CN108384010A - A kind of LED packaging plastics epoxidation modification methyl phenyl silicone resin and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of preparation of organosilicon-modified epoxy resin, and in particular relates to an epoxidation-modified methylphenyl silicone resin for LED packaging glue and a preparation method thereof. The method adopts 3-glycidyl etheroxypropyl methyl dimethoxy silane and methyl phenyl dimethoxy silane as raw materials, and synthesizes epoxidized modified methyl phenyl silicone resin through hydrolysis condensation reaction. The preparation process is simple and easy to control, has good repeatability and controllability, does not need to use organic solvents, and is environmentally friendly. The epoxidized modified methylphenyl silicone resin prepared by the method has low impurity content, no phase separation phenomenon, and has the high light transmittance, high refractive index, high thermal stability and high Adhesive and other characteristics, it is very easy to realize large-scale production in industry.

Description

Epoxy-modified methylphenyl silicone resin for LED encapsulation glue and preparation method thereof

technical field

The invention belongs to the technical field of preparation of organosilicon-modified epoxy resins, and in particular relates to an epoxidation-modified methylphenyl silicone resin for LED packaging glue and a preparation method thereof.

Background technique

Light-emitting diodes (LEDs) have a series of advantages such as stable performance, energy saving and high efficiency, safety and environmental protection, and are widely used in daily lighting, automotive lighting, mobile phones and televisions, and have become the trend and trend of future lighting technology. Encapsulation materials play an important role in improving the light output efficiency of LED lamps and prolonging their service life, so the selection of encapsulation materials is very important to the performance of LEDs. At present, the two mainstream materials used for LED packaging in the market are epoxy resin and silicone resin. Among them, in the past few decades, epoxy resin has monopolized the main market of LED packaging materials due to its advantages of low cost, good bonding performance and high mechanical strength. However, with the rapid development of high-power LED lamps in recent years, the requirements for light transmittance, refractive index and thermal stability of packaging materials are getting higher and higher, especially the packaging materials are required to be highly transparent and have a refractive index above 1.5. Therefore, traditional epoxy resin materials with large internal stress, poor heat resistance and easy yellowing are not suitable for the packaging of high-power LED lamps. Although silicone resin has good thermal stability, good weather resistance, and low surface energy, it has disadvantages such as poor adhesion and high price as a packaging material. Therefore, new packaging materials with low cost, good heat resistance and high refractive index have been researched. Materials are very important for the application of high-power LED lamps.

The silicone-modified epoxy resin prepared by combining epoxy resin with silicone resin can not only reduce the internal stress of epoxy resin, but also improve the adhesion of silicone resin and reduce production costs, so it has become a researcher in recent years. their research hotspots. At present, most of the silicone-modified epoxy resins for LED packaging adhesives reported at home and abroad are simply physically blended with silicone resins and epoxy resins to form a system with excellent comprehensive properties. This modification method can improve the overall performance of the cured product to a certain extent. For example, Chinese patent CN103897644A discloses that a silicone polymer is physically blended with an epoxy resin to synthesize a silicone-modified epoxy resin with good comprehensive performance and both advantages. The preparation process is as follows: mix organic silicon polymer, epoxy resin and additives evenly, pour into a preheated mold, remove air bubbles, place for 12 to 24 hours, then solidify, cool and demould, and obtain silicone modified ring Oxygen resin material. However, this simple physical blending makes the compatibility of silicone resin and epoxy resin poor, showing a multi-phase separation structure, so the prepared silicone epoxy resin still shows low light transmittance and low refractive index of epoxy resin. Low and poor heat resistance and other shortcomings.

Contents of the invention

In order to overcome the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a preparation method of epoxidized modified methylphenyl silicone resin for LED encapsulation glue.

Another object of the present invention is to provide an epoxidation-modified methylphenyl silicone resin for LED encapsulation prepared by the above method.

For realizing above-mentioned purpose of the invention, the technical scheme that the present invention adopts is as follows:

A preparation method for epoxidized modified methyl phenyl silicone resin for LED packaging glue, comprising the following steps:

(1) Preparation of Epoxidized Modified Methylphenyl Silicone Resin Crude Product

Mix 3-glycidyl etheroxypropylmethyldimethoxysilane and methylphenyldimethoxysilane evenly, as a reactant, add dropwise to the mixture of distilled water and barium hydroxide monohydrate catalyst to form a reaction Solution, then carry out hydrolysis condensation reaction under the condition of heating and stirring, remove the catalyst by suction filtration under reduced pressure after reaction, obtain the crude product of epoxidation modified methylphenyl silicone resin, the hydrolysis condensation reaction formula is as follows:

(2) Refined epoxidized modified methylphenyl silicone resin

Wash the crude product prepared in step (1) with deionized water for 2 to 3 times until the resin is neutral, leave to stand for stratification, then remove the supernatant liquid, and then remove the low boiling matter in the supernatant liquid to obtain Epoxidized modified methylphenyl silicone resin.

