CN110183666A - A kind of vinylsiloxane grafting containing hydrogen silicone oil and preparation method thereof - Google Patents
A kind of vinylsiloxane grafting containing hydrogen silicone oil and preparation method thereof Download PDFInfo
- Publication number
- CN110183666A CN110183666A CN201910452691.1A CN201910452691A CN110183666A CN 110183666 A CN110183666 A CN 110183666A CN 201910452691 A CN201910452691 A CN 201910452691A CN 110183666 A CN110183666 A CN 110183666A
- Authority
- CN
- China
- Prior art keywords
- silicone oil
- containing hydrogen
- vinylsiloxane
- hydrogen silicone
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/32—Post-polymerisation treatment
Abstract
The invention discloses a kind of vinylsiloxane grafting containing hydrogen silicone oils and preparation method thereof, belong to technical field of organic synthesis.It provides a kind of vinylsiloxane grafting containing hydrogen silicone oil and modified containing hydrogen silicone oil is obtained by the addition reaction of C=C key and Si -- H bond.A kind of vinylsiloxane grafting containing hydrogen silicone oil and preparation method thereof is additionally provided, step includes: that first containing hydrogen silicone oil is stirred and is slowly heated；Then solid catalyst made from platonic and vinylsiloxane are sequentially added, isothermal reaction is for a period of time；It finally cools, filters out platiniferous solid catalyst to get vinylsiloxane and be grafted containing hydrogen silicone oil；In preparation reaction system, preferably platinum content accounts for the 0.02~0.06% of containing hydrogen silicone oil quality, and the molar ratio of C=C key and Si -- H bond in containing hydrogen silicone oil is (1~1.05) in optimal ethylene radical siloxane: 1；It may be implemented in the presence of reactionless solvent, obtain the vinylsiloxane grafting containing hydrogen silicone oil that viscosity is high, hydrogen content is low.
Description
Technical field
The present invention relates to a kind of vinylsiloxane grafting containing hydrogen silicone oils and preparation method thereof, belong to the research preparation of silicone oil
Technical field.
Background technique
Vinylsiloxane has C=C double bond structure, has the effect of coupling agent and crosslinking agent concurrently, can be used for polymer
Crosslinking, it is also possible to be surface-treated, coating and filler, sealant, hydrophober etc..Containing hydrogen silicone oil has good film formation at low temp
Property, weatherability, hydrophobicity, heat resistance, insulating properties and physiological inertia etc., but with the compatibility of other organic solvents and water compared with
Difference carries out graft modification by the Si -- H bond contained to its own, introduces specific function base to expand the application of silicone oil
Group, can assign its more new capability.
The preparation method of modified silicon oil, the homogeneous catalyst generallyd use have tetrahydrofuran, methanol, second containing chloroplatinic acid
One or more of alcohol, propyl alcohol or aqueous isopropanol, although activity is higher, platinum therein is easily oxidized at high temperature, together
When these catalyst be dispersed in system, cannot be recycled, lead to higher cost, be unfavorable for industrial expanding production.And
It is both needed to be reacted in a solvent in the method for existing grafting silicone oil, but containing hydrogen silicone oil is incompatible with most of organic solvents,
The prior art uses the solvent containing toluene to containing hydrogen silicone oil, but the toxic solvent containing toluene, and Long Term Contact is to human injury
It is bigger, and environment is polluted, need to be removed the process of solvent, the production cycle is big, complex steps, and production efficiency is low.
For example, Chinese Patent Application No. is 201110021894.9, the patent Shen that application publication date is on August 17th, 2011
Please file disclose a kind of allyl ethyl ether graft polysiloxane and its preparation method and application.It should be the preparation method comprises the following steps: by alkene
Ethyl ether is grafted on containing hydrogen silicone oil by hydrosilylation, and allyl ethyl ether graft polysiloxane is made.But
On the one hand, which uses anhydrous dimethyl benzene as the solvent of reaction, and dimethylbenzene has toxicity, causes harm to the human body,
And be not readily separated and discharge, heating is easy to crosslink product when having pollution to environment, and boiling off solvent in post synthesis, into
And xanthochromia；On the other hand, the catalyst containing Pt that this method uses is liquid, is dissolved in product, is not only not readily separated, also results in
Unstable products, platinum black can be precipitated in time length, and exothermic heat of reaction is violent when addition catalyst, is unfavorable for industrial mass manufacture.
For another example, on March 20th, 2017, " Angewandte Chemie-International Edition " volume 56
13 the 3665-3669 pages of phases, Kangsang L.Lee disclose entitled " (Aminomethyl) pyridine
Complexes for the Cobalt-Catalyzed Anti-Markovnikov Hydrosilylation of
The article of Alkoxy-or Siloxy (vinyl) silanes with Alkoxy-or Siloxyhydrosilanes ", this grinds
Study carefully and discloses the cobalt for being related to siloxy-or alkoxy (vinyl) silane and siloxy-or alkoxy hydrogen silane and urge
The anti-Markovnikov's reaction changed.Cobalt-(amino methyl) pyridine complex new more than 25 kinds is developed as catalyst
Hydrosilylation for industrial related and challenging siloxy or alkoxy end-capped vinyl silanes.These
Conversion usually carries out in the presence of the alkylating agent of the cobalt complex of 0.25mol% and 0.75mol%, obtains required product, produces
Rate is up to >=98%, has > 98% Anti-Markovnikov selectivity in 30 minutes.The patent is at two ends of substrate
End provides the siloxanes more than 25 with siloxy or alkoxy-functional, and can also be applied to polymerized vinyl
And hydrogen siloxane.But the catalyst that the preparation method uses is the catalyst containing cobalt, cobalt complex is urged in hydrosilylation
The research of agent is less, and Co catalysts are mainly used for various anti-markov Elie Metchnikoff selective hydration silanization alkane in this method
The tertiary vinyl silanes of oxygroup-or siloxy (vinyl) silane and alkoxy-or siloxy hydrogen silane, this catalysis
Agent has anti-markov Elie Metchnikoff selectivity, and product will be present isomers, be unfavorable for obtaining single siloxanes.
Currently, the method for grafting silicone oil has obtained universal application, especially polyethers, ammonia alkyl, epoxyhydrocarbyl, chlorocarbon
The modified silicon oils such as base and chain alkyl, but it is the absence of the good modification containing hydrogen silicone oil of compatibility, it is therefore, more excellent for preparing performance
Different modification containing hydrogen silicone oil, in order to improve yield and save the cost, develop a kind of vinylsiloxane grafting containing hydrogen silicone oil and
In the absence of a solvent the vinylsiloxane grafting silicone oil that viscosity is high, hydrogen content is low is prepared, just in preparation method
As urgent problem to be solved.
Summary of the invention
1. to solve the problems, such as
It is poor for the compatibility of containing hydrogen silicone oil and organic solvent and water, the application of containing hydrogen silicone oil is limited, the present invention mentions
Supply a kind of vinylsiloxane grafting containing hydrogen silicone oil that carbon-carbon double bond is added on silicon hydrogen chain group by hydrosilation method,
The modification containing hydrogen silicone oil that viscosity is high, hydrogen content is low is obtained, keeps its application more extensive.
