CN104558617B - Method for preparing toughened phenyl vinyl silicone resin - Google Patents
Method for preparing toughened phenyl vinyl silicone resin Download PDFInfo
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- CN104558617B CN104558617B CN201510022031.1A CN201510022031A CN104558617B CN 104558617 B CN104558617 B CN 104558617B CN 201510022031 A CN201510022031 A CN 201510022031A CN 104558617 B CN104558617 B CN 104558617B
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Abstract
The invention discloses a method for preparing toughened phenyl vinyl silicone resin. The method comprises the following steps: mixing phenymethyldialkoxysianes, diphenyldialkoxysilane and dimethyldialkoxysilane at the weight ratio of 100: (0-20):(0-100) and then hydrolyzing to obtain a linear-chain prepolymer A; mixing phenyltrialkoxysilane and tetraalkoxysilane at the weight ratio of 100: (0-20) and then cohydrolyzing with 1,1,3,3-tetramethyldisiloxane to obtain a branch-chain prepolymer B; and mixing the linear-chain prepolymer A and the branch-chain prepolymer B, performing equilibrium polycondensation under the action of a catalyst to obtain toughened phenyl vinyl silicone resin. The toughened phenyl vinyl silicone resin adopts a linear-chain and branch-chain embedded structure, thereby obtaining certain flexibility after being cured, and avoiding the shortcomings of material hardness and brittleness. An LED package adhesive prepared by the toughened phenyl vinyl silicone resin has the advantages of good adhesion, cold and thermal shock resistance and the like.
Description
Technical field
The present invention relates to a kind of preparation method of Vinylphenyl silicon resin, the toughness being particularly suited for LED packaging plastic carries
Rise.
Background technology
Semiconductor light-emitting-diode (LED) illumination is considered as one of 21 century high-tech sector most with prospects,
It while causing illumination revolution, also will for promotion energy-saving and emission-reduction, set up conservation-minded society and make major contribution.
Organosilicon encapsulating material is used for LED and encapsulates, have light, heat stability good the features such as, it is usually by vinyl silicon
Resin, vinyl silicone oil, hydrogeneous cross-linking agent, catalyst, inhibitor etc. form.Different according to structure, packaging silicon rubber substantially can divide
For methyl silica gel and phenyl silica gel, the latter can improve the luminous flux of encapsulation LED, phenyl ring simultaneously due to having higher index of refraction
Presence can reduce the breathability of encapsulating compound, effectively improve the resistance to sulfuration grade of LED, thus obtain more and more encapsulation enterprises
Favor.But relatively methyl silica gel, the pliability of phenyl silica gel is relatively poor, especially when the hardness of encapsulating compound is higher, its with
The adhesion of support, and cold-resistant thermal shock resistance properties drastically declines, this make the LED that encapsulates in use it is possible that
The problems such as colloid and support stripping, dead lamp.Therefore, improve the pliability of phenyl packaging silicon rubber, reduce the internal stress of solidfied material, right
Reliability in lifting LED has very important significance.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, provide a kind of preparation of toughness reinforcing Vinylphenyl silicon resin
Method, the Vinylphenyl silicon resin prepared with this method is used for the preparation of LED packaging plastic, and it is good to have adhesive force, cold-hot
The advantage of impact.
