CN109880101A - A kind of LED packaging plastic epoxidation modification phenyl polysiloxane and preparation method thereof - Google Patents
A kind of LED packaging plastic epoxidation modification phenyl polysiloxane and preparation method thereof Download PDFInfo
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- CN109880101A CN109880101A CN201910145293.5A CN201910145293A CN109880101A CN 109880101 A CN109880101 A CN 109880101A CN 201910145293 A CN201910145293 A CN 201910145293A CN 109880101 A CN109880101 A CN 109880101A
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Abstract
The invention belongs to LED packaging plastic technical fields, and in particular to a kind of LED packaging plastic epoxidation modification phenyl polysiloxane and preparation method thereof.This method combines hydrolyzed collosol-gelatin and non-hydrolytic sol-gel process, first pass through intermediate of the sol-gel method synthesis containing hydroxyl of hydrolysis, then intermediate is subjected to non-hydrolytic sol-gel process with the siloxanyl monomers containing epoxy and carries out dealcoholization, to eliminate the hydroxyl in modified silicone resin, it can be effectively prevented epoxy addition, greatly improve the high temperature resistant and mechanical performance of cured product.This method is introduced into most of epoxy groups on the end group of product, increases the activity of epoxy group, is conducive to the rapid curing reaction in its later period.Thus the light transmittance of epoxidation modification phenyl polysiloxane obtained by is high, thermal stability is good.Viscosity is 500~10000mpa.s, and molecular weight is 1000~8000, and molecular weight distributing index PDI is 1.2~1.6, and refractive index is 1.50~1.55, may be used as LED packaging plastic material.
Description
Technical field
The invention belongs to LED packaging plastic technical fields, and in particular to a kind of LED packaging plastic is with epoxidation modification phenyl silicon tree
Rouge and preparation method thereof.
Background technique
Light emitting diode (LED) is a kind of novel light-emitting equipment efficiently, energy saving and environmentally friendly, consumption low with operating voltage
Electricity is small, luminous efficiency is high, emission response time is extremely short, photochromic pure, sound construction, performance is stable, the at low cost and service life is long etc.
Series of characteristics.In the today's society that energy relative shortage, pollution are got worse, the extensive use of LED has great importance.
LED is mainly by chip, lead, bracket, the composition such as encapsulating material.Wherein for encapsulating material mainly there are two effect, one is protection
Chip and frangible lead, the other is improving the light extraction efficiency of LED.Therefore encapsulating material has the service life of LED important
It influences, is the key technology of LED practical application.
With the fast development of LED, the requirement to encapsulation technology is also increasingly stringenter.Since traditional low-power LED seals
Package material there is indexs of refraction it is low, light transmittance is poor, high temperature resistant and ultraviolet ageing are poor the disadvantages of, be no longer satisfied the need in market
It asks, therefore produces that performance is good and low-cost high-power LED encapsulation material becomes the hot spot studied now.With common LED
Encapsulating material is compared, and high-capacity LED needs work under the ultraviolet radioactive of higher temperature and higher intensity, therefore great power LED
To the comprehensive performance of encapsulating material in anti-ultraviolet radiation, translucency and heat resistance, there is higher requirement.Organic siliconresin is
It is used for the active material of high-power LED encapsulation material in recent years, this is because silicone resin is the poly- of highly cross-linked reticular structure
Organosiloxane has good thermal stability, the transparency, cold-resistant thermal impact, agent of low hygroscopicity, low surface tension and low glass
The advantages that glass transition temperature.But surface of silicone resin can be low, when being used as potting resin to the bracket of LED chip
Adhesive force is inadequate, it is necessary to introduce adhesion promoting groups to improve adhesive force.Epoxy group under the high temperature conditions can be with the hydroxyl on substrate
Chemical reaction occurs and forms chemical bond, thus to substrate bonding force with higher, so being introduced into silicone resin structure
The bonding force of silicone resin can be effectively improved.