Preferably, the mass ratio of the reactant to distilled water in step (1) is 1:1˜2:1.

Preferably, the mass ratio of 3-glycidyl etheroxypropylmethyldimethoxysilane to methylphenyldimethoxysilane in step (1) is ≥2, preferably 1:4.97～1: 2.49.

Preferably, the amount of barium hydroxide monohydrate used in step (1) is 1%-2% of the total mass of the reaction solution.

Preferably, the hydrolysis condensation reaction temperature in step (1) is 60-90°C, more preferably 70-85°C.

Preferably, the hydrolysis and condensation reaction time in step (1) is 2 to 4 hours.

Preferably, the removal of low boilers described in step (2) adopts vacuum distillation.

More preferably, the vacuum distillation condition in step (2) is 80° C., 0.096 MPa.

The present invention further provides an epoxidized modified methylphenyl silicone resin for LED encapsulation adhesive, the epoxidized modified methylphenyl silicone resin is prepared by the above method, and the resin is colorless, transparent and viscous Like liquid, the viscosity is 398-1000mpa.s, the molecular weight is 1000-2000, the molecular weight distribution index PDI is 1.0-1.6, the refractive index is 1.48-1.54, and the epoxy content per 100g of epoxy modified methyl phenyl silicone resin 0.05-0.20mol.

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

(1) The present invention adopts 3-glycidyl ether oxypropyl methyl dimethoxy silane and methyl phenyl dimethoxy silane as raw materials, and synthesizes epoxidized modified methyl phenyl silicon by hydrolysis condensation reaction Resin, compared with the traditional physical blending method to prepare silicone modified epoxy resin, this method can better combine silicone resin and epoxy resin, so that the reaction product has no phase separation phenomenon, and is colorless and transparent. Viscous liquid with high light transmittance, high refractive index (1.48-1.54), high thermal stability and high adhesion (398-1000mpa.s) of silicone resin and epoxy resin. In addition, the mass ratio of 3-glycidyl etheroxypropylmethyldimethoxysilane to methylphenyldimethoxysilane is ≥2, so that the hydrolysis condensation product can be separated from water, which greatly saves operation time .

(2) The preparation process of the epoxidized modified methylphenyl silicone resin in the present invention is simple and easy to control, has good repeatability and controllability, does not need to use organic solvents, and is environmentally friendly. Using barium hydroxide monohydrate as the hydrolysis condensation reaction catalyst, the impurity content in the product is low, and it is very easy to realize large-scale production in industry.

Description of drawings

Fig. 1 is the GPC spectrogram of the epoxidized modified methylphenyl silicone resin prepared in Example 1.

Fig. 2 is the infrared spectrogram of the epoxidized modified methylphenyl silicone resin prepared in Example 1.

Detailed ways

The present invention will be further described in detail below with reference to the examples and drawings, but the implementation of the present invention is not limited thereto.

Example 1

Preparation of epoxidized modified methylphenyl silicone resin:

(1) Preparation of Epoxidized Modified Methylphenyl Silicone Resin Crude Product

22g of 3-glycidyl etheroxypropylmethyldimethoxysilane and 54.7g of methylphenyldimethoxysilane were mixed in a beaker and stirred evenly, and poured into a constant pressure dropping funnel as reactants. Take 76.7g of distilled water and 1.68g of barium hydroxide monohydrate and place them in a 250ml four-necked flask to prepare a mixture, stir and heat the mixture, and start to add the reactants dropwise when the temperature rises to 60°C, and control the reaction temperature to be 85°C. After the reactants were dropped, they were reacted at 85° C. for 4 h, and then the catalyst was removed by suction filtration under reduced pressure to obtain a crude product of epoxidized modified methylphenyl silicone resin.

