CN104231276A - Preparation method of vinyl-terminated silicon oil - Google Patents
Preparation method of vinyl-terminated silicon oil Download PDFInfo
- Publication number
- CN104231276A CN104231276A CN201410423864.4A CN201410423864A CN104231276A CN 104231276 A CN104231276 A CN 104231276A CN 201410423864 A CN201410423864 A CN 201410423864A CN 104231276 A CN104231276 A CN 104231276A
- Authority
- CN
- China
- Prior art keywords
- vinyl
- preparation
- reaction
- silicone fluid
- terminated silicone
- 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
Abstract
The invention discloses a preparation method of vinyl-terminated silicon oil, which comprises the following steps: reacting 500 parts by mass of hydroxyl-terminated linear polydimethylsiloxane, 1-10 parts by mass of vinyl mono end socket and 0.007-0.015 part by mass of trifluoromethane sulfonic acid at 55-80 DEG C for 1-2 hours, and reacting at 80-100 DEG C under the vacuum degree of 0.01-0.1 MPa for 2-4 hours; and after the reaction is finished, introducing NH3 to regulate the pH value of the reaction solution to a neutral state, and filtering to obtain the vinyl-terminated silicon oil product. The preparation method has the advantages of simple technique, mild reactions, high yield and quality of the product and low energy consumption, and is green and environment-friendly.
Description
Technical field
The present invention relates to a kind of preparation method of vinyl-terminated silicone fluid, being specifically related to a kind of is the method that vinyl-terminated silicone fluid prepared by raw material with hydroxy-end capped linear polydimethysiloxane (linear body) and vinyl list end socket.
Background technology
Vinyl silicone oil is the main raw material of add-on type liquid silicon rubber, silicon gel etc.; Also can be used as the properties-correcting agent/plastics additive/supporting material etc. of rubber unvulcanizate, tool has been widely used.As vinyl silicone oil can be used as the base-material producing high-temperature silicon disulfide rubber (HTV), be equipped with the mixing high-temperature sulfuration silicon rubber raw rubbers of preparing such as linking agent, strengthening agent, tinting material, constitution controller, antiager; Also can be used for making liquid silastic, is the main raw of injection thermoforming silicon rubber; Vinyl silicone oil and the multiple organic materials such as urethane, vinylformic acid react, and can be made into the novel material of performance more superior (weather-proof, ageing-resistant, uvioresistant, enhancing toughness etc.).
Vinyl silicone oil mainly contains end-vinyl polydimethylsiloxane (Vi-PDMS) and end-vinyl Polymethyl methacrylate (Vi-PMVS), can provide the product of different viscosity and contents of ethylene as required.
In recent years, addition-type silicon rubber due to do not produce in sulfidation by product, shrinking percentage minimum, can deep layer vulcanization, easily obtained high purity, high transparency and fire-retardant product and comparatively fast developed, be widely used in LED, electronic component embedding and electric power electric industry etc.Its sulfuration mechanism contains the polydimethylsiloxane of vinyl and the compound of hydrosilyl group-containing or polymkeric substance to carry out addition reaction of silicon with hydrogen under catalyst action, forms reticulated structure.End-vinyl polydimethylsiloxane (Vi-PDMS) is the main raw material preparing addition-type silicon rubber, generally with octamethylcyclotetrasiloxane (D
4), divinyl tetramethyl disiloxane (also known as vinyl double-seal head) is raw material, form mainly through anionic ring-opening polymerization reaction under catalyst action.The catalyzer of anionic ring-opening polymerization reaction has the oxyhydroxide of basic metal K, Na, Li or quaternary ammonium hydroxide etc.Domestic extensive employing Tetramethylammonium hydroxide [(CH
3)
4nOH] alkali glue and potassium hydroxide base glue is catalyzer.[(CH
3)
4nOH] and the catalytic activity of potassium hydroxide base glue high and after reaction removing method simple, such as [(CH
3)
4nOH] removal can pass through pyrolytic decomposition, the removal of potassium hydroxide base glue is by adding the neutralization of phosphoric acid glue, but [(CH
3)
4nOH] decompose the Trimethylamine 99 generated and remain in silicone oil and cause heavier amine taste, silicone oil can be caused opaque with the salt generated in potassium hydroxide base glue, and this preparation process has 10-15% low molecule cyclosiloxane to generate, need to be vacuumized by high temperature to remove, energy consumption is high.Building up if any Trimethylamine 99 during recovery use low molecular compound can make product occur micro-yellow phenomenon through heated oxide.
