CN113321810B - Q-type high-refraction phenyl vinyl silicone oil, and synthesis method and application thereof - Google Patents
Q-type high-refraction phenyl vinyl silicone oil, and synthesis method and application thereof Download PDFInfo
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Abstract
The invention discloses Q-type high-refraction phenyl vinyl silicone oil, a synthesis method and application thereof, wherein the silicone oil has a chemical structure expression shown in the following formula. The Q-type high-refraction phenyl vinyl silicone oil prepared by the method is used for preparing LED packaging adhesive, and the cured LED packaging adhesive has higher refractive index and light transmittance; the cross-linking density is higher than that of the common packaging adhesive, the anti-aging performance is better, and the high-power LED lamp is suitable for being used in high-power LED lamps.
Description
Technical Field
The invention relates to phenyl vinyl silicone oil, in particular to Q-type high-refraction phenyl vinyl silicone oil, a synthetic method thereof and application thereof in an LED packaging material.
Background
The high-refraction phenyl vinyl silicone oil is a main agent of the current formula material for high-power LED packaging. The refractive index of the encapsulated and cured silicon oil is determined by the phenyl content in the silicon oil, and the higher the phenyl content is, the larger the refractive index of the material is improved; in addition, the silicone oil must also have the properties of adjusting the hardness, toughness and the like of the packaging material. In order to increase the phenyl content, a larger molecular weight of linear phenyl silicone oil is often needed, which can cause the reduction of the cross-linking density after packaging and curing and reduce the toughness of the linear phenyl silicone oil, the higher the polymerization degree is, the higher the material hardness is, but the viscosity is too high, which is not beneficial to practical application, generally, the molecular weight of the linear phenyl silicone oil is less than 2 ten thousand, which limits the phenyl content; in addition, when the molecular weight distribution of the phenyl silicone oil is wide, the hardness and toughness of the cured encapsulating material are reduced. The phenyl silicone oil synthesized by the conventional method has the problems of high viscosity, non-concentrated molecular weight distribution and the like in order to achieve higher phenyl content, so that the synthesis of the high-refraction phenyl vinyl silicone oil has the advantages of moderate viscosity, stable and feasible synthesis process, stable product performance, low raw material cost and easy industrial production while the phenyl content is increased.
Patent CN101885845A synthesizes phenyl silicone oil by using low polymerization degree phenyl polysiloxane and methyl cyclosiloxane, which is difficult to synthesize high refractive silicone oil with uniform arrangement, and the stability is inferior to that of silicone oil synthesized by methyl phenyl siloxane. CN105295051A utilizes the polymerization process of an alkaline catalyst, and the obtained phenyl silicone oil has high phenyl content, but the viscosity is also greatly improved, so that the phenyl silicone oil is not beneficial to being used in a formula at downstream. Patent CN103408759A uses dimethyldichlorosilane, diphenyldichlorosilane and methylphenyldichlorosilane as raw materials, xylene as solvent, and the refractive index of the synthesized silicone oil is still relatively low. The prior literature reports a few about the synthesis method of the phenyl vinyl silicone oil with high phenyl content and low viscosity.
In combination with the problems, the invention designs and synthesizes the phenyl vinyl silicone oil with the Q-type structure, the silicone oil simultaneously considers high phenyl content and moderate system viscosity, and the synthesis process is stable and feasible and is suitable for industrial production.
Disclosure of Invention
In order to solve the technical problems, the invention provides Q-type high-refraction phenyl vinyl silicone oil, a synthesis method thereof and application in an LED packaging material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a Q-type high-refraction phenyl vinyl silicone oil has a chemical structure expression formula shown as the following formula I:
wherein n is a positive integer greater than 1, preferably n =5-10.
The synthesis method of the Q-type high-refraction phenyl vinyl silicone oil comprises the step of carrying out ring-opening polymerization reaction by taking methyl phenyl siloxane ring bodies as raw materials and taking a structure shown as a formula II as an end capping agent;
further, the ring-opening polymerization reaction process is as follows:
1) Mixing methyl phenyl siloxane ring body with an end-capping reagent shown in formula II, and then placing at 60-80 ℃ under the negative pressure of 1-10mbar, distilling and dehydrating for 2-3h;
2) Adding an acid catalyst to continue reacting for 3-5h under the nitrogen atmosphere, and adding carbonate to neutralize the acid catalyst after the reaction is finished;
3) And (3) performing short-path distillation and devolatilization, and adsorbing and filtering by using activated carbon to obtain the high-refraction phenyl vinyl silicone oil.
Further, the methylphenylsiloxane ring body is any one or a mixture of more of 2,4, 6-trimethyl-2, 4, 6-triphenylcyclotrisiloxane, 2,4,6, 8-tetramethyl-2, 4,6, 8-tetraphenylcyclotetrasiloxane and 2,4,6,8, 10-pentamethyl-2, 4,6,8, 10-pentaphenylcyclopentasiloxane.