Present invention is alternatively directed to be both needed to the problem of being reacted in a solvent in the preparation method of existing grafting silicone oil, provide
A kind of preparation method of vinylsiloxane grafting containing hydrogen silicone oil, using hydrosilation method, in the absence of a solvent, vinyl
Graft reaction occurs for siloxanes and containing hydrogen silicone oil, finally obtains colourless or pale yellow transparent oily thick liquid, as vinyl
Polysiloxane grafted containing hydrogen silicone oil.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind of vinylsiloxane grafting containing hydrogen silicone oil, general structure are as follows:
Wherein, n is positive integer, and X represents the alkyl for containing 1~8 carbon atom, Y representation methoxy or ethyoxyl.
The preparation method of above-mentioned vinylsiloxane grafting containing hydrogen silicone oil, vinylsiloxane is connect by hydrosilation method
On branch to containing hydrogen silicone oil, vinylsiloxane grafting containing hydrogen silicone oil is obtained.
Further, the steps include:
(1) containing hydrogen silicone oil is stirred and is slowly heated, warming temperature gradient is 5 DEG C/min；
(2) platiniferous solid catalyst and vinylsiloxane are sequentially added, isothermal reaction is for a period of time；
(3) it cools, filters out platiniferous solid catalyst, obtain transparency liquid, is i.e. vinylsiloxane grafting is hydrogeneous
Silicone oil.
Further, the structural formula of the containing hydrogen silicone oil are as follows:
Wherein n is positive integer.
Further, the structural formula of the vinylsiloxane are as follows:
Wherein, X represents the alkyl for containing 1~8 carbon atom, Y representation methoxy or ethyoxyl.
Further, in the step (2), platiniferous solid catalyst is added when being warming up to 55 DEG C, further heats
Vinylsiloxane is added when to 60 DEG C.
Further, the content of platinum is 2~3% in the platiniferous solid catalyst, wherein in preparation reaction system,
Platinum content accounts for the 0.02~0.06% of containing hydrogen silicone oil quality.
Further, the platiniferous solid catalyst in the step (2) is preferably using silica as the polyvinyl of carrier
Siloxanes-platinum complex, dosage are preferably the 1.0~2.0% of reactant containing hydrogen silicone oil quality.
Further, the thermostat temperature in the step (2) is 100~110 DEG C, and the reaction time is 6~7h.
Further, in the vinylsiloxane in C=C key and high containing hydrogen silicone oil the molar ratio of Si -- H bond be (1~
1.05):1。
Further, the reaction environment of the preparation method is air, nitrogen or vacuum condition.
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) present invention provides a kind of method of vinylsiloxane grafting containing hydrogen silicone oil, using solventless method Si―H addition reaction
Si -- H bond and unsaturation C=C key are carried out addition reaction by technique, generate the good Si-C key of hydrolytic stability, obtained product
Colorless and transparent, safety and environmental protection reduces impurity, method is simple, and catalyst recoverable, not only drops without removing solvent
The low harm to human body and environment, reduces synthesis procedure, shortens the production cycle, also a save production cost, improve
Product quality；
(2) vinylsiloxane of the invention grafting containing hydrogen silicone oil is a kind of modified silicon oil containing alkoxide, is
Hydrosilylation modification occurs using high containing hydrogen silicone oil and vinylsiloxane to form；During the preparation process, high by changing
Hydrogen content, the viscosity of containing hydrogen silicone oil, the C=C double bond of vinylsiloxane can prepare high performance vinylsiloxane and connect
Branch silicone oil；Specific manifestation are as follows: vinylsiloxane is grafted silicone oil in colourless or faint yellow thick, molecular weight increase, viscosity increasing
Add, hydrogen content reduce, not only have lower surface tension, but also compatibility, stability, adsorptivity, flexibility, caking property,
The performances such as lubricity and levelability improve, and can be used as coupling agent, crosslinking agent, glass antidimmer, fabric softener, coating levelling
Agent, release agent, emulsifier and defoaming agent, senior lubricant, shockproof oil, insulating oil, polish, diffusion in vacuum pump oil, fabric are whole
Agent, high-grade cleaning agent and foam stabilizer etc. are managed, may be also used in cosmetic industry, for making cream kind product, greasy skin is played, protects
Wet crease-resistant effect；
(3) the highly viscous silicone oil of the present invention has molecular weight height, anti-sticking smooth, waterproof hydrophobic, reduces surface tension, oxytolerant
Change stability and good weatherability, heat-resisting quantity, resistance to compression, lubricity be good, good insulating, colorless and odorless, nontoxic and physiology are lazy
Property etc. multifrequency natures, can be widely applied to manufacture high efficient demoulding agent, cosmetic material, electrical isolation product, modified plastic rubber additive,
The fields such as high-temperature sealing material, damping grease, lubricating grease, powdery paints；
(4) it is catalyst present invention preferably uses polyvinyl siloxane-platinum complex that silica is carrier, is
Solid-state, preparation is simple, and effective surface area is big, can come into full contact with reactant, so that catalytic activity is higher, stability is good, easily
Separation, and the catalyst after reaction is washed with anhydrous ether, can be reused after drying, save the cost；Catalyst
Dosage is affected to the conversion ratio of containing hydrogen silicone oil and the state of reaction product, and catalyst amount is too low, and conversion ratio is low, and product is not
Uniformly, unstable；Dosage is excessively high, is easy to appear crosslinking；
(5) additional amount of catalyst of the present invention is reactant containing hydrogen silicone oil quality 1.0~2.0%, and catalysis can be effectively controlled
The dosage of agent, hydrosilylation catalysis reaction completely under the dosage of the catalyst, wherein platinum content accounts for containing hydrogen silicone oil quality
0.02~0.06%, the catalytic efficiency of reaction system can be made to increase；
(6) present invention is first added catalyst and vinylsiloxane is added dropwise again, can effectively avoid reaction very exothermic；
(7) strict control reaction temperature of the present invention and reaction time, if temperature is excessively high, reactant can be partially crosslinked,
Cause final product uneven, 100~110 DEG C of constant temperature also avoid high temperature that reaction is made to generate xanthochromia, while reducing under high temperature small point
The generation of sub- substance, it is more thorough that 6~7h of reaction can be such that reaction carries out；
(8) in reactant of the present invention the molar ratio of C=C key and Si -- H bond theoretically for should be 1:1, C=C key slightly mistake
Amount can make the C=C double bond in Si -- H bond and vinylsiloxane in containing hydrogen silicone oil participate in hydrosilylation, inventor completely
By a large amount of experiment discovery, when the molar ratio of C=C key and Si -- H bond is (1~1.05): when 1, Si -- H bond reaction is completeer
Entirely；
(9) the efficient progress of energy, operation item under air, nitrogen or vacuum condition are reacted in preparation of the invention
Part is simple, is easier to carry out mass production of ethylene radical siloxane grafting containing hydrogen silicone oil.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance H spectrogram of containing hydrogen silicone oil in the present invention；
Fig. 2 is the nuclear magnetic resonance H spectrogram of 2 medium vinyl triethoxysilane containing hydrogen silicone oil of the embodiment of the present invention；
Fig. 3 is the nuclear magnetic resonance H spectrogram that containing hydrogen silicone oil is grafted in comparative example 3 of the present invention.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
One, the preparation of platiniferous solid catalyst
Embodiment 1
(1) polyvinyl siloxane-platinum complex preparation
With dehydrated alcohol by after six hydration chloroplatinic acid 2g dissolutions, vinyltriethoxysilane 8g and sodium carbonate 4g is added,
Stirring is warming up to 80 DEG C, and observation solution continues to stir 0.5h after being turned yellow by reddish orange, then cools to room temperature, filtering is (heavy
It is washed with dehydrated alcohol in shallow lake)；It after filtrate steaming removal solvent, is dissolved, and is washed till in solution without Cl with benzene-, then evaporating solvent under reduced pressure, it obtains
To oily complex compound, as polyvinyl triethoxysilane-platinum complex.