The sol-gel technology synthesis that Chinese patent CN108384010A discloses a kind of hydrolysis has both organosilicon polymer
With the good epoxidation modification silicone resin of comprehensive performance of both epoxy resin advantage.Its preparation process is: with having containing epoxy
Organic siloxane and the organosiloxane containing phenyl are raw material, and alkalescence anion-exchange resin is catalyst, in condition of heating and stirring
Under condensation reaction is hydrolyzed, be made epoxidation modification phenyl polysiloxane.The preparation process is easy to operate, but in the mistake of reaction
Cheng Zhonghui generates a large amount of reactive hydrogen, leads to epoxy addition, so that product gel.And due to the epoxidation modification of synthesis
Remaining a large amount of hydroxyl in the structure of phenyl polysiloxane, the encapsulating material of synthesis the shortcomings that there are easy xanthochromia and bad mechanical properties.
Therefore suitable and simple synthesis technology is selected, prevents epoxy gellation, the synthesis for epoxidation modification silicone resin
And its extensive use and reduction production cost have vital effect.
Summary of the invention
In order to solve the above-mentioned technical problem, changed the primary purpose of the present invention is that providing a kind of LED packaging plastic with epoxidation
The preparation method of property phenyl polysiloxane.The preparation process efficiently avoids the gel of epoxy, greatly elimination hydroxyl, to mention
The high temperature resistance and mechanical performance of high LED encapsulation material.And most of epoxy group is introduced into the end group in product, improve ring
The reactivity in the curing process of oxygroup.The epoxidation modification silicone resin that this method is prepared is colorless and transparent thick
Liquid, light transmittance, refractive index are high, and thermal stability is good, may be used as LED packaging plastic material.
Another object of the present invention is to provide a kind of LED packaging plastic epoxidation modifications obtained by above-mentioned preparation method
Phenyl polysiloxane.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of preparation method of LED packaging plastic epoxidation modification phenyl polysiloxane, comprising the following steps:
(1) the phenyl polysiloxane oligomer of terminal hydroxy group is prepared with the sol-gel method of hydrolysis
Using containing phenyl organosiloxane and distilled water as raw material, D301R type basic anionic resin be catalyst, adding
The sol gel reaction being hydrolyzed under the conditions of thermal agitation obtains the crude product of the phenyl polysiloxane of terminal hydroxy group, by crude product into
Row decompression, which filters, removes alkalescence anion-exchange resin, is then allowed to stand layering, takes subnatant, carries out vacuum distillation removing low boiling
Object obtains the phenyl polysiloxane oligomer of terminal hydroxy group.
(2) epoxidation modification phenyl polysiloxane is prepared with non-hydrolytic sol-gel
The phenyl polysiloxane oligomer of terminal hydroxy group is instilled in the organosiloxane containing epoxy, reactant is obtained, in D301R
Under the catalysis of type basic anionic resin, non-hydrolytic sol gel reaction is carried out, the crude product of preparation is subjected to decompression pumping
Filter removes alkalescence anion-exchange resin, and then vacuum distillation removing low-boiling-point substance is to get to the LED packaging plastic epoxy
Change modified phenyl polysiloxane.
Preferably, the organosiloxane containing phenyl described in step (1) is phenyltrimethoxysila,e, three ethoxy of phenyl
Base silane, dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane and aminomethyl phenyl two
One or more of Ethoxysilane.
Preferably, organosiloxane and distilled water containing phenyl in the sol gel reaction of hydrolysis described in step (1)
Mass ratio be 2:1~1:1.
Preferably, in the sol gel reaction of hydrolysis described in step (1), the use of D301R type basic anionic resin
Amount is the 0.9%~2% of raw material gross weight.
Preferably, the reaction temperature of the sol gel reaction of hydrolysis described in step (1) is 60~90 DEG C, when reaction
Between be 2~4 hours.
Preferably, the condition of vacuum distillation described in step (1) is 100 DEG C and -0.096MPa.
The phenyl polysiloxane oligomer of terminal hydroxy group described in step (1) is colorless and transparent.
