CN103524741B - A kind of Synthetic method of methyl vinyl MQ silicon resin - Google Patents
A kind of Synthetic method of methyl vinyl MQ silicon resin Download PDFInfo
- Publication number
- CN103524741B CN103524741B CN201310430580.3A CN201310430580A CN103524741B CN 103524741 B CN103524741 B CN 103524741B CN 201310430580 A CN201310430580 A CN 201310430580A CN 103524741 B CN103524741 B CN 103524741B
- Authority
- CN
- China
- Prior art keywords
- methyl vinyl
- silicon resin
- synthetic method
- weight part
- resin according
- 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.)
- Expired - Fee Related
Links
Landscapes
- Silicon Polymers (AREA)
Abstract
The present invention relates to a kind of Synthetic method of methyl vinyl MQ silicon resin, methyl vinyl MQ silicon resin prepared by the inventive method is white solid powder, with LED material medium vinyl silicone oil mixed clear mutually, not containing Si-OH and Si-OR(R is Me, Et etc.), can mix not muddy with each component of LED material.Contents of ethylene is 3wt%-5wt%, M/Q=0.6-0.9, is suitable as very much LED encapsulation material strengthening agent, can meet the requirement of LED encapsulation material high transmission rate, high tensile, high rigidity.
Description
Technical field
The present invention relates to a kind of Synthetic method of methyl vinyl MQ silicon resin.
Background technology
Along with the demand that global low-carbon economy develops, LED is with technical superioritys such as its energy-saving and environmental protection, longevity, controllabilitys, become one of global new high-tech industry most with prospects in recent years, representing LED as the light source in a new generation's illumination and display device will replace conventional light source on a large scale in the coming years.And the preparation solving power type LED encapsulation technology and packaged material is one of LED industry gordian technique, therefore produces high transmission rate, the LED material of high strength is more and more subject to people's attention.
Organosilicon LED glue has excellent resistance toheat, ultra-violet resistance energy, radiation resistance, does refractive index, high transparent and good mechanical property etc., is suitable for very much the encapsulation of LED especially great power LED.At present, many characteristics of organosilicon LED encapsulation material make it have higher requirement to the reinforced filling of self.And day by day manifest as the critical role of the reinforced filling-methyl vinyl MQ silicon resin of high-power LED encapsulation material liquid silastic.The main method of current production methyl vinyl MQ silicon resin is water glass method and silicic acid ester process, two kinds of methods respectively have relative merits, the more difficult control of molecular weight of the general character generally occurred the mainly methyl vinyl MQ silicon resin of gained, containing a large amount of unreacted Si-OH and Si-OR(R in molecule is Me, Et etc.) group, do not dissolve each other with each component of LED material, muddiness, contents of ethylene is low.The resin produced with this carries out that the organosilicon encapsulating compound printing opacity rate variance of reinforcement, intensity are low, the shelf lives exists great problem.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of Synthetic method of methyl vinyl MQ silicon resin, refers to the Synthetic method of methyl vinyl MQ silicon resin not containing the M/Q=0.6-0.9 of silicone hydroxyl and alkoxyl group for LED reinforcement especially.
Wherein the modular construction of MQ is as follows:
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of Synthetic method of methyl vinyl MQ silicon resin, comprising:
The silicon ester of 100 weight parts is added in flask, the dimethylbenzene of 20-40 weight part, the hexamethyldisiloxane of 10-20 weight part, the tetramethyl divinyl disiloxane of 5-10 weight part, the dehydrated alcohol of 5-10 weight part, the catalyzer of 2.8-3.5 weight part also opens stirring, 30-40 weight parts water is dripped in ice-water bath, 35-40 DEG C is risen to after dripping off, stirring reaction 20-40min, then 75-80 DEG C is warming up to, return stirring reaction 4-6h, stop stirring, add the alkali of 2.8-4.3 weight part, open to stir and be warming up to 120-130 DEG C of steaming and dewater and ethanol, after having steamed, stirring and refluxing reacts 4-6h at this temperature, add the treatment agent of 0.3-0.6 weight part subsequently, 1-3h is reacted at 125 DEG C, close heated and stirred system, liquid rotating in bottle is moved in separating funnel, with distilled water wash until PH=7, filtration obtains water white filtrate, revolve and steam dimethylbenzene, obtain white powder solid,
On the basis of technique scheme, the present invention can also do following improvement.
