CN108484914A - Fluorine silicon resin and preparation method thereof - Google Patents
Fluorine silicon resin and preparation method thereof Download PDFInfo
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- CN108484914A CN108484914A CN201810206365.8A CN201810206365A CN108484914A CN 108484914 A CN108484914 A CN 108484914A CN 201810206365 A CN201810206365 A CN 201810206365A CN 108484914 A CN108484914 A CN 108484914A
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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
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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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- 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
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a kind of fluorine silicon resins and preparation method thereof.Using pentafluorostyrene as raw material, phenyl-pentafluoride ethyl dimethylchlorosilane is obtained by hydrosilylation.Polycondensation reaction is carried out using phenyl-pentafluoride ethyl dimethylchlorosilane and trim,ethylchlorosilane, ethyl orthosilicate, prepares a kind of pentafluorophenyl group silicones.Secondary polycondensating process is used when preparation, is overcome pentafluorophenyl group dimethylchlorosilane and is reacted the big defect of sex differernce with one hydrolyzing chlorosilane of trialkyl of copolymerization, prepares high income.The advantages of pentafluorophenyl group silicones superior for heat resistance that the present invention obtains has preparation process simple, and low for equipment requirements, raw material are easy to get, suitable industrial amplification production.Heat resistant type fluorine silicon resin can be applied to the high molecular materials such as heat resistant type adhesive.
Description
Technical field
The present invention relates to a kind of high temperature resistant type fluorine silicon resin and preparation method thereof, the product of production can be used as macromolecule modified
Or polymeric additive, belong to organosilicon synthesis and pluronic polymer field.
Background technology
Silicones is a kind of heat cured plastics, and one of performance most outstanding is excellent thermo oxidative stability and excellent
Electrical insulation capability, it can keep its good insulation performance in wide temperature and frequency range.Silicones is typically to use
Methyl trichlorosilane, dimethyldichlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane or dichloromethyl phenylsilane it is each
Kind mixture, in the presence of organic solvent such as toluene, hydrolyzable, obtains acidic hydrolysis object at a lower temperature.What is hydrolyzed is first
Beginning product is the mixture of cricoid, line style and cross-linked polymer, usually also contains considerable hydroxyl.Hydrolysate is through washing
Acid, neutral first condensation polymer are removed, thermal oxide or further polycondensation in the presence of a catalyst in air eventually form height and hand over
The dimensional network structure of connection.
MQ resins are one of most widely used silicones, by the silica unit of single functionality（Abbreviation M units）With four
The silica unit of degree of functionality（Abbreviation Q unit）A kind of close sphere with double-layer structure of composition, molal weight are general
For 1000-8000g, the structure of M chain links and the when M of Q chain links determine the property of MQ resins, most common M in molecular structure
Structure is methyl.Other groups are introduced in MQ silicones can extend its purposes, but other knots are introduced in MQ silicones
After structure, since these structures have reactivity under certain condition, it is unfavorable for silicones heat resistance；Even if being the introduction of
Up to 8% mass loss can also occur after being heated 24 hours at 250 DEG C for the silicones of phenyl M structure.Which has limited its
Use under higher than 250 DEG C temperature conditions as nanocomposite constituents.
Invention content
The present invention provides a kind of new organosilicon for the disadvantage of heat resistance deficiency existing for existing organic siliconresin
Resin and preparation method thereof.
To reach goal of the invention of the present invention, the technical solution of use is as follows：
The chemical structural formula of a kind of fluorine silicon resin, the fluorine silicon resin is：
Wherein, R=methyl, phenyl, vinyl or hydrogen；
M=2~20；N=1~5；P=1~8.
The preparation method of above-mentioned fluorine silicon resin, includes the following steps：
（1）Using pentafluorostyrene, dimethyl dichlorosilane (DMCS) as raw material, under precious metal salt catalysis, phenyl-pentafluoride ethyl dimethyl is prepared
Chlorosilane；
（2）The mixture of phenyl-pentafluoride ethyl dimethylchlorosilane and ethyl orthosilicate is added dropwise to water/inorganic acid/organic solvent
A polycondensation reaction is carried out in mixed liquor；Then the mixture of trialkyl one chlorosilane and ethyl orthosilicate is added dropwise again, contracts again
After poly- reaction, fluorine silicon resin is prepared.
In above-mentioned technical proposal, pentafluorostyrene, precious metal salt, dimethyl dichlorosilane (DMCS) mass ratio be 1:（0.003~
0.006）∶（0.5~2）；In the mixture of phenyl-pentafluoride ethyl dimethylchlorosilane and ethyl orthosilicate, phenyl-pentafluoride ethyl dimethyl
The mass ratio of chlorosilane and ethyl orthosilicate is（1~6）∶（1~10）；The mixture of trialkyl one chlorosilane and ethyl orthosilicate
In, the mass ratio of one chlorosilane of trialkyl and ethyl orthosilicate is（1~3）∶（1~10）.