(2) using silica as polyvinyl siloxane-platinum complex catalyst preparation of carrier
20g smoke-like silica is added in the complex compound obtained in benzene dissolution (1), and flow back 8h under heating stirring, is evaporated off
Solvent, it is dry, it obtains using silica as the polyvinyl triethoxysilane of carrier-platinum complex catalyst A 24.0g,
In, product catalyst A is obtained through elemental analysis (being directed to tri- kinds of elements of Pt, C, H): Pt:3.00%；C:7.21%；H:1.13%.
Embodiment 2
(1) polyvinyl siloxane-platinum complex preparation
With dehydrated alcohol by after six hydration chloroplatinic acid 1.53g dissolutions, vinyltriethoxysilane 8g and sodium carbonate is added
4g, stirring are warming up to 80 DEG C, and observation solution continues to stir 0.5h after being turned yellow by reddish orange, then cools to room temperature, filters
(precipitating is washed with dehydrated alcohol)；It after filtrate steaming removal solvent, is dissolved, and is washed till in solution without Cl with benzene-, then remove under reduced pressure molten
Agent obtains oily complex compound, as polyvinyl triethoxysilane-platinum complex.
(2) using silica as polyvinyl siloxane-platinum complex catalyst preparation of carrier
20g smoke-like silica is added in the complex compound obtained in benzene dissolution (1), and flow back 8h under heating stirring, is evaporated off
Solvent, it is dry, it obtains using silica as the polyvinyl triethoxysilane of carrier-platinum complex catalyst B 22.0g,
In, product catalyst A is obtained through elemental analysis (being directed to tri- kinds of elements of Pt, C, H): Pt:2.53%；C:8.12%；H:1.77%.
Embodiment 3
(1) polyvinyl siloxane-platinum complex preparation
With dehydrated alcohol by after six hydration chloroplatinic acid 1.17g dissolutions, vinyltriethoxysilane 8g and sodium carbonate is added
4g, stirring are warming up to 80 DEG C, and observation solution continues to stir 0.5h after being turned yellow by reddish orange, then cools to room temperature, filters
(precipitating is washed with dehydrated alcohol)；It after filtrate steaming removal solvent, is dissolved, and is washed till in solution without Cl with benzene-, then remove under reduced pressure molten
Agent obtains oily complex compound, as polyvinyl triethoxysilane-platinum complex.
(2) using silica as polyvinyl siloxane-platinum complex catalyst preparation of carrier
20g smoke-like silica is added in the complex compound obtained in benzene dissolution (1), and flow back 8h under heating stirring, is evaporated off
Solvent, it is dry, it obtains using silica as the polyvinyl triethoxysilane of carrier-platinum complex catalyst C 21.0g,
In, product catalyst A is obtained through elemental analysis (being directed to tri- kinds of elements of Pt, C, H): Pt:2.04%；C:9.32%；H:2.11%.
Two, the preparation of vinylsiloxane grafting containing hydrogen silicone oil
Embodiment 4
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid (producer: Jinan is added in condenser pipe
Xing Feilong Chemical Co., Ltd., the name of an article: containing hydrogen silicone oil, active hydrogen content: 1.6%, viscosity 30.4), in nitrogen protection condition
Under, it opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added and obtained in embodiment 1 be with silica
The polyvinyl siloxane of carrier-platinum complex catalyst A 2.48g (wherein platinum accounts for 3%), is added dropwise ethylene when being warming up to 60 DEG C
Ethyl triethoxy silicane alkane 441g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst,
Obtain oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 155.11, and active hydrogen content 0.05%, appearance is nothing
Color transparent oily liquid.
The hydrogen nuclear magnetic resonance spectrogram of 1 containing hydrogen silicone oil of comparison diagram, the Si-H in Fig. 2 between chemical shift δ=4.7~4.9ppm
Hydrogen Proton peak is substantially reduced, the Si-CH at δ=0.60ppm2Hydrogen Proton peak occurs, the Si-CH at δ=1.25ppm2CH2Hydrogen matter
Sub- peak occurs, the Si-O-CH at δ=3.8ppm2-CH3Characteristic peak occurs, and is solvent peak at δ=7.29ppm, thus,
The oily thick liquid arrived is that vinyltriethoxysilane is grafted containing hydrogen silicone oil.
Platinum content accounts for the 0.05% of containing hydrogen silicone oil quality in the catalyst used in the present embodiment.
Embodiment 5
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid (producer: Jinan is added in condenser pipe
Xing Feilong Chemical Co., Ltd., the name of an article: containing hydrogen silicone oil, active hydrogen content: 1.6%, viscosity 30.4), in nitrogen protection condition
Under, it opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added and obtained in embodiment 2 be with silica
The polyvinyl siloxane of carrier-platinum complex catalyst B 1.09g (wherein platinum accounts for 2.53%), is added dropwise second when being warming up to 60 DEG C
Alkenyl triethoxysilane 441g continues to be heated to 100~110 DEG C of insulation reaction 6h, cools down to room temperature, filter out catalysis
Agent obtains oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 153.88, and active hydrogen content 0.05%, appearance is nothing
Color transparent oily liquid.
Comparative example 4, platinum content accounts for the 0.02% of containing hydrogen silicone oil quality in the catalyst used in the present embodiment, heat preservation
6h is reacted, the viscosity and active hydrogen content of obtained grafting silicone oil are almost consistent, thus, obtained oily thick liquid
Containing hydrogen silicone oil is grafted for vinyltriethoxysilane.
Embodiment 6
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid (producer: Jinan is added in condenser pipe
Xing Feilong Chemical Co., Ltd., the name of an article: containing hydrogen silicone oil, active hydrogen content: 1.6%, viscosity 30.4), in nitrogen protection condition
Under, it opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added and obtained in embodiment 3 be with silica
The polyvinyl siloxane of carrier-platinum complex catalyst C 2.71g (wherein platinum accounts for 2.04%), is added dropwise second when being warming up to 60 DEG C
Alkenyl triethoxysilane 441g continues to be heated to 100~110 DEG C of insulation reaction 6.5h, cools down to room temperature, filter out catalysis
Agent obtains oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 154.25, and active hydrogen content 0.05%, appearance is nothing
Color transparent oily liquid.
Comparative example 4 and embodiment 5 find that platinum content accounts for containing hydrogen silicone oil quality in the catalyst used in the present embodiment
0.04%, insulation reaction 6.5h, the viscosity and active hydrogen content of obtained grafting silicone oil are almost consistent, thus, must
The oily thick liquid arrived is that vinyltriethoxysilane is grafted containing hydrogen silicone oil.
Embodiment 7
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid (producer: Jinan is added in condenser pipe
Xing Feilong Chemical Co., Ltd., the name of an article: containing hydrogen silicone oil, active hydrogen content: 1.6%, viscosity 30.4), in nitrogen protection condition
Under, it opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added and obtained in embodiment 1 be with silica
The polyvinyl siloxane of carrier-platinum complex catalyst A 2.76g (wherein platinum accounts for 3%), is added dropwise ethylene when being warming up to 60 DEG C
Ethyl triethoxy silicane alkane 431g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst,
Obtain oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 154.72, and active hydrogen content 0.05%, appearance is nothing
Color transparent oily liquid.
