阅读说明：本技术 一种led封装硅胶用抑制剂及其制备方法和应用 (Inhibitor for LED (light-emitting diode) packaging silica gel and preparation method and application thereof ) 是由 陆文灿 黄德裕 黄振宏 于 2020-05-22 设计创作，主要内容包括：本发明公开了一种含苯基硅氧链的炔醇化合物及其制备方法和应用。所述含苯基硅氧链的炔醇化合物,具有下式所示结构式,式中,a＝5～20,b＝0～10,c＝3～6,R<Sub>1</Sub>为甲基或苯基。其以苯基含氢硅油、丙烯酸酯和甲基丁炔醇为主要原料,在催化剂作用下反应制备得到。所述化合物在甲基丁炔醇结构中引入含有苯基的硅氧链段,苯基可以改善化合物的折光系数,硅氧链段可以提高与硅胶的相容性,通过选择不同苯基含量以及不同硅氧链长的苯基含氢硅油,可以调节所得化合物的折光系数以及与硅胶的相容性。<Image he="281" wi="700" file="DDA0002503712370000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses an alkynol compound containing phenyl siloxy chains and a preparation method and application thereof. The alkynol compound containing the phenyl siloxy chain has a structural formula shown in the specification, wherein a is 5-20, b is 0-10, c is 3-6, and R is 1 Is methyl or phenyl. The catalyst is prepared by taking phenyl hydrogen-containing silicone oil, acrylic ester and methyl butynol as main raw materials and reacting under the action of a catalyst. The compound introduces a phenyl-containing siloxane chain segment into a methylbutynol structure, the phenyl can improve the refractive index of the compound, the siloxane chain segment can improve the compatibility with silica gel, and the folding of the obtained compound can be adjusted by selecting phenyl hydrogen-containing silicone oil with different phenyl contents and different siloxane chain lengthsOptical coefficient and compatibility with silica gel.)

1. An alkynol compound containing a phenyl siloxy chain is characterized by having a structural formula as follows:

wherein a is 5 to 20, b is 0 to 10, c is 3 to 6, R₁Is methyl or phenyl.

2. The method of claim 1, wherein the method comprises the steps of:

s1. preparation of intermediate

The phenyl hydrogen-containing silicone oil, the acrylate and the platinum catalyst react for 1-3 hours at 50-60 ℃ to obtain an intermediate with the following structural general formula:

wherein a is 5 to 20, b is 0 to 10, c is 3 to 6, R₁Is methyl or phenyl, R₂Is methyl or ethyl;

s2, preparation of alkynol compound containing phenyl siloxy chain

And S1, mixing the intermediate obtained in the step S1, methyl butynol, an acid catalyst and an organic solvent toluene, reacting for 3-6 h at 60-80 ℃, adding a pH regulator until the system is neutral, filtering, and removing the solvent to obtain the compound.

3. The method of claim 2, wherein in step S1, the phenyl hydrosilicone oil has a general structural formula:

wherein a is 5 to 20, b is 0 to 10, c is 3 to 6, R₁Is methyl or phenyl.

4. The method of claim 2, wherein in step S1, the acrylate is one or more of methyl acrylate and ethyl acrylate.

5. The method according to claim 2, wherein in step S1, the molar ratio of Si — H bonds of the phenyl hydrosilicone oil to C ═ C bonds of the acrylate is 1: 1.

6. the method of claim 2, wherein in step S1, the platinum catalyst is one or more selected from the group consisting of platinum tetrachloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a hydroxy alcohol, a complex of chloroplatinic acid and an olefin, and platinum diacetylacetate.

7. The method of claim 2, wherein in step S2, Si-CH of the intermediate is₂-CH₂-COOR₂The molar ratio of C-OH to methylbutynol is 1: 1.

8. the method of claim 2, wherein in step S2, the acid catalyst is concentrated sulfuric acid or p-toluenesulfonic acid.

9. The method according to claim 2, wherein the pH adjusting agent is sodium bicarbonate or sodium carbonate in step S2.

10. Use of alkynol compounds containing phenyl siloxane chains according to claim 1 for the preparation of LED encapsulating silica gel inhibitors.

Technical Field

The invention relates to the field of chemical synthesis, and particularly relates to an inhibitor for LED packaging silica gel, and a preparation method and application thereof.

