CN103524741A - Synthetic method of methyl vinyl MQ silicon resin - Google Patents
Synthetic method of methyl vinyl MQ silicon resin Download PDFInfo
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- CN103524741A CN103524741A CN201310430580.3A CN201310430580A CN103524741A CN 103524741 A CN103524741 A CN 103524741A CN 201310430580 A CN201310430580 A CN 201310430580A CN 103524741 A CN103524741 A CN 103524741A
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Abstract
The invention relates to a synthetic method of methyl vinyl MQ silicon resin. The methyl vinyl MQ silicon resin prepared by the synthetic method disclosed by the invention is white solid powder, and clear and transparent while being mutually mixed with vinyl silicon oil in an LED (Light-Emitting Diode) encapsulating material, does not contain Si-OH and Si-OR (R is Me, Et, and the like), and can be mixed with each component of the LED encapsulating material without turbidity. Vinyl content is 3wt%-5wt%, M/Q is equal to 0.6-0.9, and therefore, the methyl vinyl MQ silicon resin is very suitable for being used as an LED encapsulating reinforcing agent and capable of satisfying requirements of high light transmittance, high tensile strength and high hardness of the LED encapsulating material.
Description
Technical field
The present invention relates to a kind of methyl vinyl MQ silicone resin synthetic method.
Background technology
Demand along with global low-carbon economy development, 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, as the light source in a new generation's illumination and display device, represent that LED will be in the extensive conventional light source that the replaces coming years.And the preparation that solves power type LED encapsulation technology and packaged material is one of LED industrialization gordian technique, therefore produce high transmission rate, high-intensity LED encapsulating compound is more and more subject to people's attention.
Organosilicon LED packaging plastic 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 especially encapsulation of great power LED of LED.At present, many characteristics of organosilicon LED packaged material are had higher requirement its reinforced filling to self.And the critical role of reinforced filling-methyl vinyl MQ silicone resin of using with liquid silastic as high-power LED encapsulation material day by day manifests.The main method of producing at present methyl vinyl MQ silicone resin is water glass method and silicon ester method, two kinds of methods respectively have relative merits, the general character generally occurring is mainly the more difficult control of molecular weight of the methyl vinyl MQ silicone resin of gained, in molecule, containing a large amount of unreacted Si-OH and Si-OR(R is Me, Et etc.) group, do not dissolve each other with each component of LED encapsulating compound, muddiness, contents of ethylene is low etc.Organosilicon encapsulating compound printing opacity rate variance, intensity that the resin of producing with this carries out reinforcement 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 methyl vinyl MQ silicone resin synthetic method, refers to especially the methyl vinyl MQ silicone resin synthetic method for the not siliceous hydroxyl of LED encapsulated strengthening and the M/Q=0.6-0.9 of alkoxyl group.
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 methyl vinyl MQ silicone resin synthetic method, comprising:
To the silicon ester that adds 100 weight parts 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 is also opened and is stirred, in ice-water bath, drip 30-40 weight parts water, after dripping off, rise to 35-40 ℃, stirring reaction 20-40min, then be warming up to 75-80 ℃, return stirring reaction 4-6h, stop stirring, the alkali that adds 2.8-4.3 weight part, unlatching is stirred and is warming up to 120-130 ℃ of steaming and dewaters and ethanol, after having steamed, at this temperature, stirring and refluxing is reacted 4-6h, the treatment agent that adds subsequently 0.3-0.6 weight part, at 125 ℃, react 1-3h, 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 a kind of 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 a kind of 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 one or more the mixture in hexamethyldisiloxane, hexamethyldisilazane, tetramethyl-divinyl sily oxide;
The invention has the beneficial effects as follows:
1, the methyl vinyl MQ silicone resin that prepared by method of the present invention is white solid powder, mixes mutually clear with LED encapsulating compound medium vinyl silicone oil, containing Si-OH and Si-OR(R, is not Me, Et etc.), can mix with each component of LED encapsulating compound not muddy.
2, according to the present invention, can synthesize contents of ethylene is 3wt%-5wt%, and the product of M/Q=0.6-0.9 is suitable as LED packaged material strengthening agent very much, can meet the requirement of LED packaged material high transmission rate, high tensile, high rigidity.