Comparative example 4, the molar ratio of the C=C key and Si -- H bond that use in the present embodiment is 1.025:1, in catalyst
Platinum content accounts for the 0.06% of containing hydrogen silicone oil quality, and the viscosity and active hydrogen content of obtained grafting silicone oil are almost consistent, thus
It can obtain, obtained oily thick liquid is that vinyltriethoxysilane is grafted containing hydrogen silicone oil.
Embodiment 8
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid (producer: Jinan is added in condenser pipe
Xing Feilong Chemical Co., Ltd., the name of an article: containing hydrogen silicone oil, active hydrogen content: 1.6%, viscosity 30.4), in nitrogen protection condition
Under, it opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added and obtained in embodiment 1 be with silica
The polyvinyl siloxane of carrier-platinum complex catalyst A 2.48g (wherein platinum accounts for 3%), is added dropwise ethylene when being warming up to 60 DEG C
Ethyl triethoxy silicane alkane 421g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst,
Obtain oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 153.98, and active hydrogen content 0.05%, appearance is nothing
Color transparent oily liquid.
Comparative example 4 and embodiment 8 find, the molar ratio of the C=C key and Si -- H bond that are used in the present embodiment for 1:1,
The viscosity and active hydrogen content of obtained grafting silicone oil are almost consistent, thus, obtained oily thick liquid is ethylene
Ethyl triethoxy silicane alkane is grafted containing hydrogen silicone oil.
Here it is worth noting that, when the molar ratio of C=C key and Si -- H bond is 1:1, vinyltriethoxysilane is added
Amount is 421g, in order to make Si -- H bond fully reacting, the vinyltriethoxysilane of meeting excessive addition, inventor in actual production
Obtain by a large amount of experiment, be (1~1.05) in the molar ratio of C=C key and Si -- H bond: when 1, obtained grafted silane is produced
Measure highest.
Embodiment 9
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added, in vacuum item in condenser pipe
It under part, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with silica in embodiment 1
For polyvinyl siloxane-platinum complex catalyst A 1.66g of carrier, vinyl trimethoxy silicon is added dropwise when being warming up to 60 DEG C
Alkane 344g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, it is sticky to obtain oily
Liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 141.32, and active hydrogen content 0.15%, appearance is nothing
Color transparent oily liquid.
The data of 1 containing hydrogen silicone oil of comparison diagram, the present embodiment use vinyltrimethoxysilane to carry out under vacuum conditions
Graft reaction (molar ratio of C=C key and Si -- H bond is 1.05:1 in reactant), obtained product active hydrogen content decline stick
Degree increases, it can be seen that graft reaction can be carried out under vacuum condition using vinyltrimethoxysilane.
Embodiment 10
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added, in vacuum item in condenser pipe
It under part, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with silica in embodiment 1
For polyvinyl siloxane-platinum complex catalyst A 1.66g of carrier, vinyl trimethoxy silicon is added dropwise when being warming up to 60 DEG C
Alkane 335g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, it is sticky to obtain oily
Liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 140.85, and active hydrogen content 0.15%, appearance is nothing
Color transparent oily liquid.
Comparative example 9, it is (anti-that the present embodiment uses vinyltrimethoxysilane to carry out graft reaction under vacuum conditions
Answering the molar ratio of C=C key and Si -- H bond in object is 1.025:1), obtained product active hydrogen content and viscosity is almost consistent, by
This visible use vinyltrimethoxysilane can carry out graft reaction under vacuum condition.
Embodiment 11
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added, in vacuum item in condenser pipe
It under part, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with silica in embodiment 1
For polyvinyl siloxane-platinum complex catalyst A 1.66g of carrier, vinyl trimethoxy silicon is added dropwise when being warming up to 60 DEG C
Alkane 327g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, it is sticky to obtain oily
Liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 140.51, and active hydrogen content 0.15%, appearance is nothing
Color transparent oily liquid.
Comparative example 9 and 10 finds that the present embodiment uses vinyltrimethoxysilane to be connect under vacuum conditions
Branch reaction (in reactant the molar ratio of C=C key and Si -- H bond be 1:1), obtained product active hydrogen content and viscosity almost one
It causes, it can be seen that graft reaction can be carried out under vacuum condition using vinyltrimethoxysilane.
Here it is worth noting that, when the molar ratio of C=C key and Si -- H bond is 1:1, vinyltrimethoxysilane is added
Amount is 327g, in order to make Si -- H bond fully reacting, the vinyltrimethoxysilane of meeting excessive addition, inventor in actual production
Obtain by a large amount of experiment, be (1~1.05) in the molar ratio of C=C key and Si -- H bond: when 1, obtained grafted silane is produced
Measure highest.
Embodiment 12
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added, in air in condenser pipe
It is reacted, opens simultaneously blender and be stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A 1.93g of carrier, and vinyl methyl two is added dropwise when being warming up to 60 DEG C
Methoxy silane 307g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 145.44, and active hydrogen content 0.10%, appearance is nothing
Color transparent oily liquid.
The number of 1 containing hydrogen silicone oil of comparison diagram is it has been found that the present embodiment uses vinyl methyl dimethoxy under air conditions
Silane carries out graft reaction (molar ratio of C=C key and Si -- H bond is 1.05:1 in reactant), obtained product active hydrogen content
Decline, viscosity increase, it can be seen that graft reaction can be carried out under air conditions using vinyl methyl dimethoxysilane.
It is worth noting that the methyl in the vinyl methyl dimethoxysilane of the present embodiment can be replaced 2~8 carbon
The vinylsiloxane of the alkyl of atom generates the modified silicon oil of same using effect.For example, vinyl ethyl dimethoxy silicon
Alkane, vinyl propyl base dimethoxysilane, vinyl normal-butyl dimethoxysilane, vinyl tert-butyl dimethoxy silicon
Alkane, vinyl n-pentyl dimethoxysilane, vinyl isopentyl dimethoxysilane, vinyl neopentyl dimethoxy silicon
Alkane, vinyl n-hexyl dimethoxysilane, vinyl isohesyl dimethoxysilane, vinyl n-octyl dimethoxy silicon
Alkane, vinyl iso-octyl dimethoxysilane etc..
Embodiment 13
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added, in air in condenser pipe
It is reacted, opens simultaneously blender and be stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A 1.93g of carrier, and vinyl methyl two is added dropwise when being warming up to 60 DEG C
Methoxy silane 299g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 144.99, and active hydrogen content 0.10%, appearance is nothing
Color transparent oily liquid.
Comparative example 12, the present embodiment be grafted using vinyl methyl dimethoxysilane anti-under air conditions
Answer (in reactant the molar ratio of C=C key and Si -- H bond be 1.025:1), obtained product active hydrogen content and viscosity almost without
Variation, it can be seen that graft reaction can be carried out under air conditions using vinyl methyl dimethoxysilane.
Embodiment 14
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added, in air in condenser pipe
It is reacted, opens simultaneously blender and be stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A 1.93g of carrier, and vinyl methyl two is added dropwise when being warming up to 60 DEG C
Methoxy silane 292g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 144.78, and active hydrogen content 0.10%, appearance is nothing
Color transparent oily liquid.