In above-mentioned technical proposal, step（1）Pentafluorostyrene to be dissolved in aromatic hydrocarbon solvent, under nitrogen protection
Precious metal salt catalyst is added；Then dimethyl dichlorosilane (DMCS) is added dropwise at 50~140 DEG C；It is small to be added dropwise to complete rear insulation reaction 1 ~ 10
When, prepare phenyl-pentafluoride ethyl dimethylchlorosilane；
Step（2）In organic solvent by water, inorganic acid dispersion, phenyl-pentafluoride ethyl diformazan to be then added dropwise at 60~80 DEG C
The mixture of base chlorosilane and ethyl orthosilicate, polycondensation of heat preservation progress 0.5~1 hour after being added dropwise to complete；Then it is added dropwise again
The mixture of trialkyl one chlorosilane and ethyl orthosilicate keeps the temperature after being added dropwise to complete and carries out polycondensation reaction 1~6 hour again, system
Standby fluorine silicon resin.
In above-mentioned technical proposal, the aromatic hydrocarbon solvent is toluene, dimethylbenzene, benzotrifluoride, 1,3- bis-（Fluoroform
Base）One kind in benzene；The precious metal salt is chloroplatinic acid；One chlorosilane of the trialkyl is trim,ethylchlorosilane, dimethyl hydrogen
One kind in one chlorosilane of base, one chlorosilane of dimethyl ethenyl, one chlorosilane of pheiiyldimetliyl；The inorganic acid is the concentrated sulfuric acid
Or concentrated hydrochloric acid；The organic solvent is tetrahydrofuran.
In above-mentioned technical proposal, step（1）In, the time that dimethyl dichlorosilane (DMCS) is added dropwise is 0.5~5 hour；Step（2）
In, the time that the mixture of one chlorosilane of trialkyl and ethyl orthosilicate is added dropwise is 0.5 ~ 1 hour.
In above-mentioned technical proposal, step（1）After reaction, reaction solution obtains phenyl-pentafluoride second by being evaporated off, being evaporated under reduced pressure
Base dimethylchlorosilane；Step（2）Again after polycondensation reaction, reaction solution is through supercooling, vacuum distillation, liquid separation processing, extraction
It takes, distill water washing, drying, filtering, distillation obtain fluorine silicon resin.
The invention also discloses a kind of phenyl-pentafluoride ethyl dimethylchlorosilanes and preparation method thereof, include the following steps, will
Pentafluorostyrene is dissolved in aromatic hydrocarbon solvent, and precious metal salt catalyst is added under nitrogen protection；Then at 50~140 DEG C
Dimethyl dichlorosilane (DMCS) is added dropwise；It is added dropwise to complete rear insulation reaction 1~10 hour, prepares phenyl-pentafluoride ethyl dimethylchlorosilane.
In above-mentioned technical proposal, the aromatic hydrocarbon solvent is toluene, dimethylbenzene, benzotrifluoride, 1,3- bis-（Fluoroform
Base）One kind in benzene；The precious metal salt is chloroplatinic acid；Be added dropwise dimethyl dichlorosilane (DMCS) time be；After reaction, reaction solution
Phenyl-pentafluoride ethyl dimethylchlorosilane is obtained by being evaporated off, being evaporated under reduced pressure.
The present invention passes through polycondensation reaction by phenyl-pentafluoride ethyl dimethylchlorosilane and ethyl orthosilicate, a chlorosilane monomer
The method for synthesizing silicones, reaction equation are as follows：
Wherein, R=methyl, phenyl, vinyl or hydrogen.