Furthermore, the mixing mass ratio of the methyl phenyl siloxane ring body to the end-capping reagent shown in the formula II is (2.9-5.8): 1;
preferably, the acid catalyst is a fluorine-containing organic acid with 2-7 carbon atoms, such as trifluoromethanesulfonic acid, trifluoroacetic acid, trifluoropropionic acid and the like, and the amount of the fluorine-containing organic acid is 1-5 per mill of the total mass of the methyl phenyl siloxane ring body and the end capping agent shown in the formula II, and more preferably, the acid catalyst is trifluoromethanesulfonic acid;
preferably, the carbonate is one or more of alkali metal carbonates, such as calcium carbonate, sodium bicarbonate, magnesium carbonate, potassium carbonate and the like, and the amount of the carbonate is 3-5% of the total mass of the methyl phenyl siloxane ring body and the end capping agent shown in the formula II; more preferably, the carbonate is calcium carbonate;
preferably, step 2) is stirred for 1-2h after the carbonate is added;
preferably, the short path distillation devolatilization conditions are 100-120 ℃ and 2-10mbar.
Further, the preparation method of the end-capping reagent shown in the formula II comprises the following steps:
a. carrying out equilibrium reaction on divinyltetraphenyldisiloxane, tetraethyl orthosilicate and lower alcohol under the protection of nitrogen and in the presence of an acid catalyst; the addition of an equilibration reaction before the hydrolysis reaction is beneficial to improving the end capping activity of the divinyltetraphenyldisiloxane.
b. Adding water to continue hydrolysis reaction; preferably, water is slowly added to the reaction solution in step a so that the temperature of the solution after the reaction exotherm does not exceed 80 ℃, more preferably slowly added dropwise over a period of 0.5 to 2 hours.
c. Raising the temperature of the system to 100-110 ℃, and removing ethanol and water;
d. reducing the temperature of the system to 80-85 ℃, adding a blocking catalyst and divinyl tetraphenyl disiloxane, and continuing to react for 2-3h to remove residual ethoxy;
e. and filtering the reaction solution to remove solids, washing the reaction solution to be neutral, and distilling the reaction solution under negative pressure to remove water to obtain the vinyl methyl phenyl Q-type end-capping reagent.
In step a, the molar ratio of the divinyltetraphenyldisiloxane to the tetraethyl orthosilicate is (2-2.5): 1;
preferably, the acid catalyst is one or more of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, boric acid, phosphoric acid and the like, and sulfuric acid is more preferred; the addition amount of the acid catalyst is 0.1 to 1 percent, preferably 0.4 to 0.6 percent of the total mass of the divinyltetraphenyldisiloxane and the tetraethyl orthosilicate in the step a;
preferably, the lower alcohol is a saturated aliphatic alcohol of C1-C3, preferably ethanol; the using amount of the lower alcohol is 10-30% of the total mass of the divinyl tetraphenyl disiloxane and the tetraethyl orthosilicate in the step a;
preferably, the equilibration reaction temperature is 60-80 ℃ and the reaction time is 1-3h.
Further, in the step b, the hydrolysis reaction time is 3-6h, preferably 4-5h;
preferably, the amount of water added is 2 to 3 times by mole the amount of tetraethyl orthosilicate.
Further, in the step d, the end-capping catalyst is one or more of acetic acid, formic acid, acetic anhydride and propionic acid, and the addition amount of the end-capping catalyst is 1-10%, preferably 3-7% of the mass of the tetraethyl orthosilicate charge;
preferably, the amount of divinyltetraphenyldisiloxane added in step d is 0.5-2% of the mass of divinyltetraphenyldisiloxane charged in step a.
Further, in the step e, the conditions for removing water by negative pressure distillation are as follows: 100-120 deg.C, 1-10mbar.
The capping agent of formula II prepared by the above method preferably has a residual ethoxy content of less than 0.5%.
The Q-type high-refractive-index phenyl vinyl silicone oil prepared by the method has the viscosity of 1000-3000cp, and preferably 1500-2500cp.
The high-refractive-index LED packaging adhesive is prepared by taking the Q-type high-refractive-index phenyl vinyl silicone oil as a raw material.
Further, the LED packaging adhesive is prepared by the following method:
a high-refractive index LED packaging adhesive comprises a component A and a component B in a weight ratio of 1, wherein the component A comprises 100 parts of Q-type high-refractive index phenyl vinyl silicone oil, 30-50 parts of methyl phenyl vinyl silicone resin and 0.1-1 part of platinum catalyst in parts by weight; the component B comprises, by weight, 100 parts of Q-type high-refraction phenyl vinyl silicone oil, 15-35 parts of phenyl hydrogen silicone oil and 0.01-0.1 part of an inhibitor.
In particular, the inhibitor is ethynyl cyclohexanol.
Specifically, the viscosity of the methyl phenyl vinyl silicone resin is 800-1200cp.
Specifically, the viscosity of the phenyl hydrogen-containing silicone oil is 1800-2200cp.
