CN110229339A

CN110229339A - A kind of phenylethylene based siloxane resins, high refractive index LED encapsulation silicon resin composition and preparation method thereof

Info

Publication number: CN110229339A
Application number: CN201910442167.6A
Authority: CN
Inventors: 容敏智; 张泽平; 章明秋
Original assignee: National Sun Yat Sen University
Current assignee: Sun Yat Sen University; National Sun Yat Sen University
Priority date: 2019-05-24
Filing date: 2019-05-24
Publication date: 2019-09-13
Anticipated expiration: 2039-05-24
Also published as: CN110229339B

Abstract

The present invention relates to a kind of phenylethylene based siloxane resins, high refractive index LED encapsulation silicon resin composition and preparation method thereof.The phenylethylene based siloxane resins are prepared via a method which to obtain: S1: monomer is mixed, and organic solvent is added and obtains mixed solution, hydrolyst is added；S2: being added dropwise water at 0~60 DEG C and reaction be hydrolyzed, wash, filter, and base catalyst is added and carries out condensation reaction at 120~160 DEG C, washs, filters up to the phenylethylene based siloxane resins.The refractive index of phenylethylene based siloxane resins provided by the invention is high, and flexibility and anti-yellowing property are excellent；When being used to prepare LED encapsulation silicone resin, there is high refractive index, excellent tensile strength, adhesion strength, light transmittance and yellowing resistance energy, partial properties have reached or higher than external similar imported product level, can satisfy the basic demand of LED encapsulation；The surface welded LED device of encapsulation has excellent air-tightness.

Description

A kind of phenylethylene based siloxane resins, high refractive index LED encapsulate silicon resin composition And preparation method thereof

Technical field

The invention belongs to technical field of electronic encapsulation, and in particular to a kind of phenylethylene based siloxane resins, high refractive index LED encapsulates silicon resin composition and preparation method thereof.

Background technique

Light emitting diode (Light Emitting Diode, hereinafter referred to as LED) is that one kind can directly convert electric energy For the semiconductor element of luminous energy.Compared to the lighting method of incandescent lamp or fluorescent lamp, there is low energy, service life length, environmental protection, color Controllably, the advantages that small in size, is expected to the lighting source as a new generation and replaces conventional light source.Used in LED illumination device Encapsulating material is mainly epoxy resin and organic siliconresin.Compared to epoxy resin, organosilicon has the advantages that numerous: such as excellent Anti-ultraviolet ageing performance, weatherability, thermal stability, high transparency and high refractive index, insulating properties etc. are high-power LED encapsulation materials The ideal chose of material.

As LED manufacture technology is constantly promoted, such as large power white light LED and the maturation of reflow soldering technology, greatly The encapsulation technology of power LED has been increasingly becoming the key problem in technology of power-type LED development.Currently, the high property of power type LED encapsulation Energy organic siliconresin relies on import substantially, and main core technology is monopolized by a small number of offshore companies such as DOW CORNING, SHIN-ETSU HANTOTAI, high Cost limit the popularization of high power LED device.Therefore, demand of the industry to high refractive index transparent LED encapsulation silicon materials is got over Come more urgent.Studies in China still falls within the starting stage at present, and there are also many blank, and the organosilicon encapsulating material of domestic production is still It is only used for the mid and low-end products not high to performance requirement.High performance lED encapsulation silicone resin must have high refractive index, high light transmission Rate, resistance to ultraviolet ability, heat-proof aging ability, the performances such as low stress, and wherein, improve the key point that refractive index is problem.

The refractive index of LED chip is usually all larger than 2.5, and the refractive index of encapsulating material is much smaller, the refractive index of the two If differing too big, the light that LED chip issues can not may all take out because of total reflection, drop LED component optical efficiency It is low.Therefore the refractive index for improving encapsulating material, reduces the difference with LED chip refractive index, can significantly improve LED takes light efficiency Rate.In polysiloxanes, phenyl ring molar refraction with higher (Si-Ph Bond Refraction is 27.39, and in polymerizable organosilicon In object, Si-CH₃More only 1.75) only 7.57, Si-O key, therefore increases phenyl content, can promote polysiloxanes well Refractive index.But the increase of phenyl content will will affect the brittleness of polysiloxanes, and material is made to be easier xanthochromia.

In consideration of it, developing a kind of has high refractive index and the impregnable organosilicon encapsulating material of remaining performance is with important Research significance and application value.

Summary of the invention

It is an object of the invention to the defect for overcoming the refractive index of encapsulating material in the prior art low and deficiencies, provide one kind The preparation method of phenylethylene based siloxane resins.Selection and dosage optimization of the present invention by specific monomer, are prepared The content of phenyl greatly increases in phenylethylene based siloxane resins, improves refractive index；In addition the content of vinyl is also more Rationally, be conducive to curing reaction；Meanwhile the addition of octamethylcy-clotetrasiloxane, it is introduced in phenylethylene based siloxane resins Methylsiloxane segment, so that the flexibility of phenylethylene based siloxane resins greatly increases, finally obtained phenylethylene The refractive index of based siloxane resins is high, and flexibility and anti-yellowing property are excellent；When being used to prepare LED encapsulation silicone resin, there is height Refractive index, excellent tensile strength, adhesion strength, light transmittance and yellowing resistance energy, partial properties have reached or are higher than external similar The level of imported product can satisfy the basic demand of LED encapsulation；The surface welded LED device of encapsulation has excellent air-tightness.

Another object of the present invention is to provide above-mentioned phenylethylene based siloxane resins in preparation LED encapsulation silicone resin Application.

Another object of the present invention is to provide a kind of high refractive index LED to encapsulate silicon resin composition.

Another object of the present invention is to provide the preparation methods of above-mentioned high refractive index LED encapsulation silicon resin composition.

For achieving the above object, the present invention adopts the following technical scheme:

A kind of phenylethylene based siloxane resins, are prepared via a method which to obtain:

S1: by monomer: dimethoxydiphenylsilane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane It is mixed with tetramethyl divinyl disiloxane, organic solvent is added and obtains mixed solution, hydrolyst is added；The diphenyl Dimethoxysilane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane and tetramethyl divinyl disiloxane Mass ratio be 50~70:10~20:10~30:5~15；

S2: being added dropwise water at 30~60 DEG C and reaction be hydrolyzed, wash, vacuum distillation, and base catalyst adjusting pH is added and is 11~14, condensation reaction is carried out at 120~160 DEG C, is washed, and is evaporated under reduced pressure up to the phenylethylene based siloxane resins.

The present invention selects dimethoxydiphenylsilane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane The phenyl content of phenylethylene based siloxane resins can be improved as monomer with tetramethyl divinyl disiloxane, and obtain Suitable contents of ethylene, and then improve refractive index and solidification effect；Simultaneously by selecting octamethylcy-clotetrasiloxane, in resin Methylsiloxane segment is introduced in strand, flexibility greatly increases, the folding of finally obtained phenylethylene based siloxane resins Rate height is penetrated, flexibility and anti-yellowing property are excellent.When being used to prepare LED encapsulation silicone resin, the LED being prepared encapsulates silicon tree Rouge has high refractive index, excellent tensile strength, adhesion strength, light transmittance and yellowing resistance energy, and partial properties have reached or are higher than The level of external similar imported product, can satisfy the basic demand of LED encapsulation；The surface welded LED device of encapsulation has excellent Air-tightness.

