CN104356391A - Synthesis method of vinyl phenyl silicone oil having high content of vinyl - Google Patents
Synthesis method of vinyl phenyl silicone oil having high content of vinyl Download PDFInfo
- Publication number
- CN104356391A CN104356391A CN201410654241.8A CN201410654241A CN104356391A CN 104356391 A CN104356391 A CN 104356391A CN 201410654241 A CN201410654241 A CN 201410654241A CN 104356391 A CN104356391 A CN 104356391A
- Authority
- CN
- China
- Prior art keywords
- temperature
- vinyl
- synthetic method
- mole
- silicone oil
- 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.)
- Granted
Links
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention provides a synthesis method of vinyl phenyl silicone oil having high content of vinyl. The synthesis method comprises the following steps: (1) adding diphenyl dihydroxy silane into a liquid of sodium ethoxide and ethanol to obtain a mixture; (2) dropwise adding methyl vinyl dichlorosilane into the mixture, after the dropwise addition is completed, and maintaining the reaction for 0.5-3 hours; (3) adding toluene and water, maintaining for 0.5-1 hour, washing an organic layer with water to be neutral; (4) adding octamethylcyclotetrasiloxane or a DMC capping agent and carrying out balanced reaction for 3-5 hours in the presence of a basic catalyst; and (5) finally breaking enzyme by virtue of heating, decolorizing, filtering and removing low-boiling-point substances under a negative pressure to obtain the target product. According to the method provided by the invention, the byproduct sodium ethoxide, which is produced from the preparation of methyl phenylalkoxysilane by virtue of a sodium condensation method in the organosilicone industry, is fully utilized, the tedious process for posttreatment of sodium ethoxide is avoided, the byproduct is less and non-toxic, the raw material is easily available and low in cost; and the reaction conditions are mild and the operation is simple and feasible.
Description
Technical field
The present invention relates to field of organic polymer compound, be specifically related to the synthetic method of the compound containing silicon in a kind of high polymer main chain.
Background technology
As everyone knows, liquid silastic is the elastomerics that current each field generally uses, and the performance of its multiple excellence is less than other any elastomericss, and as excellent high and low temperature resistance, it can use in-60 DEG C ~ 315 DEG C temperature ranges; Excellent weather-resistant performance, through test determination, it can use 10 ~ 20 years in outdoor; Also have the premium propertiess such as such as electrical insulating property, hydrophobicity, anti-stickiness, biochemical consistency.And generally without large-sized processing equipment when using, after can extruding according to kind and purposes, inject, applying, in an atmosphere or the lower sulfuration of heating be elastomerics.
Add-on type liquid silicon rubber is a most important class in liquid silastic kind.It is by containing polymkeric substance based on the organopolysiloxane of vinyl, and linking agent made by the organopolysiloxane of silicon-hydrogen bond containing, under platinum catalyst exists, and a class organosilicon material of crosslinkable sulfuration under room temperature or heating.
Add-on type liquid silicon rubber do not produce in cross-linking vulcanized process by product, shrinking percentage minimum, can deep cure, corrosion-free to the material of contact, be the pouring material of electronic enterprises first-selection, as the packaged material of LED.Physical and mechanical properties after add-on type liquid silicon rubber sulfuration and electrical property can meet or exceed the level of melting silicone rubber, and due to can injection molding and compression molding, have easy to process, production efficiency is high, cost is low, the advantage such as energy-conservation, so some traditional melting silicone rubber goods replace by liquid silastic.
Vinyl silicone oil is that add-on type liquid silicon rubber must one of indispensable base polymer.The most generally use the end-vinyl polydimethylsiloxane of the various polymerization degree and vinyl-terminated silicone fluid and end-vinyl Polymethyl methacrylate and high-vinyl silicone oil.Because side switch in the middle of the latter's molecular chain contains vinyl, in sulfidation, form the structure with more high-crosslinking-degree, make the silicon rubber after sulfuration have higher hardness, higher tensile strength, application prospect is more wide.Meanwhile, if replaced by methyl phenyl a part of in base polymer molecule, can specific refractory power be improved, improve radiation hardness, resistance to low temperature.So side switch contains the phenyl silicone oil of vinyl, namely the synthesis of high-vinyl phenyl silicone oil is the key link of high-quality liquid silastic research and development.