Compared with the prior art, the method for preparing the LED packaging adhesive by using the Q-type high-refraction phenyl vinyl silicone oil has the following advantages:
(1) After curing, the material has a refractive index of more than 1.56 and high light transmittance of more than 98 percent;
(2) Because the system contains Q-type structural units, the cross-linking density is higher than that of common packaging glue, the anti-aging performance is better, and the system is suitable for being used in high-power LED lamps.
(3) The preparation method improves the refractive index, simultaneously considers the viscosity of the silicone oil, and has the advantages of moderate system viscosity, stable synthesis process and suitability for industrial production.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The main raw material sources are as follows:
divinyltetraphenyldisiloxane: 18769-05-5, shanghai Chuqing New Material science and technology Co., ltd;
tetraethyl orthosilicate: shanghai Mielin Biochemical technology Ltd
Concentrated sulfuric acid: chemical reagent Limited, national drug group, with a concentration of 98%
Phosphoric acid: 85% strength, chemical reagents of national drug group, inc
Acetic acid: 99% strength, national chemical group chemical reagent Limited
Methyl phenyl siloxane mixed ring body: siscobo silicone
PC9181 is a methylphenylcyclosiloxane mixture comprising tricyclic, tetracyclic and pentacyclic compounds, total effective components greater than 98.5%, CAS number 68037-54-7
2,4, 6-trimethyl-2, 4, 6-triphenylcyclotrisiloxane: shanghai Michelin Biochemical technology Ltd, CAS number 546-45-2
2,4,6, 8-tetramethyl-2, 4,6, 8-tetraphenylcyclotetrasiloxane: sigma Aldrich trade, inc., CAS number 77-63-4
2,4,6,8, 10-pentamethyl-2, 4,6,8, 10-pentaphenylcyclopentasiloxane: kanjab chemical Co., ltd, CAS No. 34239-75-3
Methyl phenyl vinyl silicone resin: viscosity 1000cp, shin-Etsu chemical Co., ltd;
phenyl hydrogen-containing silicone oil: viscosity 2000cp, shin-Etsu chemical Co., ltd;
platinum catalyst (containing 2% platinum): shanghai Aladdin Biotechnology, K110178
Ethynylcyclohexanol: sigma Aldrich trade company, inc
Methyl cyclosiloxane: shandong Yue organosilicon Material Ltd
Tetramethyldivinyldisiloxane: qufuchenguang chemical Co Ltd
A phenyl ring body: octaphenylcyclotetrasiloxane, a highly connected element, from organosilicon works
Octamethylcyclotetrasiloxane: shandong Yue organosilicon Material Ltd
Tetramethyldivinyldisiloxane: anhui Aiyota Silicone oil Co Ltd
Dimethyl dichlorosilane: shandong Dongye organosilicon Material Ltd
Methyl phenyl dichlorosilane: large connected element permanent silicon plant
Diphenyl dichlorosilane: large linkage element permanent organosilicon factory
Hexamethyldisiloxane: qufuchenguang chemical Co Ltd
Other raw materials and reagents can be purchased from common commercial sources without special reference.
In the performance test of the LED packaging adhesive:
the heat aging property is tested according to the standard GB/T7141-2008;
the refractive index is tested according to the standard GB/T6488-2008;
the light transmittance was tested according to standard GB/T2410-2008.
Synthesis of vinyl methyl phenyl Q-type end-capping reagent
Example 1
Taking a 5000ml three-neck flask, condensing, refluxing and protecting with nitrogen, adding 869.36g (2 mol) of divinyltetraphenyldimethoxysilane, 208.33g (1 mol) of tetraethyl orthosilicate and 215g of ethanol into a reaction kettle, slowly adding 5.3g of concentrated sulfuric acid dropwise at room temperature for 30min, heating to 60 ℃, carrying out equilibrium reaction for 1h, adding 45g of deionized water into the reaction system for 30min, continuing to react for 3h at 60 ℃, heating to normal pressure after the reaction is finished, and evaporating out ethanol and redundant water in the reaction system until the liquid temperature reaches 105 ℃; cooling to 85 ℃, adding 10.42g of acetic acid and 8.69g of divinyltetraphenyldimethoxysilane, continuing to react for 3h, filtering to remove solids after the reaction is finished, taking filtrate to wash for three times until the filtrate is neutral, and finally distilling out excessive water and low volatile matters in the system at 120 ℃ and 10mbar negative pressure to obtain the vinyl methyl phenyl Q-type end-capping agent, wherein the viscosity of the product is 105cp, and the theoretical yield is 92%. NMR H spectrum quantitatively measures 0.34% ethoxy residue in the product.
