0 modification (both-end modification) load complexing platinum catalyst
Take by weighing 10.0g (0.001mol) cetomacrogol 1000 0, maleic anhydride 0.22g (0.0022mol) puts into the flask that has magnetic agitation son, and heat temperature raising to 80 ℃ stirs it is melted fully; Continue to stir 4h, add n-hexane, stir 30min, room temperature held 6h; Generate solid, shift out n-hexane, add the 20ml carrene and be stirred to dissolving fully, sedimentation in the 500ml ether; Suction filtration, washing, the deposition of collecting is put in the vacuum drying chamber, 40 ℃ of dry 24h; Obtain modified poly (ethylene glycol), the nuclear magnetic spectrum of modified poly (ethylene glycol) is seen Fig. 4, can find out that from this figure nuclear magnetic data is described as:
1HNMR (CDCl
3, 400MHz), δ: 6.42-6.38 (d, 2H; J=16, CHCHCOO), 6.24-6.21, (d, 2H, J=12; CHCHCOO), 3.71-3.61ppm (br, 890H;-CH
2CH
2O-).
Get the above-mentioned modified poly (ethylene glycol) of 1.0g, add the 10.0ml oxolane, add chloroplatinic acid 0.00026g, 40 ℃ of stirring reaction 24h remove solvent, obtain loaded platinum catalyst, and the platinum mass content that detects in the catalyst is 0.01%.
Take by weighing the loaded platinum catalyst 0.5g of present embodiment preparation; 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 2h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate product, product detects through GC-MS; The styrene conversion rate is 91.9%, and β-addition compound product selectivity is 97.9%.
Embodiment 8: poly glycol monomethyl ether 1900 modified load complexing platinum catalysts
Take by weighing 9.5g (0.005mol) poly glycol monomethyl ether 1900, maleic anhydride 0.54g (00055mol) puts into the flask that has magnetic agitation son, and heat temperature raising to 80 ℃ stirs it is melted fully; Continue to stir 4h, add n-hexane, stir 30min, room temperature held 8h; Generate solid, shift out n-hexane, add the 20ml carrene and be stirred to dissolving fully, sedimentation in the 500ml ether; Suction filtration, washing, the deposition of collecting is put in the vacuum drying chamber, 60 ℃ of dry 24h.[0044] get the above-mentioned modified poly (ethylene glycol) of 1.0g, add the 10.0ml oxolane, add chloroplatinic acid 0.00026g, 40 ℃ of stirring reaction 24h remove solvent, obtain loaded platinum catalyst, and the platinum mass content that detects in the catalyst is 0.01%.
Take by weighing the loaded platinum catalyst 0.5g of present embodiment preparation; 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 2h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate product, product detects through GC-MS; The styrene conversion rate is 99.9%, and β-addition compound product selectivity is 98.9%.
Embodiment 9: Macrogol 2000 succinic anhydride modified load complexing platinum catalyst
Take by weighing 10.0g (0.005mol) Macrogol 2000, succinic anhydride 0.55g (0.0055mol) puts into the flask that has magnetic agitation son, and heat temperature raising to 80 ℃ stirs it is melted fully; Continue to stir 5h, add n-hexane, stir 30min, room temperature held 6h; Generate solid, shift out n-hexane, add the 20ml carrene and be stirred to dissolving fully, sedimentation in the 400ml ether; Suction filtration, washing, the deposition of collecting is put in the vacuum drying chamber, 40 ℃ of dry 24h.
Get the above-mentioned modified poly (ethylene glycol) of 1.0g, add the 10.0ml oxolane, add chloroplatinic acid 0.00026g, 40 ℃ of stirring reaction 24h remove solvent, obtain loaded platinum catalyst, and the platinum mass content that detects in the catalyst is 0.01%.
Take by weighing the loaded platinum catalyst 0.5g of present embodiment preparation; 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 2h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate product, product detects through GC-MS; The styrene conversion rate is 98.8%, and β-addition compound product selectivity is 97.2%.