Preferably, the organosiloxane containing epoxy described in step (2) is 3- glycidyl ether oxygen propyl trimethoxy
Silane, 3- glycidoxypropyltrietandysilane andysilane, 3- glycidyl ether oxygen propyl methyl dimethoxysilane, 3- shrink
Glycerol ether oxygen propyl methyldiethoxysilane, [2- (3,4- epoxycyclohexyl)] ethyl trimethoxy silane and [2- (3,4- ring
One or more of oxygen cyclohexyl)] ethyl triethoxysilane.
Preferably, in reactant described in step (2), molar ratio 1:1~1:2 of hydroxyl and alkoxy.
Preferably, the dosage of D301R type basic anionic resin described in step (2) is the 0.9% of reactant quality
~2%.
Preferably, the phenyl polysiloxane oligomer of terminal hydroxy group is instilled into the organosilicon oxygen containing epoxy described in step (2)
Time for adding in alkane is 1~2h.
Preferably, the reaction temperature of sol gel reaction non-hydrolytic described in step (2) is 80~95 DEG C, reaction
Time is 4~6h.
Low-boiling-point substance described in step (2) is the mixture of methanol, ethyl alcohol or methanol and ethyl alcohol.
Preferably, the condition of vacuum distillation described in step (2) is 120 DEG C and -0.096MPa.
The present invention further provides a kind of LED packaging plastic epoxidation modification phenyl silicon trees obtained by above-mentioned preparation method
Rouge.
Compared with the existing technology, beneficial effects of the present invention are as follows:
The present invention proposes a kind of hydrolyzed collosol-gelatin and non-hydrolytic sol-gel combined process, first passes through the molten of hydrolysis
Glue-gel method synthesizes the intermediate containing certain hydroxyl, then carries out intermediate with the siloxanyl monomers containing epoxy non-
Hydrolytic sol-gel process carries out dealcoholization.This technique is for the synthesis good epoxidation modification silicone resin of comprehensive performance
It is highly beneficial.
(1) during non-hydrolytic sol-gel, under the conditions of water-free, by making silanol carry out dealcoholization,
To eliminate the hydroxyl in modified silicone resin, the high temperature resistant and mechanical performance of cured product are greatly improved.
(2) it is divided into two steps by that will react, the structure of product is designed, so that most of epoxy groups are introduced into product
End group on, increase the activity of epoxy group, be conducive to its later period rapid curing reaction.
(3) due to the high reaction activity of hydrolyzed collosol-gelatin, the production with moderate viscosity can be synthesized in a short time
Object.Therefore new process can overcome non-hydrolytic sol-gel process poor efficiency, and greatly shorten the reaction time.
(4) due to the high reaction activity of epoxy group, so that it is in the hydrolyzed collosol-gelatin technique for containing a large amount of reactive hydrogens
It neutralizes and is easy to happen the reaction of open loop under hot conditions, and then cause product gel.Since non-hydrolytic sol-gel has phase
Epoxy group is introduced to stable environment, therefore in non-hydrolytic sol-gel process, epoxy can be effectively prevented
Open loop, so that efficiently epoxy group is introduced into the structure of silicone resin.
Therefore there is excellent property by hydrolyzed collosol-gelatin and non-hydrolytic sol-gel combined process synthesis product
Energy.The epoxidation modification phenyl polysiloxane of preparation is colorless transparent viscous liquid, and light transmittance is high, thermal stability is good.By right
Reaction condition and raw material proportioning carry out certain adjustment, can control between 500~10000mpa.s of viscosity of product, molecular weight
Between 1000~8000, molecular weight distributing index PDI is between 1.2~1.6, and refractive index is between 1.50~1.55, epoxy
(mol/100g epoxidation modification phenyl polysiloxane) content between 0.05~0.25, may be used as LED packaging plastic material.
Detailed description of the invention
Fig. 1 is the reaction principle figure of epoxidation modification phenyl polysiloxane prepared by embodiment 1.
Fig. 2 is the infrared spectrum of epoxidation modification phenyl polysiloxane prepared by embodiment 1.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
For not specifically specified technological parameter, routine techniques progress can refer to.
Embodiment 1
The present embodiment provides a kind of LED packaging plastic epoxidation modification phenyl polysiloxanes and preparation method thereof.