As China Patent Publication No. CN103881095A, denomination of invention: the preparation method of thiazolinyl silicone oil, this application case discloses a kind of preparation method of vinyl silicone oil, comprise the following steps: the first step, by weight, adding the octamethylcyclotetrasiloxane of 2300Kg with stirring, heat up, in the reactor that can vacuumize, be warming up to 65 DEG C, logical dry N
2, dehydration 1h; Second step, by weight, adds the 10.35Kg tetramethyl divinyl disiloxane of drying and the Tetramethylammonium hydroxide of 0.184Kg, temperature is risen to 100 DEG C of insulation reaction 3h; 3rd step, is warming up to 145 DEG C, broken matchmaker 1h; 4th step, continues to be warmed up to 180 DEG C, logical dry nitrogen, and the de-low molecule when vacuum tightness >-0.098MPa, until without effluent liquid; 5th step, goes vacuum, is cooled to less than 60 DEG C, discharging.Weak point is that processing step is long, complex process, and temperature of reaction is high, and energy consumption is high, quality product is not good enough.
And for example China Patent Publication No. CN103333338A, denomination of invention: a kind of vinyl silicone oil and synthetic method thereof.The invention discloses a kind of vinyl silicone oil synthetic method, described vinyl silicone oil consists of with parts by weight: 100 parts of methyl cyclosiloxane, 10-40 part t etram-ethyltetravinylcyclotetrasiloxane, the agent of 1-20 part ethenyl blocking, 0.1-1 part basic catalyst, described basic catalyst is the alkali glue catalyzer that octamethylcyclotetrasiloxane ring-opening polymerization under alkaline hydrated oxide catalysis obtains.Its synthetic method is using methyl cyclosiloxane and t etram-ethyltetravinylcyclotetrasiloxane as reaction monomers, polyreaction under ethenyl blocking agent and basic catalyst exist, polyreaction terminate after, cooling, diluted acid neutralization, washing, be separated, polymerisate rectifying removes low-boiling-point substance and obtains vinyl silicone oil.Weak point is that processing step is long and complicated, and time-consuming length, temperature of reaction is high, and energy consumption is high, feed stock conversion is low.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide that a kind of technique is simple, reaction temperature and, product yield is high and quality good, energy consumption is low, the preparation method of the vinyl-terminated silicone fluid of environmental protection.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of vinyl-terminated silicone fluid, by mass parts, 500 parts of hydroxy-end capped linear polydimethysiloxane, 1-10 part vinyl list end socket, 0.007-0.015 part trifluoromethane sulfonic acid are first reacted 1-2h at 55 DEG C-80 DEG C, again 80-100 DEG C, react 2-4h under vacuum tightness 0.01-0.1MPa, reaction terminates rear logical NH
3reaction solution is neutralized to PH for neutral, filters and namely obtain vinyl-terminated silicone fluid product.
As the preferred embodiment of the present invention, described hydroxy-end capped linear polydimethysiloxane viscosity is 80 ~ 130mPa.s, and hydroxy radical content is 0.5 ~ 1.8wt%.
As the preferred embodiment of the present invention, described vinyl list end socket is preferably Vinyldimethylethoxysilane or dimethylvinylmethoxysiiane.