Embodiment 10: Macrogol 2000 phthalic anhydride modified load complexing platinum catalyst
Take by weighing 10.0g (0.005mol) Macrogol 2000, phthalic anhydride 0.74g (0.0055mol) puts into the flask that has magnetic agitation son, and heat temperature raising to 80 ℃ stirs it is melted fully; Continue to stir 5h, add n-hexane, stir 30min, room temperature held 6h; Generate solid, shift out n-hexane, add the 20ml carrene and be stirred to dissolving fully, sedimentation in the 400ml ether; Suction filtration, washing, the deposition of collecting is put in the vacuum drying chamber, 40 ℃ of dry 24h.
Get the above-mentioned modified poly (ethylene glycol) of 1.0g, add the 10.0ml oxolane, add chloroplatinic acid 0.00026g, 40 ℃ of stirring reaction 24h remove solvent, obtain loaded platinum catalyst, and the platinum mass content that detects in the catalyst is 0.01%.
Take by weighing the loaded platinum catalyst 0.5g of present embodiment preparation; 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 2h in 60 ℃ of silicone oil baths, cooling, sedimentation, separate product, product detects through GC-MS; The styrene conversion rate is 97.8%, and β-addition compound product selectivity is 99.2%.
Embodiment 11: catalyst is reused experiment 1
Product among the embodiment 1 is removed; Catalyst stays in reactor, adds 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane, reacts 2h in 60 ℃ of silicone oil baths; Cooling, sedimentation, separate product; Product detects through GC-MS, and the styrene conversion rate is 99.6%, and β-addition compound product selectivity is 98.9%.
Embodiment 12: catalyst is reused experiment 2
Product among the embodiment 11 is removed; Catalyst stays in reactor, adds 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane, reacts 2h in 60 ℃ of silicone oil baths; Cooling, sedimentation, separate product; Product detects through GC-MS, and the styrene conversion rate is 99.8%, and β-addition compound product selectivity is 98.7%.
Embodiment 13: catalyst is reused experiment 3
Product among the embodiment 12 is removed; Catalyst stays in reactor, adds 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane, reacts 2h in 60 ℃ of silicone oil baths; Cooling, sedimentation, separate product; Product detects through GC-MS, and the styrene conversion rate is 99.3%, and β-addition compound product selectivity is 98.8%.
Embodiment 14: catalyst is reused experiment 4
Product among the embodiment 13 is removed; Catalyst stays in reactor, adds 9.6g (0.1mol) styrene and 18.0g (0.11mol) triethoxy hydrogen silane, reacts 2h in 60 ℃ of silicone oil baths; Cooling, sedimentation, separate product; Product detects through GC-MS, and the styrene conversion rate is 98.9%, and β-addition compound product selectivity is 98.7%.
Embodiment 14: the addition reaction of catalysis different alkene and silane
Take by weighing embodiment 2 catalyst 0.5g, 11.2g (0.1mol) octene and 18.0g (0.11mol) triethoxy hydrogen silane place 100 milliliters single port flask, react 2h in 60 ℃ of silicone oil baths; Cooling; Product detects through GC-MS, and the octene conversion ratio is 100%, and β-addition compound product selectivity is 99.5%.
Take by weighing embodiment 2 catalyst 0.5g; 16.8g (0.1mol) laurylene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 2h in 70 ℃ of silicone oil baths, cooling, product detects through GC-MS; The laurylene conversion ratio is 99.8%, and β-addition compound product selectivity is 99.3%.
Take by weighing embodiment 2 catalyst 0.5g; 19.6g (0.1mol) tetradecene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 3h in 70 ℃ of silicone oil baths, cooling, product detects through GC-MS; The tetradecene conversion ratio is 98.7%, and β-addition compound product selectivity is 99.1%.
Take by weighing embodiment 2 catalyst 0.5g; 25.2g (0.1mol) octadecylene and 18.0g (0.11mol) triethoxy hydrogen silane places 100 milliliters single port flask; React 3h in 90 ℃ of silicone oil baths, cooling, product detects through GC-MS; The octadecylene conversion ratio is 92.6%, and β-addition compound product selectivity is 98.0%.