According to above-mentioned technical proposal, the synthesis step of fluorine silicon resin includes that two step of silicones is synthesized with polycondensation is anti-for Si―H addition reaction
It answers, specific steps can be as follows：
（1）Hydrosilylation
By weight, 1 part of pentafluorostyrene is dissolved in 1~10 part of aromatic hydrocarbon solvent, chloroplatinic acid is added under nitrogen protection
0.003 ~ 0.006 part of catalyst, after being heated to 50 ~ 140 DEG C, in 0.5 ~ 2 part of dimethyl dichlorosilane (DMCS) is added dropwise in certain time, drip
Add subsequent continuous insulation reaction 1 ~ 10 hour.After reaction, solvent and unreacted dimethyl dichlorosilane (DMCS) is evaporated off, is evaporated under reduced pressure
Collect 132 DEG C of fractions（3.75kPa）, obtain phenyl-pentafluoride ethyl dimethylchlorosilane；
（2）Mixed silanes：By weight, 1 ~ 6 part of phenyl-pentafluoride ethyl dimethylchlorosilane is mixed with 1 ~ 10 part of ethyl orthosilicate,
Obtain mixed silanes one.By weight, 1 ~ 3 part of one chlorosilane of trialkyl is mixed with 1 ~ 10 part of ethyl orthosilicate, is mixed
Silane two；
（3）Polycondensation reaction：By weight, 1 ~ 5 part of water and 0.5 ~ 2 part of inorganic acid are dispersed in 1 ~ 20 part of tetrahydrofuran,
After heating makes mixture temperature rise to 60 ~ 80 DEG C, above-mentioned mixed silanes one are added dropwise, time for adding is no more than 80 with reacting liquid temperature
Subject to DEG C, rear insulation reaction is added 0.5 ~ 1 hour；
（4）Secondary polycondensation reaction：After polycondensation, then mixed silanes two being added at a slow speed, time for adding is 0.5 ~ 1 hour,
Add rear insulation reaction 1 ~ 6 hour；
（5）Post-processing：After reaction solution is cooled down, vacuum distillation removes coproduct ethanol and solvents tetrahydrofurane, the temperature of distillation
It it is 40~80 DEG C, vacuum degree is 0.5~20mmHg.Remaining reaction solution after distillation is poured into separatory funnel, 3 are extracted with extractant
~ 5 times, 1 ~ 5 part of extractant is used every time.Combining extraction liquid uses 1 ~ 5 part of distilled water every time to distill water washing 3 ~ 5 times.Again
0.2 ~ 1 part of addition desiccant dryness 0.5 ~ 5 hour.It is filtered to remove drier, distillation obtains the bulk solids product fluorine silicon of white
The temperature of resin, distillation is 40~80 DEG C, and vacuum degree is 0.5~20mmHg.
The present invention synthesizes phenyl-pentafluoride second using pentafluorostyrene and chlorodimethyl silane as raw material, by hydrosilylation
Base dimethylchlorosilane, then by phenyl-pentafluoride ethyl dimethylchlorosilane, trim,ethylchlorosilane, ethyl orthosilicate copolycondensation, use
Secondary polycondensating process prepares a kind of fluorine silicon resin.Compared with existing resin, phenyl-pentafluoride fluorine silicon resin of the invention has better
Thermal stability, carbon-fluorine bond bond energy is high, heat resistance is better, heats 24 hours and does not decompose under 350 DEG C and 400 atmospheric pressure, can
As heat-resisting material is constructed, the fluorine silicon resin material very excellent by heat resistance is obtained, these materials are suitable as resistance to height
Warm additive application is in a variety of composite systems.
The outstanding advantages of the present invention compared with prior art are：
1, fluorine silicon resin disclosed by the invention, unlike existing technological transformation art silicones, fluorine silicon provided by the invention
The planar structure and carbon-fluorine bond bond energy that resin is conjugated due to phenyl are big, thus provide a kind of superior organosilicon of heat resistance
Material.
2, in fluorine silicon resin preparation process disclosed by the invention, creative is solved using substep polycondensating process due to five
Pentafluorophenyl group is that rigid radical, steric hindrance are big in fluorobenzene ethyl dimethylchlorosilane, and hydrolytic reactivity is than one chlorosilane list of trialkyl
The reaction sex differernce of two kind of one chlorosilane caused by body difference, avoids excessively being crosslinked, thus prepares fluorine silicon resin high income, to 70% ~
80%；It solves existing fluorine silicon resin to be realized by polycondensation reaction, and has extracting operation, all relatively low problem of general yield in preparing.
3, fluorine content is adjustable in fluorine silicon resin provided by the invention, to improve the designability of resistance to hot product；And this
It is marketable material that invention, which prepares raw material used in fluorine silicon resin, is derived from a wealth of sources, cheap, is conducive to the industry of material
Metaplasia is produced.
Description of the drawings
Fig. 1 is the infrared spectrogram of fluorine silicon resin prepared by embodiment one；
Fig. 2 is the thermal weight loss test result figure of fluorine silicon resin prepared by embodiment one.
Specific implementation mode
Technical solution of the present invention is further elaborated with reference to the accompanying drawings and examples.
Embodiment one
（1）Phenyl-pentafluoride ethyl dimethylchlorosilane synthesizes
500mL three-necked flasks are equipped with thermometer, reflux condensing tube and constant pressure dropping funnel, oil bath heating.Sequentially add 80g first
Chloroplatinic acid catalyst 0.26g is added under nitrogen protection for benzene and 65g pentafluorostyrenes, stirring and dissolving.Heating is opened, is warming up to 80
After DEG C, 51g dichloromethylsilanes are added dropwise, time for adding is controlled at 1 hour or so.Drip subsequent continuous insulation reaction 2 hours.
After reaction, solvent and unreacted dimethyl dichlorosilane (DMCS) is evaporated off, 132 DEG C of fractions are collected in vacuum distillation（3.75kPa）, obtain five
Fluorobenzene ethyl dimethylchlorosilane 95g, it is 96.6% that gas-chromatography, which measures product purity, yield 90.9%.