Background

The LED (LIGHT EMITTING DIODE) has the advantages of energy conservation, environmental protection, long service life, high lighting effect and the like, is called as a green light source, and is widely applied to the fields of illumination, advertising boards, outdoor display screens, backlight sources and the like at present.

The materials for LED encapsulation at present mainly comprise two main types of epoxy resin and organic silicon. The organic silicon packaging adhesive is divided into two categories of low refractive index and high refractive index according to the purpose, and in some special application occasions, a medium refractive index product between the two categories can be provided. The organic silicon packaging adhesive with low refractive index has larger difference between the refractive index and the refractive index of the chip, so that part of light rays are totally reflected back to the inside of the chip to influence the light-emitting rate, and therefore, the high-end LED packaging adhesive is basically the organic silicon LED packaging adhesive with high refractive index; the high-refractive-index organic silicon LED packaging adhesive basically adopts a bi-component addition type vulcanization system, namely, a platinum complex catalyst is used for catalyzing silicon vinyl and silicon hydride to perform addition reaction to form a cross-linked body, and in the process, in order to balance curing speed and operable time, an inhibitor is required to be added for adjustment. Inhibitors are also known as inhibitors, retarders, etc.

Conventionally, the commonly used LED packaging silica gel inhibitor comprises ethynyl cyclohexanol, methyl butynol, 1, 3-triphenyl-2-propyn-1-ol, polyvinyl compound and the like. However, the compatibility of ethynyl cyclohexanol and methylbutynol with an organic silicon system is poor, and particularly, the ethynyl cyclohexanol and methylbutynol are used in LED packaging glue with medium and high refractive index to have larger influence, so that the transparency of the system is influenced, and the stability of the packaging glue is easily influenced by precipitation; 1,1, 3-triphenyl-2-propyne-1-alcohol is solid at normal temperature, has poor solubility in an organic silicon system, is not well dispersed uniformly, and influences the inhibition effect; the polyvinyl compound is used in the LED packaging silica gel with medium and high refractive indexes, and the turbidity phenomenon can occur due to the difference of the refractive indexes, so that the light transmittance is influenced.

In order to improve the compatibility problem of the inhibitor with the encapsulating silica gel, some methods for modifying the inhibitor are reported: patent CN109851629A discloses that isocyanate silane reacts with alkynyl compound to prepare silylation alkynyl inhibitor, which is used for preparing single-component silicone rubber; patent CN105418669A discloses an alkoxysilane acetylenic hydrosilylation inhibitor prepared by mixing and reacting methylbutynol or ethynyl cyclohexanol as raw material with alkoxysilane.

In the prior art, only the compatibility problem is considered, and the influence of the refractive index of the inhibitor in the silica gel system with high refractive index is ignored. Therefore, it is urgently required to develop an inhibitor which can adjust the refractive index and has good compatibility with silica gel.

Disclosure of Invention

The invention aims to solve the problem that an inhibitor influences the light transmittance and compatibility of a silica gel system in the prior art, and provides an alkynol compound containing a phenyl siloxane chain, which can simultaneously improve the compatibility of the inhibitor and the silica gel and the light transmittance of the silica gel system when being used as an LED packaging silica gel inhibitor.

Another object of the present invention is to provide a process for the preparation of the compound.

Another object of the present invention is to provide the use of said compounds.

In order to achieve the purpose, the invention adopts the following technical scheme:

an alkynol compound containing phenyl siloxy chains has the following structural formula:

wherein a is 5 to 20, b is 0 to 10, c is 3 to 6, R₁Is methyl or phenyl, R₂Is methyl or ethyl.

The alkynol compound containing the phenyl siloxane chain is formed by introducing a siloxane chain segment with phenyl into a structure of a common inhibitor methylbutynol. The phenyl can improve the refractive index of the compound, and the phenyl hydrogen-containing silicone oil with different phenyl contents can make the compound have different refractive indexes; the silica chain segment can have good compatibility with silica gel, and the compatibility of the compound and the silica gel can be adjusted by selecting phenyl hydrogen-containing silicone oil with different silica chain lengths.

The invention also provides a preparation method of the alkynol compound containing the phenyl siloxy chain, which comprises the following specific steps:

s1. preparation of intermediate

The phenyl hydrogen-containing silicone oil, the acrylate and the platinum catalyst react for 1-3 hours at the temperature of 50-60 ℃ to obtain an intermediate with the following structural general formula:

wherein a is 5 to 20, b is 0 to 10, c is 3 to 6, R₁Is methyl or phenyl, R₂Is methyl or ethyl;

s2, preparation of alkynol compound containing phenyl siloxy chain

And S1, mixing the intermediate obtained in the step S1, methyl butynol, an acid catalyst and an organic solvent toluene, reacting for 3-6 h at 60-80 ℃, adding a pH regulator until the system is neutral, filtering, heating the filtrate to 140-150 ℃, and removing the solvent in vacuum to obtain the compound.