Example 2
Taking a 5000ml three-mouth bottle, condensing, refluxing and protecting nitrogen, adding 1086.70g (2.5 mol) of divinyltetraphenyldimethoxysilane, 208.33g (1 mol) of tetraethyl orthosilicate and 388g of isopropanol into a reaction kettle, slowly adding 12.95g of concentrated sulfuric acid dropwise at room temperature for 30min, heating to 70 ℃ to balance and react for 2h, adding 36g of deionized water into the reaction system for 30min, continuing to react for 5h at 70 ℃, heating to normal pressure after the reaction is finished, evaporating ethanol, isopropanol and excessive water in the reaction system until the liquid temperature is 105 ℃, cooling to 85 ℃, adding 6.2g of acetic acid and 16g of divinyldimethoxysilane, continuing to react for 3h, filtering to remove solids after the reaction is finished, taking filtrate, washing for three times until the filtrate is neutral, and finally distilling 120 ℃,10 mbar, and removing excessive water and low volatile matters in the system under negative pressure to obtain the vinylmethylphenyl Q-type end-capping agent, wherein the viscosity of the product is 104cp, and the theoretical yield is 88%. The NMR H spectrum quantitatively determined that 0.41% of ethoxy remained in the product.
Example 3
Taking a 5000ml three-neck flask, condensing, refluxing and protecting nitrogen, adding 869.36g (2 mol) of divinyltetraphenyldimethoxysilane, 208.33g (1 mol) of tetraethyl orthosilicate and 215g of ethanol into a reaction kettle, slowly adding 5.3g of phosphoric acid dropwise at room temperature for 30min, heating to 75 ℃ for equilibrium reaction for 1.5h, heating to 45g of deionized water for 1h, adding the deionized water into the reaction system, continuing to react for 4h at 75 ℃, heating to normal pressure after the reaction is finished, distilling off the ethanol and the excess water in the reaction system until the liquid temperature is 105 ℃, cooling to 80 ℃, adding 14.5g of acetic acid and 8.69g of divinyltetraphenyldimethoxysilane, continuing to react for 3h, filtering to remove solids after the reaction is finished, taking filtrate, washing the filtrate for three times until the filtrate is neutral, and finally distilling the excess water and the low volatile in the system at 120 ℃,10 mbar and under negative pressure to obtain the vinylmethylphenyl Q-type end-capping agent, wherein the viscosity of the product is 103cp, and the theoretical yield is 85%. The NMR H spectrum quantitatively measures 0.39% ethoxy residue in the product.
Comparative example 1
Taking a 5000ml three-mouth bottle, condensing, refluxing and protecting nitrogen, adding 869.36g (2) of divinyltetraphenyldimethoxysilane, 208.33g (1 mol) of tetraethyl orthosilicate and 215g of ethanol into a reaction kettle, slowly adding 5.3g of concentrated sulfuric acid dropwise at room temperature for 30min, heating to 60 ℃, carrying out equilibrium reaction for 1h, adding 45g of deionized water into the reaction system for 30min, continuing to react for 3h at 60 ℃, heating after the reaction is finished, distilling out ethanol and excessive water in the reaction system at normal pressure until the liquid temperature is 105 ℃, then washing the reaction liquid for three times until the reaction liquid is neutral, and finally distilling the excessive water and low volatile in the system at 120 ℃,10 mbar and negative pressure to obtain the vinyl methyl phenyl Q-type end-capping agent, wherein the viscosity of the product is 102cp, and the theoretical yield is 62%. The NMR H spectrum quantitatively measures 5.3% ethoxy residues in the product.
Synthesis of Q-type high-refraction phenyl vinyl silicone oil
Example 4
100g of the vinyl methyl phenyl Q-type end-capping agent synthesized in the example 1 and 350g of the methyl phenyl siloxane mixed ring body are added into a 1000ml three-necked bottle, the temperature is increased to 80 ℃, the negative pressure is 10mbar, the distillation is carried out for 2h, the residual moisture in the raw material is removed, nitrogen is broken, 0.45g of trifluoromethanesulfonic acid is added, the reaction is continued for 5h, then 20g of calcium carbonate is added to neutralize the acid catalyst, the stirring is continued for 1h and then the filtration is carried out, the low volatility of the filtrate is removed by short-range distillation at 110 ℃ and 2mbar, the activated carbon is filtered and adsorbed, the Q-type high-refraction phenyl vinyl silicone oil is obtained, the viscosity is 1200cp, the refraction index is 1.5945, and the yield is 91%.
Example 5
100g of vinyl methyl phenyl Q-type end-capping agent synthesized in the example 2,4, 6-trimethyl-2, 4, 6-triphenyl cyclotrisiloxane 580g are added into a 1000ml three-neck flask, the temperature is raised to 60 ℃, the negative pressure is 10mbar, distillation is carried out for 3h, residual moisture in raw materials is removed, nitrogen is broken, 3.4g of trifluoromethanesulfonic acid is added, reaction is continued for 5h, 22g of sodium carbonate is added to neutralize acid catalyst, filtration is carried out after stirring is continued for 1h, low volatility of filtrate is removed by short-path distillation at 120 ℃ and 5mbar, active carbon filtration and adsorption are carried out, Q-type high-refraction phenyl vinyl silicone oil, 1980cp, the refraction index is 1.5997, and the yield is 88%.