（2）Polycondensation synthesizes fluorine silicon resin
19.4g phenyl-pentafluoride ethyl dimethylchlorosilanes and 33g ethyl orthosilicates are uniformly mixed in 100mL conical flasks, obtained
Mixed silanes one；5.5g tri-methyl-chlorosilanes and 30g ethyl orthosilicates are uniformly mixed by another take in a 100mL conical flasks, are obtained
To mixed silanes two.Two kinds of mixed silanes are spare.
500mL three-necked flasks are equipped with thermometer, reflux condensing tube and constant pressure dropping funnel, oil bath heating.First by 8g water and
The 5g concentrated sulfuric acids are carefully slowly keyed in 50g tetrahydrofurans, and after heating makes mixture temperature rise to 70 DEG C, dropwise addition is above-mentioned to be prepared in advance
Mixed silanes one, time for adding control in 45min or so.After adding, insulation reaction 0.5 ~ 1 hour.It then proceedes to be added dropwise mixed
Silane two is closed, time for adding is 1 hour, and after adding, secondary polycondensation is reacted 6 hours.
Stop reaction, reaction solution, which is first evaporated under reduced pressure, removes coproduct ethanol and solvents tetrahydrofurane, and the temperature of distillation is 60
DEG C, vacuum degree 10mmHg distills until no liquid distillates.Toluene extracts 3 times, the use of toluene amount is every time 30g.Merge extraction
Liquid is taken, to distill water washing 5 times, uses 15g distilled water every time.After washing, it is small to add the drying 5 of 6g anhydrous sodium sulfates
When.It is filtered to remove drier, is distilled under the conditions of temperature is 80 DEG C, vacuum degree is 0.5mmHg and obtains the bulk solids production of white
The fluorine-containing phenyl polysiloxane 36.3g of object, yield 72.6%.
The infrared spectrum curve of the fluorine silicon resin of above-mentioned preparation is shown in attached drawing 1；From the figure, it can be seen that 1620cm-1Place occurs
The characteristic absorption peak of phenyl ring skeleton, 2960cm-1For-CH3Middle C-H stretching vibration absworption peaks, 1410cm-1For-CH3Middle C-H's
Weak asymmetrical deformation vibration, 1260cm-1For Si-CH3- the CH of base3In face and caused by out-of-plane bending vibration.1100~1020cm-1For Si-O-Si stretching vibration absworption peaks, 804cm-1For Si-C stretching vibration absworption peaks.
The thermal weight loss test result of the thermostable fluorine silicones of above-mentioned preparation is shown in attached drawing 2；The result shows that resin is heated to
394 DEG C of 5% mass losses of appearance, and carbon yield reaches 19.8%, and it is very excellent heat-resisting that this illustrates that fluorine-containing phenyl polysiloxane has
Property.
Product fluorine silicon resin molecular structure is as follows：
Wherein, m=2~10；n =1~3；p=1~3.
Embodiment two
（1）Phenyl-pentafluoride ethyl dimethylchlorosilane synthesis technology is the same as embodiment one.
（2）Polycondensation synthesizes fluorine silicon resin
By 19.4g phenyl-pentafluoride ethyls dimethylchlorosilane, 5.5g tri-methyl-chlorosilanes and the positive silicon of 63g in 250mL conical flasks
Acetoacetic ester is uniformly mixed, and obtains mixed silanes, spare.
500mL three-necked flasks are equipped with thermometer, reflux condensing tube and constant pressure dropping funnel, oil bath heating.First by 8g water and
The 5g concentrated sulfuric acids are carefully slowly keyed in 50g tetrahydrofurans, and after heating makes mixture temperature rise to 70 DEG C, dropwise addition is above-mentioned to be prepared in advance
Mixed silanes, time for adding control in 42min or so.After adding, insulation reaction 6 hours.
Stop reaction, reaction solution, which is first evaporated under reduced pressure, removes coproduct ethanol and solvents tetrahydrofurane, and the temperature of distillation is 60
DEG C, vacuum degree 10mmHg distills until no liquid distillates.Toluene extracts 3 times, the use of toluene amount is every time 30g.Merge extraction
Liquid is taken, to distill water washing 5 times, uses 15g distilled water every time.After washing, it is small to add the drying 5 of 6g anhydrous sodium sulfates
When.It is filtered to remove drier, is distilled under the conditions of temperature is 80 DEG C, vacuum degree is 0.5mmHg and obtains the bulk solids production of white
Object fluorine silicon resin 41.6g, yield 83.2%.