Further, described catalyzer is the one in concentrated hydrochloric acid (wt%=36%), the vitriol oil (wt%=98%), trifluoromethanesulfonic acid (wt%=99%), tosic acid, perfluorinated sulfonic resin; Be preferably concentrated hydrochloric acid (wt%=36%);
Further, described alkali is the one in calcium carbonate, sodium carbonate, sodium bicarbonate, salt of wormwood; Be preferably sodium bicarbonate;
Further, described silicon ester is methyl silicate, tetraethyl silicate, silicic acid propyl ester or their polycondensate;
Further, described treatment agent is the mixture of one or more in hexamethyldisiloxane, hexamethyldisilazane, tetramethyl-divinyl sily oxide;
The invention has the beneficial effects as follows:
1, the methyl vinyl MQ silicon resin that prepared by method of the present invention is white solid powder, and with LED material medium vinyl silicone oil mixed clear mutually, not containing Si-OH and Si-OR(R is Me, Et etc.), can mix not muddy with each component of LED material.
2, according to the present invention, the product that contents of ethylene is 3wt%-5wt%, M/Q=0.6-0.9 can be synthesized, be suitable as very much LED encapsulation material strengthening agent, the requirement of LED encapsulation material high transmission rate, high tensile, high rigidity can be met.
Accompanying drawing explanation
Fig. 1 is the methyl vinyl MQ silicon resin of the embodiment of the present invention 1 preparation
1h NMR schemes;
Embodiment
Be described principle of the present invention and feature below, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
41.75g tetraethoxy is added in the there-necked flask being furnished with agitator, thermometer, prolong, 8.00g dimethylbenzene, 10.48g hexamethyldisiloxane, 3.5g tetramethyl divinyl disiloxane, 2.51g dehydrated alcohol, 1.42g concentrated hydrochloric acid (wt%=36%), and 15.15g water is dripped with the speed of 1d/s in ice-water bath, drip off rear stirring 5min, be warming up to 35 DEG C, initial reaction 25min.System temperature is risen to 78 DEG C, back flow reaction 4h.Stop stirring, add 1.45g NaHCO
3, open and stir and be warming up to 125 DEG C and steam water and ethanol, back flow reaction 4h at this temperature after having steamed, add 0.2g hexamethyldisilazane subsequently, stirring reaction 1h at 125 DEG C, close heated and stirred system, liquid rotating in bottle is moved in separating funnel, with distilled water wash until PH=7.Filtration obtains water white filtrate, filtrate is shifted filtrate in pear-shaped flask, and decompression steams the low-boiling-point substances such as dimethylbenzene, obtains 22.85g white powdery solids, yield more than 90%.By white powdery solids and vinyl silicone oil mixed nothing muddiness mutually.White powder is dissolved in deuterochloroform and carries out
1h NMR measures, and recording contents of ethylene is 3.7%(massfraction), M/Q=0.84; Detect without Si-OH and Si-OEt peak.
1h NMR test result as shown in Figure 1.In Fig. 1
1each peak position in H NMR:
Si-CH=CH
2： δ5.4～6.4
Si-CH
3： δ0～0.3
Si-OH: δ4.8～7.1
Si-OEt： δ0.9～1.3，3.7～4.2，
Can without Si-OH and Si-OEt peak from figure, vinyl measured value content is 3.7%(massfraction).
Embodiment 2
41.75g tetraethoxy is added in the there-necked flask being furnished with agitator, thermometer, prolong, 8.10g dimethylbenzene, 9.07g hexamethyldisiloxane, 3.09g tetramethyl divinyl disiloxane, 2.65g dehydrated alcohol, 1.40g concentrated hydrochloric acid (wt%=36%).And 15.20g water is dripped with the speed of 1d/s in ice-water bath, drip off rear stirring 5min.Be warming up to 35 DEG C of initial reaction 25min.System temperature is risen to 78 DEG C of reaction 4h.Stopped reaction, adds 1.43gNaHCO
3, and be warming up to 125 DEG C and steam water and ethanol.Back flow reaction 4h at this temperature after having steamed, adds 0.3g hexamethyldisiloxane subsequently and reacts 1h at this temperature, and washing is until PH=7.Filtration obtains water white filtrate, filtrate is shifted filtrate in pear-shaped flask, and decompression steams the low-boiling-point substances such as dimethylbenzene, obtains 19.56g white powdery solids, yield more than 90%.By white powdery solids and vinyl silicone oil mixed nothing muddiness mutually.White powder is dissolved in deuterochloroform and carries out
1h NMR measures, and recording contents of ethylene is 3.3%(massfraction), M/Q=0.75; Detect without Si-OH and Si-OEt peak.