Example 6
Taking 100g of the vinyl methyl phenyl Q-type end-capping agent synthesized in the example 3, adding 290g of 2,4,6, 8-tetramethyl-2, 4,6, 8-tetraphenyl cyclotetrasiloxane into a 1000ml three-neck flask, heating to 70 ℃, keeping the temperature and the negative pressure at 5mbar, distilling for 3h, removing residual water in the raw materials, breaking the air by nitrogen, adding 0.8g of trifluoroacetic acid, continuing to react for 3h, then adding 19g of calcium carbonate to neutralize the acid catalyst, continuing to stir for 1h, filtering, then distilling for a short time at 100 ℃, 8mbar to remove the low volatility in the filtrate, and filtering and adsorbing by activated carbon to obtain Q-type high-refraction phenyl vinyl silicone oil, 1050cp, the refraction index of 1.5890 and the yield of 87%.
Example 7
100g of vinyl methyl phenyl Q-type end-capping agent synthesized in the example 1, 2,4,6,8, 10-pentamethyl-2, 4,6,8, 10-pentaphenyl cyclopentasiloxane 400g are added into a 1000ml three-mouth bottle, the temperature is raised to 80 ℃, the negative pressure is 10mbar, distillation is carried out for 3 hours, residual moisture in raw materials is removed, nitrogen is evacuated, 1.25 trifluoropropionic acid is added, the reaction is continued for 4 hours, then 20g of sodium bicarbonate is added to neutralize the acid catalyst, the stirring is continued for 1 hour, then filtration is carried out, the middle and low filtrate volatilization is removed through short-path distillation at 100 ℃, active carbon is filtered and adsorbed, Q-type high-refraction phenyl vinyl silicone oil is obtained, the viscosity is 1760cp, the refraction index is 1.5990, and the yield is 86%.
Example 8
100g of the vinyl methyl phenyl Q-type end-capping agent synthesized in the example 1 and 300g of the methyl phenyl siloxane mixed ring body are added into a 1000ml three-necked bottle, the temperature is raised to 70 ℃, the negative pressure is 10mbar, the distillation is carried out for 3h, the residual moisture in the raw material is removed, nitrogen is broken, 0.4g of trifluoromethanesulfonic acid is added, the reaction is continued for 4h, then 12g of magnesium carbonate is added to neutralize the acid catalyst, the mixture is stirred for 1h and then filtered, the low volatility of the filtrate is removed by short-path distillation at 115 ℃ and 6mbar, and the activated carbon is filtered and adsorbed to obtain Q-type high-refraction phenyl vinyl silicone oil, the viscosity is 1180cp, the refraction index is 1.5940, and the yield is 84%.
Example 9
100g of the vinyl methyl phenyl Q-type end-capping agent synthesized in the embodiment 3 and 290g of the methyl phenyl siloxane mixed ring body are added into a 1000ml three-necked bottle, the temperature is raised to 60 ℃, the negative pressure is 1mbar, the distillation is carried out for 3h, the residual water in the raw materials is removed, nitrogen is broken, 1.9g of trifluoroacetic acid is added, the reaction is continued for 4h, then 19g of potassium carbonate is added to neutralize the acid catalyst, the stirring is continued for 1h and then the filtration is carried out, the low volatility in the filtrate is removed by short-path distillation at 105 ℃ and 10mbar, the activated carbon is filtered and adsorbed to obtain Q-type high-refraction phenyl vinyl silicone oil, the viscosity is 1070cp, the refraction index is 1.5895, and the yield is 85%.
Comparative example 2
100g of the vinyl methyl phenyl Q-type end-capping agent synthesized in the example 1 and 350g of the methyl phenyl siloxane mixed ring body are added into a 1000ml three-necked bottle, 0.45g of trifluoromethanesulfonic acid is added for reaction for 5h, then 20g of calcium carbonate is added for neutralizing the acid catalyst, stirring is continued for 1h, then low volatility is removed by short-range distillation at 110 ℃ and 2mbar, activated carbon is filtered and adsorbed, and Q-type high-refraction phenyl vinyl silicone oil is obtained, the viscosity is 640cp, the refraction index is 1.5423, and the yield is 82%.
Comparative example 3
100g of vinyl methyl phenyl Q-type end-capping agent synthesized in the example 1 and 350g of methyl phenyl siloxane mixed ring body are added into a 1000ml three-necked bottle, the temperature is raised to 80 ℃, the negative pressure is 10mbar, the distillation is carried out for 2h, the residual water in the raw material is removed, nitrogen is broken, 0.45g of concentrated sulfuric acid is added, the reaction is continued for 5h, then 20g of calcium carbonate neutralization acid catalyst is added, the stirring is continued for 1h, the low volatility is removed by short-range distillation at 110 ℃ and 2mbar, the activated carbon is filtered and adsorbed, and Q-type high refractive phenyl vinyl silicone oil with the viscosity of 440cp, the refractive index of 1.5389 and the yield of 44 percent is obtained.
Comparative example 4
High-refractive-index phenyl vinyl silicone oil of type Q was prepared in substantially the same manner as in example 4 except that: the raw material vinylmethylphenyl Q-type end-capping reagent was replaced with the end-capping reagent product prepared in comparative example 1. The Q-type high-refraction phenyl vinyl silicone oil is obtained, the viscosity is 3410cp, the refractive index is 1.5476, and the yield is 46%.