In addition, the preparation method simple process, easy post-processing will not generate corrosive substance.

Preferably, dimethoxydiphenylsilane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane in S1 Mass ratio with tetramethyl divinyl disiloxane is 50:15:20:5.

Under the quality proportioning, phenylethylene based siloxane resins have more excellent refraction, flexibility and color inhibition Performance.

Preferably, the mass fraction of monomer is 25~75% in S1 mixed solution.

It is further preferable that the mass fraction of monomer is 50% in S1 mixed solution.

Preferably, organic solvent is one or more of toluene, dimethylbenzene or benzene in S1.

Preferably, hydrolyst described in S1 is trifluoromethanesulfonic acid.

Make the pH of mixed solution less than 1 it is further preferable that trifluoromethanesulfonic acid is added in S1.

The dosage of water and basic catalyst can be controlled according to the requirement of existing hydrolysis and condensation reaction respectively in S2 System.

Preferably, S2 is 1~1.4:1 in the molar ratio of water and reactive group alkoxy.

Under normal circumstances, the dosage of water is the molar ratio of reactive functionality alkoxy when being 1:1, it can be achieved that preferable hydrolysis Reaction.

The speed that water droplet adds can be adjusted according to the severe degree of hydrolysis, and 30~70s mono- drips under normal circumstances Rate of addition is more appropriate, has been easy very much cyclic side products appearance fastly, influences the product transparency.

Preferably, base catalyst described in S2 be one of sodium hydroxide, potassium hydroxide or tetramethylammonium hydroxide or It is a variety of.

A kind of high refractive index LED encapsulation silicon resin composition, is grouped as by the group of following parts by weight:

The present invention is curing monomer in Karstedt using phenylethylene based siloxane resins, phenyl hydrogen-containing siloxane resin Solidify under the action of catalyst；And the preferably hyperbranched phenyl siloxane reinforcing agent of compatibility is selected, so that silicone resin solidfied material Crosslinking points more concentrate, can effective dispersive stress, or even formed " island structure ", play toughening and reinforcing effect；It selects The caking property and adhesive force of organic silicon rigidity-increasing stick raising silicone resin solidfied material and LED substrate, and obstruct the water in air etc., it obtains The LED encapsulation silicon resin composition phenyl content with higher arrived and suitable contents of ethylene, refractive index is high, has simultaneously Preferable flexibility and yellowing resistance, partial properties have reached or higher than external similar imported product level, can satisfy LED The basic demand of encapsulation；The surface welded LED device of encapsulation has excellent air-tightness.It is specific: tensile strength up to 1.4~ 4.1 MPa, adhesion strength are up to 0.3~1.2MPa, 450nm light transmittance close to 90%, shore hardness up to 60~85 A, refraction Rate is up to 1.56.

It should be understood that the high refractive index LED that Karstedt catalyst is unit quality (g) encapsulates silicon resin composition 10~20ppm of middle addition.

Preferably, the high refractive index LED encapsulation silicon resin composition is grouped as by the group of following parts by weight:

Preferably, the phenyl hydrogen-containing siloxane resin is prepared by the following procedure method and obtains: by monomer: phenyl trimethoxy Silane, dimethoxydiphenylsilane, tetramethyl-ring tetrasiloxane and tetramethyl disiloxane, water and hydrolysis catalyst are mixed It closes, organic solvent is added and obtains mixed solution, is warming up to 30~60 DEG C of 1~5h of hydrolysis, then be warming up to 110~140 DEG C of points of water 2~11h is reacted, washing is evaporated under reduced pressure up to the phenyl hydrogen-containing siloxane resin；The phenyltrimethoxysila,e, hexichol The mass ratio of base dimethoxysilane, tetramethyl-ring tetrasiloxane and tetramethyl disiloxane be 15~25:45~55:10~ 20:1.5~15.

The present invention provides a kind of preparation method of phenyl hydrogen-containing siloxane resin, and this method is by selecting phenyl trimethoxy As monomer, obtained phenyl contains for silane, dimethoxydiphenylsilane, tetramethyl-ring tetrasiloxane and tetramethyl disiloxane The phenyl content of hydridosiloxane resin is higher, refractive index with higher；The selection of tetramethyl-ring tetrasiloxane simultaneously, so that benzene Si -- H bond and methylsiloxane segment are introduced simultaneously in the strand of base hydrogen-containing siloxane resin, can not only be effective as handing over Join agent to use, and flexibility greatly increases.

Phenylethylene based siloxane resins are prepared in ad hoc approach and the refractive index of phenyl hydrogen-containing siloxane resin is close, Further compensate for what routine techniques medium vinyl silicone resin and hydrogen-containing siloxane resin caused by refractive index difference The problem of encapsulating material poor optical properties；In addition, the refractive index of the two is higher, by the mating reaction of the two, further mention The high refractive index of LED encapsulation silicon resin composition, has more excellent comprehensive performance.

Preferably, the phenyltrimethoxysila,e, dimethoxydiphenylsilane, tetramethyl-ring tetrasiloxane and tetramethyl The mass ratio of base disiloxane is 20:40:25:5.

Under the quality proportioning, phenyl hydrogen-containing siloxane resin has molecular weight appropriate, viscosity and silicone hydroxyl content, with And more excellent refractive index and strand flexibility.

Preferably, the mass concentration of monomer is 25~75% in mixed solution.

It is further preferable that the mass concentration of monomer is 50% in mixed solution.

Preferably, the organic solvent is one or more of toluene, dimethylbenzene or benzene.

Preferably, the hydrolysis catalyst is concentrated hydrochloric acid, glacial acetic acid or AMBERLYST-15WET strong-acid type cation One or more of exchanger resin.

Preferably, the molar ratio of the water and hydrolysis groups alkoxy is 1~1.4:1.

Preferably, the mass ratio of the phenyltrimethoxysila,e and hydrolysis catalyst be 15~25:1.2~ 5.8。

Preferably, the hyperbranched phenyl siloxane reinforcing agent is prepared via a method which to obtain: by monomer: hexamethyl two Siloxanes and tetramethyl divinyl disiloxane, water and acid catalyst mixing, are added organic solvent and obtain mixed solution, benzene is added dropwise Base trimethoxy silane, then 0.5~4h of hydrolysis at 30~50 DEG C are warming up to 50~120 DEG C the reaction was continued 1~3h, Washing is evaporated under reduced pressure up to the hyperbranched phenyl siloxane reinforcing agent；The hexamethyldisiloxane, tetramethyl divinyl Disiloxane and the mass ratio of phenyltrimethoxysila,e are 5~15:10~20:15~25.

The present invention provides a kind of preparation methods of specific hyperbranched phenyl siloxane reinforcing agent.

The hyperbranched phenyl siloxane that the ad hoc approach is prepared, reaction process is simple, molecular weight can easily be accommodated, and It is good with the compatibility of high refractive index encapsulation silicone resin, when being used for LED encapsulation silicon resin composition, it can further improve silicon tree The toughness and intensity of rouge solidfied material.

