CN101279292B - Catalyst for hydrosilylation of olefins containing fluorine and preparation - Google Patents
Catalyst for hydrosilylation of olefins containing fluorine and preparation Download PDFInfo
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- CN101279292B CN101279292B CN2008100615551A CN200810061555A CN101279292B CN 101279292 B CN101279292 B CN 101279292B CN 2008100615551 A CN2008100615551 A CN 2008100615551A CN 200810061555 A CN200810061555 A CN 200810061555A CN 101279292 B CN101279292 B CN 101279292B
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Abstract
The present invention discloses a catalyst used for olefin fluorin-included silicon hydrongen addition reaction and a preparation method thereof. The present invention pertains to the catalyst and the preparation method in the catalyzing art, in particular to a catalyst and a preparation method thereof for macromolecule loading type metal silicon hydrogen addition reaction. The present invention takes styrene as a main prosoma of a polymer and uses a special function group compound to generate a polystyrene small ball body containing the function group by polyreaction of an evocating agent in a certain solvent, then loads platinic chloride to form the macromolecule loading type catalyst for catalyzing the hydrosilation reaction. The catalyst prepared by the present invention relates to a macromolecule loading type catalyst which has the characteristics of effective activation, easily being separated from the catalyst product after reaction, being able to be recycled, simple preparation method, easy control, better repeatability and having a certain economic and social benefits. The present invention has broad usages in the fields such as organic synthesis, etc.
Description
Technical field
The present invention relates to the Catalysts and its preparation method in the catalytic field, specifically is a kind of macromolecule loading type metallic silicon catalyst for addition reaction of hydrogen and preparation method thereof.
Background technology
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 polymer.In recent years, the addition of Fluorine containing olefine silicon hydrogen generates the field that the fluorine silicon monomer becomes a popular research gradually.Before the present invention, the addition of Fluorine containing olefine silicon hydrogen directly uses chloroplatinic acid as catalyst usually, and in addition, Speier catalyst and Karstedt catalyst have certain catalytic activity.Though these catalyst system and catalyzings have greater activity, reaction is carried out under high-temperature and high-pressure conditions often, and after the reaction end, catalyst is difficult to reclaim, and the catalyst cost is higher.By adding SnCl
2Platinum catalyst is carried out modification, make catalysis efficiency obtain certain raising, but the recovery of catalyst still is a urgent problem.Utilize A1
2O
3, SiO
2Make the prepared catalyst of carrier, effect is not very desirable.Prepare catalyst with activated carbon supported Pt or Pt+Cu, obtained catalytic effect preferably, but catalyst can not recycle once more.
The homogeneous phase platinum catalyst has obtained extensive use as Speier catalyst or Karstedt catalyst in the organic fluorinated silicone industry is produced, but the catalyst separation difficulty can't reclaim, can not be recycling, make that the catalyst cost is higher; Then there are shortcomings such as easy inactivation in the heterogeneous catalyst of inorganic carrier load platinum.Therefore, novel, the reusable catalyst of preparation is used for the Fluorine containing olefine hydrosilylation and has important application prospects.
Summary of the invention
The present invention is directed to deficiency of the prior art, a kind of better technical scheme has been proposed, the technical problem that solves has provided a kind of heterogeneous catalyst preparation method who is applicable to the Fluorine containing olefine hydrosilylation that has, reaction condition gentleness when this catalyst uses, safety, effectively, with convenient product separation, recyclable utilization again.
The present invention is achieved by following technical scheme:
A kind of loaded catalyst that is used for the Fluorine containing olefine hydrosilylation is characterized in that having following chemical general formula:
In the formula: n=3-12, m=1-1000, k=1-1000, n, m, k are integer.
A kind of preparation method who is used for the loaded catalyst of Fluorine containing olefine hydrosilylation comprises the steps:
(1) be in oxolane or ethanol or ethanol and the aqueous mixtures at solvent, add styrene and with azodiisobutyronitrile or ABVN or potassium peroxydisulfate as initator; Functional polyethylene glycol as crosslinking agent and with 2-vinylpyridine, 4-vinylpridine as the functional group compound, polymerisation forms the polystyrene macromolecule carrier.