Current finding patent mostly is synthesis end-vinyl phenyl silicone oil, and the technology of synthesizing high-vinyl phenyl silicone oil is then little, and method is comparatively single, namely uses vinylcyclosiloxanes polyreaction to introduce the vinyl of side switch.Rarely seen Patents (CN102432883A) is: after being hydrolyzed by phenyl alkoxysilane; again with vinylcyclosiloxanes, methyl cyclosiloxane and end-capping reagent; balance is produced under nitrogen protection; this method raw material type is many; cost is high; byproduct of reaction is more, and ring body low conversion rate, product yield is low.
Summary of the invention
For the weak point of this area, the object of the invention is the synthetic method proposing a kind of high-vinyl-content vinyl phenyl silicone oil.The object of the present invention is to provide the synthetic method of high-vinyl phenyl silicone oil of a kind of novelty, environmental protection.Present method makes full use of a kind of harmful side product in silicone industry, and cost is low, simple for process, the few and reusable edible of byproduct of reaction.
For realizing the object of the invention, the synthetic method of high-vinyl phenyl silicone oil of the present invention, for raw material with Diphenylsilanediol and methylvinyldichlorosilane, under the effect of sodium ethylate, condensation removes hydrogenchloride, then balanced reaction under basic catalyst condition, finally by decolouring, filtering and remove, low-boiling-point substance obtains.
Another object of the present invention is the vinyl phenyl silicone oil that the described synthetic method of proposition obtains.
The technical scheme realizing above-mentioned purpose of the present invention is:
A synthetic method for high-vinyl-content vinyl phenyl silicone oil, comprises step:
(1) in the solution that the sodium ethylate Diphenylsilanediol of w mole being joined 0.2 ~ 4.5 times w mole mixes with 2 ~ 15 times of w moles ethanol;
(2) under 5 ~ 15 DEG C of temperature, agitation condition, in the mixture of step (1) gained, drip the methylvinyldichlorosilane of 0.1 ~ 2.3 times w mole, dropwise and maintain reaction 0.5 ~ 3 hour;
(3) raised temperature is to remove the ethanol in reaction system, then system is cooled, at ambient temperature, adds the toluene of 1 ~ 5 times w mole and the water of 0.5 ~ 2 times w mole, maintains 0.5 ~ 1 hour after washing organic layer to neutral;
(4) raised temperature is to remove the toluene solvant in system, then system is cooled, at ambient temperature, add D4 (octamethylcyclotetrasiloxane) or DMC (the dimethyl siloxane mixed methylcyclosiloxane of 0.6 ~ 2.5 times w mole, D3 ~ D5) and the end-capping reagent of 0.01 ~ 0.5 times w mole, balanced reaction 3 ~ 5 hours under basic catalyst existent condition;
(5) finally by the broken enzyme of intensification, decolouring, filtration, under condition of negative pressure, remove low-boiling-point substance, obtain object product.
The reaction formula of the synthetic method that the present invention proposes is as follows:
Wherein, a, b, c, m, n, x are positive number.
Further, the raised temperature described in step (3) is for being warming up to 80 ~ 85 DEG C;
Wherein, the sodium ethylate that step (1) uses can prepare the coproduct ethanol sodium of methylphenyl alkoxysilane for prepared by sodium condensation method, can directly use the alcohol sodium alcohol solution produced in production.
Preferably, in step (2) drip methylvinyldichlorosilane amount be 0.35 ~ 0.7 times of w mole.
Wherein, the raised temperature described in step (4) is for being warming up to 100 ~ 120 DEG C;
Wherein, the end-capping reagent described in step (4) is divinyl tetramethyl disiloxane or end-vinyl dimethyl silicone oil.
Wherein, the basic catalyst described in step (4) is Tetramethylammonium hydroxide or hydroxide ethyl ammonium;
Wherein, the temperature of the balanced reaction described in step (4) is 105 ~ 120 DEG C;
Wherein, the broken enzyme temperature described in step (5) is 140 ~ 150 DEG C;
Wherein, temperature when removing low-boiling-point substance in step (5) is 170 ~ 190 DEG C, and described negative pressure refers to that the gauge pressure of equipment is-0.08 ~-0.09MPa.Described decolouring uses gac or diatomite to decolour.
Vinyl phenyl silicone oil synthesized by synthetic method of the present invention.