（3）Prepare organic silicon adhesive
250mL three-necked flasks are equipped with thermometer, water knockout drum and reflux condensing tube, constant pressure addition funnel, oil bath heating.Successively plus
Enter 107 glue 16.8g and 16g toluene, stirring is warming up to 80 DEG C, adds 0.18g dibutyl tin laurates（DBTL）.Logical nitrogen, drop
0.13g dimethyl diethoxysilanes are added to be dissolved in the solution in 2.5g toluene, 30min is added, insulation reaction 3h.Then, add
The fluorine silicon resin for entering the above-mentioned preparations of 20g is dissolved in solution in 25g toluene, increases temperature to 110 DEG C, reflux water-dividing reacts for 24 hours.
Hexamethyldisilazane 0.12g, isopropanol 0.46g, heat preservation slaking reaction 5h is added in polycondensation product.Stop after reaction anti-
It answers, cooling, discharging obtains organic silicon pressure-sensitive adhesive.
Toluene 200g, organic silicon pressure-sensitive adhesive 4g and dibenzoyl peroxide are sequentially added in a reservoir（BPO）
0.1g, after stirring evenly, obtained dilution glue with glue spreader gluing on polyester film, control bondline thickness is 0.05 ~
0.06mm.2min is dried after gluing at 90 DEG C, then 5 min of drying cures at 150 DEG C.According to GB/T 2792-1998：Pressure
180 ° of peeling strength test methods of sensitive adhesive, it is 30.5N to measure organic pressure-sensitive gel peel strength（2.5cm）.According to GB/T
17875-1999：Pressure-sensitive adhesive accelerated aging test method, measure adhesive at 250 DEG C compression resistant and oxidation up to after 72h,
180 ° of peel strengths are 28.5N（2.5cm）, illustrate that adhesive heat resistance is superior.
Embodiment three
（1）Phenyl-pentafluoride ethyl dimethylchlorosilane synthesizes
500mL three-necked flasks are equipped with thermometer, reflux condensing tube and constant pressure dropping funnel, oil bath heating.Sequentially add 40g tri-
Chloroplatinic acid catalyst 0.1g is added under nitrogen protection for methyl fluoride benzene and 32g pentafluorostyrenes, stirring and dissolving.Open heating, heating
To after 80 DEG C, 26g dichloromethylsilanes are added dropwise, time for adding is controlled at 1 hour or so.Drip subsequent continuous insulation reaction
1.5 hour.After reaction, solvent and unreacted dimethyl dichlorosilane (DMCS) is evaporated off, 132 DEG C of fractions are collected in vacuum distillation
（3.75kPa）, phenyl-pentafluoride ethyl dimethylchlorosilane 46g is obtained, it is 95.8% that gas-chromatography, which measures product purity, yield 84.6%.
（2）Polycondensation synthesizes pentafluorophenyl group vinyl polysiloxane
19.5g phenyl-pentafluoride ethyl dimethylchlorosilanes and 32g ethyl orthosilicates are uniformly mixed in 100mL conical flasks, obtained
Mixed silanes one；Another take in a 100mL conical flasks mixes one chlorosilane of 6g dimethyl ethenyls and 31g ethyl orthosilicates
It is even, mixed silanes two are obtained, it is spare.
500mL three-necked flasks are equipped with thermometer, reflux condensing tube and constant pressure dropping funnel, oil bath heating.First by 10g water
It is carefully slowly keyed in 60g tetrahydrofurans with the 6g concentrated sulfuric acids, after heating makes mixture temperature rise to 72 DEG C, dropwise addition is above-mentioned to match in advance
Good mixed silanes one, time for adding are controlled in 1h.A polycondensation reaction 0.5 hour after adding.After polycondensation, continue
Mixed silanes two are added dropwise, time for adding is 1 hour, and after completion of dropwise addition, heat preservation carries out secondary polycondensation.
Stop reaction, reaction solution, which is first evaporated under reduced pressure, removes coproduct ethanol and solvents tetrahydrofurane, and the temperature of distillation is 60
DEG C, vacuum degree 10mmHg distills until no liquid distillates.Toluene extracts 3 times, the use of toluene amount is every time 30g.Merge extraction
Liquid is taken, to distill water washing 5 times, uses 15g distilled water every time.After washing, it is small to add the drying 5 of 6g anhydrous sodium sulfates
When.It is filtered to remove drier, is distilled under the conditions of temperature is 80 DEG C, vacuum degree is 0.5mmHg and obtains the bulk solids production of white
Object pentafluorophenyl group vinyl polysiloxane 34.1g, yield 68.2%.
Product molecule structure is as follows：
Wherein, m=2~8；n =2~4；p=2~4.
（3）Prepare organic silicon adhesive
250mL three-necked flasks are equipped with thermometer, water knockout drum and reflux condensing tube, constant pressure addition funnel, oil bath heating.Successively plus
Enter 107 glue 17.2g and 20g toluene, stirring is warming up to 80 DEG C, adds 0.18g dibutyl tin laurates（DBTL）.Logical nitrogen, drop
0.15g dimethyl diethoxysilanes are added to be dissolved in the solution in 2.5g toluene, 30min is added, insulation reaction 3h.Then, add
The fluorine silicon resin for entering the above-mentioned preparations of 28g is dissolved in solution in 25g toluene, increases temperature to 110 DEG C, reflux water-dividing reacts for 24 hours.
Hexamethyldisilazane 0.1g, isopropanol 0.5g, heat preservation slaking reaction 5h is added in polycondensation product.Stop reaction after reaction,
Cooling, discharging, obtains organic silicon pressure-sensitive adhesive.
Toluene 200g, organic silicon pressure-sensitive adhesive 4g and dibenzoyl peroxide are sequentially added in a reservoir（BPO）
0.1g, after stirring evenly, obtained dilution glue with glue spreader gluing on polyester film, control bondline thickness is 0.05 ~
0.06mm.2min is dried after gluing at 90 DEG C, then 5 min of drying cures at 150 DEG C.According to GB/T 2792-1998：Pressure
180 ° of peeling strength test methods of sensitive adhesive, it is 29.6N to measure organic pressure-sensitive gel peel strength（2.5cm）.According to GB/T
17875-1999：Pressure-sensitive adhesive accelerated aging test method, measure adhesive at 250 DEG C compression resistant and oxidation up to after 72h,
180 ° of peel strengths are 28.1N（2.5cm）.
Example IV
（1）Phenyl-pentafluoride ethyl dimethylchlorosilane synthesis step is the same as embodiment one.
（2）Polycondensation synthesizes fluorine silicon resin
19.5g phenyl-pentafluoride ethyl dimethylchlorosilanes and 32g ethyl orthosilicates are uniformly mixed in 100mL conical flasks, obtained
Mixed silanes one；One chlorosilane of 10g 3,5-dimethylphenyls and 31.5g ethyl orthosilicates are mixed in another 100mL conical flasks
It is even, obtain mixed silanes two；Two kinds of mixed silanes are spare.
500mL three-necked flasks are equipped with thermometer, reflux condensing tube and constant pressure dropping funnel, oil bath heating.First by 9g water and
The 6.5g concentrated sulfuric acids are carefully slowly keyed in 55g tetrahydrofurans, and after heating makes mixture temperature rise to 75 DEG C, dropwise addition is above-mentioned to match in advance
Good mixed silanes one, time for adding are controlled in 1h.A polycondensation reaction 0.5 hour after adding.After polycondensation, continue
Mixed silanes two are added dropwise, time for adding is 1 hour, and after completion of dropwise addition, heat preservation carries out secondary polycondensation reaction 5 hours.
Stop reaction, reaction solution, which is first evaporated under reduced pressure, removes coproduct ethanol and solvents tetrahydrofurane, and the temperature of distillation is 60
DEG C, vacuum degree 10mmHg distills until no liquid distillates.The use of dimethylbenzene amount is every time 30g with xylene extraction 3 times.
Combining extraction liquid uses 15g distilled water every time to distill water washing 5 times.After washing, it is dry to add 6g anhydrous magnesium sulfates
Dry 5 hours.It is filtered to remove drier, is distilled under the conditions of temperature is 80 DEG C, vacuum degree is 0.5mmHg and obtains the loose solid of white
Body product fluorine silicon resin 33.8g, yield 67.6%.
Product molecule structure is as follows：
Wherein, m=2~9；n =2~4；p=2~5.
（3）Prepare organic silicon adhesive
250mL three-necked flasks are equipped with thermometer, water knockout drum and reflux condensing tube, constant pressure addition funnel, oil bath heating.Successively plus
Enter 107 glue 17.8g and 25g toluene, stirring is warming up to 80 DEG C, adds 0.16g dibutyl tin laurates（DBTL）.Logical nitrogen, drop
0.15g dimethyl diethoxysilanes are added to be dissolved in the solution in 2.5g toluene, 30min is added, insulation reaction 3h.Then, add
The fluorine silicon resin for entering the above-mentioned preparations of 26g is dissolved in solution in 25g toluene, increases temperature to 110 DEG C, reflux water-dividing reacts for 24 hours.
Hexamethyldisilazane 0.1g, isopropanol 0.5g, heat preservation slaking reaction 5h is added in polycondensation product.Stop reaction after reaction,
Cooling, discharging, obtains organic silicon pressure-sensitive adhesive.