As the preferred embodiment of the present invention, described vinyl list end socket is 3-8 part, and described trifluoromethane sulfonic acid is 0.009-0.012 part.
The present invention is with hydroxy-end capped linear polydimethysiloxane and vinyl list end socket for raw material, and under trifluoromethane sulfonic acid catalyst action, vacuumize the vinyl-terminated silicone fluid of polycondensation synthesis ethenyl blocking after middle low-temp reaction, principal reaction equation is:
R=-CH in formula
3or-C
2h
5
The great amount of hydroxy group of the linear polydimethysiloxane that Raw of the present invention is hydroxy-end capped and the alkoxyl group of vinyl list end socket are first in the condensation reaction of middle occurs at low temperatures Sheng Yi functional group, generate small molecular alcohol, then vacuumize at a certain temperature and make, between hydroxyl and hydroxyl, polycondensation occurs, synthesis of vinyl silicone oil, generates water byproduct.Vacuumize the water that can make to occur between hydroxyl and hydroxyl polycondensation generation to remove in time, reaction is carried out to the direction generating the finished product.
The vinyl silicone oil viscosity of the feed ratio impact preparation of linear polydimethysiloxane hydroxy-end capped during reaction and vinyl list end socket raw material and corresponding contents of ethylene.The feed ratio of linear polydimethysiloxane hydroxy-end capped within the specific limits and vinyl list end socket raw material is less, and the silicon oil viscosity of preparation is less, and corresponding contents of ethylene is higher; On the contrary, the silicon oil viscosity of the larger preparation of feed ratio is about large, and corresponding contents of ethylene is less.
Compared with prior art, advantage of the present invention is:
1, technique is simple, reaction conditions is gentle, and preparation method of the present invention vacuumizes de-low molecule step without the need to high temperature, and technical process shortens, and aftertreatment is simple, and facility investment is little;
2, low, the environmental protection of energy consumption, reaction process generates without low molecular compound, therefore vacuumizes de-low molecule without the need to high temperature, provide significant conservation energy consumption, meets the developing direction of " Green Chemistry ";
3, yield is high, good product quality, preparation method of the present invention take trifluoromethayl sulfonic acid as catalyzer, have that catalytic activity is high, consumption is few, easy neutralization and easily filtering after neutralization, the advantages such as product water white transparency, and further simplify postprocessing working procedures, reaction yield is more than 99.38%, reach as high as 99.7%, the utilization ratio of vinyl list end socket can reach more than 80%.
Embodiment
By the following examples the present invention is described in further detail, but the present invention is not limited to described embodiment.
Embodiment 1
Hydroxy-end capped linear polydimethysiloxane (Zhejiang Transit Fluorine Silicon Material Co., Ltd. is first added in 1000mL reactor, viscosity 80mPa.s (25 DEG C), hydroxy radical content 1.8wt%) 500g, add Vinyldimethylethoxysilane 1.5g again, after stirring 10min, add trifluoromethayl sulfonic acid 0.007g, 80 DEG C of reaction 1h are warming up under stirring, reactor being evacuated to vacuum tightness again at 80 DEG C is that 0.1MPa reacts 4h, terminates reaction, logical NH in reactor
3reaction solution is neutralized to PH for neutral, the trifluoromethane sulfonic acid ammonium that removed by filtration generates, obtains colourless vinyl-terminated silicone fluid product, viscosity is 80195mPa.s (25 DEG C), contents of ethylene is 0.051wt%, and yield is 99.38%, and the utilization ratio of vinyl list end socket is 82.5%.