Comparative example 12 and 13 find, the present embodiment under air conditions using vinyl methyl dimethoxysilane into
Row graft reaction (molar ratio of C=C key and Si -- H bond is 1:1 in reactant), obtained product active hydrogen content and viscosity is several
It is unchanged, it can be seen that graft reaction can be carried out under air conditions using vinyl methyl dimethoxysilane.
Here it is worth noting that, when the molar ratio of C=C key and Si -- H bond is 1:1, vinyl methyl dimethoxysilane
Additive amount is 292g, in order to make Si -- H bond fully reacting, the vinyl methyl dimethoxy silicon of meeting excessive addition in actual production
Alkane, inventor obtain by a large amount of experiment, are (1~1.05) in the molar ratio of C=C key and Si -- H bond: when 1, obtaining
Grafted silane yield highest.
Embodiment 15
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added in condenser pipe, is protected in nitrogen
It under the conditions of shield, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A2.21g of carrier, and vinyl methyl two is added dropwise when being warming up to 60 DEG C
Ethoxysilane 372g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 150.43, and active hydrogen content 0.08%, appearance is nothing
Color transparent oily liquid.
The number of 1 containing hydrogen silicone oil of comparison diagram is it has been found that the present embodiment uses vinyl methyl diethoxy under a nitrogen atmosphere
Silane carries out graft reaction (molar ratio of C=C key and Si -- H bond is 1.05:1 in reactant), obtained product active hydrogen content
Decline, viscosity increase, it can be seen that graft reaction can be carried out under condition of nitrogen gas using vinyl methyl diethoxy silane.
It is worth noting that the methyl in the vinyl methyl diethoxy silane of the present embodiment can be replaced 2~8 carbon
The vinylsiloxane of the alkyl of atom generates the modified silicon oil of same using effect.For example, vinyl ethyl diethoxy silicon
Alkane, vinyl propyl diethoxy silane, vinyl normal-butyl diethoxy silane, vinyl tert-butyl diethoxy silane,
Vinyl n-pentyl diethoxy silane, vinyl neopentyl diethoxy silane, vinyl n-hexyl diethoxy silane, second
Alkenyl isohesyl diethoxy silane, vinyl n-octyl diethoxy silane, vinyl iso-octyl diethoxy silane etc..
Embodiment 16
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added in condenser pipe, is protected in nitrogen
It under the conditions of shield, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A 2.21g of carrier, and vinyl methyl two is added dropwise when being warming up to 60 DEG C
Ethoxysilane 363g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 150.12, and active hydrogen content 0.08%, appearance is nothing
Color transparent oily liquid.
Comparative example 15, the present embodiment use vinyl methyl diethoxy silane be grafted instead under a nitrogen atmosphere
(molar ratio of C=C key and Si -- H bond is 1.025:1 in reactant) is answered, obtained product active hydrogen content and viscosity is hardly
Become, it can be seen that graft reaction can be carried out under condition of nitrogen gas using vinyl methyl diethoxy silane.
Embodiment 17
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added in condenser pipe, is protected in nitrogen
It under the conditions of shield, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A 2.21g of carrier, and vinyl methyl two is added dropwise when being warming up to 60 DEG C
Ethoxysilane 354g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 149.88, and active hydrogen content 0.08%, appearance is nothing
Color transparent oily liquid.
Comparative example 15 and 16 find, the present embodiment use under a nitrogen atmosphere vinyl methyl diethoxy silane into
Row graft reaction (molar ratio of C=C key and Si -- H bond is 1:1 in reactant), obtained product active hydrogen content and viscosity becomes
Change little, it can be seen that graft reaction can be carried out under condition of nitrogen gas using vinyl methyl diethoxy silane.
Here it is worth noting that, when the molar ratio of C=C key and Si -- H bond is 1:1, vinyl methyl diethoxy silane
Additive amount is 354g, in order to make Si -- H bond fully reacting, the vinyl methyl diethoxy silicon of meeting excessive addition in actual production
Alkane, inventor obtain by a large amount of experiment, are (1~1.05) in the molar ratio of C=C key and Si -- H bond: when 1, obtaining
Grafted silane yield highest.
Embodiment 18
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added in condenser pipe, is protected in nitrogen
It under the conditions of shield, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A2.48g of carrier, and vinyl-dimethyl base is added dropwise when being warming up to 60 DEG C
Ethoxysilane 302g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 151.24, and active hydrogen content 0.05%, appearance is nothing
Color transparent oily liquid.
The number of 1 containing hydrogen silicone oil of comparison diagram is it has been found that the present embodiment uses vinyl-dimethyl base oxethyl under a nitrogen atmosphere
Silane carries out graft reaction (molar ratio of C=C key and Si -- H bond is 1.05:1 in reactant), obtained product active hydrogen content
Decline, viscosity increase, it can be seen that graft reaction can be carried out under condition of nitrogen gas using vinyl dimethylethoxysilane.
It is worth noting that the methyl in the vinyl dimethylethoxysilane of the present embodiment can be replaced 2~8 carbon
The vinylsiloxane of the alkyl of atom generates the modified silicon oil of same using effect.For example, vinyl methyl ethyl ethyoxyl
Silane, vinyl ethyl propyl base oxethyl silane, vinyl di-n-butyl Ethoxysilane, vinyl di-t-butyl ethyoxyl
Silane, two n-pentyl Ethoxysilane of vinyl, vinyl diisoamyl Ethoxysilane, vinyl di-n-hexyl ethyoxyl silicon
Alkane, the new hexyl Ethoxysilane of vinyl two, vinyl di-n-octyl Ethoxysilane, vinyl diisooctyl Ethoxysilane
Deng.
Embodiment 19
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added in condenser pipe, is protected in nitrogen
It under the conditions of shield, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A 2.48g of carrier, and vinyl-dimethyl base is added dropwise when being warming up to 60 DEG C
Ethoxysilane 288g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 150.78, and active hydrogen content 0.05%, appearance is nothing
Color transparent oily liquid.
Comparative example 18, the present embodiment use vinyl dimethylethoxysilane be grafted instead under a nitrogen atmosphere
(molar ratio of C=C key and Si -- H bond is 1:1 in reactant) is answered, obtained product active hydrogen content is constant with viscosity, thus may be used
Graft reaction can be carried out using vinyl dimethylethoxysilane under condition of nitrogen gas by seeing.
Embodiment 20
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added in condenser pipe, is protected in nitrogen
It under the conditions of shield, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A 2.48g of carrier, and vinyl-dimethyl base is added dropwise when being warming up to 60 DEG C
Ethoxysilane 295g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 151.46, and active hydrogen content 0.05%, appearance is nothing
Color transparent oily liquid.
Comparative example 18 and 19 find, the present embodiment use under a nitrogen atmosphere vinyl dimethylethoxysilane into
Row graft reaction (in reactant the molar ratio of C=C key and Si -- H bond be 1.025:1), obtained product active hydrogen content and glutinous
It spends constant, it can be seen that graft reaction can be carried out under condition of nitrogen gas using vinyl dimethylethoxysilane.
Here it is worth noting that, when the molar ratio of C=C key and Si -- H bond is 1:1, vinyl dimethylethoxysilane
Additive amount is 295g, in order to make Si -- H bond fully reacting, the vinyl-dimethyl base oxethyl silicon of meeting excessive addition in actual production
Alkane, inventor obtain by a large amount of experiment, are (1~1.05) in the molar ratio of C=C key and Si -- H bond: when 1, obtaining
Grafted silane yield highest.