Toluene 200g, organic pressure-sensitive gel 4g and dibenzoyl peroxide are sequentially added in a reservoir（BPO）0.1g is stirred
After mixing uniformly, for obtained dilution glue with glue spreader gluing on polyester film, control bondline thickness is 0.05 ~ 0.06mm.It applies
2min is dried after glue at 90 DEG C, then 5 min of drying cures at 150 DEG C.According to GB/T 2792-1998：Pressure-sensitive adhesive
180 ° of peeling strength test methods, it is 29.8N to measure organic pressure-sensitive gel peel strength（2.5cm）.According to GB/T 17875-
1999：Pressure-sensitive adhesive accelerated aging test method, measuring adhesive, compression resistant and oxidation are up to after 72h at 250 DEG C, 180 ° of strippings
It is 28.3N from intensity（2.5cm）.
Embodiment five
（1）Phenyl-pentafluoride ethyl dimethylchlorosilane synthesis step is the same as embodiment one.
（2）Polycondensation synthesizes pentafluorophenyl group vinyl polysiloxane
20g phenyl-pentafluoride ethyl dimethylchlorosilanes and 30g ethyl orthosilicates are uniformly mixed in 100mL conical flasks, mixed
Close silane one；One chlorosilane of 3g dimethyl ethenyls and 30g ethyl orthosilicates are uniformly mixed in another 100mL conical flasks,
Mixed silanes two are obtained, it is spare.
500mL three-necked flasks are equipped with thermometer, reflux condensing tube and constant pressure dropping funnel, oil bath heating.First by 8g water and
The 6g concentrated sulfuric acids are carefully slowly keyed in 50g tetrahydrofurans, after heating makes mixture temperature rise to 71 DEG C, are added dropwise at a slow speed above-mentioned advance
The mixed silanes one prepared, time for adding are controlled in 1h.A polycondensation reaction 0.5 hour after adding.After polycondensation, after
Continuous that mixed silanes two are added dropwise, time for adding is 1 hour, and after completion of dropwise addition, heat preservation carries out secondary polycondensation reaction 5 hours.
Stop reaction, reaction solution, which is first evaporated under reduced pressure, removes coproduct ethanol and solvents tetrahydrofurane, and the temperature of distillation is 60
DEG C, vacuum degree 10mmHg distills until no liquid distillates.Toluene extracts 3 times, the use of toluene amount is every time 25g.Merge extraction
Liquid is taken, to distill water washing 5 times, uses 12g distilled water every time.After washing, it is small to add the drying 5 of 5g anhydrous sodium sulfates
When.It is filtered to remove drier, is distilled under the conditions of temperature is 80 DEG C, vacuum degree is 0.5mmHg and obtains the bulk solids production of white
Object pentafluorophenyl group vinyl polysiloxane 35.6g, yield 71.2%.
Product molecule structure is as follows：
Wherein, m=2~12；n=2~5；p=1~4.
（3）Prepare organic silicon adhesive
250mL three-necked flasks are equipped with thermometer, water knockout drum and reflux condensing tube, constant pressure addition funnel, oil bath heating.Successively plus
Enter 107 glue 18.1g and 25g toluene, stirring is warming up to 80 DEG C, adds 0.2g dibutyl tin laurates（DBTL）.Logical nitrogen, is added dropwise
0.15g dimethyl diethoxysilanes are dissolved in the solution in 2.8g toluene, and 30min is added, insulation reaction 3h.Then, it is added
The fluorine silicon resin of the above-mentioned preparations of 27g is dissolved in the solution in 25g toluene, increases temperature to 110 DEG C, reflux water-dividing reacts for 24 hours.Contracting
Hexamethyldisilazane 0.1g, isopropanol 0.5g, heat preservation slaking reaction 5h is added in poly- product.Stop reaction after reaction, it is cold
But it, discharges, obtains organic silicon pressure-sensitive adhesive.
Toluene 200g, organic pressure-sensitive gel 4g and dibenzoyl peroxide are sequentially added in a reservoir（BPO）0.1g is stirred
After mixing uniformly, for obtained dilution glue with glue spreader gluing on polyester film, control bondline thickness is 0.05 ~ 0.06mm.It applies
2min is dried after glue at 90 DEG C, then 5 min of drying cures at 150 DEG C.According to GB/T 2792-1998：Pressure-sensitive adhesive
180 ° of peeling strength test methods, it is 30.3N to measure organic pressure-sensitive gel peel strength（2.5cm）.According to GB/T 17875-
1999：Pressure-sensitive adhesive accelerated aging test method, measuring adhesive, compression resistant and oxidation are up to after 72h at 250 DEG C, 180 ° of strippings
It is 29.1N from intensity（2.5cm）.
Claims (10)
1. a kind of fluorine silicon resin, which is characterized in that the chemical structural formula of the fluorine silicon resin is：
Wherein, R=methyl, phenyl, vinyl or hydrogen；
M=2~20；N=1~5；P=1~8.