Beneficial effect of the present invention is:
The method that the present invention proposes, take full advantage of in organosilicon industry, prepared by sodium condensation method prepares the coproduct ethanol sodium of methylphenyl alkoxysilane, avoids the loaded down with trivial details technique of sodium ethylate aftertreatment, solves wherein waste of raw materials, cause the problem of environmental pollution; By product is few and nontoxic, only has ethanol and sodium-chlor, and ethanol easily reclaims and recycles, and sodium-chlor can as other industrial raw materials; Starting material are easy to get, and cost is low; Reaction conditions is gentle, and operation is simple; Reaction not only produces without the three wastes, does not produce hazardous and noxious substances, and solves the harmful side product of other production process, be beneficial to environment protection, have very large society, economy, environmental benefit.
Adopt the high-vinyl phenyl silicone oil of the present invention's synthesis; viscosity is 1000 ~ 6000mPa.s; specific refractory power is 1.44 ~ 1.53; contents of ethylene is 0.8 ~ 6.5%; both there is high transparent; high refractive index, radiation hardness, high-low temperature resistant; the premium propertiess such as weather-resistant; the physical and mechanical properties after liquid silastic sulfuration can be increased substantially again, the high-quality liquid silastic of preparation various uses can be widely used in, as perfusion material; semi-conductor chip coating; fiber optic protection layer, injection molding silicon rubber, LED joint sealant etc.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
If do not specialize, reagent used in embodiment is conventional commercial reagent, the conventional means that technique means used in embodiment is well known to those skilled in the art.
Embodiment 1
280g Diphenylsilanediol is added in the 2000ml there-necked flask containing 66g sodium ethylate and 440g alcohol mixed solution, temperature is controlled at 10 DEG C, under agitation condition, slow dropping 68g methylvinyldichlorosilane, after dropwising, holding temperature and stirring, react 3 hours.Heat up, at 85 DEG C of temperature, remove ethanol, system is cooled to room temperature, add 150g toluene and 20g water, stir 30min, repeatedly wash organic layer to neutral.At 120 DEG C of temperature, remove toluene solvant, system is cooled to room temperature, add 270g D4,3.5g divinyl tetramethyl disiloxane and 0.2g Tetramethylammonium hydroxide, under stirring and 110 DEG C of temperature condition, react 4 hours.React complete, be warming up to 140 DEG C of broken enzymes, after adding activated carbon decolorizing, filtration, under gauge pressure-0.09MPa, 180 DEG C of conditions, remove low-boiling-point substance, obtain water white high-vinyl phenyl silicone oil, productive rate is 92%.
After testing, the refractive index of gained object product is 1.473, and viscosity is 2280mPa.s, and contents of ethylene is 5.11%.
Embodiment 2
280g Diphenylsilanediol is added in the 2000ml there-necked flask containing 76g sodium ethylate and 450g alcohol mixed solution, control at 7 DEG C, under agitation condition in temperature, slow dropping 78g methylvinyldichlorosilane, after dropwising, holding temperature and stirring, react 2.5 hours.Heat up, at 82 DEG C of temperature, remove ethanol, system is cooled to room temperature, add 150g toluene and 15g water, stir 30min, repeatedly wash organic layer to neutral.At 110 DEG C of temperature, remove toluene solvant, system is cooled to room temperature, add 300g D4,1.8g divinyl tetramethyl disiloxane and 0.2g Tetramethylammonium hydroxide, under stirring and 110 DEG C of temperature condition, react 3 hours.React complete, be warming up to 140 DEG C of broken enzymes, after adding activated carbon decolorizing, filtration, under-0.09MPa, 190 DEG C of conditions, remove low-boiling-point substance, obtain water white high-vinyl phenyl silicone oil, productive rate is 85%.
After testing, the refractive index of gained object product is 1.465, and viscosity is 5300mPa.s, and contents of ethylene is 2.86%.
Embodiment 3
330g Diphenylsilanediol is added in the 2000ml there-necked flask containing 66g sodium ethylate and 440g alcohol mixed solution, control at 12 DEG C, under agitation condition in temperature, slow dropping 68g methylvinyldichlorosilane, after dropwising, holding temperature and stirring, react 3 hours.Heat up, at 85 DEG C of temperature, remove ethanol, system is cooled to room temperature, add 150g toluene and 20g water, stir 30min, repeatedly wash organic layer to neutral.At 120 DEG C of temperature, remove toluene solvant, system is cooled to room temperature, add 270g D4,3.5g divinyl tetramethyl disiloxane and 0.2g Tetramethylammonium hydroxide, under stirring and 110 DEG C of temperature condition, react 4 hours.React complete, be warming up to 140 DEG C of broken enzymes, after adding activated carbon decolorizing, filtration, under-0.09MPa, 180 DEG C of conditions, remove low-boiling-point substance, obtain water white high-vinyl phenyl silicone oil, productive rate is 87%.