Comparative example 5
The vinylphenyl silicone oil was prepared according to the method in CN 101885845A:
under the condition of nitrogen protection and condensation reflux, 246.4g of diphenyldimethoxysilane, 180g of deionized water, 0.25g of potassium hydroxide and 200g of methanol are added into a 1000ml reaction kettle, stirring and heating are carried out to carry out hydrolysis condensation reaction, the reaction is continued for 3h after heating to 60 ℃, then the temperature is raised, the methanol is distilled out under normal pressure until the liquid temperature is raised to 70 ℃, the distillation is stopped, 10ml of hydrochloric acid solution with the concentration of 1mol/L is added for neutralization, the reaction liquid is cooled, kept stand and phase-separated to remove the lower-layer aqueous phase, water washing is carried out for three times until the reaction liquid is neutral, then the low volatile matter is removed from the organic phase under the conditions of negative pressure of 10mbar and 100 ℃ for 2h, the hydroxyl-terminated low polymerization degree phenyl siloxane product is prepared, and the polymerization degree is 10 according to the nuclear magnetic hydrogen spectrum test.
50g of hydroxyl-terminated low-polymerization-degree phenylsiloxane, 30g of methyl cyclosiloxane and 5g of tetramethyl divinyl disiloxane are put into a 250ml three-mouth bottle, the mixture is stirred and heated to 180 ℃, when the mixture becomes translucent, 0.3g of saturated aqueous solution of potassium hydroxide is added, the mixture is continuously stirred for 5h, cooled to room temperature, 0.1g of concentrated hydrochloric acid is added, the mixture is continuously stirred for 2h, 1g of sodium carbonate is added, the mixture is continuously stirred for 2h, the stirring is stopped, the reaction mixed liquid is filtered for 3 times, filtrate is collected into the three-mouth bottle, low-boiling-point substances are removed in vacuum at 180 ℃, and finally the target product of vinyl phenyl silicone oil is vinyl phenyl silicone oil, the viscosity of the vinyl phenyl silicone oil is 3710cp, the refractive index of the vinyl phenyl silicone oil is 1.5579, and the yield of the vinyl phenyl silicone oil is 61%.
Comparative example 6
The vinylphenyl silicone oil was prepared according to the method in CN 105295051A:
filling nitrogen to remove air, adding 1mol of 2,4, 6-trimethyl-2, 4, 6-triphenyl cyclotrisiloxane and 25mol of isopropanol into a reaction bottle, stirring and heating to 60 ℃, adding 0.5mol of dehydrated octamethylcyclotetrasiloxane and 0.5mol of tetramethyldivinyl disiloxane, uniformly stirring, then adding 10g of tetramethylammonium hydroxide, uniformly stirring, and keeping the temperature at 80 ℃ for reaction for 2 hours; then the temperature is increased to 120 ℃ for reaction for 8h. Then vacuumizing and heating to 180 ℃, reacting for 4 hours at constant temperature, and cooling. When the temperature is reduced to below 60 ℃, adding toluene and active carbon, stirring for 2 hours, filtering, washing, and removing the solvent and micromolecules by rotary evaporation to obtain the vinyl phenyl silicone oil. The product viscosity is 3900cp, the refractive index is 1.5510, and the yield is 67%.
Comparative example 7
The methyl phenyl silicone oil was prepared according to the method in CN 103408759A:
80ml of xylene, 50ml of acetone, 10.32g of dimethyldichlorosilane, 19.11g of methylphenyldichlorosilane and 5.06g of diphenyldichlorosilane are added into a 500ml three-neck flask, and the mixture is stirred and mixed uniformly at the temperature of 30 ℃; dropwise adding a mixed hydrolysate of 100ml of acetone and 57.6ml of distilled water into a three-neck flask by using a constant-pressure titration funnel, and controlling the dropwise adding speed to keep 1d/2s; after the dropwise addition, the reaction is continued for 10 hours at 30 ℃ and the hydrolysis is finished. Standing and layering hydrolysate, washing hydrolysate on the upper layer to be neutral by using distilled water at 50 ℃ to obtain siloxane prepolymer, then adding 0.811g of hexamethyldisiloxane and 0.3450g of stannous octoate (the mass is 1 percent of the total mass of the monomers) at 100 ℃ to perform condensation reaction for 4 hours, washing the hydrolysate to be neutral by using distilled water at 50 ℃ after the reaction is finished, and then evaporating solvent and low-boiling-point substances under the reduced pressure condition at 130 ℃ to obtain the product. The product viscosity is 3760cp, the refractive index is 1.5519, and the yield is 64%.