(1) preparation of the phenyl polysiloxane of terminal hydroxy group
Take the D301R type alkalescence anion-exchange resin of 97.2g deionized water and 1.71g in equipped with magnetic stir bar, temperature
It spends in the four-hole boiling flask of the 250ml of controller, control reaction temperature is 85 DEG C.Then by 54.69g aminomethyl phenyl dimethoxy silicon
Alkane and 19.8g phenyltrimethoxysila,e after mixing, are added dropwise and enter flask.Complete, beginning timing is dripped off to raw material.React 2h
Afterwards, decompression filters removal catalyst.Then filtrate moves to separatory funnel washing, and (water is in upper layer target product under for stratification
Layer).It takes lower layer's product to be evaporated under reduced pressure under 100 DEG C and -0.096Mpa, removes the small-molecule substances such as water, methanol, can obtain
It is clear thick liquid to the phenyl polysiloxane oligomer of terminal hydroxy group.It is 790mpa.s, yield through detection viscosity
87.23%.Fig. 1 shows the reaction principles of the reaction.
(2) preparation of Gao Zhehuan oxidation modification phenyl polysiloxane
Take the phenyl polysiloxane of 50g step (1) synthesis terminal hydroxy group and the 3- glycidyl ether oxygen propyl trimethoxy of 35.45g
Then the D301R type alkali of 1wt% is added in the three-necked flask of the 150ml equipped with magnetic stir bar, temperature controller in base silane
Property anion exchange resin, control reaction temperature be 95 DEG C.After reaction time is 4h, decompression, which filters, removes catalyst, then will
Filtrate is transferred in round bottom distilling flask, a small amount of water of the by-product under the conditions of 120 DEG C and -0.096Mpa in removing system,
Methanol is clear thick liquid to get the LED packaging plastic epoxidation modification phenyl polysiloxane is arrived.Fig. 1 shows this
The reaction principle of reaction.Viscosity is detected as 4720mpa.s, yield 90.04%, number-average molecular weight 4137g/mol divides equally again
Son amount is 6334g/mol, molecular weight distributing index 1.531, epoxide number 0.20mol/100g.
Embodiment 2
The present embodiment provides a kind of LED packaging plastic epoxidation modification phenyl polysiloxanes and preparation method thereof.
(1) preparation of the phenyl polysiloxane of terminal hydroxy group
Take the D301R type alkalescence anion-exchange resin of 129.6g deionized water and 2.24g in equipped with magnetic stir bar, temperature
It spends in the four-hole boiling flask of the 250ml of controller, control reaction temperature is 85 DEG C.Then by 54.69g aminomethyl phenyl dimethoxy silicon
Alkane and 39.66g phenyltrimethoxysila,e after mixing, are added dropwise and enter flask.Complete, beginning timing is dripped off to raw material.Reaction
After 2h, decompression filters removal catalyst.Then filtrate moves to separatory funnel washing, and (water exists stratification in upper layer target product
Lower layer).It takes lower layer's product to be evaporated under reduced pressure under 100 DEG C and -0.096Mpa, removes the small-molecule substances such as water, methanol
The phenyl polysiloxane oligomer of terminal hydroxy group is obtained, is clear thick liquid.It is 1480mpa.s, yield through detection viscosity
88.57%.
(2) preparation of Gao Zhehuan oxidation modification phenyl polysiloxane
Take the phenyl polysiloxane of 50g step (1) synthesis terminal hydroxy group and [2- (3,4- epoxycyclohexyl)] ethyl of 36.96g
Then trimethoxy silane is added 1wt%'s in the three-necked flask of the 150ml equipped with magnetic stir bar, temperature controller
D301R type alkalescence anion-exchange resin, control reaction temperature are 95 DEG C.After reaction time is 4h, decompression, which filters, removes catalysis
Then filtrate is transferred in round bottom distilling flask by agent, the by-product under the conditions of 120 DEG C/- 0.096Mpa in removing system is few
The water of amount, methanol are clear thick liquid to get the LED packaging plastic epoxidation modification phenyl polysiloxane is arrived.Through
Detection viscosity is 5793mpa.s, yield 92.71%.