After testing, the refractive index of gained object product is 1.495, and viscosity is 3050mPa.s, and contents of ethylene is 4.20%.
Embodiment 4
280g Diphenylsilanediol is added in the 2000ml there-necked flask containing 100g sodium ethylate and 500g alcohol mixed solution, control at 10 DEG C, under agitation condition in temperature, slow dropping 98g methylvinyldichlorosilane, after dropwising, holding temperature and stirring, react 3 hours.Heat up, at 85 DEG C of temperature, remove ethanol, system is cooled to room temperature, add 150g toluene and 25g water, stir 30min, repeatedly wash organic layer to neutral.At 120 DEG C of temperature, remove toluene solvant, system is cooled to room temperature, add 270g DMC, 3.5g divinyl tetramethyl disiloxane and 0.2g Tetramethylammonium hydroxide, under stirring and 110 DEG C of temperature condition, react 4 hours.React complete, be warming up to 140 DEG C of broken enzymes, after adding activated carbon decolorizing, filtration, under-0.09MPa, 180 DEG C of conditions, remove low-boiling-point substance, obtain water white high-vinyl phenyl silicone oil, productive rate is 94%.
After testing, the refractive index of gained object product is 1.468, and viscosity is 2700mPa.s, and contents of ethylene is 5.52%.
Embodiment 5
420g Diphenylsilanediol is added in the 2000ml there-necked flask containing 112g sodium ethylate and 500g alcohol mixed solution, control at 10 DEG C, under agitation condition in temperature, slow dropping 105g methylvinyldichlorosilane, after dropwising, holding temperature and stirring, react 3 hours.Heat up, at 85 DEG C of temperature, remove ethanol, system is cooled to room temperature, add 150g toluene and 30g water, stir 30min, repeatedly wash organic layer to neutral.At 120 DEG C of temperature, remove toluene solvant, system is cooled to room temperature, add 250g DMC, 3.5g divinyl tetramethyl disiloxane and 0.2g Tetramethylammonium hydroxide, under stirring and 110 DEG C of temperature condition, react 4 hours.React complete, be warming up to 140 DEG C of broken enzymes, after adding activated carbon decolorizing, filtration, under-0.09MPa, 180 DEG C of conditions, remove low-boiling-point substance, obtain water white high-vinyl phenyl silicone oil, productive rate is 85%.
After testing, the refractive index of gained object product is 1.530, and viscosity is 4380mPa.s, and contents of ethylene is 5.01%.
Embodiment 6
200g Diphenylsilanediol is added in the 2000ml there-necked flask containing 86g sodium ethylate and 440g alcohol mixed solution, control at 10 DEG C, under agitation condition in temperature, slow dropping 68g methylvinyldichlorosilane, after dropwising, holding temperature and stirring, react 3 hours.Heat up, at 85 DEG C of temperature, remove ethanol, system is cooled to room temperature, add 150g toluene and 20g water, stir 30min, repeatedly wash organic layer to neutral.At 120 DEG C of temperature, remove toluene solvant, system is cooled to room temperature, add 500g D4,5.2g divinyl tetramethyl disiloxane and 0.2g Tetramethylammonium hydroxide, under stirring and 110 DEG C of temperature condition, react 4 hours.React complete, be warming up to 140 DEG C of broken enzymes, after adding activated carbon decolorizing, filtration, under-0.09MPa, 180 DEG C of conditions, remove low-boiling-point substance, obtain water white high-vinyl phenyl silicone oil, productive rate is 95%.
After testing, the refractive index of gained object product is 1.460, and viscosity is 2580mPa.s, and contents of ethylene is 3.31%.
Embodiment 7
150g Diphenylsilanediol is added in the 2000ml there-necked flask containing 46g sodium ethylate and 440g alcohol mixed solution, control at 10 DEG C, under agitation condition in temperature, slow dropping 33g methylvinyldichlorosilane, after dropwising, holding temperature and stirring, react 3 hours.Heat up, at 85 DEG C of temperature, remove ethanol, system is cooled to room temperature, add 150g toluene and 10g water, stir 30min, repeatedly wash organic layer to neutral.At 120 DEG C of temperature, remove toluene solvant, system is cooled to room temperature, add 450g DMC, 3.5g divinyl tetramethyl disiloxane and 0.2g Tetramethylammonium hydroxide, under stirring and 110 DEG C of temperature condition, react 4 hours.React complete, be warming up to 140 DEG C of broken enzymes, after adding activated carbon decolorizing, filtration, under-0.09MPa, 180 DEG C of conditions, remove low-boiling-point substance, obtain water white high-vinyl phenyl silicone oil, productive rate is 95%.