For achieving the above object, the present invention employs the following technical solutions：The toughness reinforcing Vinylphenyl silicon resin of the present invention
Preparation method, comprises the following steps：
（1）By methyl phenyl di-alkoxy silane, diphenyl dialkoxy silicane, dimethyldialkylammonium TMOS by weight
Ratio 100：0~20：After 0 ~ 100 mixing, it is added to together with solvent, catalyst in reactor, solvent load is silane gross weight
50% ~ 200%, catalyst amount is the 0.1% ~ 5% of silane gross weight, and Deca deionized water is hydrolyzed, and reaction temperature is 30 ~ 80
C, the consumption of deionized water is 1 ~ 5 times of alkoxy radical molar total amount, and the response time is 60 ~ 300 minutes, and it is pre- that reaction obtains straight chain
Polymers A；
（2）By phenyl trialkoxysilane and tetraalkoxysilane by weight 100：After 0 ~ 20 mixing, and organosilicon envelope
Head agent, solvent, catalyst are added in reactor together, and closure agent consumption is the 5 ~ 35% of silane gross weight, and solvent load is silicon
The 50% ~ 200% of alkane gross weight, catalyst amount is the 0.1% ~ 5% of silane gross weight, and Deca deionized water is hydrolyzed, reaction
Temperature is 30 ~ 80 C, and the consumption of deionized water is 1 ~ 5 times of alkoxy radical molar total amount, and the response time is 30 ~ 300 minutes, reaction
Obtain side chain prepolymer B；
（3）By linear prepolymers A and side chain prepolymer B by weight 1：0.5 ~ 10 mixing, balance contracting under catalyst action
Poly-, reaction temperature is 80 ~ 150 C, and the response time is 30 ~ 600 minutes, obtains toughness reinforcing Vinylphenyl silicon resin.
Further, described methyl phenyl di-alkoxy silane, diphenyl dialkoxy silicane, dimethyldialkylammonium epoxide silicon
The weight of alkane is than for 100：0.01~20：0.01~100.
In the present invention, described solvent is by one or more of toluene, dimethylbenzene, ethanol, propanol according to any proportioning
Mixing composition.
In the present invention, described catalyst is by sulphuric acid, hydrochloric acid, trifluoromethanesulfonic acid, acid cation exchange resin
Kind or several according to any proportioning mix composition.
In the present invention, described closure agent is by vinyl double-seal head, hexamethyl disiloxane, vinyl list end socket, methyl
One or more of single end socket mixes composition according to any proportioning.
Compared with prior art, the invention has the beneficial effects as follows：Described tough Vinylphenyl silicon resin have straight chain section and
The mutually embedding structure of segment, have certain pliability after making resin solidification, it is to avoid the hard and crisp shortcoming of material.Use this increasing
The LED packaging plastic of tough phenyl vinyl polysiloxane preparation has that adhesive force is good, the advantage of cold-resistant thermal shock.
Specific embodiment
Below by way of example, the present invention is further described.
Embodiment 1：
182g aminomethyl phenyl dimethoxysilane, 12g dimethyldimethoxysil,ne, 200g toluene, 1g concentrated sulphuric acid are added
Enter in four-hole boiling flask, Deca 40g deionized water is hydrolyzed, react 3 hours under 60 C, solvent is distilled off, wash, be dried
Obtain linear prepolymers A1；
290g phenyltrimethoxysila,e, 50g vinyl double-seal head, 300g toluene, 1g concentrated sulphuric acid are added to four mouthfuls of burnings
In bottle, Deca 80g deionized water is hydrolyzed, and reacts 2 hours, solvent is distilled off under 70 C, washes, to be dried to obtain side chain pre-
Polymers B1；
By 20g linear prepolymers A1 and 80g side chain prepolymer prepolymer B1 mixing, plus 1g concentrated sulphuric acid, balance under 100 C
Polycondensation 3 hours, reactant through washing, be dried, de- low obtain toughness reinforcing Vinylphenyl silicon resin C1.
Embodiment 2：
By 210g aminomethyl phenyl diethoxy silane, 7.5g dimethyldiethoxysilane, 12g diphenyl dimethoxy silicon
Alkane, 150g dimethylbenzene, 5g concentrated hydrochloric acid are added in four-hole boiling flask, and Deca 50g deionized water is hydrolyzed, and under 70 C, reaction 4 is little
When, solvent is distilled off, washes, be dried to obtain linear prepolymers A2；
By 225g phenyltrimethoxysila,e, 45g tetraethoxysilane, 50g vinyl double-seal head, 5g hexamethyl two silica
Alkane, 400g toluene, 1g concentrated sulphuric acid are added in four-hole boiling flask, and Deca 60g deionized water is hydrolyzed, and react 5 hours under 30 C,
Solvent is distilled off, washes, be dried to obtain side chain prepolymer B2；
By 24g linear prepolymers A2 and 70g side chain prepolymer B2 mixing, plus 0.1g trifluoromethanesulfonic acid, balance under 150 C
Polycondensation 30 minutes, reactant through washing, be dried, de- low obtain toughness reinforcing Vinylphenyl silicon resin C2.