Embodiment 3
The present embodiment provides a kind of LED packaging plastic epoxidation modification phenyl polysiloxanes and preparation method thereof.
(1) preparation of the phenyl polysiloxane of terminal hydroxy group
Take the D301R type alkalescence anion-exchange resin of 97.2g deionized water and 1.71g in equipped with magnetic stir bar, temperature
It spends in the four-hole boiling flask of the 250ml of controller, control reaction temperature is 85 DEG C.Then by 73.31g dimethoxydiphenylsilane
After mixing with 19.8g phenyltrimethoxysila,e, it is added dropwise and enters flask.Complete, beginning timing is dripped off to raw material.React 2h
Afterwards, decompression filters removal catalyst.Then filtrate moves to separatory funnel washing, and (water is in upper layer target product under for stratification
Layer).It takes lower layer's product to be evaporated under reduced pressure under 100 DEG C and -0.096Mpa, removes the small-molecule substances such as water, methanol, can obtain
It is clear thick liquid to the phenyl polysiloxane oligomer of terminal hydroxy group.It is 1273mpa.s, yield through detection viscosity
89.54%.
(2) preparation of Gao Zhehuan oxidation modification phenyl polysiloxane
Take the phenyl polysiloxane of 50g step (1) synthesis terminal hydroxy group and the 3- glycidyl ether oxygen propyl trimethoxy of 23.63g
Then the D301R type alkali of 1wt% is added in the three-necked flask of the 150ml equipped with magnetic stir bar, temperature controller in base silane
Property anion exchange resin, control reaction temperature be 95 DEG C.After reaction time is 4h, decompression, which filters, removes catalyst, then will
Filtrate is transferred in round bottom distilling flask, a small amount of water of the by-product under the conditions of 120 DEG C and -0.096Mpa in removing system,
Methanol is clear thick liquid to get the LED packaging plastic epoxidation modification phenyl polysiloxane is arrived.It is viscous through detecting
Degree is 2680mpa.s, yield 91.18%.
Embodiment 4
The present embodiment provides a kind of LED packaging plastic epoxidation modification phenyl polysiloxanes and preparation method thereof.
(1) preparation of the phenyl polysiloxane of terminal hydroxy group
Take the D301R type alkalescence anion-exchange resin of 97.2g deionized water and 1.71g in equipped with magnetic stir bar, temperature
It spends in the four-hole boiling flask of the 250ml of controller, control reaction temperature is 85 DEG C.Then by 73.31g dimethoxydiphenylsilane
After mixing with 19.8g phenyltrimethoxysila,e, it is added dropwise and enters flask.Complete, beginning timing is dripped off to raw material.React 2h
Afterwards, decompression filters removal catalyst.Then filtrate moves to separatory funnel washing, and (water is in upper layer target product under for stratification
Layer).It takes lower layer's product to be evaporated under reduced pressure under 100 DEG C and -0.096Mpa, removes the small-molecule substances such as water, methanol, can obtain
The phenyl polysiloxane oligomer of terminal hydroxy group is clear thick liquid.It is 1273mpa.s, yield through detection viscosity
89.54%.
(2) preparation of Gao Zhehuan oxidation modification phenyl polysiloxane
Take the phenyl polysiloxane of 50g step (1) synthesis terminal hydroxy group and the 3- glycidyl ether oxygen propyl trimethoxy of 35.45g
Then the D301R type alkali of 1wt% is added in the three-necked flask of the 150ml equipped with magnetic stir bar, temperature controller in base silane
Property anion exchange resin, control reaction temperature be 85 DEG C.After reaction time is 4h, decompression, which filters, removes catalyst, then will
Filtrate is transferred in round bottom distilling flask, a small amount of water of the by-product under the conditions of 120 DEG C and -0.096Mpa in removing system,
Methanol obtains the LED packaging plastic epoxidation modification phenyl polysiloxane, is clear thick liquid.Through detecting viscosity
For 2139mpa.s, yield 89.51%.
Embodiment 5
The present embodiment provides a kind of LED packaging plastic epoxidation modification phenyl polysiloxanes and preparation method thereof.