Preferably, the structural formula of the hyperbranched phenyl siloxane reinforcing agent is as follows:

The present invention has included a kind of structural formula of hyperbranched phenyl siloxane reinforcing agent, and preceding method is prepared super The structure of branching phenyl siloxane reinforcing agent is substantially similar, and difference is only that hyperbranched algebra is different, functional end-group The position of vinyl and content difference.

Preferably, the hexamethyldisiloxane, tetramethyl divinyl disiloxane and phenyltrimethoxysila,e Mass ratio is 12.5:12.5:25.

Preferably, the mass concentration of monomer is 25~75% in mixed solution.

Preferably, the molar ratio of the water and hydrolysising group alkoxy is 0.4~0.75:1.

Preferably, the mass ratio of the hexamethyldisiloxane and acid catalyst is 5~15:2~6.

Preferably, the organic silicon rigidity-increasing stick is prepared via a method which to obtain: by monomer: phenyltrimethoxysila,e, After dimethoxydiphenylsilane, methylvinyldimethoxysilane and tetramethyl divinyl disiloxane mixing, it is added Organic solvent obtains mixed solution, and hydrolysis catalyst is added, reaction is hydrolyzed at 30~50 DEG C, washs, and adds after revolving Enter silane coupling agent and condensation catalyst, is warming up to 80~140 DEG C of 1~7h of reaction；Washing filters up to the organosilicon Tackifier；The phenyltrimethoxysila,e, diphenyl Dimethoxane base silane, methylvinyldimethoxysilane, tetramethyl The mass ratio of base divinyl disiloxane and silane coupling agent is 15~25:25~35:10~20:2~15:10~20.

Preferably, the phenyltrimethoxysila,e, dimethoxydiphenylsilane, methyl ethylene dimethoxy silicon The mass ratio of alkane, tetramethyl divinyl disiloxane and silane coupling agent is 20:30:15:5:15.

Preferably, the mass concentration of monomer is 25~75% in mixed solution.

Preferably, the hydrolyst is trifluoromethanesulfonic acid.

It is further preferable that trifluoromethanesulfonic acid is added to pH less than 1.

Preferably, the silane coupling agent is one or more of KH-550, KH-560 or KH-570.

Preferably, the mass ratio of the phenyltrimethoxysila,e and silane coupling agent is 15~25:2~7.

Preferably, the condensation catalyst is one of potassium hydroxide, sodium hydroxide or tetramethylammonium hydroxide Or it is several.

The preparation method of above-mentioned high refractive index LED encapsulation silicon resin composition, includes the following steps: phenyl vinyl silicon Oxygen alkane and the mixing of phenyl hydrogen-containing siloxane, add hyperbranched phenyl siloxane, silicone resin tackifier and Karstedt catalyst, Stirring, de-bubbled, gradually elevated cure encapsulates silicon resin composition up to the high refractive index LED.

Preferably, it is steeped using vacuum outgas.

Preferably, the solidification process is to be warming up to 100~150 DEG C of solidifications with the heating rate of 5~20 DEG C/min.

Specifically, 100 DEG C of solidification 1h are warming up to the heating rate of 10~20 DEG C/min, then proceed to be warming up to 130 DEG C Solidify 2h, is continuously heating to 150 DEG C of solidification 3h.

Above-mentioned high refractive index LED encapsulation silicon resin composition as encapsulating material in LED encapsulation using also in this hair In bright protection scope.

Compared with prior art, the invention has the following beneficial effects:

The present invention passes through selection and the dosage optimization of specific monomer, benzene in the phenylethylene based siloxane resins being prepared The content of base greatly increases, and improves refractive index；In addition the content of vinyl is also relatively reasonable, is conducive to curing reaction and is fitted In the degree of cross linking；Meanwhile the addition of octamethylcy-clotetrasiloxane, methyl silicon oxygen is introduced in phenylethylene based siloxane resins Alkane segment, so that the flexibility of phenylethylene based siloxane resins greatly increases,；Hyperbranched phenyl siloxane reinforcing agent and organic Silicon tackifier can be further improved the mechanical strength and caking property of final material, when being used to prepare LED encapsulation silicone resin, have Good heat resistance and anti-yellowing property, tensile strength up to 1.4~4.1MPa, adhesion strength up to 0.3~1.2MPa, Close to 90%, shore hardness up to 60~85A, refractive index has reached or is higher than up to 1.56, partial properties and steps 450nm light transmittance The portioned products such as figure, DOW CORNING have many advantages, such as cheap, simple process, can satisfy the basic demand of LED encapsulation, tool There are industrial potentiality；The surface welded LED device of encapsulation has excellent air-tightness.

Detailed description of the invention

Fig. 1 is the infrared spectroscopy for the phenylethylene based siloxane resins that embodiment 1 provides；

Fig. 2 is the nucleus magnetic hydrogen spectrum for the phenylethylene based siloxane resins that embodiment 1 provides；

Fig. 3 is the infrared spectroscopy for the phenyl hydrogen-containing siloxane resin that embodiment 17 provides；

Fig. 4 is the nucleus magnetic hydrogen spectrum for the phenyl hydrogen-containing siloxane resin that embodiment 17 provides；

Fig. 5 is the infrared spectroscopy for the hyperbranched phenyl siloxane reinforcing agent that embodiment 33 provides；

Fig. 6 is the nucleus magnetic hydrogen spectrum for the hyperbranched phenyl siloxane reinforcing agent that embodiment 33 provides；

Fig. 7 is the infrared spectroscopy for the organic silicon rigidity-increasing stick that embodiment 45 provides；

Fig. 8 is the nucleus magnetic hydrogen spectrum for the organic silicon rigidity-increasing stick that embodiment 45 provides；

Fig. 9 is that the red ink test result of the surface welded LED packaging of embodiment 56 and comparative example 1, comparative example 2 is shone Piece.

Specific embodiment

Below with reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed The condition suggested according to manufacturer；Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention And replacement belongs to scope of the present invention.

Using the tensile property of universal testing machine test solidfied material, according to method as defined in national standard GB/T 16421-1996 Dumbbell shape tensile bars are poured, 5 Duplicate Samples is at least tested and is averaged.

Using the adhesive property of universal testing machine test solidfied material, referring to national standard GB/T13936-92 measurement silicone resin to aluminium The tensile shear strength of piece is evaluated, and is at least tested 5 Duplicate Samples and is averaged.

The hardness of examination solidfied material is measured using shore A type hardness tester, is at least tested 5 Duplicate Samples and is averaged.

Using the light transmission of Japanese Shimadzu Corporation UV-3150 type ultraviolet-visible-near infrared spectrometer test solidfied material Rate.In addition, carrying out light transmittance test, then the method according to ASTM E313 D1925 description to the solidfied material of different ageing times Calculate yellowness index.

Liquid silicone is tested using the 2WE-T type digital display Abbe refractometer of Shanghai Li Guang precision instrument Co., Ltd and is consolidated The refractive index of compound (with a thickness of 1mm), using naphthalene bromide as correcting medium.

The air-tightness that surface welded LED packaging is examined using red ink permeability test, if air-tightness is bad, after experiment Device inside has red ink infiltration, and the observing to experiment front and back using optical microscopy.

Embodiment 1

The present embodiment provides a kind of phenylethylene based siloxane resins, preparation method is as follows.