Embodiment 2
Hydroxy-end capped linear polydimethysiloxane (Zhejiang Transit Fluorine Silicon Material Co., Ltd. is first added in 1000mL reactor, viscosity 90mPa.s (25 DEG C), hydroxy radical content 1.4wt%) 500g, add Vinyldimethylethoxysilane 3.58g again, after stirring 10min, add trifluoromethayl sulfonic acid 0.009g, 75 DEG C of reaction 1.2h are warming up under stirring, after being warming up to 85 DEG C again, reactor being evacuated to vacuum tightness is react 3.5h after 0.08MPa, terminate reaction, logical NH in reactor
3reaction solution is neutralized to PH for neutral, the trifluoromethane sulfonic acid ammonium that removed by filtration generates, obtains colourless vinyl-terminated silicone fluid product, viscosity is 12550mPa.s (25 DEG C), contents of ethylene is 0.121wt%, and yield is 99.42%, and the utilization ratio of vinyl list end socket is 81.6%.
Embodiment 3
Hydroxy-end capped linear polydimethysiloxane (Zhejiang Transit Fluorine Silicon Material Co., Ltd. is first added in 1000mL reactor, viscosity 100mPa.s (25 DEG C), hydroxy radical content 0.82wt%) 500g, add Vinyldimethylethoxysilane 5.6g again, after stirring 10min, add trifluoromethayl sulfonic acid 0.012g, 70 DEG C of reaction 1.5h are warming up under stirring, after being warming up to 90 DEG C again, reactor being evacuated to vacuum tightness is that 0.05MPa reacts 3h, terminate reaction, logical NH in reactor
3reaction solution is neutralized to PH for neutral, the trifluoromethane sulfonic acid ammonium that removed by filtration generates, obtains colourless vinyl-terminated silicone fluid product, viscosity is 4310mPa.s (25 DEG C), contents of ethylene is 0.187wt%, and yield is 99.50%, and the utilization ratio of vinyl list end socket is 81.2%.
Embodiment 4
Hydroxy-end capped linear polydimethysiloxane (Zhejiang Transit Fluorine Silicon Material Co., Ltd. is first added in 1000mL reactor, viscosity 110mPa.s (25 DEG C), hydroxy radical content 0.76wt%) 500g, add Vinyldimethylethoxysilane 8.20g again, after stirring 10min, add trifluoromethayl sulfonic acid 0.015g, 60 DEG C of reaction 1.8h are warming up under stirring, after being warming up to 95 DEG C again, reactor being evacuated to vacuum tightness is react 2.5h after 0.03MPa, terminate reaction, logical NH in reactor
3reaction solution is neutralized to PH for neutral, the trifluoromethane sulfonic acid ammonium that removed by filtration generates, obtains colourless vinyl-terminated silicone fluid product, viscosity is 1690mPa.s (25 DEG C), contents of ethylene is 0.270wt%, and yield is 99.56%, and the utilization ratio of vinyl list end socket is 80.5%.
Embodiment 5
Hydroxy-end capped linear polydimethysiloxane (Zhejiang Transit Fluorine Silicon Material Co., Ltd. is first added in 1000mL reactor, viscosity 130mPa.s (25 DEG C), hydroxy radical content 0.52wt%) 500g, add dimethylvinylmethoxysiiane 5.3g again, after stirring 10min, add trifluoromethayl sulfonic acid 0.01g, 55 DEG C of reaction 2h are warming up under stirring, after being warming up to 100 DEG C again, reactor being evacuated to vacuum tightness is that 0.01MPa reacts 2h, terminates reaction, logical NH in reactor
3reaction solution is neutralized to PH for neutral, the trifluoromethane sulfonic acid ammonium that removed by filtration generates, obtains colourless vinyl-terminated silicone fluid product, viscosity is 3905mPa.s (25 DEG C), contents of ethylene is 0.196wt%, and yield is 99.7%, and the utilization ratio of vinyl list end socket is 80.1%.
Claims (5)
1. the preparation method of a vinyl-terminated silicone fluid, it is characterized in that by mass parts, 500 parts of hydroxy-end capped linear polydimethysiloxane, 1-10 part vinyl list end socket, 0.007-0.015 part trifluoromethane sulfonic acid are first reacted 1-2h at 55 DEG C-80 DEG C, again 80-100 DEG C, react 2-4h under vacuum tightness 0.01-0.1MPa, reaction terminates rear logical NH
3reaction solution is neutralized to PH for neutral, filters and namely obtain vinyl-terminated silicone fluid product.