2. the preparation method of fluorine silicon resin described in claim 1, which is characterized in that include the following steps：
（1）Using pentafluorostyrene, dimethyl dichlorosilane (DMCS) as raw material, under precious metal salt catalysis, phenyl-pentafluoride ethyl dimethyl is prepared
Chlorosilane；
（2）The mixture of phenyl-pentafluoride ethyl dimethylchlorosilane and ethyl orthosilicate is added dropwise to water/inorganic acid/organic solvent
A polycondensation reaction is carried out in mixed liquor；Then the mixture of trialkyl one chlorosilane and ethyl orthosilicate is added dropwise again, contracts again
After poly- reaction, fluorine silicon resin is prepared.
3. the preparation method of fluorine silicon resin according to claim 2, which is characterized in that pentafluorostyrene, precious metal salt, methyl
The mass ratio of dichlorosilane is 1:（0.003~0.006）∶（0.5~2）；Phenyl-pentafluoride ethyl dimethylchlorosilane and positive silicic acid second
In the mixture of ester, the mass ratio of phenyl-pentafluoride ethyl dimethylchlorosilane and ethyl orthosilicate is（1~6）∶（1~10）；Three hydrocarbon
In the mixture of one chlorosilane of base and ethyl orthosilicate, the mass ratio of one chlorosilane of trialkyl and ethyl orthosilicate is（1~3）∶
（1~10）.
4. the preparation method of fluorine silicon resin according to claim 2, which is characterized in that
Step（1）For pentafluorostyrene is dissolved in aromatic hydrocarbon solvent, precious metal salt catalyst is added under nitrogen protection；
Then dimethyl dichlorosilane (DMCS) is added dropwise at 50~140 DEG C；It is added dropwise to complete rear insulation reaction 1 ~ 10 hour, prepares phenyl-pentafluoride ethyl two
Methylchlorosilane；
Step（2）In organic solvent by water, inorganic acid dispersion, phenyl-pentafluoride ethyl diformazan to be then added dropwise at 60~80 DEG C
The mixture of base chlorosilane and ethyl orthosilicate, polycondensation of heat preservation progress 0.5~1 hour after being added dropwise to complete；Then it is added dropwise again
The mixture of trialkyl one chlorosilane and ethyl orthosilicate keeps the temperature after being added dropwise to complete and carries out polycondensation reaction 1~6 hour again, system
Standby fluorine silicon resin.
5. the preparation method of fluorine silicon resin according to claim 4, which is characterized in that the aromatic hydrocarbon solvent be toluene,
Dimethylbenzene, benzotrifluoride, 1,3- are bis-（Trifluoromethyl）One kind in benzene；The precious metal salt is chloroplatinic acid；The trialkyl one
Chlorosilane is trim,ethylchlorosilane, one chlorosilane of dimethyl hydrogen-based, one chlorosilane of dimethyl ethenyl, one chlorine silicon of pheiiyldimetliyl
One kind in alkane；The inorganic acid is the concentrated sulfuric acid or concentrated hydrochloric acid；The organic solvent is tetrahydrofuran.
6. the preparation method of fluorine silicon resin according to claim 4, which is characterized in that step（1）In, methyl dichloro silicon is added dropwise
The time of alkane is 0.5~5 hour；Step（2）In, the time that the mixture of one chlorosilane of trialkyl and ethyl orthosilicate is added dropwise is
0.5~1 hour.
7. the preparation method of fluorine silicon resin according to claim 4, which is characterized in that step（1）After reaction, reaction solution
Phenyl-pentafluoride ethyl dimethylchlorosilane is obtained by being evaporated off, being evaporated under reduced pressure；Step（2）Again after polycondensation reaction, reaction solution
Fluorine silicon resin is obtained through supercooling, vacuum distillation, liquid separation processing, extraction, distillation water washing, drying, filtering, distillation.
8. a kind of preparation method of phenyl-pentafluoride ethyl dimethylchlorosilane, which is characterized in that include the following steps, by phenyl-pentafluoride second
Alkene is dissolved in aromatic hydrocarbon solvent, and precious metal salt catalyst is added under nitrogen protection；Then methyl is added dropwise at 50~140 DEG C
Dichlorosilane；It is added dropwise to complete rear insulation reaction 1 ~ 10 hour, prepares phenyl-pentafluoride ethyl dimethylchlorosilane.
9. the preparation method of phenyl-pentafluoride ethyl dimethylchlorosilane according to claim 8, which is characterized in that the aromatic hydrocarbon
Class solvent is toluene, dimethylbenzene, benzotrifluoride, 1,3- bis-（Trifluoromethyl）One kind in benzene；The precious metal salt is chloroplatinic acid；
Be added dropwise dimethyl dichlorosilane (DMCS) time be；After reaction, reaction solution obtains phenyl-pentafluoride ethyl diformazan by being evaporated off, being evaporated under reduced pressure
Base chlorosilane.
10. phenyl-pentafluoride ethyl dimethyl chloride prepared by the preparation method of phenyl-pentafluoride ethyl dimethylchlorosilane described in claim 8
Silane.
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