Embodiment 21
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added in condenser pipe, is protected in nitrogen
It under the conditions of shield, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A 2.76g of carrier, and vinyl-dimethyl base is added dropwise when being warming up to 60 DEG C
Methoxy silane 270g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 149.57, and active hydrogen content 0.05%, appearance is nothing
Color transparent oily liquid.
The number of 1 containing hydrogen silicone oil of comparison diagram is it has been found that the present embodiment uses vinyl-dimethyl ylmethoxy under a nitrogen atmosphere
Silane carries out graft reaction (molar ratio of C=C key and Si -- H bond is 1.05:1 in reactant), obtained product active hydrogen content
Decline, viscosity increase, it can be seen that graft reaction can be carried out under condition of nitrogen gas using vinyl-dimethyl methoxylsilane.
It is worth noting that the methyl in the vinyl-dimethyl methoxylsilane of the present embodiment can be replaced 2~8 carbon
The vinylsiloxane of the alkyl of atom generates the modified silicon oil of same using effect.For example, vinyl methyl ethyl methoxyl group
Silane, vinyl ethyl propyl methoxy silane, vinyl di-n-butyl methoxy silane, vinyl di-t-butyl methoxyl group silicon
Alkane, two n-pentyl methoxy silane of vinyl, vinyl diisoamyl methoxy silane, vinyl di-n-hexyl methoxyl group silicon
Alkane, the new hexyl methoxy silane of vinyl two, vinyl di-n-octyl methoxy silane, vinyl diisooctyl methoxy silane
Deng.
Embodiment 22
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added in condenser pipe, is protected in nitrogen
It under the conditions of shield, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A 2.76g of carrier, and vinyl-dimethyl base is added dropwise when being warming up to 60 DEG C
Methoxy silane 263g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 149.18, and active hydrogen content 0.05%, appearance is nothing
Color transparent oily liquid.
Comparative example 21, the present embodiment use vinyl-dimethyl methoxylsilane be grafted instead under a nitrogen atmosphere
It answers (in reactant the molar ratio of C=C key and Si -- H bond be 1.025:1), obtained product active hydrogen content and viscosity almost one
It causes, it can be seen that graft reaction can be carried out under condition of nitrogen gas using vinyl-dimethyl methoxylsilane.
Embodiment 23
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added in condenser pipe, is protected in nitrogen
It under the conditions of shield, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, be added obtained with dioxy in embodiment 1
SiClx is polyvinyl siloxane-platinum complex catalyst A 2.76g of carrier, and vinyl-dimethyl base is added dropwise when being warming up to 60 DEG C
Methoxy silane 257g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out catalyst, obtain
Oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 148.92, and active hydrogen content 0.05%, appearance is nothing
Color transparent oily liquid.
Comparative example 21 and 22 find, the present embodiment use under a nitrogen atmosphere vinyl-dimethyl methoxylsilane into
Row graft reaction (molar ratio of C=C key and Si -- H bond is 1:1 in reactant), obtained product active hydrogen content and viscosity is several
It is consistent, it can be seen that graft reaction can be carried out under condition of nitrogen gas using vinyl-dimethyl methoxylsilane.
Here it is worth noting that, when the molar ratio of C=C key and Si -- H bond is 1:1, vinyl-dimethyl methoxylsilane
Additive amount is 257g, in order to make Si -- H bond fully reacting, the vinyl-dimethyl ylmethoxy silicon of meeting excessive addition in actual production
Alkane, inventor obtain by a large amount of experiment, are (1~1.05) in the molar ratio of C=C key and Si -- H bond: when 1, obtaining
Grafted silane yield highest.
Above embodiments 4~23 are that more slightly excessive than theoretical ratio (excessive part has been subjected to the place that rounds up to C=C key
Reason) obtained product.
Comparative example 1
This comparative example is substantially the same manner as Example 4, the difference is that: using anhydrous in the reaction system of this comparative example
Solvent of the dimethylbenzene as reaction.
Thermometer is being housed, in the four-hole boiling flask of blender, 138g methyl hydrogen is added in condenser pipe in anhydrous dimethyl benzene
Silicone oil opens simultaneously blender and is stirred under the conditions of nitrogen protection, is then to slowly warm up to 55 DEG C, and vinyl three is added dropwise
Ethoxysilane 441g is added obtained using silica as the polyvinyl silicon oxygen of carrier in embodiment 1 when being warming up to 60 DEG C
Alkane-platinum complex catalyst A 2.48g continues to be heated to 100~110 DEG C of insulation reaction 7h, cools down to room temperature, filter out and urge
Agent steams anhydrous dimethyl benzene, obtains oily thick liquid.
The viscosity that silicone oil is grafted as obtained by this comparative example is 140.21, and active hydrogen content 0.10%, appearance is micro-
Yellow oily liquid.
The number of 1 containing hydrogen silicone oil of comparison diagram is it has been found that the present embodiment uses three ethoxy of vinyl in anhydrous dimethyl benzene solvent
Base silane carries out graft reaction, and obtained product active hydrogen content decline, viscosity is higher, but also needs to boil off product after the completion of synthesizing
In dimethylbenzene, it is complex, and heat up distillation during product section be crosslinked, occur xanthochromia.Moreover, this comparative example is first
When reactant being added to add catalyst again, temperature is significantly raised.
Comparative example 2
This comparative example is substantially the same manner as Example 4, the difference is that: this comparative example is entitled using a piece
“(Aminomethyl)pyridine Complexes for the Cobalt-Catalyzed Anti-Markovnikov
Hydrosilylation of Alkoxy-or Siloxy(vinyl)silanes with Alkoxy-or
Cobalt-(amino methyl) pyridine complex in the document of Siloxyhydrosilanes " is as catalyst of the invention.
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added in condenser pipe, is protected in nitrogen
It under the conditions of shield, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, the complexing of cobalt-(amino methyl) pyridine is added
Vinyltriethoxysilane 441g is added dropwise when being warming up to 60 DEG C in object catalyst 2.48g, continues to be heated to 100~110 DEG C of heat preservations
7h is reacted, room temperature is cooled down to, filters out catalyst, obtain oily thick liquid.
The viscosity that silicone oil is grafted as obtained by this comparative example is 53.23, and active hydrogen content 0.86%, appearance is colourless
Transparent oily liquid.
The number of 1 containing hydrogen silicone oil of comparison diagram it has been found that this comparative example in cobalt-(amino methyl) pyridine complex catalyst action
Lower to carry out graft reaction using vinyltriethoxysilane, obtained product active hydrogen content is declined, and viscosity is lower.
Cobalt-(amino methyl) pyridine complex catalyst complex manufacturing process is primarily adapted for use in and reacts with anti-markov Elie Metchnikoff
Tool limited quantity alkoxy or Siloxysilane vinyl alkane and vinyl-arene, and the product of this comparative example
Viscosity is too small, is not suitable for alkoxy or siloxy (vinyl) silane.Inventor analyzes reason are as follows: by markovnikov's rule
Determine: in the electrophilic addition reaction of alkene, the anodic group of addition reagent will be added to olefinic double bonds (or three key) band substituent group
On the carbon atom of less (or hydrogeneous more), it is illustrated occurs in addition reaction in addition reagent and alkene, such as there may be
When two isomers, one such structure is often only generated.The cobalt catalysis that this comparative example is reacted in anti-markov Elie Metchnikoff
Two kinds of isomer products may be generated under agent catalytic action, wherein easily generate Si-C-C-Si structure and
Structure is unfavorable for the silicone oil of single grafting needed for obtaining the present invention, and therefore, Co catalysts are not suitable for silicon hydrogen of the invention and add
At reaction.