2. the preparation method of vinyl-terminated silicone fluid according to claim 1, it is characterized in that described hydroxy-end capped linear polydimethysiloxane viscosity is 80 ~ 130mPa.s, hydroxy radical content is 0.5 ~ 1.8wt%.
3. the preparation method of vinyl-terminated silicone fluid according to claim 1, is characterized in that described vinyl list end socket is Vinyldimethylethoxysilane or dimethylvinylmethoxysiiane.
4. the preparation method of vinyl-terminated silicone fluid according to claim 1, is characterized in that described vinyl list end socket is 3-8 part.
5. the preparation method of vinyl-terminated silicone fluid according to claim 1, is characterized in that described trifluoromethane sulfonic acid is 0.009-0.012 part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410423864.4A CN104231276A (en) | 2014-08-26 | 2014-08-26 | Preparation method of vinyl-terminated silicon oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410423864.4A CN104231276A (en) | 2014-08-26 | 2014-08-26 | Preparation method of vinyl-terminated silicon oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104231276A true CN104231276A (en) | 2014-12-24 |
Family
ID=52220249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410423864.4A Pending CN104231276A (en) | 2014-08-26 | 2014-08-26 | Preparation method of vinyl-terminated silicon oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104231276A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669980A (en) * | 2016-02-17 | 2016-06-15 | 合肥工业大学 | Phenyl-fluoride alkyl main chain boron-containing alpha, omega-vinyl end silicone oil and preparation method thereof |
| CN106589377A (en) * | 2015-10-15 | 2017-04-26 | 青岛科技大学 | Vinyl-phenyl-containing polysiloxane and preparation method thereof |
| CN112832027A (en) * | 2021-02-05 | 2021-05-25 | 义乌市皓祺服饰有限公司 | Preparation method of rain-proof antifouling all-cotton shirt fabric |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0133975A1 (en) * | 1983-08-01 | 1985-03-13 | Dow Corning Corporation | Method and novel catalyst compositions for preparing polyorganosiloxanes |
| US5109093A (en) * | 1989-02-09 | 1992-04-28 | Dow Corning Limited | Process for producing organosilicon products |
| US5939507A (en) * | 1997-04-21 | 1999-08-17 | Dow Corning Toray Silicone Co., Ltd. | Method for manufacturing siloxane compounds |
| CN1414991A (en) * | 1999-12-17 | 2003-04-30 | 罗狄亚化学公司 | Method for preparing polyorganosiloxanes by polymerisation catalysed catalytic system based of triflic acid ortriflic acid derivatives |
| CN101885845A (en) * | 2010-07-16 | 2010-11-17 | 东莞市贝特利新材料有限公司 | Method for synthesizing vinyl phenyl silicone oil |
| CN103387586A (en) * | 2013-07-24 | 2013-11-13 | 山东省科学院新材料研究所 | Preparation method of vinyl-terminated siloxane |
-
2014
- 2014-08-26 CN CN201410423864.4A patent/CN104231276A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0133975A1 (en) * | 1983-08-01 | 1985-03-13 | Dow Corning Corporation | Method and novel catalyst compositions for preparing polyorganosiloxanes |
| US5109093A (en) * | 1989-02-09 | 1992-04-28 | Dow Corning Limited | Process for producing organosilicon products |
| US5939507A (en) * | 1997-04-21 | 1999-08-17 | Dow Corning Toray Silicone Co., Ltd. | Method for manufacturing siloxane compounds |
| CN1414991A (en) * | 1999-12-17 | 2003-04-30 | 罗狄亚化学公司 | Method for preparing polyorganosiloxanes by polymerisation catalysed catalytic system based of triflic acid ortriflic acid derivatives |