After testing, the refractive index of gained object product is 1.445, and viscosity is 1280mPa.s, and contents of ethylene is 2.11%
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (9)
1. a synthetic method for high-vinyl-content vinyl phenyl silicone oil, is characterized in that, comprises step:
(1) in the solution that the sodium ethylate Diphenylsilanediol of w mole being joined 0.2 ~ 4.5 times w mole mixes with 2 ~ 15 times of w moles ethanol;
(2) under 5 ~ 15 DEG C of temperature, agitation condition, in the mixture of step (1) gained, drip the methylvinyldichlorosilane of 0.1 ~ 2.3 times w mole, dropwise and maintain reaction 0.5 ~ 3 hour;
(3) raised temperature is to remove the ethanol in reaction system, then system is cooled, at ambient temperature, adds the toluene of 1 ~ 5 times w mole and the water of 0.5 ~ 2 times w mole, maintains 0.5 ~ 1 hour after washing organic layer to neutral;
(4) raised temperature is to remove the toluene solvant in system, then system is cooled, at ambient temperature, the octamethylcyclotetrasiloxane of 0.6 ~ 2.5 times w mole or the end-capping reagent of DMC and 0.01 ~ 0.5 times w mole is added, balanced reaction 3 ~ 5 hours under basic catalyst existent condition;
(5) finally by the broken enzyme of intensification, decolouring, filtration, under condition of negative pressure, remove low-boiling-point substance, obtain object product.
2. synthetic method according to claim 1, is characterized in that, the raised temperature described in step (3) is for being warming up to 80 ~ 85 DEG C.
3. synthetic method according to claim 1, is characterized in that, the raised temperature described in step (4) is for being warming up to 100 ~ 120 DEG C.
4. synthetic method according to claim 1, is characterized in that, the end-capping reagent described in step (4) is divinyl tetramethyl disiloxane or end-vinyl dimethyl silicone oil.
5. synthetic method according to claim 1, is characterized in that, the basic catalyst described in step (4) is Tetramethylammonium hydroxide or hydroxide ethyl ammonium.
6. synthetic method according to claim 1, is characterized in that, the temperature of the balanced reaction described in step (4) is 105 ~ 120 DEG C.
7. synthetic method according to claim 1, is characterized in that, the broken enzyme temperature described in step (5) is 140 ~ 150 DEG C.
8. synthetic method according to claim 1, is characterized in that, temperature when removing low-boiling-point substance in step (5) is 170 ~ 190 DEG C, and described negative pressure refers to that the gauge pressure of equipment is-0.08 ~-0.09MPa.
9. the arbitrary described vinyl phenyl silicone oil synthesized by synthetic method of claim 1 ~ 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410654241.8A CN104356391B (en) | 2014-11-17 | 2014-11-17 | The synthetic method of high-vinyl-content vinyl phenyl silicone oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410654241.8A CN104356391B (en) | 2014-11-17 | 2014-11-17 | The synthetic method of high-vinyl-content vinyl phenyl silicone oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104356391A true CN104356391A (en) | 2015-02-18 |
| CN104356391B CN104356391B (en) | 2017-03-08 |
Family
ID=52523714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410654241.8A Active CN104356391B (en) | 2014-11-17 | 2014-11-17 | The synthetic method of high-vinyl-content vinyl phenyl silicone oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104356391B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480411A (en) * | 2020-11-03 | 2021-03-12 | 湖北双键精细化工有限公司 | High-yield low-cost phenyl silicone oil synthesis process |
| 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 |
| CN115028839A (en) * | 2022-07-11 | 2022-09-09 | 桂林宝龙达新材料有限公司 | Preparation method of methyl phenoxy silicone oil |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0962480A2 (en) * | 1998-06-03 | 1999-12-08 | Dow Corning Corporation | Sheet and tube siloxane polymers containing multiple pendent groups |
| JP2009173760A (en) * | 2008-01-23 | 2009-08-06 | Kaneka Corp | Liquid polysiloxane-based compound having polyhedron structure, composition using the compound and its cured product |
| CN101979427A (en) * | 2010-11-10 | 2011-02-23 | 扬州晨化科技集团有限公司 | Preparation method of methyl phenyl vinyl silicon resin for packaging light-emitting diode (LED) |