(2) Refined epoxidized modified methylphenyl silicone resin

Wash the crude product of epoxidized modified methylphenyl silicone resin with deionized water 3-4 times to neutrality, let it stand and separate layers, and then transfer the lower clear liquid to a round bottom distillation flask, at 80 ° C, 0.096 The moisture in the system is removed under the condition of MPa, so as to obtain a colorless and transparent epoxidized modified methylphenyl silicone resin. The detected viscosity is 700mpa.s, the yield is 70.14%, the number average molecular weight is 1030 (see Figure 1), the weight average molecular weight is 1620 (see Figure 1), and the molecular weight distribution index is 1.5724. The infrared spectrogram of Fig. 2 shows that the product prepared by this method has the structure of epoxidized modified methylphenyl silicone resin.

Example 2

Preparation of epoxidized modified methylphenyl silicone resin:

(1) Preparation of Epoxidized Modified Methylphenyl Silicone Resin Crude Product

22g of 3-glycidyl etheroxypropylmethyldimethoxysilane and 54.7g of methylphenyldimethoxysilane were mixed in a beaker and stirred evenly, and poured into a constant pressure dropping funnel as reactants. Take 86.4g of distilled water and 1.68g of barium hydroxide monohydrate and place them in a 250ml four-necked flask to prepare a mixture. Stir and heat the mixture. When the temperature rises to 60°C, start to add the reactants dropwise, and control the reaction temperature to 70°C. After the reactants were dropped, they were reacted at 70° C. for 4 h, and then the catalyst was removed by suction filtration under reduced pressure to obtain a crude product of epoxidized modified methylphenyl silicone resin.

(2) Refined epoxidized modified methylphenyl silicone resin

Wash the crude product of epoxidized modified methylphenyl silicone resin with deionized water 3-4 times to neutrality, let it stand and separate layers, and then transfer the lower clear liquid to a round bottom distillation flask, at 80 ° C, 0.096 The moisture in the system is removed under the condition of MPa, so as to obtain a colorless and transparent epoxidized modified methylphenyl silicone resin. The detected viscosity is 480mpa.s, and the yield is 68.35%.

Example 3

Preparation of epoxidized modified methylphenyl silicone resin:

(1) Preparation of Epoxidized Modified Methylphenyl Silicone Resin Crude Product

22g of 3-glycidyl etheroxypropylmethyldimethoxysilane and 54.7g of methylphenyldimethoxysilane were mixed in a beaker and stirred evenly, and poured into a constant pressure dropping funnel as reactants. Take 86.4g of distilled water and 3.36g of barium hydroxide monohydrate and place them in a 250ml four-neck flask to prepare a mixture. Stir and heat the mixture. When the temperature rises to 60°C, start to add the reactants dropwise, and control the reaction temperature to 85°C. After the reactants were dropped, they were reacted at 85° C. for 4 h, and then the catalyst was removed by suction filtration under reduced pressure to obtain a crude product of epoxidized modified methylphenyl silicone resin.

(2) Refined epoxidized modified methylphenyl silicone resin

Wash the crude product of epoxidized modified methylphenyl silicone resin with deionized water 3-4 times to neutrality, let it stand and separate layers, and then transfer the lower clear liquid to a round bottom distillation flask, at 80 ° C, 0.096 The moisture in the system is removed under the condition of MPa, so as to obtain a colorless and transparent epoxidized modified methylphenyl silicone resin. The detected viscosity is 1000mpa.s, and the yield is 85.65%.

Example 4

Preparation of epoxidized modified methylphenyl silicone resin:

(1) Preparation of Epoxidized Modified Methylphenyl Silicone Resin Crude Product

Take 11g of 3-glycidyl etheroxypropylmethyldimethoxysilane and 54.7g of methylphenyldimethoxysilane in a beaker, mix and stir evenly, and pour them into a constant pressure dropping funnel as reactants. Take 75.6g of distilled water and 1.41g of barium hydroxide monohydrate and place them in a 250ml four-necked flask to prepare a mixture, stir and heat the mixture, and start to add the reactant dropwise when the temperature rises to 60°C, and control the reaction temperature to 85°C. After the reactants were dropped, they were reacted at 85° C. for 4 h, and then the catalyst was removed by suction filtration under reduced pressure to obtain a crude product of epoxidized modified methylphenyl silicone resin.

(2) Refined epoxidized modified methylphenyl silicone resin

Wash the crude product of epoxidized modified methylphenyl silicone resin with deionized water 3-4 times to neutrality, let it stand and separate layers, and then transfer the lower clear liquid to a round bottom distillation flask, at 80 ° C, 0.096 The moisture in the system is removed under the condition of MPa, so as to obtain a colorless and transparent epoxidized modified methylphenyl silicone resin. The detected viscosity is 530mpa.s, and the yield is 78.14%.