Embodiment 3：
182g aminomethyl phenyl dimethoxysilane, 360g toluene, 6g concentrated hydrochloric acid are added in four-hole boiling flask, Deca 90g
Deionized water is hydrolyzed, and reacts 1 hour, solvent is distilled off, washes, be dried to obtain linear prepolymers A3 under 80 C；
By 290g phenyltrimethoxysila,e, 50g vinyl double-seal head, 40g hexamethyl disiloxane, 350g toluene, 40g
Ethanol, 19g acid cation exchange resin are added in four-hole boiling flask, and Deca 80g deionized water is hydrolyzed, and react under 70 C
30 minutes, Filtration of catalyst, solvent is distilled off, is dried to obtain side chain prepolymer B3；
By 10g linear prepolymers A3 and 100g side chain prepolymer B3 mixing, plus 0.5g concentrated sulphuric acid, equilibrium polycondensation under 80 C
10 hours, reactant through washing, be dried, de- low obtain toughness reinforcing Vinylphenyl silicon resin C3.
Embodiment 4：
By 100g aminomethyl phenyl dimethoxysilane, 100g dimethyldiethoxysilane, 200g toluene, 4g concentrated hydrochloric acid
It is added in four-hole boiling flask, Deca 33g deionized water is hydrolyzed, reacts 5 hours under 30 C, solvent is distilled off, wash, do
Dry obtain linear prepolymers A4；
By 290g phenyltrimethoxysila,e, 40g Vinyldimethylethoxysilane（Vinyl list end socket）, 60g six
Tetramethyldisiloxane, 200g toluene, 100g isopropanol, 1.5g concentrated sulphuric acid are added in four-hole boiling flask, and Deca 70g deionized water enters
Row hydrolysis, reacts 5 hours under 40 C, solvent is distilled off, washes, be dried to obtain side chain prepolymer B4；
By 60g linear prepolymers A4 and 40g side chain prepolymer B4 mixing, plus 0.5g concentrated sulphuric acid, equilibrium polycondensation 3 under 80 C
Hour, reactant through washing, be dried, de- low obtain toughness reinforcing Vinylphenyl silicon resin C4.
Embodiment 5：
By 100g aminomethyl phenyl dimethoxysilane, 20g diphenyl diethoxy silane, 200g toluene, 0.6g fluoroform
Sulfonic acid is added in four-hole boiling flask, and Deca 30g deionized water is hydrolyzed, and reacts 4 hours, solvent, water are distilled off under 70 C
Wash, be dried to obtain linear prepolymers A5；
280g phenyltrimethoxysila,e, 14g vinyl double-seal head, 350g dimethylbenzene, 40g ethanol, 3g concentrated sulphuric acid are added
Enter in four-hole boiling flask, Deca 60g deionized water is hydrolyzed, react 2 hours under 60 C, Filtration of catalyst, distillation removes
Remove solvent, be dried to obtain side chain prepolymer B5；
By 80g linear prepolymers A5 and 40g side chain prepolymer B5 mixing, plus 0.5g concentrated sulphuric acid, equilibrium polycondensation 8 under 80 C
Hour, reactant through washing, be dried, de- low obtain toughness reinforcing Vinylphenyl silicon resin C5.
Embodiment 6：
Compared with Example 2, difference is aminomethyl phenyl diethoxy silane, dimethoxydiphenylsilane and dimethyl
The common 229.5g of diethoxy silane by weight 100：0.01：0.01 mixing, other conditions are constant, finally give toughness reinforcing vinyl
Phenyl polysiloxane C6.
Comparative example 1：
By 290g phenyltrimethoxysila,e, 68g aminomethyl phenyl dimethoxysilane, 58g vinyl double-seal head, 400g first
Benzene, 1g concentrated sulphuric acid are added in four-hole boiling flask, and Deca 100g deionized water is hydrolyzed, and react 5 hours, be distilled off under 70 C
Solvent, washing, is dried, de- low obtains Vinylphenyl silicon resin D1.