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Infrared and nuclear magnetic spectrogram difference is as depicted in figs. 1 and 2, and molecular weight, appearance and refractive index data are as shown in table 1.

1260cm in Fig. 1^-1Belong to Si-CH₃Symmetric curvature vibration；1406cm^-1Belong to the C=C scissors of Si-Vi Bending vibration；1429,1473,1457 and 1592cm^-1Belong to the C=C stretching vibration of Si-Ph；2959cm^-1Belong to CH₃'s Stretching vibration；3050 and 3070cm^-1The C-H stretching vibration of phenyl ring is belonged to, preliminary proof is successfully prepared phenyl vinyl silicon Oxygen alkane prepolymer, in 860cm^-1With 3700-3600 cm^-1Between there is not the peak Si-OH, illustrate condensation reaction carry out more Thoroughly.

Chemical shift ownership is as follows in Fig. 2: 6.99~7.74ppm belongs to Si-Ph；0~0.27ppm belongs to Si- CH₃.Do not occur peak in 1.59ppm or so, illustrates the ratio for showing that preparation process can be such that condensation reaction carries out without containing Si-OH Relatively completely.

Embodiment 2

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into Row condensation reaction 0.5h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon Oxygen alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 3

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into Row condensation reaction 5h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 4

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 120 DEG C into Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 5

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 160 DEG C into Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 6

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% sodium hydroxide is added and adjusts pH, at 150 DEG C into Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 7

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 2% tetramethylammonium hydroxide is added and adjusts pH, 150 DEG C Lower progress condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl Silicone resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 8

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.5% potassium hydroxide is added and adjusts pH, at 150 DEG C into Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 9

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water are depressurized at 55 DEG C with Rotary Evaporators, 1% potassium hydroxide is added and adjusts pH, is carried out at 150 DEG C Condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenylethylene radical siloxane Resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 10

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 60 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 11

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 6g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 12

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 8g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 13

By 50g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 10g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 14

By 50g dimethoxydiphenylsilane, 5g methylvinyldimethoxysilane, 20g octamethylcy-clotetrasiloxane, 5g tetramethyl divinyl disiloxane mixes postposition in a round bottom flask, and it is 50% that toluene, which is added, and is made into monomer mass ratio Mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and rubs with reactive functionality etc. Reaction is hydrolyzed by the pure water of ratio in you, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to during solution is in Property.Abstraction solvent and water are depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, contracts at 150 DEG C Reaction 2h is closed, separatory funnel is moved to and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtain phenylethylene radical siloxane tree Rouge.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 15

By 30g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 5g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 16

By 60g dimethoxydiphenylsilane, 15g methylvinyldimethoxysilane, four silicon oxygen of 20g prestox ring In a round bottom flask, addition toluene is made into monomer mass ratio and is for alkane, 10g tetramethyl divinyl disiloxane mixing postposition 50% mixed solution, 0.1g trifluoromethanesulfonic acid, which is added dropwise, makes solution in acidity.It is slowly added dropwise at 40 DEG C, in 3h and reactive functional group Reaction is hydrolyzed in the pure water of group's equimolar ratio, hydrolyzes 1h after being added dropwise again.Solution is moved into separatory funnel, is washed to solution It is in neutrality.Abstraction solvent and water is depressurized at 55 DEG C with Rotary Evaporators, 0.1% potassium hydroxide is added and adjusts pH, at 150 DEG C into Row condensation reaction 2h moves to separatory funnel and is washed to neutrality, 150 DEG C of vacuum abstraction solvents and water, obtains phenyl vinyl silicon oxygen Alkane resin.Molecular weight, appearance and refractive index data are as shown in table 1.

Embodiment 17

The present embodiment provides a kind of phenyl hydrogen-containing siloxane resin, preparation method is as follows.

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 11h.Solution is transferred in 500ml separatory funnel, It is washed to solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.It is infrared With nuclear magnetic spectrogram respectively as shown in Fig. 3 and Fig. 4, molecular weight, appearance and refractive index data are as shown in table 2.

Fig. 3 middle infrared absorption peak ownership is as follows: 1260cm^-1Belong to Si-CH₃Symmetric curvature vibration；1430 Hes 1593cm^-1Belong to the C=C stretching vibration of Si-Ph；2166cm^-1Belong to the stretching vibration of Si-H； 2963cm^-1It belongs to CH₃Stretching vibration；3072cm^-1The C-H stretching vibration of phenyl ring is belonged to, preliminary proof is successfully prepared hydrogen-containing siloxane pre-polymerization Object, in 860cm^-1And 3700-3600cm^-1Between there is not the peak Si-OH, illustrate condensation reaction carry out more thoroughly.

Chemical shift ownership is as follows in Fig. 4: 6.99~7.74ppm belongs to Si-Ph；5.17~6.13ppm is belonged to Si-H；0~0.22ppm belongs to Si-CH₃。

Embodiment 18

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 120 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight, Appearance and refractive index data are as shown in table 2.

Embodiment 19

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 110 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight, Appearance and refractive index data are as shown in table 2.

Embodiment 20

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 140 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight, Appearance and refractive index data are as shown in table 2.

Embodiment 21

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 19.5g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, It is washed to solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecule Amount, appearance and refractive index data are as shown in table 2.

Embodiment 22

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 3.5g concentrated hydrochloric acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight, Appearance and refractive index data are as shown in table 2.

Embodiment 23

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 2gAMBERLYST-15WET strongly acidic cation-exchange is set in a round bottom flask, The toluene of the quality such as addition, is warming up to 50 DEG C of hydrolysis 4h, then be warming up to 130 DEG C, connects water segregator, and water is divided to react 4h.It will Solution is transferred in 500ml separatory funnel, is washed to solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are For phenyl hydrogen-containing siloxane resin.Molecular weight, appearance and refractive index data are as shown in table 2.

Embodiment 24

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 2h.Solution is transferred in 500ml separatory funnel, water It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight, Appearance and refractive index data are as shown in table 2.

Embodiment 25

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 3h.Solution is transferred in 500ml separatory funnel, water It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight, Appearance and refractive index data are as shown in table 2.

Embodiment 26

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 6h.Solution is transferred in 500ml separatory funnel, water It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight, Appearance and refractive index data are as shown in table 2.

Embodiment 27

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 1.2g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight, Appearance and refractive index data are as shown in table 2.

Embodiment 28

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 4.8g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight, Appearance and refractive index data are as shown in table 2.

Embodiment 29

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 1.5g tetramethyl disiloxane, 13g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C of hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred to 500ml separatory funnel In, it is washed to solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Point Son amount, appearance and refractive index data are as shown in table 2.

Embodiment 30

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 10g Tetramethyl disiloxane, 13g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 130 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight, Appearance and refractive index data are as shown in table 2.

Embodiment 31

Weigh 20g phenyltrimethoxysila,e, 50g dimethoxydiphenylsilane, 5g tetramethyl-ring tetrasiloxane, 5g tetra- Tetramethyldisiloxane, 13g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C of water Solution reaction 4h, then 140 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, is washed It is presented to solution neutral.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.It is molecular weight, outer It sees and refractive index data is as shown in table 2.