Embodiment 3
39.45g tetraethoxy is added in the there-necked flask being furnished with agitator, thermometer, prolong, 8.25g dimethylbenzene, 10.36g hexamethyldisiloxane, 3.53g tetramethyl divinyl disiloxane, 2.40g dehydrated alcohol, 1.43g concentrated hydrochloric acid (wt%=36%).And 14.32g water is dripped with the speed of 1d/s in ice-water bath, drip off rear stirring 5min.Be warming up to 35 DEG C of initial reaction 25min.System temperature is risen to 78 DEG C of reaction 4.5h.Stopped reaction, adds 1.40gNaHCO
3and be warming up to 125 DEG C and steam water and ethanol.After having steamed, return stirring reacts 4h at this temperature, adds 0.2g hexamethyldisiloxane subsequently and reacts 1h at this temperature, and washing is until PH=7.Filtration obtains water white filtrate, filtrate is shifted filtrate in pear-shaped flask, and decompression steams the low-boiling-point substances such as dimethylbenzene, obtains 22.10g white powdery solids, yield more than 90%.By white powdery solids and vinyl silicone oil mixed nothing muddiness mutually.White powder is dissolved in deuterochloroform and carries out
1h NMR measures, and recording contents of ethylene is 3.4%(massfraction), M/Q=0.9; Detect without Si-OH and Si-OEt peak.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. a Synthetic method of methyl vinyl MQ silicon resin, is characterized in that, comprising:
The silicon ester of 100 weight parts is added in flask, the dimethylbenzene of 20-40 weight part, the hexamethyldisiloxane of 10-20 weight part, the tetramethyl divinyl disiloxane of 5-10 weight part, the dehydrated alcohol of 5-10 weight part, the catalyzer of 2.8-3.5 weight part also opens stirring, 30-40 weight parts water is dripped in ice-water bath, 35-40 DEG C is risen to after dripping off, stirring reaction 20-40mi n, then 75-80 DEG C is warming up to, return stirring reaction 4-6h, stop stirring, add the alkali of 2.8-4.3 weight part, open to stir and be warming up to 120-130 DEG C of steaming and dewater and ethanol, after having steamed, stirring and refluxing reacts 4-6h at this temperature, add the treatment agent of 0.3-0.6 weight part subsequently, 1-3h is reacted at 125 DEG C, close heated and stirred system, liquid rotating in bottle is moved in separating funnel, with distilled water wash until pH=7, filtration obtains water white filtrate, revolve and steam dimethylbenzene, obtain white powder solid,
Described treatment agent is the mixture of one or more in hexamethyldisiloxane, hexamethyldisilazane, tetramethyl-divinyl sily oxide.
2. a kind of Synthetic method of methyl vinyl MQ silicon resin according to claim 1, is characterized in that, described catalyzer is the one in 36% concentrated hydrochloric acid, 98% vitriol oil, 99% trifluoromethanesulfonic acid, tosic acid, perfluorinated sulfonic resin.
3. a kind of Synthetic method of methyl vinyl MQ silicon resin according to claim 2, is characterized in that, described catalyzer is 36% concentrated hydrochloric acid.
4. a kind of Synthetic method of methyl vinyl MQ silicon resin according to claim 1, is characterized in that, described alkali is the one in calcium carbonate, sodium carbonate, sodium bicarbonate, salt of wormwood.
5. a kind of Synthetic method of methyl vinyl MQ silicon resin according to claim 4, is characterized in that, described alkali is sodium bicarbonate.