Example 5

Preparation of epoxidized modified methylphenyl silicone resin:

(1) Preparation of Epoxidized Modified Methylphenyl Silicone Resin Crude Product

22g of 3-glycidyl etheroxypropylmethyldimethoxysilane and 54.7g of methylphenyldimethoxysilane were mixed in a beaker and stirred evenly, and poured into a constant pressure dropping funnel as reactants. Take 38.4g of distilled water and 1.34g of barium hydroxide monohydrate and place them in a 250ml four-necked flask to prepare a mixture, stir and heat the mixture, and start to add the reactant dropwise when the temperature rises to 60°C, and control the reaction temperature to be 85°C. After the reactants were dropped, they were reacted at 85° C. for 4 h, and then the catalyst was removed by suction filtration under reduced pressure to obtain a crude product of epoxidized modified methylphenyl silicone resin.

(2) Refined epoxidized modified methylphenyl silicone resin

Wash the crude product of epoxidized modified methylphenyl silicone resin with deionized water 3-4 times to neutrality, let it stand and separate layers, and then transfer the lower clear liquid to a round bottom distillation flask, at 80 ° C, 0.096 The moisture in the system is removed under the condition of MPa, so as to obtain a colorless and transparent epoxidized modified methylphenyl silicone resin. The detected viscosity is 398mpa.s, and the yield is 79.14%.

Example 6

Preparation of epoxidized modified methylphenyl silicone resin:

(1) Preparation of Epoxidized Modified Methylphenyl Silicone Resin Crude Product

22g of 3-glycidyl etheroxypropylmethyldimethoxysilane and 54.7g of methylphenyldimethoxysilane were mixed in a beaker and stirred evenly, and poured into a constant pressure dropping funnel as reactants. Take 86.4g of distilled water and 1.68g of barium hydroxide monohydrate and place them in a 250ml four-necked flask to prepare a mixture, stir and heat the mixture, and start to add the reactants dropwise when the temperature rises to 60°C, and control the reaction temperature to be 85°C. After the reactants were dropped, they were reacted at 85° C. for 4 h, and then the catalyst was removed by suction filtration under reduced pressure to obtain a crude product of epoxidized modified methylphenyl silicone resin.

(2) Refined epoxidized modified methylphenyl silicone resin

Wash the crude product of epoxidized modified methylphenyl silicone resin with deionized water 3-4 times to neutrality, let it stand and separate layers, and then transfer the lower clear liquid to a round bottom distillation flask, at 80 ° C, 0.096 The moisture in the system is removed under the condition of MPa, so as to obtain a colorless and transparent epoxidized modified methylphenyl silicone resin. The detected viscosity is 420mpa.s, and the yield is 63.90%.

Example 7

Preparation of epoxidized modified methylphenyl silicone resin:

(1) Preparation of Epoxidized Modified Methylphenyl Silicone Resin Crude Product

22g of 3-glycidyl etheroxypropylmethyldimethoxysilane and 54.7g of methylphenyldimethoxysilane were mixed in a beaker and stirred evenly, and poured into a constant pressure dropping funnel as reactants. Take 76.7g of distilled water and 1.68g of barium hydroxide monohydrate and place them in a 250ml four-necked flask to prepare a mixture, stir and heat the mixture, and start to add the reactants dropwise when the temperature rises to 60°C, and control the reaction temperature to 60°C. After the reactants were dropped, they were reacted at 60° C. for 4 h, and then the catalyst was removed by suction filtration under reduced pressure to obtain a crude product of epoxidized modified methylphenyl silicone resin.

(2) Refined epoxidized modified methylphenyl silicone resin

Wash the crude product of epoxidized modified methylphenyl silicone resin with deionized water 3-4 times to neutrality, let it stand and separate layers, and then transfer the lower clear liquid to a round bottom distillation flask, at 80 ° C, 0.096 The moisture in the system is removed under the condition of MPa, so as to obtain a colorless and transparent epoxidized modified methylphenyl silicone resin.