Comparative example 3
This comparative example is substantially the same manner as Example 4, the difference is that: this comparative example, which uses, the tetrahydro containing chloroplatinic acid
Furans is as catalyst of the invention.
Thermometer is being housed, in the four-hole boiling flask of blender, 138g Methyl Hydrogen Polysiloxane Fluid is added in condenser pipe, is protected in nitrogen
It under the conditions of shield, opens simultaneously blender and is stirred, be then to slowly warm up to 55 DEG C, the tetrahydrofuran catalysis containing chloroplatinic acid is added
Agent 2.48g is added dropwise vinyltriethoxysilane 441g and cools down in 60~70 DEG C of insulation reaction 12h when being warming up to 60 DEG C
Room temperature isolates catalyst, obtains oily thick liquid.
The viscosity that silicone oil is grafted as obtained by the present embodiment is 120.23, and active hydrogen content 0.07%, appearance is nothing
Color transparent oily liquid.
Comparison diagram 2 is grafted the hydrogen nuclear magnetic resonance spectrogram of silicone oil, the C=C in Fig. 3 between chemical shift δ=5.1~5.2ppm
Unsaturated double-bond Hydrogen Proton peak slightly increases, and the Si-H Hydrogen Proton peak between δ=4.7~4.9ppm obviously increases, and δ=
Si-CH at 0.60ppm2Hydrogen Proton peak is significantly raised, and miscellaneous peak increases between δ=1.0~1.3ppm, it may be possible to remaining catalysis
Caused by agent and solvent, therefore the available oily thick liquid of this comparative example is that vinyltriethoxysilane is grafted Silicon Containing Hydrogen
Oil, but the viscosity decline of product, active hydrogen content increase.
Although the method using this comparative example can also be grafted success, since the boiling point of tetrahydrofuran is lower, reaction temperature
Only up to control at 60~70 DEG C, reaction rate is slower, the reaction time be than embodiment more than 2 4~5 hours, and it is anti-in catalysis
Black precipitate is precipitated during answering or in product placement process, catalyst is difficult to recycle use, and higher cost is not suitable for work
Industry production.
Above-described embodiment is only one kind of embodiment of the present invention, not limits embodiment described in the invention, only
If should all cover without prejudice to the spiritual and improvement carried out under principle or same replacement of the invention in right of the invention
In claimed range.
Claims (10)
1. a kind of vinylsiloxane is grafted containing hydrogen silicone oil, it is characterised in that: its general structure are as follows:
Wherein, n is positive integer, and X represents the alkyl for containing 1~8 carbon atom, Y representation methoxy or ethyoxyl.
2. a kind of preparation method of vinylsiloxane grafting containing hydrogen silicone oil described in claim 1, it is characterised in that: by ethylene
Radical siloxane is grafted on containing hydrogen silicone oil by hydrosilation method, obtains vinylsiloxane grafting containing hydrogen silicone oil.
3. a kind of preparation method of vinylsiloxane grafting containing hydrogen silicone oil according to claim 2, it is characterised in that: its
Step are as follows:
(1) containing hydrogen silicone oil is stirred and is slowly heated；
(2) platiniferous solid catalyst and vinylsiloxane are sequentially added, isothermal reaction is for a period of time；
(3) it cools, filters out platiniferous solid catalyst, obtain vinylsiloxane grafting containing hydrogen silicone oil.
4. a kind of preparation method of vinylsiloxane grafting containing hydrogen silicone oil according to claim 2 or 3, feature exist
In: the structural formula of the containing hydrogen silicone oil are as follows:
Wherein n is positive integer.
5. a kind of preparation method of vinylsiloxane grafting containing hydrogen silicone oil according to claim 2 or 3, feature exist
In: the structural formula of the vinylsiloxane are as follows:
Wherein, X represents the alkyl for containing 1~8 carbon atom, Y representation methoxy or ethyoxyl.
6. a kind of preparation method of vinylsiloxane grafting containing hydrogen silicone oil according to claim 3, it is characterised in that: institute
It states in step (2), platiniferous solid catalyst is added when being warming up to 55 DEG C, be further heated to that vinyl silicon is added at 60 DEG C
Oxygen alkane.
7. a kind of preparation method of vinylsiloxane grafting containing hydrogen silicone oil, feature according to claim 3 or 6 exist
In: the content of platinum is 2~3% in the platiniferous solid catalyst, wherein in preparation reaction system, platinum content accounts for Silicon Containing Hydrogen
The 0.02~0.06% of oil quality.
8. a kind of preparation method of vinylsiloxane grafting containing hydrogen silicone oil according to claim 7, it is characterised in that: institute
The platiniferous solid catalyst in step (2) is stated preferably using silica as polyvinyl siloxane-platinum complex of carrier.
9. a kind of preparation method of vinylsiloxane grafting containing hydrogen silicone oil according to claim 3, it is characterised in that: institute
Stating the thermostat temperature in step (2) is 100~110 DEG C, and the reaction time is 6~7h.
10. a kind of preparation method of vinylsiloxane grafting containing hydrogen silicone oil according to claim 2 or 3, feature exist
In: the molar ratio of C=C key and Si -- H bond in containing hydrogen silicone oil is (1~1.05) in the vinylsiloxane: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910452691.1A CN110183666A (en) | 2019-05-28 | 2019-05-28 | A kind of vinylsiloxane grafting containing hydrogen silicone oil and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910452691.1A CN110183666A (en) | 2019-05-28 | 2019-05-28 | A kind of vinylsiloxane grafting containing hydrogen silicone oil and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110183666A true CN110183666A (en) | 2019-08-30 |
Family
ID=67718382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910452691.1A Pending CN110183666A (en) | 2019-05-28 | 2019-05-28 | A kind of vinylsiloxane grafting containing hydrogen silicone oil and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110183666A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171321A (en) * | 2020-02-24 | 2020-05-19 | 华南理工大学 | Long-chain alkyl silicone oil type silicon paste and preparation method and application thereof |
| CN111266134A (en) * | 2020-03-26 | 2020-06-12 | 万华化学集团股份有限公司 | Complex platinum supported catalyst and application thereof in preparation of asymmetric silane |
| CN112142978A (en) * | 2020-08-04 | 2020-12-29 | 广州回天新材料有限公司 | Preparation method of low-volatility hydrogen-containing silicone oil |
| CN112592477A (en) * | 2020-11-25 | 2021-04-02 | 深圳市优宝新材料科技有限公司 | Modified organic silicon polymer, preparation method thereof and lithium secondary battery |
| CN112852198A (en) * | 2021-03-15 | 2021-05-28 | 安徽瑞邦橡塑助剂集团有限公司 | Grain film release agent and preparation method thereof |
| CN113881239A (en) * | 2021-11-16 | 2022-01-04 | 深圳市华源宏新材料有限公司 | Methyl hydrogen-containing silicone rubber and preparation method thereof |
| CN113957720A (en) * | 2021-09-27 | 2022-01-21 | 广东仙图科技研究有限公司 | Hydrophilic deepening dust-free silicone oil and preparation method and use method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5080356A (en) * | 1973-11-16 | 1975-06-30 | ||
| JPH08231727A (en) * | 1994-08-24 | 1996-09-10 | Tonen Corp | Copolymer containing silicon and its production |
| CN102757649A (en) * | 2011-04-28 | 2012-10-31 | 信越化学工业株式会社 | Addition solidifying type organosilicone composition and photosemiconductor apparatus using the same |
| CN102977377A (en) * | 2012-12-04 | 2013-03-20 | 昆山市张浦彩印厂 | Solvent-free method for preparing polyether modified polysiloxane antifoaming agent |
| CN103214895A (en) * | 2013-04-26 | 2013-07-24 | 广东省石油化工研究院 | Organic silicon coating leveling agent and preparation method thereof |
| CN103224511A (en) * | 2013-04-02 | 2013-07-31 | 东华大学 | Hydrophobic-surface treatment agent and preparation method thereof |
| CN103288864A (en) * | 2013-05-13 | 2013-09-11 | 东华大学 | Hydrophobic organosilicone surfactant prepared by solid-phase continuous catalytic synthesis and preparation method thereof |
| CN105504289A (en) * | 2015-09-17 | 2016-04-20 | 杭州乐道战略材料研究院有限公司 | Preparation method of polyether-modified silicone oil |
| CN108191906A (en) * | 2018-01-12 | 2018-06-22 | 邯郸市富奥新材料有限公司 | A kind of organo-silicon compound for improving super-hydrophobic coat durability and preparation method thereof |
-
2019
- 2019-05-28 CN CN201910452691.1A patent/CN110183666A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5080356A (en) * | 1973-11-16 | 1975-06-30 | ||
| JPH08231727A (en) * | 1994-08-24 | 1996-09-10 | Tonen Corp | Copolymer containing silicon and its production |
| CN102757649A (en) * | 2011-04-28 | 2012-10-31 | 信越化学工业株式会社 | Addition solidifying type organosilicone composition and photosemiconductor apparatus using the same |
| CN102977377A (en) * | 2012-12-04 | 2013-03-20 | 昆山市张浦彩印厂 | Solvent-free method for preparing polyether modified polysiloxane antifoaming agent |
| CN103224511A (en) * | 2013-04-02 | 2013-07-31 | 东华大学 | Hydrophobic-surface treatment agent and preparation method thereof |
| CN103214895A (en) * | 2013-04-26 | 2013-07-24 | 广东省石油化工研究院 | Organic silicon coating leveling agent and preparation method thereof |
| CN103288864A (en) * | 2013-05-13 | 2013-09-11 | 东华大学 | Hydrophobic organosilicone surfactant prepared by solid-phase continuous catalytic synthesis and preparation method thereof |
| CN105504289A (en) * | 2015-09-17 | 2016-04-20 | 杭州乐道战略材料研究院有限公司 | Preparation method of polyether-modified silicone oil |
| CN108191906A (en) * | 2018-01-12 | 2018-06-22 | 邯郸市富奥新材料有限公司 | A kind of organo-silicon compound for improving super-hydrophobic coat durability and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| KANGSANG L. LEE: "(Aminomethyl)pyridine Complexes for the Cobalt-Catalyzed Anti-Markovnikov Hydrosilylation of Alkoxy- or Siloxy(vinyl)silanes with Alkoxy- or Siloxyhydrosilanes", 《ANGEW. CHEM. INT. ED》 * |
| 吴世敏等: "《简明精细化工大辞典》", 30 June 1999, 辽宁科学技术出版社 * |
| 戴延凤等: "不饱和烃硅氢加成催化剂固载化研究进展", 《化学试剂》 * |
| 黄文润: "《硅油及其应用》", 31 July 2018, 四川科学技术出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171321A (en) * | 2020-02-24 | 2020-05-19 | 华南理工大学 | Long-chain alkyl silicone oil type silicon paste and preparation method and application thereof |
| CN111266134A (en) * | 2020-03-26 | 2020-06-12 | 万华化学集团股份有限公司 | Complex platinum supported catalyst and application thereof in preparation of asymmetric silane |
| CN112142978A (en) * | 2020-08-04 | 2020-12-29 | 广州回天新材料有限公司 | Preparation method of low-volatility hydrogen-containing silicone oil |
| CN112592477A (en) * | 2020-11-25 | 2021-04-02 | 深圳市优宝新材料科技有限公司 | Modified organic silicon polymer, preparation method thereof and lithium secondary battery |
| CN112852198A (en) * | 2021-03-15 | 2021-05-28 | 安徽瑞邦橡塑助剂集团有限公司 | Grain film release agent and preparation method thereof |
| CN113957720A (en) * | 2021-09-27 | 2022-01-21 | 广东仙图科技研究有限公司 | Hydrophilic deepening dust-free silicone oil and preparation method and use method thereof |
| CN113957720B (en) * | 2021-09-27 | 2024-01-05 | 广东仙图科技研究有限公司 | Hydrophilic deepened dust-free silicone oil and preparation method and use method thereof |
| CN113881239A (en) * | 2021-11-16 | 2022-01-04 | 深圳市华源宏新材料有限公司 | Methyl hydrogen-containing silicone rubber and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110183666A (en) | A kind of vinylsiloxane grafting containing hydrogen silicone oil and preparation method thereof | |
| US4150048A (en) | Nonhydrolyzable siloxane block copolymers of organosiloxanes and organic ethers | |
| JP2583412B2 (en) | Hydroxyl group-containing siloxane compound | |
| US20110301254A1 (en) | Process for preparing organic silicon compounds | |
| CA2242303C (en) | Vacuum for the manufacture of siloxane oxyalkylene copolymers | |
| US7829734B2 (en) | Tetramethyl siloxane reaction | |
| US5087720A (en) | Polysilethylenesiloxane | |
| JPH0718078A (en) | Organopolysiloxanee and production thereof | |
| US4242466A (en) | Polyurethanes and their preparation | |
| US6218560B1 (en) | Surface-active organosilicon compounds | |
| JPH06172536A (en) | Room temperature curing silicone sealant and its preparation | |
| US5523375A (en) | Silicone polyether carboxylic acids | |
| JP3150288B2 (en) | Multifunctional perhalogenated polyorganosiloxane and method for producing the same | |
| CN108997582A (en) | A kind of preparation method of the single-ended polysiloxane fluid containing active hydrogen | |
| WO1996018670A1 (en) | Method for preparing essentially cyclene-free polyorganosiloxanes and organofunctional siloxanes | |
| JPH0488024A (en) | Production of carbinol group-containing organopolysiloxane | |
| CN107698617A (en) | Organosilicon polymer containing silica octatomic ring, its synthesis and application | |
| EP3071585B1 (en) | Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation | |
| JP3466238B2 (en) | Organopolysiloxane and method for producing the same | |
| EP2528927B1 (en) | Silicon polyethers and method of producing the same | |
| US3564037A (en) | Novel polysiloxane-polyalkylene copolymers | |
| EP0568318A1 (en) | Trifunctional siloxane hydride fluids | |
| US4990643A (en) | Method for preparing carboxy functional silicones | |
| JP2715652B2 (en) | Method for producing hydrogen polysiloxane | |
| CA1055507A (en) | Sulfolanyloxyalkyl cyclic polysiloxanes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190830 |
|
| RJ01 | Rejection of invention patent application after publication |