(1) preparation of the phenyl polysiloxane of terminal hydroxy group
Take the D301R type alkalescence anion-exchange resin of 97.2g deionized water and 1.71g in equipped with magnetic stir bar, temperature
It spends in the four-hole boiling flask of the 250ml of controller, control reaction temperature is 85 DEG C.Then by 54.69g aminomethyl phenyl dimethoxy silicon
Alkane and 19.8g phenyltrimethoxysila,e after mixing, are added dropwise and enter flask.Complete, beginning timing is dripped off to raw material.React 2h
Afterwards, decompression filters removal catalyst.Then filtrate moves to separatory funnel washing, and (water is in upper layer target product under for stratification
Layer).It takes lower layer's product to be evaporated under reduced pressure under 100 DEG C and -0.096Mpa, removes the small-molecule substances such as water, methanol, can obtain
It is clear thick liquid to the phenyl polysiloxane oligomer of terminal hydroxy group.It is 790mpa.s, yield through detection viscosity
87.23%.
(2) preparation of Gao Zhehuan oxidation modification phenyl polysiloxane
Take the phenyl polysiloxane of 50g step (1) synthesis terminal hydroxy group and the 3- glycidyl ether oxygen propyl methyl two of 33.05g
Then the D301R of 1wt% is added in the three-necked flask of the 150ml equipped with magnetic stir bar, temperature controller in methoxy silane
Type alkalescence anion-exchange resin, control reaction temperature are 95 DEG C.After reaction time is 4h, decompression, which filters, removes catalyst, so
Filtrate is transferred in round bottom distilling flask afterwards, the by-product under the conditions of 120 DEG C and -0.096Mpa in removing system is a small amount of
Water, methanol obtain the LED packaging plastic epoxidation modification phenyl polysiloxane, are clear thick liquid.It is viscous through detecting
Degree is 2576mpa.s, yield 86.24%.
Embodiment 6
The present embodiment provides a kind of LED packaging plastic epoxidation modification phenyl polysiloxanes and preparation method thereof.
(1) preparation of the phenyl polysiloxane of terminal hydroxy group
Take the D301R type alkalescence anion-exchange resin of 97.2g deionized water and 1.84g in equipped with magnetic stir bar, temperature
It spends in the four-hole boiling flask of the 250ml of controller, control reaction temperature is 85 DEG C.Then by 63.1g aminomethyl phenyl diethoxy silicon
Alkane and 24.0g phenyl triethoxysilane after mixing, are added dropwise and enter flask.Complete, beginning timing is dripped off to raw material.React 2h
Afterwards, decompression filters removal catalyst.Then filtrate moves to separatory funnel washing, and (water is in upper layer target product under for stratification
Layer).It takes lower layer's product to be evaporated under reduced pressure under 100 DEG C and -0.096Mpa, removes the small-molecule substances such as water, methanol, can obtain
It is clear thick liquid to the phenyl polysiloxane oligomer of terminal hydroxy group.It is 487mpa.s, yield through detection viscosity
83.23%.
(2) preparation of Gao Zhehuan oxidation modification phenyl polysiloxane
Take the phenyl polysiloxane of 50g step (1) synthesis terminal hydroxy group and the 3- glycidyl ether oxygen propyl trimethoxy of 35.45g
Then the D301R type alkali of 1wt% is added in the three-necked flask of the 150ml equipped with magnetic stir bar, temperature controller in base silane
Property anion exchange resin, control reaction temperature be 95 DEG C.After reaction time is 4h, decompression, which filters, removes catalyst, then will
Filtrate is transferred in round bottom distilling flask, a small amount of water of the by-product under the conditions of 120 DEG C and -0.096Mpa in removing system,
Methanol obtains the LED packaging plastic epoxidation modification phenyl polysiloxane, is clear thick liquid.Through detecting viscosity
For 2962mpa.s, yield 91.28%.
Embodiment 7
The present embodiment provides a kind of LED packaging plastic epoxidation modification phenyl polysiloxanes and preparation method thereof.