Comparative example 2：
By 290g phenyltrimethoxysila,e, 50g aminomethyl phenyl dimethoxysilane, 15g aminomethyl phenyl diethoxy silicon
Alkane, 58g vinyl double-seal head, 350g toluene, 0.5g trifluoromethanesulfonic acid are added in four-hole boiling flask, and Deca 80g deionized water enters
Row hydrolysis, reacts 7 hours under 65 C, solvent is distilled off, and washing, is dried, de- low obtains Vinylphenyl silicon resin D2.
Take toughness reinforcing Vinylphenyl silicon resin C1 ~ 6 of 65g, Vinylphenyl silicon resin D1 ~ 2,35g poly- methyl hydrogen benzene respectively
Radical siloxane, the catalyst of 0.2g platiniferous 3000ppm, 0.1g ethynylcyclohexanol, 1g viscosifier, it is uniformly mixed, obtain
LED packaging silicon rubber.
Above-mentioned silica gel is poured into mould, 150 °C are toasted 3 hours, obtain solidfied material, for Mechanics Performance Testing：Shore is hard
Degree presses GB/T531.1-2008 test, and tensile strength and percentage elongation press GB/T 528-2009 test.
Above-mentioned silica gel is used for 5050 paster LED encapsulation, 150 °C of bakings obtain packaged sample in 3 hours, survey for reliability
Examination：Red ink test is sample to be placed in 100 °C of boiling water boil 3 hours, and record red ink penetrates into the ratio of sample；Cold and hot
Shock-testing is that sample is placed in thermal shock test chamber, -40 ~ 100 °C, circulates 100 times, the ratio of the record dead lamp of LED chip
Rate.
Test result is as shown in table 1, as can be seen from the table, in the case that hardness is close, by toughness reinforcing ethenylphenyl
The tensile strength of silica gel solidfied material that silicones C1 ~ 6 are prepared and percentage elongation is substantially better than comparative example it was demonstrated that this toughness reinforcing ethylene
Base phenyl polysiloxane really can effectively improve the toughness of solidfied material；Can also be seen by red ink test and thermal shock test result
Go out, LED is used for by the silica gel that C1 ~ 6 are prepared and encapsulates, the reliability of LED can be made to be greatly improved.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 | |
| Hardness（Shore D） | 40 | 50 | 45 | 30 | 48 | 47 | 45 | 35 |
| Tensile strength（MPa） | 3.6 | 4.8 | 4 | 3.2 | 4.3 | 4.6 | 3.5 | 2.8 |
| Elongation at break（%） | 62 | 48 | 55 | 84 | 40 | 52 | 30 | 35 |
| Red ink permeates | 0/100 | 0/100 | 0/100 | 0/100 | 0/100 | 0/100 | 92/100 | 56/100 |
| The dead lamp of thermal shock | 0/100 | 2/100 | 0/100 | 0/100 | 5/100 | 0/100 | 67/100 | 28/100 |
Listed above be only the present invention be embodied as example.It is clear that the invention is not restricted to above example is sub, at this
In the spirit and scope of the claims of invention, any modifications and changes that the present invention is made, all it is considered as this
Bright protection domain.