Example 8

Preparation of epoxidized modified methylphenyl silicone resin:

(1) Preparation of Epoxidized Modified Methylphenyl Silicone Resin Crude Product

22g of 3-glycidyl etheroxypropylmethyldimethoxysilane and 54.7g of methylphenyldimethoxysilane were mixed in a beaker and stirred evenly, and poured into a constant pressure dropping funnel as reactants. Take 76.7g of distilled water and 1.68g of barium hydroxide monohydrate and place them in a 250ml four-neck flask to prepare a mixture, stir and heat the mixture, and start to drop the reactants when the temperature rises to 60°C, and control the reaction temperature to 90°C. After the reactants were dropped, they were reacted at 90° C. for 2 h, and then the catalyst was removed by suction filtration under reduced pressure to obtain a crude product of epoxidized modified methylphenyl silicone resin.

(2) Refined epoxidized modified methylphenyl silicone resin

Wash the crude product of epoxidized modified methylphenyl silicone resin with deionized water 3-4 times to neutrality, let it stand and separate layers, and then transfer the lower clear liquid to a round bottom distillation flask, at 80 ° C, 0.096 The moisture in the system is removed under the condition of MPa, so as to obtain a colorless and transparent epoxidized modified methylphenyl silicone resin.

The above content is a further detailed description of the present invention in combination with specific embodiments, but the embodiments of the present invention are not limited by the above examples, and any other changes that do not deviate from the spirit or principle of the present invention, Replacement, modification, combination and simplification are all within the protection scope of the present invention.

Claims (9)

1. a kind of preparation method of LED packaging plastics epoxidation modification methyl phenyl silicone resin, which is characterized in that including following step Suddenly：

(1) epoxidation modification methyl phenyl silicone resin crude product is prepared

3- glycidyl ether oxypropyl methyl dimethoxy silanes and aminomethyl phenyl dimethoxysilane are uniformly mixed, as Reactant is added dropwise in the mixture of distilled water and dried barium hydroxide catalyst, is constituted reaction solution, is then stirred in heating Condensation reaction is hydrolyzed under the conditions of mixing, decompression, which filters, after reaction removes catalyst, obtains epoxidation modification aminomethyl phenyl silicon tree The crude product hydrolysis-condensation reaction formula of fat is as follows：

(2) epoxidation modification methyl phenyl silicone resin is refined

The middle crude product prepared of step (1) is washed with deionized 2~3 times, until resin is in neutrality, stratification then takes Subnatant, then the low-boiling-point substance in clear liquid is removed, obtain epoxidation modification methyl phenyl silicone resin.

2. the preparation method of LED packaging plastics epoxidation modification methyl phenyl silicone resin, feature exist according to claim 1 In：3- glycidyl ether oxypropyl methyl dimethoxy silanes described in step (1) and aminomethyl phenyl dimethoxysilane Mass ratio >=2.

3. the preparation method of LED packaging plastics epoxidation modification methyl phenyl silicone resin, feature exist according to claim 1 In：The dosage of dried barium hydroxide described in step (1) is the 0.8%~2% of reaction solution gross mass.

4. the preparation method of LED packaging plastics epoxidation modification methyl phenyl silicone resin, feature exist according to claim 1 In：The mass ratio of reactant and distilled water described in step (1) is 1:1~2:1.

5. the preparation method of LED packaging plastics epoxidation modification methyl phenyl silicone resin, feature exist according to claim 1 In：Hydrolysis-condensation reaction temperature described in step (1) is 60~90 DEG C.

6. according to the preparation side of any one of Claims 1 to 5 LED packaging plastics epoxidation modification methyl phenyl silicone resin Method, it is characterised in that：The hydrolysis-condensation reaction time described in step (1) is 2~4 hours.

7. according to the preparation side of any one of Claims 1 to 5 LED packaging plastics epoxidation modification methyl phenyl silicone resin Method, it is characterised in that：The removing of low-boiling-point substance described in step (2) uses distillation under vacuum.

8. the preparation method of LED packaging plastics epoxidation modification methyl phenyl silicone resin, feature exist according to claim 7 In：It is 80 DEG C that condition is evaporated under reduced pressure described in step (2), 0.096MPa.

9. a kind of LED packaging plastics epoxidation modification methyl phenyl silicone resin, it is characterised in that：The epoxidation modification methylbenzene Base silicones is prepared by any one of claim 1~8 the method, which is colorless transparent viscous liquid, viscosity For 398~1000mpa.s, molecular weight is 1000~2000, and molecular weight distributing index PDI is 1.0~1.6, refractive index 1.48 ~1.54, the epoxy content per 100g epoxidation modification methyl phenyl silicone resins is 0.05~0.20mol.