Embodiment 32

Weigh 30g phenyltrimethoxysila,e, 40g dimethoxydiphenylsilane, 15g tetramethyl-ring tetrasiloxane, 5g Tetramethyl disiloxane, 13g H₂O and 3.5g glacial acetic acid is set in a round bottom flask, and the toluene of the quality such as addition is warming up to 50 DEG C Hydrolysis 4h, then 140 DEG C are warming up to, water segregator is connected, water is divided to react 4h.Solution is transferred in 500ml separatory funnel, water It is washed till solution and neutrality is presented.150 DEG C of decompression abstraction solvents and water, products therefrom are phenyl hydrogen-containing siloxane resin.Molecular weight, Appearance and refractive index data are as shown in table 2.

Embodiment 33

The present embodiment provides a kind of hyperbranched phenyl siloxane reinforcing agent, preparation method is as follows.

Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H₂O and 2% concentrated hydrochloric acid mix Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Infrared and core For magnetic spectrum figure respectively as shown in Fig. 5 and Fig. 6, molecular weight, appearance and refractive index data are as shown in table 3.

Fig. 5 middle infrared absorption peak ownership is as follows: 1253cm^-1Belong to Si-CH₃Symmetric curvature vibration；1430,1474 and 1594cm^-1Belong to the C=C stretching vibration of Si-Ph；2958cm^-1Belong to CH₃Stretching vibration；3051 and 3073cm^-1Return Belong to the C-H stretching vibration of phenyl ring, preliminary proof is successfully prepared hyperbranched phenyl siloxane, in 860cm^-1And 3700- 3600cm^-1Between there is not the peak Si-OH, illustrate condensation reaction carry out more thoroughly.

Chemical shift ownership is as follows in Fig. 6: 6.70~8.00ppm belongs to Si-Ph；5.28~6.28ppm belongs to Si- Vi；3.17~3.80ppm belongs to O-CH₃；0~0.31ppm belongs to Si-CH₃。

Embodiment 34

Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H₂O and 2% concentrated hydrochloric acid mix Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 50 DEG C the reaction was continued 2h, solution is transferred to Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight, Appearance and refractive index data are as shown in table 3.

Embodiment 35

Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H₂O and 2% concentrated hydrochloric acid mix Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 100 DEG C the reaction was continued 2h, solution is shifted To separatory funnel, it is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecule Amount, appearance and refractive index data are as shown in table 3.

Embodiment 36

Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H₂O and 2% glacial acetic acid mix Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight, Appearance and refractive index data are as shown in table 3.

Embodiment 37

Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H₂O and 1% concentrated sulfuric acid mix Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight, Appearance and refractive index data are as shown in table 3.

Embodiment 38

Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H₂O and 1% concentrated hydrochloric acid mix Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight, Appearance and refractive index data are as shown in table 3.

Embodiment 39

Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H₂O and 5% concentrated hydrochloric acid mix Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight, Appearance and refractive index data are as shown in table 3.

Embodiment 40

Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 8g H₂O and 2% glacial acetic acid mix Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight, Appearance and refractive index data are as shown in table 3.

Embodiment 41

Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 10g H₂O and 2% glacial acetic acid mix Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 0.5h, solution is shifted To separatory funnel, it is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecule Amount, appearance and refractive index data are as shown in table 3.

Embodiment 42

Weigh 3g hexamethyldisiloxane, 3g tetramethyl divinyl disiloxane, 6g H₂O and 2% glacial acetic acid, mixing In a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50% to postposition, and 20g phenyl is added dropwise Trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to point Liquid funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.It is molecular weight, outer It sees and refractive index data is as shown in table 3.

Embodiment 43

Weigh 30g hexamethyldisiloxane, 30g tetramethyl divinyl disiloxane, 6g H₂O and 2% glacial acetic acid mix Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 20g benzene is added dropwise Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight, Appearance and refractive index data are as shown in table 3.

Embodiment 44

Weigh 10g hexamethyldisiloxane, 10g tetramethyl divinyl disiloxane, 6g H₂O and 2% glacial acetic acid mix Close postposition in a round bottom flask, the toluene of the quality such as addition is made into the mixed solution that monomer mass ratio is 50%, and 30g benzene is added dropwise Base trimethoxy silane, after being added dropwise to complete at 50 DEG C hydrolysis 2h, be warming up to 80 DEG C the reaction was continued 2h, solution is transferred to Separatory funnel is washed to neutrality, 150 DEG C of decompression abstraction solvents and water, obtains hyperbranched phenyl siloxane reinforcing agent.Molecular weight, Appearance and refractive index data are as shown in table 3.

Embodiment 45

The present embodiment provides a kind of organic silicon rigidity-increasing stick, preparation method is as follows.

Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h. Reaction solution is transferred in 500ml separatory funnel, neutrality is washed to, 150 DEG C of vacuum distillations remove solvent and water, obtain organosilicon Tackifier.Infrared and nuclear magnetic spectrogram difference is as shown in Figure 7 and Figure 8, and molecular weight, appearance and refractive index data are as shown in table 4.

Fig. 7 middle infrared absorption peak ownership is as follows: 909cm^-1Belong to the vibration of epoxy group；1084cm^-1Belong to C-O- The stretching vibration of C；1408cm^-1Belong to the C=C scissors bending vibration of Si-Vi；1430 and 1593cm^-1Belong to Si-Ph's C=C stretching vibration；2941cm^-1Belong to CH₃Stretching vibration； 3051cm^-1The C-H stretching vibration of phenyl ring is belonged to, tentatively Proof is successfully prepared organic silicon rigidity-increasing stick, in 860cm^-1And 3700-3600cm^-1Between there is not the peak Si-OH, illustrate to contract Close the more thorough of reaction progress.

Chemical shift ownership is as follows in Fig. 8: 6.99~7.74ppm belongs to Si-Ph；5.54~6.19ppm belongs to Si- Vi；3.03~3.60ppm belongs to O-CH₃；2.48ppm belonging to epoxy group；0~0.30ppm belongs to Si-CH₃。

Embodiment 46

Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 80 DEG C of reaction 5h.It will Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing Stick.Molecular weight, appearance and refractive index data are as shown in table 4.

Embodiment 47

Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 140 DEG C of reaction 5h.It will Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing Stick.Molecular weight, appearance and refractive index data are as shown in table 4.

Embodiment 48

Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 1h.It will Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing Stick.Molecular weight, appearance and refractive index data are as shown in table 4.

Embodiment 49

Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 3h. Reaction solution is transferred in 500ml separatory funnel, neutrality is washed to, 150 DEG C of vacuum distillations remove solvent and water, obtain organosilicon Tackifier.Molecular weight, appearance and refractive index data are as shown in table 4.

Embodiment 50

Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later And water, 15g KH560 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h.Reaction solution is shifted Into 500ml separatory funnel, it is washed to neutrality, 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing stick.Molecule Amount, appearance and refractive index data are as shown in table 4.

Embodiment 51

Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later And water, 15g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 3h.Reaction solution is shifted Into 500ml separatory funnel, it is washed to neutrality, 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing stick.Molecule Amount, appearance and refractive index data are as shown in table 4.