| CN101885845A (en) * | 2010-07-16 | 2010-11-17 | 东莞市贝特利新材料有限公司 | Method for synthesizing vinyl phenyl silicone oil |
| CN103387586A (en) * | 2013-07-24 | 2013-11-13 | 山东省科学院新材料研究所 | Preparation method of vinyl-terminated siloxane |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589377A (en) * | 2015-10-15 | 2017-04-26 | 青岛科技大学 | Vinyl-phenyl-containing polysiloxane and preparation method thereof |
| CN105669980A (en) * | 2016-02-17 | 2016-06-15 | 合肥工业大学 | Phenyl-fluoride alkyl main chain boron-containing alpha, omega-vinyl end silicone oil and preparation method thereof |
| CN105669980B (en) * | 2016-02-17 | 2018-08-28 | 合肥工业大学 | A kind of alpha, omega end vinyl silicone oil of phenyl-fluoride hydrocarbon backbone boracic and preparation method thereof |
| CN112832027A (en) * | 2021-02-05 | 2021-05-25 | 义乌市皓祺服饰有限公司 | Preparation method of rain-proof antifouling all-cotton shirt fabric |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102558563B (en) | Preparation method for high-viscosity 107 glue | |
| CN102977377A (en) | Solvent-free method for preparing polyether modified polysiloxane antifoaming agent | |
| CN104231276A (en) | Preparation method of vinyl-terminated silicon oil | |
| CN101613475A (en) | Preparing MQ silicon resin by organic acid catalysis | |
| CN105498748A (en) | Tungsten oxide nanosheets, preparation method and catalysis application thereof | |
| CN105384936B (en) | A kind of preparation method of multi-vinyl silicone oil | |
| CN103087320B (en) | Preparation method of hydroxyl-terminated polymethylphenyl silicone oil | |
| CN105680045B (en) | A kind of preparation method of high stability amorphous manganous silicate | |
| CN107138167A (en) | A kind of preparation method of the multiphase hetero-junctions Nano cadmium sulphide of special appearance | |
| CN107649153A (en) | A kind of method that solvent-thermal method prepares BiOCl photochemical catalysts | |
| CN101225063A (en) | Method for preparing cysteamine hydrochloride by basic hydrolysis | |
| CN103910661B (en) | A kind of method using methanthiol to produce Methyl disulfide with sulfur cross-linking method | |
| CN104119832B (en) | A kind of organic silicon potting adhesive preparation method and applications | |
| CN104119208B (en) | The unordered mesoporous hydroxyapatite of a kind of phosphoric acid modification catalyzes and synthesizes the method for Bisphenol F | |
| CN102924721A (en) | Method for continuously preparing vinyl silicone oil | |
| CN103087317A (en) | Manufacturing method of high-molecular-weight polyphenylene sulfide sulfone | |
| CN104692573B (en) | Wastewater treatment method in process of synthesizing bis-[gamma-triethoxysilylpropyl]-tetrasulfide through aqueous phase method | |
| CN102584696B (en) | Catalytic synthesis method for rubber antioxidant RD | |
| CN107043111B (en) | A method of silica gel is prepared using silicon monosulfide hydrolysis | |
| CN101367940A (en) | Preparation method for small-numerator hydroxyl silicone oil | |
| CN103665381A (en) | Synthesis method of hydroxyl capped polydimethylsiloxane | |
| CN1294119C (en) | Method for synthesizing bifunctionality initiator DIOOH | |
| CN104803393B (en) | One kind prepares stearic acid（Sodium）The method of/Kaolinite/organic Intercalation Compoundies | |
| KR101217383B1 (en) | METHOD OF PREPARING FURFURAL USING lNORGANIC ACID MODIFED SILICA BEAD | |
| CN102276558A (en) | Preparation method of 2-(4-chlorophenethyl)-2-tert-butyl oxirane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141224 |