Accompanying drawing explanation
Fig. 1 is the methyl vinyl MQ silicone resin of the embodiment of the present invention 1 preparation
1h NMR figure;
Embodiment
Below principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
In the there-necked flask of being furnished with agitator, thermometer, prolong, add 41.75g tetraethoxy, 8.00g dimethylbenzene, 10.48g hexamethyldisiloxane, 3.5g tetramethyl divinyl disiloxane, 2.51g dehydrated alcohol, 1.42g concentrated hydrochloric acid (wt%=36%), and the speed with 1d/s drips 15.15g water in ice-water bath, drip off rear stirring 5min, be warming up to 35 ℃, initial reaction 25min.System temperature is risen to 78 ℃, back flow reaction 4h.Stop stirring, add 1.45g NaHCO
3, open and to stir and to be warming up to 125 ℃ and steam water and ethanol, after having steamed at this temperature back flow reaction 4h, add subsequently 0.2g hexamethyldisilazane, stirring reaction 1h at 125 ℃, closes heated and stirred system, liquid rotating in bottle is moved in separating funnel, use distilled water wash until PH=7.Filtration obtains water white filtrate, and filtrate is shifted to filtrate to pyriform flask, and decompression steams the low-boiling-point substances such as dimethylbenzene, obtains 22.85g white powder solid, and yield is more than 90%.White powder solid and vinyl silicone oil is mixed without muddy mutually.White powder is dissolved in deuterochloroform and is carried out
1h NMR measures, and recording contents of ethylene is 3.7%(massfraction), M/Q=0.84; Detection is 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 be without Si-OH and Si-OEt peak from figure, vinyl measured value content is 3.7%(massfraction).
Embodiment 2
In the there-necked flask of being furnished with agitator, thermometer, prolong, add 41.75g tetraethoxy, 8.10g dimethylbenzene, 9.07g hexamethyldisiloxane, 3.09g tetramethyl divinyl disiloxane, 2.65g dehydrated alcohol, 1.40g concentrated hydrochloric acid (wt%=36%).And in ice-water bath, the speed with 1d/s drips 15.20g water, drips off rear stirring 5min.Be warming up to 35 ℃ of initial reaction 25min.System temperature is risen to 78 ℃ of reaction 4h.Stopped reaction, adds 1.43gNaHCO
3, and be warming up to 125 ℃ and steam water and ethanol.After having steamed at this temperature back flow reaction 4h, add subsequently 0.3g hexamethyldisiloxane to react 1h at this temperature, washing until PH=7.Filtration obtains water white filtrate, and filtrate is shifted to filtrate to pyriform flask, and decompression steams the low-boiling-point substances such as dimethylbenzene, obtains 19.56g white powder solid, and yield is more than 90%.White powder solid and vinyl silicone oil is mixed without muddy mutually.White powder is dissolved in deuterochloroform and is carried out
1h NMR measures, and recording contents of ethylene is 3.3%(massfraction), M/Q=0.75; Detection is without Si-OH and Si-OEt peak.