Embodiment 52

Weigh 25g phenyltrimethoxysila,e, 35g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy In a round bottom flask, the toluene of the quality such as addition is made into monomer for silane, 4.5g tetramethyl divinyl disiloxane mixing postposition The mixed solution that mass ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, It hydrolyzes 1h again later, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings are except molten later Agent and water, are added 5g KH560 and 10g KH570 silane coupling agent, and the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h. Reaction solution is transferred in 500ml separatory funnel, neutrality is washed to, 150 DEG C of vacuum distillations remove solvent and water, obtain organosilicon Tackifier.Molecular weight, appearance and refractive index data are as shown in table 4.

Embodiment 53

Weigh 20g phenyltrimethoxysila,e, 30g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 8g tetramethyl divinyl disiloxane mixing postposition The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h. Reaction solution is transferred in 500ml separatory funnel, neutrality is washed to, 150 DEG C of vacuum distillations remove solvent and water, obtain organosilicon Tackifier.Molecular weight, appearance and refractive index data are as shown in table 4.

Embodiment 54

Weigh 15g phenyltrimethoxysila,e, 25g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h.It will Reaction solution is transferred in 500ml separatory funnel, is washed to neutrality, and 150 DEG C of vacuum distillations remove solvent and water, obtain organic silicon rigidity-increasing Stick.Molecular weight, appearance and refractive index data are as shown in table 4.

Embodiment 55

Weigh 20g phenyltrimethoxysila,e, 35g diphenyl Dimethoxane base silane, 15g methyl ethylene dimethoxy In a round bottom flask, the toluene of the quality such as addition is made into monomer matter for silane, 5g tetramethyl divinyl disiloxane mixing postposition The mixed solution that amount ratio is 50% is added 8 drop trifluoromethanesulfonic acids, reaction is hydrolyzed at 40 DEG C, certain water is added dropwise in 2h, it It hydrolyzes 1h again afterwards, solution is transferred in 500ml separatory funnel, be washed to solution and neutrality is presented.95 DEG C of revolvings remove solvent later And water, 5g KH560 and 10g KH570 silane coupling agent is added, the potassium hydroxide of 0.1wt% is warming up to 100 DEG C of reaction 5h. Reaction solution is transferred in 500ml separatory funnel, neutrality is washed to, 150 DEG C of vacuum distillations remove solvent and water, obtain organosilicon Tackifier.Molecular weight, appearance and refractive index data are as shown in table 4.

Embodiment 56

The present embodiment provides high refractive index LED to encapsulate silicon resin composition, and preparation method is as follows.

By the 50g phenyl hydrogen-containing siloxane tree in the 50g phenylethylene based siloxane resins and embodiment 17 in embodiment 1 Rouge mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 15g in embodiment 33, the 1.5g organic silicon rigidity-increasing in embodiment 45 The Karstedt catalyst of stick and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven 1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.It is sealed using surface-mount type Dress technique is packaged component, and detects electronic part package after-poppet and silicone resin air-tightness using red ink experiment, As illustrated in fig. 9.

Embodiment 57

By the 50g phenyl hydrogen-containing siloxane tree in the 50g phenylethylene based siloxane resins and embodiment 17 in embodiment 1 Rouge mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 10g in embodiment 33, the 1.5g organosilicon thickening in embodiment 45 The Karstedt catalyst of agent and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven 1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.

Embodiment 58

By the 40g phenyl hydrogen-containing siloxane tree in the 40g phenylethylene based siloxane resins and embodiment 17 in embodiment 1 Rouge mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 15g in embodiment 33, the 1.5g organic silicon rigidity-increasing in embodiment 45 The Karstedt catalyst of stick and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven 1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.

Embodiment 59

By the 50g phenyl hydrogen-containing siloxane in the 50g phenylethylene based siloxane resins and embodiment 27 in embodiment 14 Resin mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 15g in embodiment 38, the 1.5g organic silicon rigidity-increasing in embodiment 51 The Karstedt catalyst of stick and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven 1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.

Embodiment 60

By the 50g phenyl hydrogen-containing siloxane in the 50g phenylethylene based siloxane resins and embodiment 31 in embodiment 11 Resin mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 15g in embodiment 36, the 1.5g organic silicon rigidity-increasing in embodiment 47 The Karstedt catalyst of stick and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven 1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.

Embodiment 61

By the 50g phenyl hydrogen-containing siloxane tree in the 50g phenylethylene based siloxane resins and embodiment 26 in embodiment 1 Rouge mixing adds the hyperbranched phenyl siloxane reinforcing agent of the 15g in embodiment 44, the 1.5g organic silicon rigidity-increasing in embodiment 52 The Karstedt catalyst of stick and 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications in baking oven 1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h obtain transparent silicon resin cured product.Performance is as shown in table 5.

Comparative example 1

By the 50g phenylethylene based siloxane resins in embodiment 1, the 50g phenyl hydrogen-containing siloxane tree in embodiment 17 Rouge mixing, is added the Karstedt catalyst of 10ppm, stirs evenly, and vacuum defoamation to bubble-free occurs, and is placed in 100 in baking oven DEG C solidification 1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h, acquisition transparent silicon resin cured product.Performance is as shown in table 5.Use table Mounted packaging technology is packaged component, and using red ink experiment detection electronic part package after-poppet and silicone resin gas Close property, as shown in figure 9b.

Comparative example 2

By the 50g phenyl hydrogen-containing siloxane tree in the 50g phenylethylene based siloxane resins and embodiment 17 in embodiment 1 Rouge mixing, adds the Karstedt catalyst of the 15g hyperbranched phenyl MT siloxanes and 10ppm in embodiment 33, and stirring is equal Even, vacuum defoamation to bubble-free occurs, and is placed in 100 DEG C of solidifications 1h, 130 DEG C of solidifications 2h, 150 DEG C of solidification 3h in baking oven, obtains saturating Bright silicone resin cured product.Performance is as shown in table 5.Component is packaged using surface-mount type packaging technology, and uses red ink Water experiment detection electronic part package after-poppet and silicone resin air-tightness, as is shown in fig. 9 c.

The Nature comparison of the phenylethylene based siloxane resins prepared under 1 different condition of table

Such as table 1, the phenylethylene based siloxane resins being prepared under different condition in embodiment 1~16 all have higher Refractive index, by change preparation condition, the molecular weight and mobility of adjustable phenylethylene based siloxane resins, specifically such as Under: Examples 1 to 3 shows that when condensation reaction time is shorter, generation is mainly the lower oligomer of molecular weight, mobility Preferably；With the extension of condensation reaction, the decline of product mobility is more inconvenient for subsequent cure operation.1,4,5 table of embodiment Bright, influence of the temperature to polymer is complex, and increasing temperature can be improved ring-opening reaction rate, improves the molecule of polymer Amount, but excessively high temperature can accelerate the progress of depolymerization back reaction, instead phenyl content is reduced, refractive index is caused to decline.It is real It applies example 1,6,7 and shows that three kinds of resulting molecular weight of product of catalysts polymerization are very close, but NaOH catalytic polymerization institute The product appearance obtained is creamy white, (CH₃)₄NOH catalytic polymerization resulting product appearance is faint yellow in cream, and KOH makees catalytic polymerization Resulting product appearance is in colorless and transparent, and molecular weight and refractive index reach requirement, therefore KOH is that more preferably condensation reaction is urged Agent.When embodiment 1,8,9 shows that the amount of catalyst is excessive, rate of polymerization is too fast, and system is not easy to control, leads to the saturating of product Light rate reduces.Embodiment 1,10 shows that hydrolysis temperature directly affects the hydrolysis rate of monomer and the appearance of final polymer, temperature It is excessively high to result even in gel, it is difficult to obtain transparent uniform liquid.Embodiment 1,11,12,13,14 shows end-capping reagent tetramethyl The content of divinyl disiloxane can effectively control the molal weight of polymer, with the increase of end-capping reagent dosage, gather Adduct molecule amount gradually reduces, if end-capping reagent is not added, the molecular weight of product is difficult to control, and is easy gelation；And add end-capping reagent Product can be made with dimethylvinylsiloxy silicon substrate sealing end, with hydrogen-containing siloxane solidification process, hydrosilylation can prolong Long chain improves the performance of cured product；Methylvinyldimethoxysilane content can also play the second for adjusting product The effect of amount vinyl content.Embodiment 1,15,16 show dimethoxydiphenylsilane content can effectively adjust phenyl content and Refractive index, but content increase also results in mobility reduction.

The Nature comparison of the phenyl hydrogen containing siloxane resin prepared under 2 different condition of table

Such as table 2, the phenyl hydrogen containing siloxane resin being prepared under different condition in embodiment 17~32 all have compared with High refractive index, by change preparation condition, the molecular weight and mobility of adjustable phenyl hydrogen containing siloxane resin, specifically As follows: embodiment 17,21,24,25,26 shows that with the extension of reaction time, relative molecular weight first increases to be reduced afterwards, works as contracting When the conjunction time is shorter, the unreacted silicone hydroxyl of remaining in system, so that condensation degree is inadequate, molecular weight is smaller；It is super when the time After crossing 4h, polymer molecule depolymerization rate is greater than polycondensation rate, and the extension condensation time can make molecular weight become smaller, but can guarantee to gather It is more regular to close object rearrangement.When embodiment 18,19,20,21 shows that condensation temp is lower, it is condensed not exclusively between silanol, product is in Existing milky；And excessively high temperature can make polymer depolymerization rate increase, so that molecular weight of product reduces；Condensation temp 130 DEG C when prepolymer it is colorless and transparent and molecular weight is suitable, be more preferably condensation temp.Embodiment 20,21 shows water to product Refractive index influences less, but can very big influence on the appearance of system；With increasing for amount of water, lead to the hydrolysis speed of each monomer Rate is inconsistent, so that hydrolyzate is inhomogenous, and then is cyclized between the silanol that hydrolysis may be made to generate, milky is presented in product.It is real It applies example 20,22,23 and shows that three kinds of different catalysts have certain catalytic effect, the molecular weight product of concentrated hydrochloric acid preparation is little, has Color；For strong-acid cation-exchange resin since catalytic activity is slightly lower, molecular weight of product is not big enough, although having reacted filtering can remove It goes, it is also possible to may be crushed and influence the transparency of product in whipping process；The prepolymer of glacial acetic acid preparation is colourless Bright, molecular weight and refractive index are relatively met the requirements, and are more preferably catalyst.Embodiment 20,27,28 shows to use with catalyst The increase of amount, molecular weight become larger until stabilization.Embodiment 20,29,30 shows the content of end-capping reagent tetramethyl disiloxane The molal weight of polymer can be effectively controlled, with the increase of end-capping reagent dosage, polymer molecular weight is gradually reduced.Implement Example 20,31,32 shows that adjusting raw material proportioning can change molecular weight of product and refractive index, general phenyltrimethoxysila,e phase Raising to content can increase molecular weight and refractive index, but also be easy to cause solidfied material brittleness larger.

The Nature comparison of the hyperbranched phenyl siloxane reinforcing agent prepared under 3 different condition of table

Such as table 3, the hyperbranched phenyl siloxane reinforcing agent being prepared under different condition in embodiment 33~44 is all had Higher refractive index, by change preparation condition, the molecular weight and mobility of adjustable hyperbranched phenyl siloxane reinforcing agent, Specific as follows: when embodiment 33,34,35 shows that condensation temp is lower, collision probability is lower between silicone hydroxyl at this time, effective collision It reduces, the extent of reaction reduces, and the polymer molecular weight of generation is smaller, and mobility is preferable；If condensation temp is excessively high, point of system Son movement is fierce, and the effective collision between silicone hydroxyl is accelerated, and the progress of condensation reaction is promoted, and the molecular weight of product of generation is larger, Molecular chain movement becomes difficult, so that polymer viscosity significantly becomes larger, becomes gel when serious.Embodiment 33,36,37 shows not Same catalyst is affected to the hydrolytic condensation of siloxanes, and sulphuric acid catalysis activity is higher, and molecular weight of product is obviously greater than Glacial acetic acid and concentrated hydrochloric acid catalysate, glacial acetic acid and concentrated hydrochloric acid product be more preferably under same catalyst concentration.Embodiment 33,38,39 Show the raising in scope of experiment with catalyst amount, the hydrolysis of siloxanes and condensation rate are continuously increased, the extent of reaction It improves, the polymer molecular weight of generation also increases, and the viscosity of product at this time increases.Embodiment 36,40,41 shows different Apparent difference can occur for the viscosity of amount of water, product, and when amount of water is more, product has a large amount of hydroxyl, due to molecule Between hydrogen bond action the viscosity of product can be made to become larger；When amount of water is less, the polymer molecular weight after condensation is smaller, viscosity compared with It is low, good fluidity, but the polymer molecular weight generated is too low, can decline to the reinforcing effect of material, therefore, in order to ensure that product has Certain reinforcing effect and suitable molecular weight need to control the ratio of water and methoxy functional group.36,42,43 table of embodiment Bright, the ratio of hexamethyldisiloxane and tetramethyl divinyl disiloxane end-capping reagent is affected to molecular weight of product, when When end-capping reagent dosage is lower, molecular weight is larger, and mobility decline, the active group of molecule chain end such as vinyl can be reduced, instead It answers site to reduce, when being added in matrix, effective reinforcement cannot be carried out to matrix；When end-capping reagent dosage is excessive, molecule Measure lower, the viscosity of product is smaller at this time, but excessive end-capping reagent causes reaction site to increase, if at this time as reinforced filling, Also the mechanical property such as degraded toughness that can make product is added in matrix, and material easily becomes fragile.When the variation of end-capping reagent ratio, also mean The variation of phenyltrimethoxysila,e content, in conjunction with embodiment 44, as a result also turn out improve phenyltrimethoxysila,e contain Amount, can increase the refractive index of product.

The Nature comparison of the organic silicon rigidity-increasing stick prepared under 4 different condition of table

Such as table 4, the organic silicon rigidity-increasing stick being prepared under different condition in embodiment 45~55 all has higher refraction Rate, by changing preparation condition, the molecular weight and mobility of adjustable organic silicon rigidity-increasing stick be specific as follows: embodiment 45,46, After 47 show that condensation temp influences less the refractive index of product, but condensation molecular weight first becomes larger with the raising of reaction temperature Reduce.Embodiment 45,48,49 shows that the extension with the condensation time, condensation reach dynamic equilibrium, and product molecule amount is larger, So that the mobility of product declines, viscosity becomes larger；And with the extension of condensation time, the siloxanes for being condensed generation is reset more Sufficiently, the copolymer of generation is further rearranged into regular structure.Embodiment 45,50,51 shows KH560 depositing due to amino It is light yellow product can be made to have, and individually the compounding in the smaller situation of KH570 KH560 content does not affect the face of product Color, furthermore coupling agent influences molecular weight of product and refractive index little.Embodiment 45,52,53 shows with end-capping reagent dosage Increase, the number-average molecular weight of product gradually decreases, and illustrates that end-capping reagent can carry out very big adjusting to the molecular weight of polymer；This Outside, it can be seen that end-capping reagent dosage refractive index is affected, as end-capping reagent dosage increases, phenyl content relative reduction, folding The rate of penetrating gradually decreases.Embodiment 45,54,55 shows can be by control phenyltrimethoxysila,e and diphenyl Dimethoxane The additional amount of base silane adjusts refractive index, and phenyl content of monomer is higher, and refractive index is bigger；But refractive index is not more Gao Yue It is good, when refractive index difference is larger, it will lead to and decline with the compatibility of other components, influence final LED encapsulation silicone resin solidfied material Light transmittance.

5 silicone resin Solidified enzyme of table compares

Embodiment 56,57,58, comparative example 1 and comparative example 2 show hyperbranched phenyl siloxane reinforcing agent and organic silicon rigidity-increasing The increase of stick ratio plays a significant role the mechanical strength and adhesion strength that improve product.Embodiment 56,59,60 shows By reasonably select different condition under composition, can reach higher comprehensive performance, by with several commercialization silicone resin Comparison, show using this method preparation silicone resin have more excellent refractive index, tensile strength and adhesion strength.

Fig. 9 is the surface welded LED wrapper of embodiment 56 (Fig. 9-a), comparative example 1 (Fig. 9-b) and comparative example 2 (Fig. 9-c) The red ink test result photo of part.From figure it is found that embodiment 56 encapsulate substrate in red ink 80 DEG C boil two hours after, Chip interior does not have red ink infiltration, and the caking property of the silicone material and substrate that illustrate preparation is preferable, can effectively obstruct The intrusion of steam, oxygen and dust etc. has enough air-tightness.And it is not added with hyperbranched phenyl siloxane reinforcing agent and organic The product (comparative example 1) of silicon tackifier and product (comparative example 2) edge for being not added with tackifier have a small amount of red ink to seep Thoroughly.

Those of ordinary skill in the art will understand that embodiment here be to help reader understand it is of the invention Principle, it should be understood that protection scope of the present invention is not limited to such specific embodiments and embodiments.This field it is common Technical staff disclosed the technical disclosures can make the various various other tools for not departing from essence of the invention according to the present invention Body variations and combinations, these variations and combinations are still within the scope of the present invention.

Claims

1. a kind of phenylethylene based siloxane resins, which is characterized in that be prepared via a method which to obtain:

S1: by monomer: dimethoxydiphenylsilane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane and four Divinyl disiloxane mixing is added organic solvent and obtains mixed solution, hydrolyst is added；The diphenyl two Methoxy silane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane and tetramethyl divinyl disiloxane Mass ratio is 50~70:10~20:10~30:5~15；

S2: being added dropwise water at 30~60 DEG C and reaction be hydrolyzed, wash, vacuum distillation, be added base catalyst adjust pH for 11~ 14, condensation reaction is carried out at 120~160 DEG C, is washed, and is evaporated under reduced pressure up to the phenylethylene based siloxane resins.

2. phenylethylene based siloxane resins according to claim 1, which is characterized in that diphenyl dimethoxy silicon in S1 Alkane, methylvinyldimethoxysilane, octamethylcy-clotetrasiloxane and tetramethyl divinyl disiloxane mass ratio be 50:15:20:5。

3. phenylethylene based siloxane resins according to claim 1, which is characterized in that the quality of monomer in S1 mixed solution Score is 25~75%.

4. a kind of high refractive index LED encapsulates silicon resin composition, which is characterized in that be grouped as by the group of following parts by weight:

5. high refractive index LED encapsulates silicon resin composition according to claim 4, which is characterized in that by following parts by weight Group be grouped as:

6. high refractive index LED encapsulates silicon resin composition according to claim 4, which is characterized in that the phenyl Silicon Containing Hydrogen Oxygen alkane resin is prepared by the following procedure method and obtains: by monomer: phenyltrimethoxysila,e, dimethoxydiphenylsilane, tetramethyl Basic ring tetrasiloxane and tetramethyl disiloxane, water and the mixing of hydrolysis catalyst, are added organic solvent and obtain mixed solution, rise Temperature is to 30~60 DEG C of 1~5h of hydrolysis, then is warming up to 110~140 DEG C of points of water and reacts 2~11h, and washing is evaporated under reduced pressure to obtain the final product The phenyl hydrogen-containing siloxane resin；The phenyltrimethoxysila,e, dimethoxydiphenylsilane, tetramethyl cyclotetrasiloxane silicon oxygen The mass ratio of alkane and tetramethyl disiloxane is 15~25:45~55:10~20:1.5~15.

7. high refractive index LED encapsulates silicon resin composition according to claim 4, which is characterized in that the hyperbranched phenyl Siloxanes reinforcing agent is prepared via a method which to obtain: by monomer: two silicon oxygen of hexamethyldisiloxane and tetramethyl divinyl Alkane, water and acid catalyst mixing, are added organic solvent and obtain mixed solution, phenyltrimethoxysila,e is added dropwise, then 30~50 0.5~4h of hydrolysis at DEG C, is warming up to 50~120 DEG C the reaction was continued 1~3h, and washing is evaporated under reduced pressure up to described hyperbranched Phenyl siloxane reinforcing agent；The hexamethyldisiloxane, tetramethyl divinyl disiloxane and phenyltrimethoxysila,e Mass ratio be 5~15:10~20:15~25.

8. high refractive index LED encapsulates silicon resin composition according to claim 7, which is characterized in that the hyperbranched phenyl The structural formula of siloxanes reinforcing agent is as follows:

9. high refractive index LED encapsulates silicon resin composition according to claim 4, which is characterized in that the organosilicon thickening Agent is prepared via a method which to obtain: by monomer: phenyltrimethoxysila,e, dimethoxydiphenylsilane, methyl ethylene After dimethoxysilane and tetramethyl divinyl disiloxane mixing, organic solvent is added and obtains mixed solution, hydrolysis is added and urges Reaction washing is hydrolyzed at 30~50 DEG C, silane coupling agent and condensation catalyst is added after revolving, is warming up to for agent 80~140 DEG C of 1~7h of reaction；Washing filters up to the organic silicon rigidity-increasing stick；The phenyltrimethoxysila,e, diphenyl The matter of Dimethoxane base silane, methylvinyldimethoxysilane, tetramethyl divinyl disiloxane and silane coupling agent Amount is than being 15~25:25~35:10~20:2~15:10~20.

10. the preparation method of any high refractive index LED encapsulation silicon resin composition of claim 4~9, which is characterized in that Include the following steps: to mix phenylethylene radical siloxane and phenyl hydrogen-containing siloxane, adds hyperbranched phenyl siloxane, silicon Tackifier resin and Karstedt catalyst, stirring, de-bubbled solidify up to high refractive index LED encapsulation silicone resin combination Object.