Take by weighing embodiment 2 catalyst 0.5g, 11.2g (0.1mol) octene and 12.6g (0.11mol) methyl dichloro hydrogen silane place 100 milliliters single port flask, react 2h in 40 ℃ of silicone oil baths; Cooling; Product detects through GC-MS, and the octene conversion ratio is 100%, and β-addition compound product selectivity is 99.4%.
Take by weighing embodiment 2 catalyst 0.5g; 16.8g (0.1mol) laurylene and 12.6g (0.11mol) methyl dichloro hydrogen silane places 100 milliliters single port flask; React 2h in 40 ℃ of silicone oil baths, cooling, product detects through GC-MS; The laurylene conversion ratio is 99.8%, and β-addition compound product selectivity is 99.0%.
Take by weighing embodiment 2 catalyst 0.5g; 19.6g (0.1mol) tetradecene and 12.6g (0.11mol) methyl dichloro hydrogen silane places 100 milliliters single port flask; React 3h in 40 ℃ of silicone oil baths, cooling, product detects through GC-MS; The tetradecene conversion ratio is 98.5%, and β-addition compound product selectivity is 98.2%.
Take by weighing embodiment 2 catalyst 0.5g; 25.2g (0.1mol) octadecylene and 12.6g (0.11mol) methyl dichloro hydrogen silane places 100 milliliters single port flask; React 3h in 40 ℃ of silicone oil baths, cooling, product detects through GC-MS; The octadecylene conversion ratio is 93.6%, and β-addition compound product selectivity is 96.5%.
Take by weighing embodiment 2 catalyst 0.5g; 11.2g (0.1mol) octene and 14.9g (0.11mol) 3,5-dimethylphenyl hydrogen silane places 100 milliliters single port flask; React 3h in 60 ℃ of silicone oil baths, cooling, product detects through GC-MS; The octene conversion ratio is 100%, and β-addition compound product selectivity is 99.5%.
Take by weighing embodiment 2 catalyst 0.5g; 16.8g (0.1mol) laurylene and 14.9g (0.11mol) 3,5-dimethylphenyl hydrogen silane places 100 milliliters single port flask; React 3h in 60 ℃ of silicone oil baths, cooling, product detects through GC-MS; The laurylene conversion ratio is 98.8%, and β-addition compound product selectivity is 99.2%.
Take by weighing embodiment 2 catalyst 0.5g; 19.6g (0.1mol) tetradecene and 14.9g (0.11mol) 3,5-dimethylphenyl hydrogen silane places 100 milliliters single port flask; React 4h in 90 ℃ of silicone oil baths, cooling, product detects through GC-MS; The tetradecene conversion ratio is 93.5%, and β-addition compound product selectivity is 98.2%.
Take by weighing embodiment 2 catalyst 0.5g; 25.2g (0.1mol) octadecylene and 14.9g (0.11mol) 3,5-dimethylphenyl hydrogen silane places 100 milliliters single port flask; React 4h in 90 ℃ of silicone oil baths, cooling, product detects through GC-MS; The octadecylene conversion ratio is 87.6%, and β-addition compound product selectivity is 95.5%.
Catalyst of the present invention uses as catalyst in the hydrosilylation of alkene and silane containing hydrogen, and alkene can be for amylene, hexene, heptene, octene, certain herbaceous plants with big flowers alkene, hendecene, laurylene, tetradecene, hexadecylene, octadecylene, styrene, p-methylstyrene, to chlorostyrene or p-chloromethyl styrene; Silane containing hydrogen can be triethoxy hydrogen silane, trimethoxy hydrogen silane, methyl dichloro hydrogen silane, dimethyl chloride hydrogen silane or 3,5-dimethylphenyl hydrogen silane.
Should be understood that this embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (6)
1. platinum catalyst for hydrosilylation; It is characterized in that: obtain containing carboxyl or contain carboxyl and the macromolecule carrier of ethylene linkage with anhydride modified polyethylene glycol or poly glycol monomethyl ether; Again this macromolecule carrier and chloroplatinic acid complexing are obtained described platinum catalyst for hydrosilylation, the load capacity of platinum is 0.002wt%～5wt% in the wherein said platinum catalyst for hydrosilylation; Described molecular weight polyethylene glycol is 1000～20000, and the poly glycol monomethyl ether molecular weight is 1000～15000; The mol ratio of described polyethylene glycol or poly glycol monomethyl ether and acid anhydrides is 0.25～2:1.
2. platinum catalyst for hydrosilylation according to claim 1 is characterized in that: described acid anhydrides is succinic anhydride, maleic anhydride or phthalic anhydride.
3. the preparation method of a platinum catalyst for hydrosilylation according to claim 1 and 2; Described preparation method comprises: obtain containing carboxyl or contain carboxyl and the macromolecule carrier of ethylene linkage with anhydride modified polyethylene glycol or poly glycol monomethyl ether; Again this macromolecule carrier and chloroplatinic acid complexing are obtained described platinum catalyst for hydrosilylation, it is characterized in that:
The method of described anhydride modified polyethylene glycol or poly glycol monomethyl ether is: polyethylene glycol or poly glycol monomethyl ether mix the back and under 60～140 ℃, are stirred to fusing fully with acid anhydrides, and reaction 2～12h adds solvent and constantly stirs 30min, under 0～30 ℃, leaves standstill 2～12h; Generate solid, filter, washing; The solid that obtains is dissolved in the carrene, uses the ether solvents reprecipitation, filter; Washing 20～60 ℃ of following vacuum drying, obtains containing carboxyl or contains carboxyl and the macromolecule carrier of ethylene linkage;
The method of described macromolecule carrier and chloroplatinic acid complexing is: be solvent with the oxolane; With chloroplatinic acid and oxolane complexing macromolecule carrier; Obtain described platinum catalyst for hydrosilylation after removing tetrahydrofuran solvent, the mass ratio of described macromolecule carrier and oxolane is 1:10 ~ 50, and the mass ratio of chloroplatinic acid and macromolecule carrier is 1:20 ~ 50000; The reaction temperature of said macromolecule carrier and chloroplatinic acid complexing is 20～80 ℃, and the reaction time is 8～24h.
4. preparation method according to claim 4 is characterized in that: described solvent is pentane, n-hexane, normal heptane, normal octane or n-decane; Ether solvents is ether or butyl ether.
5. the application of a platinum catalyst for hydrosilylation according to claim 1 and 2 is characterized in that: the platinum catalyst for hydrosilylation that in the hydrosilylation of alkene and silane containing hydrogen, adds effective dose makes this hydrosilylation of its catalysis.
6. the application of platinum catalyst for hydrosilylation according to claim 5 is characterized in that: described alkene is amylene, hexene, heptene, octene, certain herbaceous plants with big flowers alkene, hendecene, laurylene, tetradecene, hexadecylene, octadecylene, styrene, p-methylstyrene, to chlorostyrene or p-chloromethyl styrene; Described silane containing hydrogen is triethoxy hydrogen silane, trimethoxy hydrogen silane, methyl dichloro hydrogen silane, dimethyl chloride hydrogen silane or 3,5-dimethylphenyl hydrogen silane.
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| TWI686429B (en) * | 2014-09-19 | 2020-03-01 | 美商摩曼帝夫特性材料公司 | Platinum (ii) diene complexes for controlled siloxane crosslinking |
| DE102018210886A1 (en) * | 2018-07-03 | 2020-01-09 | Evonik Degussa Gmbh | Process for the preparation of alkylalkoxysilanes |
| CN112724407B (en) * | 2020-12-03 | 2023-06-27 | 浙江工业大学 | Preparation method of dodecyl modified silicone oil |
| CN113244963B (en) * | 2021-05-17 | 2022-05-27 | 杭州师范大学 | Polyethylene glycol N, P coordination non-noble metal catalyst, preparation thereof and application thereof in olefin catalytic hydrosilylation reaction |
| CN113893873A (en) * | 2021-11-04 | 2022-01-07 | 枣阳市华威硅氟材料有限公司 | Pt @ zeolite immobilized catalyst and preparation method and application thereof |
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