In step S1, the general structural formula of the phenyl hydrogen silicone oil is:

wherein a is 5 to 20, b is 0 to 10, c is 3 to 6, R₁Is methyl or phenyl.

Preferably, in step S1, the acrylate is one or a combination of methyl acrylate and ethyl acrylate.

Preferably, in step S1, the molar ratio of Si — H bonds of the phenyl hydrogen silicone oil to C ═ C bonds of the acrylate is 1: 1.

preferably, in step S1, the platinum catalyst is one or more of platinum tetrachloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a hydroxyl alcohol, a complex of chloroplatinic acid and an olefin, or platinum diacetylacetate.

Preferably, in step S1, the amount of platinum catalyst is 0.05% of the total mass of the monomers.

Preferably, in step S2, Si-CH of the intermediate₂-CH₂-COOR₂The molar ratio of C-OH to methylbutynol is 1: 1.

preferably, in step S2, the acid catalyst is concentrated sulfuric acid or p-toluenesulfonic acid.

Preferably, in step S2, the amount of the acid catalyst is 0.5-3% of the total mass of the monomers.

Preferably, in step S2, the pH adjusting agent is sodium bicarbonate or sodium carbonate.

The alkynol compound containing the phenyl-silicon-oxygen chain is applied to preparation of the LED packaging silica gel inhibitor.

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

the invention discloses an alkynol compound containing phenyl siloxy chains, which is characterized in that a siloxy chain segment with phenyl is introduced into a structure of a common inhibitor methyl butynol. The phenyl can improve the refractive index of the compound, the phenyl hydrogen-containing silicone oil with different phenyl contents can be selected to enable the compound to have different refractive indexes, and when the compound is used as an inhibitor, the compound is compatible with silica gel with similar refractive index, so that the refractive index of a silica gel system containing the inhibitor can be improved; the silica chain segment can have good compatibility with silica gel, and the compatibility of the compound and the silica gel can be adjusted by selecting phenyl hydrogen-containing silicone oil with different silica chain lengths.

Detailed Description

The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the present invention are commercially available.

In the following examples, phenyl hydrogen-containing silicone oils with different siloxane chain lengths and different phenyl contents used for preparing the compounds were prepared by self-preparation, and the structural general formula thereof is:

wherein a is 5 to 20, b is 0 to 10, c is 3 to 6, R₁Is methyl or phenyl

When R is₁When the methyl is adopted, the synthesis method comprises the following steps:

adding 4mol of hexamethyldisiloxane, a mol of tetramethyltetraphenylcyclotetrasiloxane, b mol of octamethylcyclotetrasiloxane and c mol of tetramethylcyclotetrasiloxane into a reactor, uniformly stirring, adding concentrated sulfuric acid accounting for 5.0-8.0% of the total mass of the materials, starting stirring, heating to 60-90 ℃, reacting for 5-10 hours, cooling to room temperature, adding sodium carbonate to neutralize to neutrality under the condition of stirring, and filtering to obtain the phenyl hydrogen-containing silicone oil; (example 2 wherein a is 20, b is 10, and c is 3; example 3 wherein a is 20, b is 0, and c is 3; example 4 wherein a is 5, b is 10, and c is 6).

When R is₁When the phenyl is adopted, the synthesis method comprises the following steps:

adding 4mol of hexamethyldisiloxane, a mol of octaphenylcyclotetrasiloxane, b mol of octamethylcyclotetrasiloxane and cmol of tetramethylcyclotetrasiloxane into a reactor, stirring uniformly, adding concentrated sulfuric acid accounting for 5.0-8.0% of the total mass of the materials, starting stirring, heating to 60-90 ℃, reacting for 5-10 hours, cooling to room temperature, adding sodium carbonate to neutralize to neutrality under the condition of stirring, and filtering to obtain the phenyl hydrogen-containing silicone oil. (in the starting material of example 1, a is 5, b is 10, and c is 3).

In the following examples, the refractive index of the prepared compound is tested, and the specific test method refers to GB/T614-2006.