(1) preparation of the phenyl polysiloxane of terminal hydroxy group
Take the D301R type alkalescence anion-exchange resin of 97.2g deionized water and 1.71g in equipped with magnetic stir bar, temperature
It spends in the four-hole boiling flask of the 250ml of controller, control reaction temperature is 85 DEG C.Then by 54.69g aminomethyl phenyl dimethoxy silicon
Alkane and 19.8g phenyltrimethoxysila,e after mixing, are added dropwise and enter flask.Complete, beginning timing is dripped off to raw material.React 2h
Afterwards, decompression filters removal catalyst.Then filtrate moves to separatory funnel washing, and (water is in upper layer target product under for stratification
Layer).It takes lower layer's product to be evaporated under reduced pressure under 100 DEG C and -0.096Mpa, removes the small-molecule substances such as water, methanol, can obtain
It is clear thick liquid to the phenyl polysiloxane oligomer of terminal hydroxy group.It is 790mpa.s, yield through detection viscosity
87.23%.
(2) preparation of Gao Zhehuan oxidation modification phenyl polysiloxane
Take the phenyl polysiloxane of 50g step (1) synthesis terminal hydroxy group and the 3- glycidyl ether oxygen propyl trimethoxy of 35.45g
Then the D301R type of 0.5wt% is added in the three-necked flask of the 150ml equipped with magnetic stir bar, temperature controller in base silane
Alkalescence anion-exchange resin, control reaction temperature are 95 DEG C.After reaction time is 4h, decompression, which filters, removes catalyst, then
Filtrate is transferred in round bottom distilling flask, the by-product under the conditions of 120 DEG C and -0.096Mpa in removing system is a small amount of
Water, methanol obtain the LED packaging plastic epoxidation modification phenyl polysiloxane, are clear thick liquid.It is viscous through detecting
Degree is 1925mpa.s, yield 86.67%.
Embodiment 8
The present embodiment provides a kind of LED packaging plastic epoxidation modification phenyl polysiloxanes and preparation method thereof.
(1) preparation of the phenyl polysiloxane of terminal hydroxy group
Take the D301R type alkalescence anion-exchange resin of 97.2g deionized water and 1.84g in equipped with magnetic stir bar, temperature
It spends in the four-hole boiling flask of the 250ml of controller, control reaction temperature is 85 DEG C.Then by 63.1g aminomethyl phenyl diethoxy silicon
Alkane and 24.0g phenyl triethoxysilane after mixing, are added dropwise and enter flask.Complete, beginning timing is dripped off to raw material.React 2h
Afterwards, decompression filters removal catalyst.Then filtrate moves to separatory funnel washing, and (water is in upper layer target product under for stratification
Layer).It takes lower layer's product to be evaporated under reduced pressure under 100 DEG C and -0.096Mpa, removes the small-molecule substances such as water, methanol, can obtain
It is clear thick liquid to the phenyl polysiloxane oligomer of terminal hydroxy group.It is 487mpa.s, yield through detection viscosity
83.23%.
(2) preparation of Gao Zhehuan oxidation modification phenyl polysiloxane
Take the phenyl polysiloxane of 50g step (1) synthesis terminal hydroxy group and [2- (3,4- epoxycyclohexyl)] ethyl of 36.96g
Then trimethoxy silane is added 1wt%'s in the three-necked flask of the 150ml equipped with magnetic stir bar, temperature controller
D301R type alkalescence anion-exchange resin, control reaction temperature are 95 DEG C.After reaction time is 4h, decompression, which filters, removes catalysis
Then filtrate is transferred in round bottom distilling flask by agent, the by-product under the conditions of 120 DEG C and -0.096Mpa in removing system
A small amount of water, methanol obtain the LED packaging plastic epoxidation modification phenyl polysiloxane, are clear thick liquid.Through
Detection viscosity is 2809mpa.s, yield 91.85%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of LED packaging plastic epoxidation modification phenyl polysiloxane, which comprises the following steps:
(1) the phenyl polysiloxane oligomer of terminal hydroxy group is prepared with the sol-gel method of hydrolysis
Using containing phenyl organosiloxane and distilled water as raw material, D301R type basic anionic resin be catalyst, stirred in heating
The sol gel reaction being hydrolyzed under the conditions of mixing obtains the crude product of the phenyl polysiloxane of terminal hydroxy group, crude product is subtracted
Pressure, which filters, removes alkalescence anion-exchange resin, is then allowed to stand layering, takes subnatant, carries out vacuum distillation removing low-boiling-point substance,
Obtain the phenyl polysiloxane oligomer of terminal hydroxy group；
(2) epoxidation modification phenyl polysiloxane is prepared with non-hydrolytic sol-gel
The phenyl polysiloxane oligomer of terminal hydroxy group is instilled in the organosiloxane containing epoxy, reactant is obtained, in D301R type alkali
Under the catalysis of property resin anion (R.A.), non-hydrolytic sol gel reaction is carried out, the crude product of preparation is subjected to decompression suction filtration, is removed
Alkalescence anion-exchange resin is removed, then vacuum distillation removing low-boiling-point substance is to get to the LED packaging plastic epoxidation modification
Phenyl polysiloxane.