Application example 1
The Q-type high-refraction phenyl vinyl silicone oil synthesized in the embodiment 4 is used as one of formula main agents of the LED packaging adhesive, and the LED packaging adhesive is prepared according to the following steps:
preparing a component A: sequentially putting 100g of Q-type high-refraction phenyl vinyl silicone oil and 45g of methyl phenyl vinyl silicone resin into a 250ml reaction kettle for stirring, wherein the stirring speed is 1200r/min, starting vacuum to keep-0.1 Mpa, starting heating to raise the temperature of materials to 55 ℃, and continuously preserving heat for 2 hours; regulating the rotating speed to 500r/min, cooling to below 30 ℃, adding 0.1 part of platinum catalyst, and stirring in vacuum for 30min to obtain the component A.
Preparing a component B: and sequentially putting 100g of Q-type high-refraction phenyl vinyl silicone oil, 15g of phenyl hydrogen-containing silicone oil and 0.01g of ethynyl cyclohexanol into a 250ml reaction kettle for stirring, wherein the stirring speed is 1200r/min, the vacuum is started and kept at-0.1 MPa, and the vacuum stirring is carried out for 30min, so as to obtain the component B.
Mixing the component A and the component B at the speed of 250r/min, stirring for 5min, and curing at room temperature. The prepared cured product is tested for thermal aging performance, refractive index, light transmittance and other data, and the test results are shown in table 1.
Application examples 2 to 6
LED encapsulating adhesives were prepared by the methods of application example 1, respectively, except that Q-type high-refractive phenyl vinyl silicone oil used was replaced with Q-type high-refractive phenyl vinyl silicone oil prepared in examples 5 to 9, respectively. The performance tests in table 1 were also performed.
Comparative application example 1
An LED package adhesive was prepared according to the method of application example 1, except that Q-type high-refractive phenyl vinyl silicone oil was replaced with commercially conventional linear phenyl vinyl silicone oil (IoTA 252, eyota silicone oil Co., ltd.). The performance tests in table 1 were also performed.
Comparative examples 2 to 7 of application
LED encapsulating adhesives were prepared according to the method of application example 1, respectively, except that Q-type high-refractive phenyl vinyl silicone oil used was replaced with Q-type high-refractive phenyl vinyl silicone oil prepared in comparative examples 2 to 7, respectively. The performance tests in table 1 were also performed.
TABLE 1 results of Performance test
| Thermal aging resistance | Refractive index/%) | Transmittance (a) | |
| Application example 1 | No embrittlement after 24 hours | 1.5910 | 98.7 |
| Application example 2 | No embrittlement after 24 hours | 1.5872 | 98.2 |
| Application example 3 | No embrittlement after 24 hours | 1.5713 | 98.1 |
| Application example 4 | No embrittlement after 24 hours | 1.5840 | 98.3 |
| Application example 5 | No embrittlement after 24 hours | 1.5790 | 98.4 |
| Application example 6 | No embrittlement after 24 hours | 1.5850 | 98.2 |
| Comparative application example 1 | No embrittlement after 24 hours | 1.4913 | 96.3 |
| Comparative application example 2 | Embrittlement for 24 hours | 1.5112 | 97.2 |
| Comparative application example 3 | No embrittlement after 24 hours | 1.5223 | 96.3 |
| Comparative application example 4 | No embrittlement after 24 hours | 1.5321 | 91.4 |
| Comparative application example 5 | Embrittlement for 24 hours | 1.5511 | 93.2 |
| Comparative application example 6 | No embrittlement after 24 hours | 1.4987 | 93.5 |
| Application comparative example 7 | Embrittlement for 24 hours | 1.5120 | 94.1 |
The result shows that the Q-type high-refraction phenyl vinyl silicone oil prepared by the invention is used as a formula main agent of the LED packaging adhesive, and after curing, the refractive index is higher, and the light transmittance reaches more than 98%. The cross-linking density of the system containing the Q-type structural unit is higher than that of common packaging glue, so that the system has good ageing resistance and does not brittle within 24 hours, and is suitable for being used in high-power LED lamps.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be considered as the protection scope of the present invention.
Claims (24)
1. The Q-type high-refraction phenyl vinyl silicone oil is characterized by having a chemical structure expression shown in the following formula I:
wherein n =5-10.
2. The method for synthesizing Q-type high-refraction phenyl vinyl silicone oil according to claim 1, which is characterized by comprising the step of carrying out ring-opening polymerization reaction by taking methyl phenyl siloxane ring bodies as raw materials and taking a structure shown as a formula II as an end-capping reagent;
3. the method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to claim 2, wherein the ring-opening polymerization reaction process is as follows:
1) Mixing methyl phenyl siloxane ring body with an end-capping agent shown in formula II, and then placing at 60-80 ℃ and under the negative pressure of 1-10mbar, and distilling and dehydrating for 2-3h;
2) Adding an acid catalyst to continue reacting for 3-5h under the nitrogen atmosphere, and adding carbonate to neutralize the acid catalyst after the reaction is finished;
3) And (3) performing short-path distillation and devolatilization, and adsorbing and filtering by using activated carbon to obtain the high-refraction phenyl vinyl silicone oil.