| CN102432883A (en) * | 2011-09-09 | 2012-05-02 | 汕头市骏码凯撒有限公司 | Preparation method of phenyl-vinyl silicon oil |
| CN104086999A (en) * | 2014-06-22 | 2014-10-08 | 烟台恒迪克能源科技有限公司 | High-refractive-index LED packaging organosilicone resin and preparation method thereof |
-
2014
- 2014-11-17 CN CN201410654241.8A patent/CN104356391B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0962480A2 (en) * | 1998-06-03 | 1999-12-08 | Dow Corning Corporation | Sheet and tube siloxane polymers containing multiple pendent groups |
| JP2009173760A (en) * | 2008-01-23 | 2009-08-06 | Kaneka Corp | Liquid polysiloxane-based compound having polyhedron structure, composition using the compound and its cured product |
| CN101979427A (en) * | 2010-11-10 | 2011-02-23 | 扬州晨化科技集团有限公司 | Preparation method of methyl phenyl vinyl silicon resin for packaging light-emitting diode (LED) |
| CN102432883A (en) * | 2011-09-09 | 2012-05-02 | 汕头市骏码凯撒有限公司 | Preparation method of phenyl-vinyl silicon oil |
| CN104086999A (en) * | 2014-06-22 | 2014-10-08 | 烟台恒迪克能源科技有限公司 | High-refractive-index LED packaging organosilicone resin and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480411A (en) * | 2020-11-03 | 2021-03-12 | 湖北双键精细化工有限公司 | High-yield low-cost phenyl silicone oil synthesis process |
| 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 |
| CN115028839A (en) * | 2022-07-11 | 2022-09-09 | 桂林宝龙达新材料有限公司 | Preparation method of methyl phenoxy silicone oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104356391B (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101003686B (en) | Curable silicone rubber composition and cured product thereof | |
| CN103012797B (en) | Preparation method of methyl phenyl vinyl silicone oil | |
| CN102965069B (en) | A kind of resistance to sulfuration LED silica gel | |
| CN102898650B (en) | MTQ silicon resin with T-chain unit containing phenyl and preparation method thereof | |
| CN105315675A (en) | Ultraviolet light-curing composition | |
| CN104892942A (en) | Tackifier for addition-type organic silicon rubber and preparation method thereof | |
| CN110305486A (en) | A kind of silicon gel and preparation method thereof | |
| CN104388039B (en) | Dealcoholized type room temperature vulcanized organosilicon sealant of single component high transparency and preparation method thereof | |
| CN103242532B (en) | Preparation method of environment-friendly solventless liquid silicone resin | |
| CN106008983A (en) | Silicon-boron tackifier and preparation method and application thereof | |
| CN105802532A (en) | Silicon boron tackifier, preparation method thereof and application thereof in double-component LED packaging gel | |
| CN104232015B (en) | The list packaging organic silicon rubber packaging plastic of a kind of high-power type white light LEDs and preparation method | |
| CN104073215A (en) | Preparation method for nano silicon dioxide modified organic silicon sealant for packaging of light emitting diode (LED) | |
| CN105860083A (en) | Methods for preparing modified vinyl silicone resin and organosilicone sealing compound containing modified vinyl silicone resin | |
| CN106433551A (en) | Thermal shock resistant high-refraction LED packaging glue composition and preparation method thereof | |
| CN102433005B (en) | Liquid phenyl silica gel for LED and preparation method thereof | |
| KR20140024244A (en) | Hydrosilicone resin and preparation process thereof | |
| CN106751893A (en) | A kind of refractive power LED encapsulation add-on type liquid silicon rubbers high and preparation method thereof | |
| CN104140533A (en) | Vinyl-containing phenyl hydro silicone resin and preparation method thereof | |
| CN104356391A (en) | Synthesis method of vinyl phenyl silicone oil having high content of vinyl | |
| CN102234429A (en) | Composition for silicone resin | |
| CN104449551B (en) | A kind of high folding LED of resistance to xanthochromia packaging silicon rubber | |
| CN104087000A (en) | Organosilicon material for LED (Light-Emitting Diode) package and preparation method thereof | |
| TW202012510A (en) | Manufacturing method for cured silicone product, cured silicone product, and optical member | |
| CN105419336A (en) | High-elongation dealcoholization type room-temperature vulcanized silicone rubber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |