CN107857882A - fluorosilicone oil and preparation method thereof - Google Patents
fluorosilicone oil and preparation method thereof Download PDFInfo
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- CN107857882A CN107857882A CN201710998841.XA CN201710998841A CN107857882A CN 107857882 A CN107857882 A CN 107857882A CN 201710998841 A CN201710998841 A CN 201710998841A CN 107857882 A CN107857882 A CN 107857882A
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- 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
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- 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
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- 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
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Abstract
The invention relates to the technical field of organosilicon industry, and aims to solve the problems that the low-viscosity end-functional group fluorosilicone oil in the current domestic market is single in variety (mainly hydroxyl-terminated low-molecular-weight fluorosilicone oil) and poor in quality, the invention provides high-purity fluorosilicone oil with low viscosity and high functional group content and a preparation method thereof, the fluorosilicone oil has a structural formula shown in (I), the content of siloxane ring bodies in the obtained product is extremely low or even zero,
Description
Technical field
The present invention relates to silicone industry technical field, is specifically related to a kind of new fluorosilicon oil and preparation method thereof.
Background technology
In recent years, fluoro-containing group introducing polysiloxanes is turned into new study hotspot.Fluoropolymer not only has one
As the superior heat resistance of siloxanes, weatherability, but also the shortcomings that dimethyl silicone polymer oil resistant, poor solvent resistance can be overcome,
By lubricant, defoamer, releasing agent and the fabric of its preparation, the water proof anti-soil finishing agent etc. of leather, aircraft, automobile,
The industrial circles such as machinery, chemical industry, light industry, weaving are widely applied.Wherein, the end function base fluorosilicon oil of low-viscosity not only has
The shared high-low temperature resistant of standby fluorine silicon materials and oil resistant characteristic, and because the presence of a large amount of end function bases has higher chemistry again
Activity, so as to have special purposes.Intermediate and molecular weight regulator such as fluorosioloxane rubber, it is total to other organic matters
The poly- copolymer prepared with property or it is used as fabric hydrophobic/hate the finishing agent of oil, the defoamer of organic solvent, change
Cosmetic additive etc., the antistructurizing agent of heat cure fluorosioloxane rubber is particularly useful as, hard charcoal black track producing particle and silicon can be suppressed
Physical absorption and chemical bonding effect between rubber raw rubber molecule, prevent the generation of structuring, finally make white carbon uniform
Ground is dispersed in silicone rubber compounds, reaches the purpose of reinforcement.
However, the low-viscosity end function base fluorosilicon oil single varieties on current domestic market, mainly hydroxy-end capped is low
Molecular weight fluorosilicon oil, and quality is bad：First, molecular weight distribution is distributed (it is poor that explanation prepares controllability) in multiple acromion, second,
There is the more ring body D of accessory substance methyl trifluoro propyl siloxanes four in product4F (due to its boiling point more than 280 DEG C, be difficult to lead to
Cross and be distilled off).
The content of the invention
To solve the problems, such as the low-viscosity end function base fluorosilicon oil single varieties on current domestic market and quality is bad,
The present invention provides a kind of low-viscosity, high functional group content, the fluorosilicon oil and preparation method thereof of high-purity, siloxanes in products therefrom
The content of ring body is extremely low, even zero.
The present invention is achieved by the following technical solutions：
A kind of fluorosilicon oil has the structural formula as shown in (I)：
Wherein, R=H or OH.
As R=H, the fluorosilicon oil is 1,1,3,5,7,9,9- seven methyl -3,5,7- tri- (3,3,3- trifluoro propyl) five
Siloxanes.
The methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven, the preparation of 7- tri- (3,3,3- trifluoro propyl) five siloxanes
Method is：By 1,1,3,3- tetramethyl disiloxane (i.e. hydrogeneous double seal head, MMH), 1,3,5- trimethyls -1,3,5- tri- (3,3,
3- trifluoro propyls) cyclotrisiloxane (i.e. D3F after) being mixed in the reactor with catalyst A, 0~80 DEG C of stirring reaction 0.5~
6h, room temperature is then cooled under stirring, removes catalyst, be evaporated under reduced pressure, under the conditions of 109~110 DEG C/800Pa of collection
Cut produce hydrogen end-blocking the methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven, 7- tri- (3,3,3- trifluoro propyl) five siloxanes.