4. The method for synthesizing Q-type high refractive phenyl vinyl silicone oil according to claim 3, wherein the methyl phenyl siloxane ring body is any one or a mixture of 2,4, 6-trimethyl-2, 4, 6-triphenyl cyclotrisiloxane, 2,4,6, 8-tetramethyl-2, 4,6, 8-tetraphenylcyclotetrasiloxane and 2,4,6,8, 10-pentamethyl-2, 4,6,8, 10-pentaphenylcyclopentasiloxane.
5. The method for synthesizing Q-type high-refraction phenyl vinyl silicone oil according to claim 4, wherein the mixing mass ratio of the methyl phenyl siloxane ring body to the end-capping agent shown in the formula II is (2.9-5.8): 1.
6. The method for synthesizing Q-type high-refraction phenyl vinyl silicone oil according to claim 4, wherein the acidic catalyst is a fluorine-containing organic acid with 2-7 carbon atoms, and the dosage of the acidic catalyst is 1-5 per mill of the total mass of the methyl phenyl siloxane ring body and the end capping agent shown in the formula II.
7. The method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to claim 6, wherein the acidic catalyst is trifluoromethanesulfonic acid.
8. The method for synthesizing Q-type high-refraction phenyl vinyl silicone oil according to claim 4, wherein the carbonate is one or more of alkali metal carbonates, and the amount of the carbonate is 3-5% of the total mass of the methyl phenyl siloxane ring body and the end capping agent shown in the formula II.
9. The method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to claim 8, wherein the carbonate is calcium carbonate.
10. The method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to claim 4, wherein step 2) is further stirred for 1-2 hours after the carbonate is added.
11. The method for synthesizing Q-type high-refraction phenyl vinyl silicone oil according to claim 4, wherein the short path distillation devolatilization condition is 100-120 ℃ and 2-10mbar.
12. The method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to any one of claims 2 to 11, wherein the method for preparing the end-capping agent represented by formula II comprises the following steps:
a. carrying out equilibrium reaction on divinyltetraphenyldisiloxane, tetraethyl orthosilicate and lower alcohol in the presence of an acid catalyst;
b. adding water to continue hydrolysis reaction;
c. raising the temperature of the system to 100-110 ℃, and removing ethanol and water;
d. reducing the temperature of the system to 80-85 ℃, adding a capping catalyst and divinyl tetraphenyl disiloxane, and continuously reacting for 2-3h;
e. and filtering the reaction solution to remove solids, washing the reaction solution to be neutral, and distilling the reaction solution under negative pressure to remove water to obtain the vinyl methyl phenyl Q-type end capping reagent.
13. The method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to claim 12, wherein in the step a, the molar ratio of divinyltetraphenyldisiloxane to tetraethyl orthosilicate is (2-2.5): 1.
14. the method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to claim 13, wherein the acid catalyst is one or more of sulfuric acid, hydrochloric acid, nitric acid, boric acid, and phosphoric acid; the amount of acid catalyst added is 0.1-1% of the total mass of divinyltetraphenyldisiloxane and tetraethylorthosilicate in step a.
15. The method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to claim 13, wherein the lower alcohol is a C1-C3 saturated aliphatic alcohol; the lower alcohol is used in an amount of 10-30% of the total mass of the divinyltetraphenyldisiloxane and the tetraethyl orthosilicate in the step a.
16. The method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to claim 13, wherein the equilibration reaction temperature is 60-80 ℃ and the reaction time is 1-3h.
17. The method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to claim 12, wherein in the step b, the hydrolysis reaction time is 3-6h.
18. The method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to claim 17, wherein in the step b, the hydrolysis reaction time is 4 to 5 hours.
19. The method for synthesizing Q-type high-refractive phenyl vinyl silicone oil according to claim 17, wherein the amount of water added is 2 to 3 times by mole as much as tetraethyl orthosilicate.
20. The method for synthesizing Q-type high-refraction phenyl vinyl silicone oil according to claim 12, wherein in the step d, the end-capping catalyst is one or more of acetic acid, formic acid, acetic anhydride and propionic acid, and the addition amount of the end-capping catalyst is 1-10% of the feeding mass of tetraethyl orthosilicate.
21. The method for synthesizing Q-type high-refraction phenyl vinyl silicone oil according to claim 20, wherein in the step d, the addition amount of the end-capping catalyst is 3-7% of the feeding mass of tetraethyl orthosilicate.
22. The method for synthesizing Q-type high-refraction phenyl vinyl silicone oil according to claim 20, wherein the amount of divinyltetraphenyldisiloxane added in step d is 0.5-2% of the mass of divinyltetraphenyldisiloxane charged in step a.
23. The method for synthesizing Q-type high-refraction phenyl vinyl silicone oil according to claim 12, wherein in step e, the conditions for removing water by negative pressure distillation are as follows: 100-120 deg.C, 1-10mbar.
24. An LED packaging adhesive with high refractive index, which is characterized by being prepared from the Q-type high-refractive phenyl vinyl silicone oil in claim 1 or the Q-type high-refractive phenyl vinyl silicone oil prepared by the method in any one of claims 2 to 23.
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