Embodiment 3
In the there-necked flask of being furnished with agitator, thermometer, prolong, add 39.45g tetraethoxy, 8.25g dimethylbenzene, 10.36g hexamethyldisiloxane, 3.53g tetramethyl divinyl disiloxane, 2.40g dehydrated alcohol, 1.43g concentrated hydrochloric acid (wt%=36%).And in ice-water bath, the speed with 1d/s drips 14.32g water, drips off rear stirring 5min.Be warming up to 35 ℃ of initial reaction 25min.System temperature is risen to 78 ℃ of reaction 4.5h.Stopped reaction, adds 1.40gNaHCO
3and be warming up to 125 ℃ and steam water and ethanol.The stirring reaction 4h that refluxes at this temperature after having steamed, adds 0.2g hexamethyldisiloxane to react 1h subsequently at this temperature, and washing is until PH=7.Filtration obtains water white filtrate, and filtrate is shifted to filtrate to pyriform flask, and decompression steams the low-boiling-point substances such as dimethylbenzene, obtains 22.10g white powder solid, and yield is more than 90%.White powder solid and vinyl silicone oil is mixed without muddy mutually.White powder is dissolved in deuterochloroform and is carried out
1h NMR measures, and recording contents of ethylene is 3.4%(massfraction), M/Q=0.9; Detection is without Si-OH and Si-OEt peak.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (7)
1. a methyl vinyl MQ silicone resin synthetic method, is characterized in that, comprising:
To the silicon ester that adds 100 weight parts 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 is also opened and is stirred, in ice-water bath, drip 30-40 weight parts water, after dripping off, rise to 35-40 ℃, stirring reaction 20-40min, then be warming up to 75-80 ℃, return stirring reaction 4-6h, stop stirring, the alkali that adds 2.8-4.3 weight part, unlatching is stirred and is warming up to 120-130 ℃ of steaming and dewaters and ethanol, after having steamed, at this temperature, stirring and refluxing is reacted 4-6h, the treatment agent that adds subsequently 0.3-0.6 weight part, at 125 ℃, react 1-3h, 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.
2. a kind of methyl vinyl MQ silicone resin synthetic method according to claim 1, is characterized in that, described catalyzer is a kind of in 36% concentrated hydrochloric acid, 98% vitriol oil, 99% trifluoromethanesulfonic acid, tosic acid, perfluorinated sulfonic resin.
3. a kind of methyl vinyl MQ silicone resin synthetic method according to claim 2, is characterized in that, described catalyzer is 36% concentrated hydrochloric acid.
4. a kind of methyl vinyl MQ silicone resin synthetic method according to claim 1, is characterized in that, described alkali is a kind of in calcium carbonate, sodium carbonate, sodium bicarbonate, salt of wormwood.
5. a kind of methyl vinyl MQ silicone resin synthetic method according to claim 4, is characterized in that, described alkali is sodium bicarbonate.
6. a kind of methyl vinyl MQ silicone resin synthetic method according to claim 1, is characterized in that, described silicon ester is methyl silicate, tetraethyl silicate, silicic acid propyl ester or their polycondensate.
7. a kind of methyl vinyl MQ silicone resin synthetic method according to claim 1, is characterized in that, described treatment agent is one or more the mixture in hexamethyldisiloxane, hexamethyldisilazane, tetramethyl-divinyl sily oxide.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788657A (en) * | 2014-01-24 | 2014-05-14 | 东南大学 | Preparation method of polymer for packaging large-scale integrated circuit |
| CN105585714A (en) * | 2015-12-16 | 2016-05-18 | 东莞兆舜有机硅科技股份有限公司 | Anti-ultraviolet organic silicon resin, preparation method and application thereof |
| CN107674207A (en) * | 2017-09-22 | 2018-02-09 | 山东盛宇新材料有限公司 | A kind of preparation method of high folding LED encapsulation phenylethylene ylmethyl MQ silicones |
| CN108368341A (en) * | 2015-12-21 | 2018-08-03 | 住友化学株式会社 | Organosilicon resin composition and semiconductor light-emitting elements encapsulating material |
| 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 |
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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 |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788657A (en) * | 2014-01-24 | 2014-05-14 | 东南大学 | Preparation method of polymer for packaging large-scale integrated circuit |
| CN103788657B (en) * | 2014-01-24 | 2016-06-08 | 东南大学 | A kind of preparation method for lsi package polymer |
| CN105585714A (en) * | 2015-12-16 | 2016-05-18 | 东莞兆舜有机硅科技股份有限公司 | Anti-ultraviolet organic silicon resin, preparation method and application thereof |
| 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 |
| CN108368341A (en) * | 2015-12-21 | 2018-08-03 | 住友化学株式会社 | Organosilicon resin composition and semiconductor light-emitting elements encapsulating material |
| CN107674207A (en) * | 2017-09-22 | 2018-02-09 | 山东盛宇新材料有限公司 | A kind of preparation method of high folding LED encapsulation phenylethylene ylmethyl MQ silicones |
| 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 |
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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. |
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Granted publication date: 20150902 Termination date: 20190918 |