Wherein, 1,1,3,3- tetramethyl disiloxane and 1,3,5- trimethyls -1,3,5- tri- (3,3,3- trifluoro propyl) ring
The mol ratio of trisiloxanes is 1.05~10: 1.
Described catalyst A is in storng-acid cation exchange resin, the concentrated sulfuric acid, trifluoromethanesulfonic acid or Emathlite
One kind, preferably storng-acid cation exchange resin.
Catalyst A and 1,3,5- trimethyls -1,3, the mass ratio of 5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane are
0.005~0.5: 1, preferably 0.1~0.2: 1.
Described reaction temperature is 0~80 DEG C, preferably room temperature~50 DEG C.
As R=OH, the fluorosilicon oil is 1,9- dihydroxy -1,1,3,5,7,9,9- seven methyl -3,5,7- tri- (3,3,3-
Trifluoro propyl) five siloxanes.
1,9- dihydroxy -1,1,3,5,7,9,9- seven methyl -3,5, the system of 7- tri- (3,3,3- trifluoro propyl) five siloxanes
Preparation Method is：By 1,1,3,3- tetramethyl disiloxane, 1,3,5- trimethyls -1,3, the silicon of 5- tri- (3,3,3- trifluoro propyl) ring three
After oxygen alkane mixes in the reactor with catalyst A, in 0~80 DEG C of 0.5~6h of stirring reaction, then it is cooled under stirring
Room temperature, remove catalyst, be evaporated under reduced pressure, collect 109~110 DEG C/800Pa under the conditions of cut produce hydrogen end-blocking fluorosilicon oil (1,
1,3,5,7,9,9- seven methyl -3,5,7- tri- (3,3,3- trifluoro propyl) five siloxanes)；Then by gained hydrogen block fluorosilicon oil with
After deionized water, catalyst B and reaction dissolvent mixing, 1~6h of stirring reaction at 0~60 DEG C, room temperature is cooled to, is then passed through
Catalyst is filtered out, removes under the conditions of the 110 DEG C/600Pa and hydroxy-end capped fluorosilicon oil 1 is produced after low-boiling-point substance, 9- dihydroxy -1,
1,3,5,7,9,9- seven methyl -3,5,7- tri- (3,3,3- trifluoro propyl) five siloxanes.
1,1,3,3- tetramethyl disiloxane and 1,3,5- trimethyls -1,3, the silica of 5- tri- (3,3,3- trifluoro propyl) ring three
The mol ratio of alkane is 1.05~10: 1.
Described catalyst A is in storng-acid cation exchange resin, the concentrated sulfuric acid, trifluoromethanesulfonic acid or Emathlite
One kind, preferably storng-acid cation exchange resin.
Catalyst A and 1,3,5- trimethyls -1,3, the mass ratio of 5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane are
0.005~0.5: 1, preferably 0.1~0.2: 1.
Described catalyst B is selected from Pd/C, H2PtCl6In one kind, preferably Pd/C.
Catalyst B and hydrogen end-blocking fluorosilicon oil mass ratio are 0.005~0.2: 1, preferably 0.01~0.05: 1.
Described reaction dissolvent is a kind of in dichloromethane, chloroform, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran, and preferably four
Hydrogen furans.
Fluorosilicon oil prepared by the present invention has clear and definite molecular structure, is a micromolecular compound, can be used as function fluorine silicon
Oil directly uses, and also chain extender can be used as to be used to prepare full-bodied fluorine silicon product, and preparation condition is gentle, efficient, controllable, silicon
Oxygen alkane ring body by-products content is low, simple purification.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) the invention provides a kind of fluorosilicon oil, it can directly use as function fluorosilicon oil, can also be used for as chain extender
Prepare full-bodied fluorine silicon product.
(2) preparation method of new fluorosilicon oil provided by the invention, with reaction speed is fast, reaction condition is gentle, product
The advantages that functional group content is high, equipment and technique are simple, is especially preparing fluorosioloxane rubber constitution controller micromolecular hydroxyl silicon
There is obvious advantage in terms of oil and fluorine silicon chain extender.
Embodiment
Below by embodiment, technical scheme is described in further detail, it is raw materials used in embodiment
It is prepared by commercially available or use conventional method.
But embodiment is not limiting the scope of the invention, can also have many operative combination, this area it is general
Logical professional and technical personnel can be exported directly to all situations from following examples, should be protection scope of the present invention.
Embodiment 1
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 20 DEG C of oil baths, add 28g storng-acid cation exchange resins, stirring reaction 4h, GC detection D3F conversion ratios are
92.4%.Room temperature is cooled under stirring, is filtered to remove resin, is evaporated under reduced pressure and collects the production under the conditions of 109~110 DEG C/800Pa
Thing produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five silicon
Oxygen alkane, yield 87.3%.Density at 25 DEG C is 1.11, refractive index 1.373.
Embodiment 2
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 30 DEG C of oil baths, add 28g storng-acid cation exchange resins, stirring reaction 2h, GC detection D3F conversion ratios are
93.8%.Room temperature is cooled under stirring, is filtered to remove resin, is evaporated under reduced pressure and collects the production under the conditions of 109~110 DEG C/800Pa
Thing produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five silicon
Oxygen alkane, yield 90.5%.
Embodiment 3
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 40 DEG C of oil baths, add 28g storng-acid cation exchange resins, stirring reaction 1h, GC detection D3F conversion ratios are
91.3%.Room temperature is cooled under stirring, is filtered to remove resin, is evaporated under reduced pressure and collects the production under the conditions of 109~110 DEG C/800Pa
Thing produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five silicon
Oxygen alkane, yield 86.5%.
Embodiment 4
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 50 DEG C of oil baths, add 28g storng-acid cation exchange resins, stirring reaction 1h, GC detection D3F conversion ratios are
92.1%.Room temperature is cooled under stirring, is filtered to remove resin, is evaporated under reduced pressure and collects the production under the conditions of 109~110 DEG C/800Pa
Thing produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five silicon
Oxygen alkane, yield 87.0%.
Embodiment 5
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 60 DEG C of oil baths, add 28g storng-acid cation exchange resins, stirring reaction 45min, GC detection D3F conversion ratios are
92.6%.Room temperature is cooled under stirring, is filtered to remove resin, is evaporated under reduced pressure and collects the production under the conditions of 109~110 DEG C/800Pa
Thing produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five silicon
Oxygen alkane, yield 85.7%.
Embodiment 6
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 80 DEG C of oil baths, add 28g storng-acid cation exchange resins, stirring reaction 30min, GC detection D3F conversion ratios are
93.1%.Room temperature is cooled under stirring, is filtered to remove resin, is evaporated under reduced pressure and collects the production under the conditions of 109~110 DEG C/800Pa
Thing produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five silicon
Oxygen alkane, yield 86.9%.
Embodiment 7
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 40 DEG C of oil baths, add 9.36g storng-acid cation exchange resins, stirring reaction 2h, GC detection D3F conversion ratios are
90.3%.Room temperature is cooled under stirring, is filtered to remove resin, is evaporated under reduced pressure and collects the production under the conditions of 109~110 DEG C/800Pa
Thing produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five silicon
Oxygen alkane, yield 86.1%.
Embodiment 8
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 40 DEG C of oil baths, add 18.7g storng-acid cation exchange resins, stirring reaction 75min, GC detection D3F conversion ratios
For 91.2%.Room temperature is cooled under stirring, is filtered to remove resin, under the conditions of being evaporated under reduced pressure and collecting 109~110 DEG C/800Pa
Product produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five
Siloxanes, yield 87.0%.
Embodiment 9
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 30 DEG C of oil baths, add 57g storng-acid cation exchange resins, stirring reaction 45min, GC detection D3F conversion ratios are
94.0%.Room temperature is cooled under stirring, is filtered to remove resin, is evaporated under reduced pressure and collects the production under the conditions of 109~110 DEG C/800Pa
Thing produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five silicon
Oxygen alkane, yield 91.1%.
Embodiment 10
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 50 DEG C of oil baths, add the 4.68g concentrated sulfuric acids, stirring reaction 2h, GC detection D3F conversion ratios are 92.1%.It is cold under stirring
But to room temperature, it is transferred in separatory funnel and is washed to the neutral removing concentrated sulfuric acid, be evaporated under reduced pressure and collect 109~110 DEG C/800Pa
Under the conditions of product produce water white transparency hydrogen end-blocking the methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven, 7- tri- (3,3,3- tri-
Fluoropropyl) five siloxanes, yield 88.2%.
Embodiment 11
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 50 DEG C of oil baths, add the 2g concentrated sulfuric acids, stirring reaction 6h, GC detection D3F conversion ratios are 93.7%.It is cooled under stirring
Room temperature, it is transferred in separatory funnel and is washed to the neutral removing concentrated sulfuric acid, be evaporated under reduced pressure and collect 109~110 DEG C/800Pa conditions
Under product produce water white transparency hydrogen end-blocking the methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven, (3,3, the 3- trifluoropropyls of 7- tri-
Base) five siloxanes, yield 88.9%.
Embodiment 12
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 40 DEG C of oil baths, add 1.2g trifluoromethanesulfonic acids, stirring reaction 6h, GC detection D3F conversion ratios are 92.2%.Under stirring
Be cooled to room temperature, be transferred in separatory funnel be washed to it is neutral remove catalyst, be evaporated under reduced pressure and collect 109~110 DEG C/
Product under the conditions of 800Pa produce water white transparency hydrogen end-blocking the methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven, 7- tri- (3,3,
3- trifluoro propyls) five siloxanes, yield 88.1%.
Embodiment 13
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 134g MMHWith 234g D3F, so
After be placed in 80 DEG C of oil baths, add 25g Emathlites, stirring reaction 45min, GC detection D3F conversion ratios are 96.3%.Under stirring
Room temperature is cooled to, is filtered to remove Emathlite, is evaporated under reduced pressure and collects the product under the conditions of 109~110 DEG C/800Pa and produce nothing
The transparent hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of color, 7- tri- (3,3,3- trifluoro propyl) five siloxanes, is received
Rate 92.6%.
Embodiment 14
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 150g MMHWith 234g D3F, so
After be placed in 60 DEG C of oil baths, add 30g Emathlites, stirring reaction 1.5h, GC detection D3F conversion ratios are 92.7%.Under stirring
Room temperature is cooled to, is filtered to remove Emathlite, is evaporated under reduced pressure and collects the product under the conditions of 109~110 DEG C/800Pa and produce nothing
The transparent hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of color, 7- tri- (3,3,3- trifluoro propyl) five siloxanes, is received
Rate 88.8%.
Embodiment 15
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 70.4g MMHWith 234g D3F, so
After be placed in 40 DEG C of oil baths, add 18.7g storng-acid cation exchange resins, stirring reaction 2h, GC detection D3F conversion ratios are
94.3%.Room temperature is cooled under stirring, is filtered to remove resin, is evaporated under reduced pressure and collects the production under the conditions of 109~110 DEG C/800Pa
Thing produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five silicon
Oxygen alkane, yield 90.7%.
Embodiment 16
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 270g MMHWith 234g D3F, so
After be placed in 40 DEG C of oil baths, add 11.7g storng-acid cation exchange resins, stirring reaction 2h, GC detection D3F conversion ratios are
93.5%.Room temperature is cooled under stirring, is filtered to remove resin, is evaporated under reduced pressure and collects the production under the conditions of 109~110 DEG C/800Pa
Thing produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five silicon
Oxygen alkane, yield 89.6%.
Embodiment 17
Equipped with mechanical agitation, thermometer, spherical condensation tube 1L there-necked flasks in add 335g MMHWith 117g D3F, so
After be placed in 40 DEG C of oil baths, add 6g storng-acid cation exchange resins, stirring reaction 2h, GC detection D3F conversion ratios are
95.1%.Room temperature is cooled under stirring, is filtered to remove resin, is evaporated under reduced pressure and collects the production under the conditions of 109~110 DEG C/800Pa
Thing produces the hydrogen end-blocking methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven of water white transparency, 7- tri- (3,3,3- trifluoro propyl) five silicon
Oxygen alkane, yield 91.7%.
Embodiment 18
Equipped with magnetic agitation, thermometer, spherical condensation tube 500mL there-necked flasks in add prepared by 151g embodiments 1
1,1,3,5,7,9,9- seven methyl -3,5,7- tri- (3,3,3- trifluoro propyl) five siloxanes, 18g deionized waters, 5g 10%
Pd/C and 150ml1,4- dioxane, it is subsequently placed in 0 DEG C of ice-water bath, stirring reaction 4h, then Filtration of catalyst, in
Removed under the conditions of 110 DEG C/600Pa and the hydroxy-end capped fluorosilicon oil 1 of water white transparency is produced after low-boiling-point substance, 9- dihydroxy -1,1,3,5,
7,9,9- seven methyl -3,5,7- tri- (3,3,3- trifluoro propyl) five siloxanes, yield 85.2%, Si-OH contents 5.22wt%.25
DEG C when density be 1.20, refractive index 1.379.
Embodiment 19
Equipped with magnetic agitation, thermometer, spherical condensation tube 500mL there-necked flasks in add prepared by 151g embodiments 2
1,1,3,5,7,9,9- seven methyl -3,5,7- tri- (3,3,3- trifluoro propyl) five siloxanes, 45g deionized waters, 0.01g
H2PtCl6Hydrate and 200ml tetrahydrofurans, then the stirring reaction 2h at 60 DEG C, then Filtration of catalyst, in 110
DEG C/600Pa under the conditions of remove the hydroxy-end capped fluorosilicon oil 1 of water white transparency produced after low-boiling-point substance, 9- dihydroxy -1,1,3,5,7,9,
The methyl -3,5 of 9- seven, 7- tri- (3,3,3- trifluoro propyl) five siloxanes, yield 80.7%, Si-OH contents 5.15wt%.
Embodiment 20
Equipped with magnetic agitation, thermometer, spherical condensation tube 500mL there-necked flasks in add prepared by 151g embodiments 3
1,1,3,5,7,9,9- seven methyl -3,5,7- tri- (3,3,3- trifluoro propyl) five siloxanes, 36g deionized waters, 7.5g 5%
Pd/C and 200ml tetrahydrofurans, then stirring reaction 3h at room temperature, then Filtration of catalyst, in 110 DEG C/600Pa bars
Removed under part and the hydroxy-end capped fluorosilicon oil 1 of water white transparency is produced after low-boiling-point substance, 9- dihydroxy -1,1,3,5,7,9,9- seven methyl -
3,5,7- tri- (3,3,3- trifluoro propyl) five siloxanes, yield 87.4%, Si-OH contents 5.30wt%.
Embodiment 21
Equipped with magnetic agitation, thermometer, spherical condensation tube 500mL there-necked flasks in add prepared by 151g embodiments 4
1,1,3,5,7,9,9- seven methyl -3,5,7- tri- (3,3,3- trifluoro propyl) five siloxanes, 45g deionized waters, 5g 5% Pd/
C and 200ml chloroforms, the then stirring reaction 3h at 30 DEG C, then Filtration of catalyst, takes off under the conditions of 110 DEG C/600Pa
Except the hydroxy-end capped fluorosilicon oil 1 that water white transparency is produced after low-boiling-point substance, 9- dihydroxy -1,1,3,5,7,9,9- seven methyl -3,5,7-
Three (3,3,3- trifluoro propyl) five siloxanes, yield 82.3%, Si-OH contents 5.26wt%.
Claims (10)
1. a kind of fluorosilicon oil, it is characterised in that the fluorosilicon oil has the structural formula as shown in (I)：
Wherein, R=H or OH.
2. a kind of fluorosilicon oil according to claim 1, it is characterised in that the fluorosilicon oil is 1,1,3,5,7,9,9- seven first
Base -3,5,7- tri- (3,3,3- trifluoro propyl) five siloxanes.
A kind of 3. fluorosilicon oil according to claim 1, it is characterised in that the fluorosilicon oil is 1,9- dihydroxy -1,1,3,
5,7,9,9- seven methyl -3,5,7- tri- (3,3,3- trifluoro propyl) five siloxanes.
4. a kind of preparation method of fluorosilicon oil as claimed in claim 1 or 2, it is characterised in that by 1,1,3,3- tetramethyl two
Siloxanes, 1,3,5- trimethyls -1,3,5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane mix in the reactor with catalyst A
Afterwards, in 0~80 DEG C of 0.5~6h of stirring reaction, room temperature is then cooled under stirring, removes catalyst, is evaporated under reduced pressure, is received
Cut under the conditions of 109~110 DEG C/800Pa of collection is that hydrogen blocks the methyl -3,5 of fluorosilicon oil 1,1,3,5,7,9,9- seven, 7- tri-
(3,3,3- trifluoro propyl) five siloxanes.
A kind of 5. preparation method of fluorosilicon oil according to claim 4, it is characterised in that the silica of 1,1,3,3- tetramethyl two
Alkane and 1,3,5- trimethyls -1,3, the mol ratio of 5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane is 1.05~10: 1.
6. the preparation method of a kind of fluorosilicon oil according to claim 4, it is characterised in that described catalyst A is selected from strong
One kind in acid cation exchange resin, the concentrated sulfuric acid, trifluoromethanesulfonic acid or Emathlite, catalyst A and 1,3,5- trimethyls-
The mass ratio of 1,3,5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane is 0.005~0.5: 1.
A kind of 7. preparation method of the fluorosilicon oil described in claim 1 or 3, it is characterised in that：By the silicon of 1,1,3,3- tetramethyl two
Oxygen alkane, 1,3,5- trimethyls -1,3,5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane mix in the reactor with catalyst A
Afterwards, in 0~80 DEG C of 0.5~6h of stirring reaction, room temperature is then cooled under stirring, removes catalyst, is evaporated under reduced pressure, is received
Collect the cut under the conditions of 109~110 DEG C/800Pa, that is, obtain hydrogen end-blocking fluorosilicon oil；Then gained hydrogen is blocked into fluorosilicon oil with going
After ionized water, catalyst B and reaction dissolvent mixing, 1~6h of stirring reaction at 0~60 DEG C, room temperature is cooled to, it is then filtered
Catalyst is removed, removes under the conditions of the 110 DEG C/600Pa and hydroxy-end capped fluorosilicon oil 1 is produced after low-boiling-point substance, 9- dihydroxy -1,1,
3,5,7,9,9- seven methyl -3,5,7- tri- (3,3,3- trifluoro propyl) five siloxanes.
A kind of 8. preparation method of fluorosilicon oil according to claim 7, it is characterised in that the silica of 1,1,3,3- tetramethyl two
Alkane and 1,3,5- trimethyls -1,3, the mol ratio of 5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane is 1.05~10: 1.
9. the preparation method of a kind of fluorosilicon oil according to claim 7, it is characterised in that described catalyst A is selected from strong
One kind in acid cation exchange resin, the concentrated sulfuric acid, trifluoromethanesulfonic acid or Emathlite, catalyst A and 1,3,5- trimethyls-
The mass ratio of 1,3,5- tri- (3,3,3- trifluoro propyl) cyclotrisiloxane is 0.005~0.5: 1.
10. the preparation method of a kind of fluorosilicon oil according to claim 7, it is characterised in that described catalyst B is selected from
Pd/C、H2PtCl6In one kind, the mass ratio of catalyst B and hydrogen end-blocking fluorosilicon oil is 0.005~0.2: 1.
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| CN109851789A (en) * | 2018-08-30 | 2019-06-07 | 深圳市冠恒新材料科技有限公司 | A kind of add-on type fluorine silicon liquid glue and preparation method thereof |
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