2. the preparation method of LED packaging plastic epoxidation modification phenyl polysiloxane according to claim 1, feature exist
In: the organosiloxane containing phenyl described in step (1) is phenyltrimethoxysila,e, phenyl triethoxysilane, hexichol
Base dimethoxysilane, diphenyl diethoxy silane, aminomethyl phenyl dimethoxysilane and aminomethyl phenyl diethoxy silane
One or more of.
3. the preparation method of LED packaging plastic epoxidation modification phenyl polysiloxane according to claim 1, feature exist
In: it is sweet that the organosiloxane containing epoxy described in step (2) is 3- glycidyl ether oxygen propyl trimethoxy silicane, 3- shrinks
Oily ether oxygen propyl triethoxysilane, 3- glycidyl ether oxygen propyl methyl dimethoxysilane, 3- glycidyl ether oxygen propyl
Methyldiethoxysilane, [2- (3,4- epoxycyclohexyl)] ethyl trimethoxy silane and [2- (3,4- epoxycyclohexyl)] second
One or more of ethyl triethoxy silicane alkane.
4. the preparation method of LED packaging plastic epoxidation modification phenyl polysiloxane according to claim 1, feature exist
In:
The mass ratio of organosiloxane and distilled water in the sol gel reaction of hydrolysis described in step (1) containing phenyl is
2:1~1:1；
In the sol gel reaction of hydrolysis described in step (1), the dosage of D301R type basic anionic resin is that raw material is total
The 0.9%~2% of weight.
5. the preparation method of LED packaging plastic epoxidation modification phenyl polysiloxane according to claim 1, feature exist
In: the reaction temperature of the sol gel reaction of hydrolysis described in step (1) is 60~90 DEG C, and the reaction time is 2~4 hours.
6. the preparation method of LED packaging plastic epoxidation modification phenyl polysiloxane according to claim 1, feature exist
In:
In reactant described in step (2), molar ratio 1:1~1:2 of hydroxyl and alkoxy；
The dosage of D301R type basic anionic resin described in step (2) is the 0.9%~2% of reactant quality.
7. the preparation method of LED packaging plastic epoxidation modification phenyl polysiloxane according to claim 1, feature exist
In: the reaction temperature of non-hydrolytic sol gel reaction described in step (2) is 80~95 DEG C, and the reaction time is 4~6h.
8. the preparation method of LED packaging plastic epoxidation modification phenyl polysiloxane according to claim 1, feature exist
In: when the phenyl polysiloxane oligomer of terminal hydroxy group being instilled the dropwise addition in the organosiloxane containing epoxy described in step (2)
Between be 1~2h.
9. the preparation method of LED packaging plastic epoxidation modification phenyl polysiloxane according to claim 1, feature exist
In:
The condition of vacuum distillation described in step (1) is 100 DEG C and -0.096MPa；
The condition of vacuum distillation described in step (2) is 120 DEG C and -0.096MPa.
10. a kind of LED packaging plastic epoxidation modification phenyl polysiloxane, it is characterised in that: by any one of claim 1~9 institute
The preparation method stated obtains.
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