Claims (4)
1. a kind of preparation method of toughness reinforcing Vinylphenyl silicon resin is it is characterised in that comprise the following steps：
(1) by methyl phenyl di-alkoxy silane, diphenyl dialkoxy silicane, dimethyldialkylammonium TMOS by weight
100：0～20：After 0～100 mixing, it is added to together with solvent, catalyst in reactor, solvent load is silane gross weight
50%～200%, catalyst amount is the 0.1%～5% of silane gross weight, and Deca deionized water is hydrolyzed, reaction temperature
For 30～80 DEG C, the consumption of deionized water is 1～5 times of alkoxy radical molar total amount, and the response time is 60～300 minutes, reaction
Obtain linear prepolymers A；
(2) by phenyl trialkoxysilane and tetraalkoxysilane by weight 100：After 0～20 mixing, and organosilicon end socket
Agent, solvent, catalyst are added in reactor together, and closure agent consumption is the 5～35% of silane gross weight, and solvent load is silicon
The 50%～200% of alkane gross weight, catalyst amount is the 0.1%～5% of silane gross weight, and Deca deionized water carries out water
Solution, reaction temperature is 30～80 DEG C, and the consumption of deionized water is 1～5 times of alkoxy radical molar total amount, the response time is 30～
300 minutes, reaction obtained side chain prepolymer B；Described closure agent is by one of vinyl double-seal head, vinyl list end socket or two
Plant and mix composition according to any proportioning；
(3) by linear prepolymers A and side chain prepolymer B by weight 1：0.5～10 mixing, equilibrium polycondensation under catalyst action,
Reaction temperature is 80～150 DEG C, and the response time is 30～600 minutes, obtains toughness reinforcing Vinylphenyl silicon resin.
2. toughness reinforcing Vinylphenyl silicon resin according to claim 1 preparation method it is characterised in that：Described methylbenzene
Base dialkoxy silicane, diphenyl dialkoxy silicane, the weight of dimethyldialkylammonium TMOS are than for 100：0.01～20：
0.01～100.
3. toughness reinforcing Vinylphenyl silicon resin according to claim 1 preparation method it is characterised in that：Described solvent by
One or more of toluene, dimethylbenzene, ethanol, propanol mix composition according to any proportioning.
4. toughness reinforcing Vinylphenyl silicon resin according to claim 1 preparation method it is characterised in that：Described catalyst
It is made up of according to the mixing of any proportioning one or more of sulphuric acid, hydrochloric acid, trifluoromethanesulfonic acid, acid cation exchange resin.
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| CN109504340B (en) * | 2018-11-20 | 2021-02-09 | 烟台德邦科技股份有限公司 | High-strength organic silicon heat-conducting sealant and preparation method thereof |
| CN110591098A (en) * | 2019-10-09 | 2019-12-20 | 浙江新安化工集团股份有限公司 | Methyl phenyl vinyl silicone oil and preparation method and application thereof |
| CN112280044B (en) * | 2020-11-04 | 2022-03-18 | 山东省科学院新材料研究所 | Low-viscosity high-strength toughened silicone resin composition and preparation method thereof |
| CN113845841A (en) * | 2021-11-09 | 2021-12-28 | 株洲时代电气绝缘有限责任公司 | Modified organic silicon solvent-free impregnating varnish and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475689A (en) * | 2008-12-03 | 2009-07-08 | 杭州师范大学 | Preparation of methyl phenyl vinyl silicon resin |
| CN101717512A (en) * | 2009-11-20 | 2010-06-02 | 苏州大学 | Method for preparing methyl phenyl vinyl silicone resin |
| CN103360603A (en) * | 2013-06-21 | 2013-10-23 | 深圳市森日有机硅材料有限公司 | Phenyl vinyl silicone resin for packaging LED (light-emitting diode) and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475689A (en) * | 2008-12-03 | 2009-07-08 | 杭州师范大学 | Preparation of methyl phenyl vinyl silicon resin |
| CN101717512A (en) * | 2009-11-20 | 2010-06-02 | 苏州大学 | Method for preparing methyl phenyl vinyl silicone resin |
| CN103360603A (en) * | 2013-06-21 | 2013-10-23 | 深圳市森日有机硅材料有限公司 | Phenyl vinyl silicone resin for packaging LED (light-emitting diode) and preparation method thereof |
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Address after: Hangzhou City, Zhejiang province 311122 Yuhang District Xianlin Street Xian Xing Road No. 31-33 Patentee after: Hangzhou Hangzhou Ke optoelectronic group Limited by Share Ltd Address before: Hangzhou City, Zhejiang province 311122 Yuhang District Xianlin Street Xian Xing Road No. 31-33 Patentee before: Hangzhou Hangke Photoelectric Co., Ltd. |