As preferably, styrene and solvent quality ratio are 1: 1～1: 20, and initator and styrene mol ratio are 1: 100～1: 500; Better selection, styrene and solvent quality ratio are 1: 2～1: 10, initator and styrene mol ratio are 1: 200～1: 350.Other organic solvent also has result of use in the present invention.As preferably, it is azodiisobutyronitrile (AIBN) that described polymer support prepares used initator.As preferably, described crosslinking agent and styrene mol ratio are 1: 5～1: 200, and functional group compound and styrene mol ratio are 1: 5～1: 300, and reaction temperature is 60～140 ℃, and the reaction time is 4～48h.As preferably, described crosslinking agent and styrene mol ratio are 1: 20～1: 150, and functional group compound and styrene mol ratio are 1: 20～1: 200, and reaction temperature is 70～100 ℃, and the reaction time is 20～32h.As better selection, crosslinking agent and styrene mol ratio are 1: 100～1: 120, and functional group compound and styrene mol ratio are 1: 150～1: 180, and reaction temperature is 70～100 ℃, and the reaction time is 20～32h.As preferably, the molecular weight of described functional polyethylene glycol is 200,300,400 or 600; It is better when functional polyethylene glycol is the allyl functional polyethylene glycol.
(2) load chloroplatinic acid on carrier then forms the macromolecule loading type catalyst that the Fluorine containing olefine silicon hydrogenation is used.As preferably, the process of load chloroplatinic acid is to be solvent with the oxolane on carrier, with chloroplatinic acid tetrahydrofuran solution dipping polystyrene macromolecule carrier, wherein, polystyrene macromolecule carrier and oxolane mass ratio are 1: 5～1: 20, and chloroplatinic acid and polystyrene macromolecule carrier mass ratio are 1: 20～1: 200, and reaction temperature is 30～80 ℃, reaction time is 8～24h, generates target product.The beneficial effect that the present invention has is:
1, because the catalyst of the present invention's preparation is the macromolecule loading type catalyst, have efficient catalytic, reaction is finished rear catalyst and is separated from product easily, recyclable characteristics such as recycle have also increased new varieties for being used for the synthetic catalyst of fluorine silicon monomer simultaneously.
2, the silicon hydrogenation of the catalyst aims Fluorine containing olefine of the present invention preparation has good catalytic effect, can catalysis the addition reaction of itself and multiple silane containing hydrogen.
3, preparation method provided by the invention is simple, is easy to control, and reappearance is relatively good, has the certain economic social benefit.
The specific embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1:
The preparation of polystyrene macromolecule carrier is a solvent with the oxolane:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 100mL oxolane, 50g styrene, 1.5g allyl polyglycol, 0.25g AIBN, sealed reactor is warming up to 70 ℃, stirring reaction 16h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get white powder.
Embodiment 2:
The preparation of polystyrene macromolecule carrier is a solvent with the oxolane:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 100mL oxolane, 50g styrene, 7.5g allyl polyglycol, 0.25g AIBN.Sealed reactor is warming up to 80 ℃, stirring reaction 26h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get white powder.
Embodiment 3:
The preparation of polystyrene macromolecule carrier is a solvent with ethanol:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 100mL ethanol, 50g styrene, 1.5g allyl polyglycol, 0.25g AIBN.Sealed reactor is warming up to 90 ℃, stirring reaction 24h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get white powder.
Embodiment 4:
Containing the preparation of pyridine radicals polystyrene macromolecule carrier, is solvent with ethanol and aqueous mixtures:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 10mL water, 90mL ethanol, 50g styrene, 1.5g allyl polyglycol, 0.25g AIBN, add 2-vinylpyridine 2.5g.Sealed reactor is warming up to 70 ℃, stirring reaction 24h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get pale yellow powder.
Embodiment 5:
Containing the preparation of pyridine polystyrene macromolecule carrier, is solvent with the oxolane:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 100mL oxolane, 50g styrene, 7.5g allyl polyglycol, 0.25g AIBN, add 2-vinylpyridine 2.5g, sealed reactor, be warming up to 100 ℃, stirring reaction 20h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get pale yellow powder.
Embodiment 6:
Containing the preparation of pyridine polystyrene macromolecule carrier, is solvent with the oxolane:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 100mL oxolane, 50g styrene, 1.5g allyl polyglycol, 0.25g AIBN, add 4-vinylpridine 2.5g, sealed reactor, be warming up to 120 ℃, stirring reaction 30h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get pale yellow powder.
Embodiment 7:
Containing the preparation of pyridine polystyrene macromolecule carrier, is solvent with ethanol:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 100mL ethanol, 50g styrene, 7.5g allyl polyglycol, 0.25gAIBN, add 4-vinylpridine 7.5g, sealed reactor is warming up to 70 ℃, stirring reaction 40h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get pale yellow powder.
Embodiment 8:
Containing the preparation of pyridine polystyrene macromolecule carrier, is solvent with ethanol:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 100mL ethanol, 50g styrene, 1.5g allyl polyglycol, 0.25g AIBN, add 2-vinylpyridine 5.0g, sealed reactor is warming up to 80 ℃, stirring reaction 20h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get pale yellow powder.
Embodiment 9:
Containing the preparation of pyridine radicals polystyrene macromolecule carrier, is solvent with the oxolane:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 100mL oxolane, 50g styrene, 1.5g allyl polyglycol, 0.25g AIBN, add 2-vinylpyridine 5.0g, sealed reactor, be warming up to 100 ℃, stirring reaction 28h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get pale yellow powder.
Embodiment 10:
Containing the preparation of pyridine radicals polystyrene macromolecule carrier, is solvent with ethanol:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 100mL ethanol, 50g styrene, 1.5g allyl polyglycol, 0.25gAIBN, add 2-vinylpyridine 5.0g, sealed reactor is warming up to 70 ℃, stirring reaction 10h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get pale yellow powder.
Embodiment 11:
Containing the preparation of pyridine radicals polystyrene macromolecule carrier, is solvent with ethanol:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 100mL ethanol, 50g styrene, 1.5g allyl polyglycol, 0.25g AIBN, add 4-vinylpridine 5.0g, sealed reactor is warming up to 70 ℃, stirring reaction 20h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get pale yellow powder.
Embodiment 12:
Containing the preparation of pyridine radicals polystyrene macromolecule carrier, is solvent with ethanol and aqueous mixtures:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 10mL water, 90mL ethanol, 50g styrene, 1.5g allyl polyglycol, 0.25g AIBN, add 4-vinylpridine 2.5g.Sealed reactor is warming up to 130 ℃, stirring reaction 14h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get white powder.
Embodiment 13:
Containing the preparation of pyridine radicals polystyrene macromolecule carrier, is solvent with ethanol and aqueous mixtures:
Have gas inlet and outlet can the 250mL reactor of airtight stirring in, add 10mL water, 90mL ethanol, 50g styrene, 3.0g allyl polyglycol, 0.25g AIBN, add 4-vinylpridine 2.5g.Sealed reactor is warming up to 70 ℃, stirring reaction 24h.Remove solvent in the reaction product liquid, product is dissolved in the carrene, in methyl alcohol, disperse, the sedimentation moulding.Filter, water and methyl alcohol wash respectively three times, put into 60 ℃ of vacuum drying 8h of vacuum drying chamber, get white powder.
Embodiment 14:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 1,6.6mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0152g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 1wt%.
Embodiment 15:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 1,9.86mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0152g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 1.5wt%.
Embodiment 16:
The preparation of macromolecule carrier load platinum catalyst
In the 250mL reaction bulb, add the 100mL oxolane, the macromolecule polysterol bead that obtains among the 10.0g embodiment 1,6.6mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0152g/mL), temperature refluxes, stirs, floods 24h down for 60 ℃.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 1wt%.
Embodiment 17:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 2,6.6mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0152g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 1wt%.
Embodiment 18:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 3,6.6mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0152g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 1wt%.
Embodiment 19:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 4,6.6mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0152g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 1wt%.
Embodiment 20:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 5,6.6mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0304g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 2wt%.
Embodiment 21:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 6,6.6mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0304g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 2wt%.
Embodiment 22:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 7,6.6mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0304g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 2wt%.
Embodiment 23:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 8,6.6mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0076g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 0.5wt%.
Embodiment 24:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 8,6.58mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0152g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 1wt%.
Embodiment 25:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 9,6.6mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0152g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 1wt%.
Embodiment 26:
The preparation of macromolecule carrier load platinum catalyst
Add the 100mL oxolane in the 250mL reaction bulb, the macromolecule polysterol bead that obtains among the 10.0g embodiment 11,6.6mL chloroplatinic acid tetrahydrofuran solution (Pt 0.0152g/mL) stir, flood 24h under the room temperature.Rotary Evaporators is removed solvents tetrahydrofurane, and 40 ℃ of vacuum drying are to constant weight, cool off pale yellow powder, Pt content is 1wt%.
Embodiment 27:
The trifluoro propene hydrosilylation
Take by weighing the catalyst that obtains among the 0.02g embodiment 14 and put into the 10mL reaction bulb that has magnetic stir bar, add 1.07g triethoxy hydrogen silane, feed trifluoro propene gas, replace 3 times, screw the polytetrafluoroethylene (PTFE) stopper, keep simultaneously being communicated with to keep pressure, be warming up to 60 ℃, reaction 5h at 0.1MPa with the trifluoro propene steel cylinder.Be cooled to room temperature, the GC assay products, productive rate is 81.2%.
Embodiment 28:
The trifluoro propene hydrosilylation
Take by weighing the catalyst that obtains among the 0.02g embodiment 20 and put into the 10mL reaction bulb that has magnetic stir bar, add 1.07g triethoxy hydrogen silane, feed trifluoro propene gas, replace 3 times, screw the polytetrafluoroethylene (PTFE) stopper, keep simultaneously being communicated with to keep pressure, be warming up to 60 ℃, reaction 5h at 0.1MPa with the trifluoro propene steel cylinder.Be cooled to room temperature, the GC assay products, productive rate is 94.2%.
Embodiment 29:
The trifluoro propene hydrosilylation
Take by weighing the catalyst that obtains among the 0.02g embodiment 21 and put into the 10mL reaction bulb that has magnetic stir bar, add 1.07g triethoxy hydrogen silane, feed trifluoro propene gas, replace 3 times, screw the polytetrafluoroethylene (PTFE) stopper, keep simultaneously being communicated with to keep pressure, be warming up to 60 ℃, reaction 15h at 0.1MPa with the trifluoro propene steel cylinder.Be cooled to room temperature, the GC assay products, productive rate is 73.2%.
Embodiment 30:
The trifluoro propene hydrosilylation, catalyst is reused embodiment 1:
After product separates among the embodiment 28, keep catalyst in reaction bulb, add 1.07g triethoxy hydrogen silane, feed trifluoro propene gas, replace 3 times, screw the polytetrafluoroethylene (PTFE) stopper, keep simultaneously being communicated with to keep pressure, be warming up to 60 ℃, reaction 10h at 0.1MPa with the trifluoro propene steel cylinder.Be cooled to room temperature, the GC assay products, productive rate is 94.6%.
Embodiment 31:
Trifluoro propene hydrosilylation, catalyst are reused and are implemented 2:
After product separates among the embodiment 30, keep catalyst in reaction bulb, add 1.07g triethoxy hydrogen silane, feed trifluoro propene gas, replace 3 times, screw the polytetrafluoroethylene (PTFE) stopper and keep simultaneously keeping being communicated with to keep pressure at 0.1MPa with the trifluoro propene steel cylinder, be warming up to 70 ℃, reaction 21h.Be cooled to room temperature, the GC assay products, productive rate is 95.1%.
Embodiment 32:
Trifluoro propene hydrosilylation, catalyst are reused and are implemented 3:
After product separates among the embodiment 31, keep catalyst in reaction bulb, add 1.07g triethoxy hydrogen silane, feed trifluoro propene gas, replace 3 times, screw the polytetrafluoroethylene (PTFE) stopper and keep simultaneously keeping being communicated with to keep pressure at 0.1MPa with the trifluoro propene steel cylinder, be warming up to 50 ℃, reaction 15h.Be cooled to room temperature, the GC assay products, productive rate is 92.7%.
Embodiment 33:
Trifluoro propene hydrosilylation, catalyst are reused and are implemented 4:
After product separates among the embodiment 32, keep catalyst in reaction bulb, add 1.07g triethoxy hydrogen silane, feed trifluoro propene gas, replace 3 times, screw the polytetrafluoroethylene (PTFE) stopper and keep simultaneously keeping being communicated with to keep pressure at 0.1MPa with the trifluoro propene steel cylinder, be warming up to 40 ℃, reaction 5h.Be cooled to room temperature, the GC assay products, productive rate is 82.2%.
Claims (8)
1. a Preparation of catalysts method that is used for the Fluorine containing olefine hydrosilylation is characterized in that comprising the steps:
(1) be in oxolane or ethanol or ethanol and the aqueous mixtures at solvent, add styrene and initator, described initator is azodiisobutyronitrile or ABVN or potassium peroxydisulfate, add crosslinking agent allyl polyglycol and functional group compound, described functional group compound is 2-vinylpyridine, 4-vinylpridine, and polymerisation forms the polystyrene macromolecule carrier;
(2) load chloroplatinic acid on carrier then forms the macromolecule loading type catalyst that the Fluorine containing olefine silicon hydrogenation is used.
2. preparation method according to claim 1 is characterized in that described styrene and solvent quality ratio is 1: 1～1: 20, and initator and styrene mol ratio are 1: 100～1: 500.
3. preparation method according to claim 2 is characterized in that described styrene and solvent quality ratio is 1: 2～1: 10, and initator and styrene mol ratio are 1: 200～1: 350.
4. preparation method according to claim 1 is characterized in that described initator is an azodiisobutyronitrile.
5. preparation method according to claim 1, the molecular weight that it is characterized in that described allyl polyglycol is 200,300,400 or 600.
6. preparation method according to claim 1, it is characterized in that described crosslinking agent and styrene mol ratio are 1: 5～1: 200, functional group compound and styrene mol ratio are 1: 5～1: 300, and reaction temperature is 60～140 ℃, and the reaction time is 4～48h.
7. preparation method according to claim 7, it is characterized in that described crosslinking agent and styrene mol ratio are 1: 20～1: 150, functional group compound and styrene mol ratio are 1: 20～1: 200, and reaction temperature is 70～100 ℃, and the reaction time is 20～32h.
8. preparation method according to claim 1, it is characterized in that described on carrier the process of load chloroplatinic acid be to be solvent with the oxolane, with chloroplatinic acid tetrahydrofuran solution dipping polystyrene macromolecule carrier, wherein, polystyrene macromolecule carrier and oxolane mass ratio are 1: 5～1: 20, and chloroplatinic acid and polystyrene macromolecule carrier mass ratio are 1: 20～1: 200, and reaction temperature is 30～80 ℃, reaction time is 8～24h, generates target product.
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| CN104628759A (en) * | 2013-11-13 | 2015-05-20 | 浙江省化工研究院有限公司 | Fluoroalkyl alkoxy silane and preparation method thereof |
| CN104497033B (en) * | 2014-11-14 | 2018-12-14 | 衢州氟硅技术研究院 | A kind of synthetic method of long-chain fluorohydrocarbon ylmethyl chlorosilane |
| CN112121862A (en) * | 2020-10-15 | 2020-12-25 | 江西赣江新区有机硅创新研究院有限公司 | Magnetic immobilized platinum catalyst and preparation method and application thereof |
| CN112121861A (en) * | 2020-10-15 | 2020-12-25 | 江西赣江新区有机硅创新研究院有限公司 | Magnetically-recoverable immobilized platinum catalyst and preparation method and application thereof |
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