6. a kind of Synthetic method of methyl vinyl MQ silicon resin according to claim 1, is characterized in that, described silicon ester is methyl silicate, tetraethyl silicate, silicic acid propyl ester or their polycondensate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310430580.3A CN103524741B (en) | 2013-09-18 | 2013-09-18 | A kind of Synthetic method of methyl vinyl MQ silicon resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310430580.3A CN103524741B (en) | 2013-09-18 | 2013-09-18 | A kind of Synthetic method of methyl vinyl MQ silicon resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103524741A CN103524741A (en) | 2014-01-22 |
| CN103524741B true CN103524741B (en) | 2015-09-02 |
Family
ID=49927123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310430580.3A Expired - Fee Related CN103524741B (en) | 2013-09-18 | 2013-09-18 | A kind of Synthetic method of methyl vinyl MQ silicon resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103524741B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788657B (en) * | 2014-01-24 | 2016-06-08 | 东南大学 | A kind of preparation method for lsi package polymer |
| CN105585714B (en) * | 2015-12-16 | 2019-04-19 | 东莞兆舜有机硅科技股份有限公司 | A kind of anti-ultraviolet organic siliconresin, preparation method and its usage |
| WO2017110623A1 (en) * | 2015-12-21 | 2017-06-29 | 住友化学株式会社 | Silicone resin composition and sealing material for semiconductor light emitting element |
| CN107674207B (en) * | 2017-09-22 | 2021-09-03 | 山东盛宇新材料有限公司 | Preparation method of phenyl vinyl methyl MQ silicon resin for high-fold LED packaging |
| CN110498925A (en) * | 2019-09-16 | 2019-11-26 | 南昌大学 | A kind of preparation method of reinforcement silicon rubber MQ resin |
| CN114262438A (en) * | 2021-12-30 | 2022-04-01 | 合盛硅业股份有限公司 | Method for preparing powder MQ silicon resin |
| CN116120557A (en) * | 2022-12-29 | 2023-05-16 | 湖北晟特新材料有限公司 | MQ silicon resin without waste emission and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875725A (en) * | 2010-07-14 | 2010-11-03 | 广州市高士实业有限公司 | Vinyl silicon resin for reinforcing organic silicon pouring sealant and preparation method thereof |
-
2013
- 2013-09-18 CN CN201310430580.3A patent/CN103524741B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875725A (en) * | 2010-07-14 | 2010-11-03 | 广州市高士实业有限公司 | Vinyl silicon resin for reinforcing organic silicon pouring sealant and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103524741A (en) | 2014-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103524741B (en) | A kind of Synthetic method of methyl vinyl MQ silicon resin | |
| CN101891893A (en) | Preparation method of phenyl-based hydrogen-based silicone resin for encapsulating LED | |
| CN101899159B (en) | Silicone resin for one-component LED packaging materials and preparation method thereof | |
| CN101343365A (en) | Preparation method for methyl phenyl vinyl polysiloxane for packaging LED | |
| CN102875811A (en) | Preparation method for phenyl vinyl MQ silicone resin | |
| CN103951827B (en) | A kind of phenyl-based hydrogen-based MQ silicones and preparation method thereof | |
| CN104073215A (en) | Preparation method for nano silicon dioxide modified organic silicon sealant for packaging of light emitting diode (LED) | |
| CN103131189A (en) | Inorganic or organic hybridization nanocomposite for packaging light emitting diode (LED) and preparation method thereof | |
| CN105400446A (en) | Tackifier for high-refractive index LED liquid casting glue and preparation method thereof | |
| CN109824903A (en) | A kind of high refractive index boracic organic silicon rigidity-increasing stick and preparation method thereof | |
| CN102504613B (en) | Preparation method of modified fumed silica for LED packaging reinforcement | |
| CN104232015B (en) | The list packaging organic silicon rubber packaging plastic of a kind of high-power type white light LEDs and preparation method | |
| CN104087000B (en) | A kind of LED organosilicon material for packaging and preparation method thereof | |
| CN103834178B (en) | Organic silicon resin as well as preparation method and application thereof | |
| CN104449551B (en) | A kind of high folding LED of resistance to xanthochromia packaging silicon rubber | |
| CN106700993A (en) | Organosilicone modified epoxy resin packaging material and LED packaging adhesive | |
| CN101665572A (en) | Organic silicon resin for encapsulating LED and preparation method thereof | |
| CN103044918A (en) | Organosilicone resin/epoxy resin hybrid materials for packaging light emitting diodes | |
| CN103224837B (en) | Rapid and green preparation method of epoxidation soybean oil | |
| CN102876281B (en) | Preparation method for nano TiO2 modified high-refractive index organic silica gel for chip on board-light emitting diode (COB-LED) pressing strip | |
| CN102617860A (en) | Preparation method for organic silicon resin | |
| CN106281208A (en) | A kind of anti-glue of organosilicon three and preparation method and application | |
| CN104031392A (en) | Addition-type silica gel, and preparation method and application thereof | |
| CN102660121A (en) | High-refractive-index TiO2Semi-gel modified transparent silicone resin and preparation method thereof | |
| CN103232707B (en) | Curable silicone rubber composition and solidifying product thereof and coating and curing method |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190412 Address after: 264006 Kaifeng Road 3-3 Renewable Resource Processing Demonstration Zone, Yantai Development Zone, Shandong Province Patentee after: Yantai Darbond Technology Co., Ltd. Address before: 264006 No. 98 Jinshajiang Road, Yantai Development Zone, Yantai City, Shandong Province Patentee before: Yantai Debang Advanced Silicon Materials Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150902 Termination date: 20190918 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |