An organic silicon compound and its preparation method and application

Abstract

The present application relates to the technical field of organosilicon materials, and in particular to an organosilicon compound and its preparation method and application. The organosilicon compound provided in the present application is obtained by the reaction of an isocyanate prepolymer and a hydrosilane, and the groups at both ends of its main chain are active hydrogen groups and vinyl groups, respectively. The groups at both ends of the main chain of the organosilicon compound provided in the present application are active hydrogen groups and vinyl groups, respectively. These two groups have different reactivity and can react selectively to a certain extent. After the encapsulation glue is left standing at room temperature for a long time or is heated, the hydrogen groups and vinyl groups can regularly cross-link the raw low molecular weight silicone oil and silicone resin in the encapsulation glue, thereby improving the mechanical properties of the encapsulation glue after curing and improving the encapsulation effect.

Description

Technical Field

[0001] The present application relates to the technical field of organosilicon materials, and in particular to an organosilicon compound and a preparation method and application thereof. Background Art

[0002] Packaging glue refers to a type of electronic glue or adhesive that can seal, encapsulate or pot certain components (such as resistors and capacitors in the electronics industry, etc.). After potting, it can play the role of waterproofing, moisture-proof, shock-proof, dust-proof, heat dissipation, and confidentiality. Common packaging glues mainly include epoxy packaging glue, silicone packaging glue, polyurethane packaging glue, and ultraviolet light curing packaging glue. Among them, silicone packaging glue has the advantages of high temperature resistance, aging resistance, and high light shielding rate, so it is widely used in electronics, photovoltaics and other fields.

[0003] The mechanical strength of silicone encapsulants is generally poor. In the prior art, reinforcing fillers are usually added to improve the mechanical strength. However, after adding reinforcing fillers, the viscosity of the silicone encapsulant tends to increase rapidly, resulting in difficulty in flow, slow filling during use, incomplete filling, and gaps, resulting in reduced encapsulation effect or even failure. Therefore, it is very necessary to provide a compound that does not affect the viscosity of the encapsulant and can improve the mechanical strength of the encapsulant after curing. Summary of the invention

[0004] The embodiment of the present application provides an organosilicon compound to solve the problem of affecting the viscosity of the packaging glue when the reinforcing filler is used to improve the mechanical strength of the packaging glue in the related art.

[0005] In a first aspect, the present application provides an organosilicon compound obtained by reacting an isocyanate prepolymer and a hydrosilane, wherein the groups at both ends of the main chain of the organosilicon compound are an active hydrogen group and a vinyl group, respectively.

[0006] In some embodiments, the structural formula of the organosilicon compound is:

[0007]

[0008] Where: R 1 , R 2 is an alkyl group or a phenyl group; R 3 is a straight-chain alkane or a cycloalkane; R 4 is a hydrogen group or a methyl group; R 5 is ethyl or propyl; the value of n is 20-100. The main chain structure of the organosilicon compound contains carbamate and acrylate groups, both of which have excellent bonding effects on highly polar substrates and inorganic substrates. Therefore, adding organosilicon compounds to the encapsulation adhesive can effectively improve its adhesion to highly polar and highly polar substrates.

[0009] In some preferred embodiments, R 1 It is methyl, ethyl, propyl or butyl.

[0010] In some preferred embodiments, R 3 The structural formula is C m H 2m , the value of m is 1, 2, 3…10.

[0011] In some embodiments, the viscosity of the organosilicon compound is 50-1000 cps, the vinyl content at the main chain end is 0.1-1 wt %, and the hydrogen content at the main chain end is 0.01-0.2 wt %.

[0012] In some embodiments, the isocyanate prepolymer is obtained by reacting a hydroxyl-containing siloxane, a diisocyanate and a hydroxyl acrylate.

[0013] In some embodiments, the hydroxyl-containing siloxane is α,ω-dihydroxy polysiloxane.

[0014] In some embodiments, the diisocyanate is any one of hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexyl dimethylene diisocyanate, and norbornane diisocyanate.

[0015] In some embodiments, the hydroxyacrylate is any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

[0016] In some embodiments, the hydrogen-containing silane is any one of dimethyl monochlorosilane, dimethylethoxysilane, and 1,1,3,3-tetramethyldisiloxane.

[0017] In a second aspect, the present application provides a method for preparing the above-mentioned organosilicon compound, comprising the following steps: mixing 10-500 parts by mass of isocyanate prepolymer, 10-500 parts by mass of hydrogen-containing silane, 10-100 parts by mass of hydrochloric acid and 10-100 parts by mass of water, heating to reflux at 30-100°C, and after the reaction is completed, standing, washing and drying to obtain the organosilicon compound.

[0018] In some embodiments, the hydrogen-containing silane is any one of dimethyl monochlorosilane, dimethylethoxysilane, and 1,1,3,3-tetramethyldisiloxane.

[0019] In some embodiments, the isocyanate prepolymer is prepared by the following process: 10-300 parts of hydroxyl-containing siloxane, 20-700 parts of diisocyanate, 10-300 parts of hydroxy acrylate, 10-1000 parts of organic solvent and 0.01-5 parts of catalyst are mixed by mass, and heated to reflux reaction at 50-120°C. After the reaction is completed, the isocyanate prepolymer is obtained by reduced pressure distillation, separation and purification.

[0020] In some embodiments, the hydroxyl-containing siloxane is α,ω-dihydroxy polysiloxane having a degree of polymerization of 20-100.

[0021] In some embodiments, the diisocyanate is any one of hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexyl dimethylene diisocyanate, and norbornane diisocyanate.

[0022] In some embodiments, the hydroxyacrylate is any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

[0023] In some embodiments, the organic solvent is a mixture of one or more of acetone, xylene, N,N-dimethylformamide, ethyl acetate, and butyl acetate.

[0024] In some embodiments, the catalyst is any one of dibutyltin dilaurate, stannous octoate, lead isooctanoate, and tetrabutyl titanate.

[0025] In a third aspect, the present application also provides the use of the above-mentioned organosilicon compound, wherein the organosilicon compound is used to prepare packaging glue.

[0026] The beneficial effects of the technical solution provided by this application include:

[0027] 1. The present application utilizes isocyanate prepolymer and hydrogen-containing silane to react to prepare an organosilicon compound. The main chain end groups of the organosilicon compound are active hydrogen groups and vinyl groups, respectively. These two groups have different reactivity and can react selectively to a certain extent. After the encapsulation glue is left standing at room temperature for a long time or heated, the hydrogen groups and vinyl groups can orderly cross-link the low molecular weight silicone oil and silicone resin in the encapsulation glue, thereby improving the mechanical properties of the encapsulation glue after curing and improving the encapsulation effect.

[0028] 2. The viscosity of the organosilicon compound provided in the present application is 50-1000 cps. After being added to the organosilicon encapsulating adhesive, it will not affect the viscosity of the encapsulating adhesive, ensuring that the encapsulating adhesive still has a low viscosity and good fluidity before curing. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0030] Figure 1 This is a schematic flow chart of the method for preparing the organosilicon compound provided in Example 1 of the present application. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solution and advantages of the embodiments of the present application clearer, the technical solution in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0032] The embodiment of the present application provides an organosilicon compound, which can solve the problem of affecting the viscosity of the packaging glue when the reinforcing filler is used to improve the mechanical strength of the packaging glue in the related art.

[0033] The structural formula of the organosilicon compound provided in this application is:

[0034]

[0035] Where: R 1 , R 2 is an alkyl group or a phenyl group; R 3 is a straight-chain alkane or a cycloalkane; R 4 is a hydrogen group or a methyl group; R 5 It is ethyl or propyl; the value of n is 20-100.

[0036] The structural formula of the organosilicon compound of the present application may specifically be:

[0037]

[0038] Example 1

[0039] refer to Figure 1 , Example 1 of the present application provides a method for preparing an organosilicon compound, comprising the following steps:

[0040] Step S101, in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel and filled with nitrogen, 10 parts of α, ω-dihydroxy polymethylsiloxane with a degree of polymerization of 20, 50 parts of hexamethylene diisocyanate, 20 parts of hydroxyethyl acrylate, 100 parts of acetone, and 0.01 parts of lead isooctanoate are added respectively, and reflux reaction is carried out at 80° C. for 5 hours, and then 30 parts of hexamethylene diisocyanate are added dropwise again, and the reaction is continued for 5 hours. After the reaction is completed, acetone is removed by vacuum distillation, and by-products are removed by column chromatography to obtain an isocyanate prepolymer;

[0041] Step S102, add 10 parts of distilled water, 10 parts of concentrated hydrochloric acid, 50 parts of dimethyl monochlorosilane and 10 parts of isocyanate prepolymer into a flask, reflux at 60°C for 5 hours, and after the reaction is completed, stand and separate, remove the lower layer of acid-containing aqueous solution, wash with sodium bicarbonate aqueous solution 5 times, and finally dry with anhydrous calcium chloride to obtain an organosilicon compound with a viscosity of 58 mPa·s.

[0042] The structural formula of organosilicon compounds is:

[0043]

[0044] Among them, R 1 is methyl; R 2 is methyl; R 3 C 2 H 4 ; R 4 is a hydrogen group; R 5 The value of n is 30-50, the vinyl content at the main chain end is 0.3-0.6wt%, and the hydrogen content at the main chain end is 0.04-0.08wt%.

[0045] Example 2

[0046] Example 2 of the present application provides a method for preparing an organosilicon compound, comprising the following steps:

[0047] Step S101, in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel and filled with nitrogen, 150 parts of α, ω-dihydroxy polymethylphenylsiloxane with a polymerization degree of 50, 500 parts of trimethylhexamethylene diisocyanate, 20 parts of hydroxyethyl methacrylate, 1000 parts of xylene, and 0.8 parts of dibutyltin dilaurate are added respectively, and reflux reaction is carried out at 60° C. for 10 hours, and then 120 parts of trimethylhexamethylene diisocyanate is added dropwise again, and the reaction is continued for 4 hours. After the reaction is completed, xylene is removed by reduced pressure distillation, and by-products are removed by column chromatography to obtain an isocyanate prepolymer;

[0048] Step S102, add 100 parts of distilled water, 75 parts of concentrated hydrochloric acid, 400 parts of dimethylethoxysilane and 300 parts of isocyanate prepolymer into a flask, reflux at 60°C for 15 hours, and after the reaction is completed, stand and separate, remove the lower layer of acid-containing aqueous solution, wash with sodium bicarbonate aqueous solution 5 times, and finally dry with anhydrous calcium chloride to obtain an organosilicon compound with a viscosity of 94 mPa·s.

[0049] The structural formula of organosilicon compounds is:

[0050]

[0051] Among them, R 1 is methyl; R 2 is ethyl; R 3 C 3 H 6 ; R 4 is methyl; R 5 The value of n is 20-40. The vinyl content at the main chain end is 0.2-0.4wt%, and the hydrogen content at the main chain end is 0.1-0.15wt%.

[0052] Example 3

[0053] Example 3 of the present application provides a method for preparing an organosilicon compound, comprising the following steps:

[0054] Step S101, in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel and filled with nitrogen, 300 parts of α, ω-dihydroxy polyphenylethyl siloxane with a polymerization degree of 100, 500 parts of isophorone diisocyanate, 30 parts of hydroxypropyl acrylate, 1000 parts of N,N-dimethylformamide, and 5 parts of tetrabutyl titanate are added respectively, and refluxed at 50° C. for 10 hours, and then 180 parts of isophorone diisocyanate is added dropwise again, and the reaction is continued for 5 hours, and then N,N-dimethylformamide is removed by reduced pressure distillation, and by-products are removed by column chromatography to obtain an isocyanate prepolymer;

[0055] Step S102, add 100 parts of distilled water, 100 parts of concentrated hydrochloric acid, 500 parts of 1,1,3,3-dimethyldisiloxane and 300 parts of isocyanate prepolymer into a flask, reflux at 50°C for 20 hours, and after the reaction is completed, stand and separate, remove the lower layer of acid-containing aqueous solution, wash with sodium bicarbonate aqueous solution 10 times, and finally dry with anhydrous calcium chloride to obtain an organosilicon compound with a viscosity of 180 mPa·s.

[0056] The structural formula of organosilicon compounds is:

[0057]

[0058] Among them, R 1 is propyl; R 2 is propyl; R 3 C 3 H 6 ; R 4 is methyl; R 5 The value of n is 70-90. The vinyl content at the main chain end is 0.7-0.9wt%, and the hydrogen content at the main chain end is 0.04-0.08wt%.

[0059] Example 4

[0060] Example 4 of the present application provides a method for preparing an organosilicon compound, comprising the following steps:

[0061] Step S101, in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel and filled with nitrogen, 50 parts of α, ω-dihydroxy polyphenylsiloxane with a degree of polymerization of 60, 400 parts of 1,4-cyclohexyl dimethylene diisocyanate, 300 parts of hydroxypropyl methacrylate, 800 parts of acetone and 200 parts of xylene, and 3 parts of stannous octoate are added respectively, and refluxed at 100° C. for 1 hour, and then 140 parts of 1,4-cyclohexyl dimethylene diisocyanate is added dropwise again, and the reaction is continued for 5 hours, and then acetone and xylene are removed by reduced pressure distillation, and by-products are removed by column chromatography to obtain an isocyanate prepolymer;

[0062] Step S102, add 80 parts of distilled water, 75 parts of concentrated hydrochloric acid, 350 parts of dimethylsilane and 360 parts of isocyanate prepolymer into a flask, reflux at 90°C for 2h, and after the reaction, let it stand for stratification, remove the lower layer of acid-containing aqueous solution, wash with sodium bicarbonate aqueous solution 5 times, and finally dry with anhydrous calcium chloride to obtain an organosilicon compound with a viscosity of 60mPa·s.

[0063] The structural formula of organosilicon compounds is:

[0064]

[0065] Among them, R 1 is ethyl; R 2 is methyl; R 3 The structural formula is C 6 H 12 ; R 4 is methyl; R 5 The value of n is 25-55. The vinyl content at the main chain end is 0.5-0.75wt%, and the hydrogen content at the main chain end is 0.12-0.16wt%.

[0066] Next, the organosilicon compounds of Examples 1 to 4 were used to prepare organosilicon encapsulation adhesives, and the performance of the prepared organosilicon encapsulation adhesives was tested.

[0067] The preparation process of silicone encapsulation adhesive is as follows:

[0068] (1) By weight, 20 parts of a vinyl silicone oil with a viscosity of 500 cps and a vinyl content of 2 wt%, 50 parts of a vinyl silicone oil with a viscosity of 1000 cps and a vinyl content of 0.8 wt%, 30 parts of a vinyl silicone resin with a vinyl content of 1.2 wt% and 0.5 parts of a Custer catalyst are placed in a mixer and uniformly mixed to form component A;

[0069] (2) By mass, 60 parts of a vinyl silicone oil having a viscosity of 1000 cps and a vinyl content of 1.3 wt%, 20 parts of a vinyl silicone resin having a vinyl content of 1.4 wt%, 10 parts of a hydrogenated silicone oil having a hydrogen content of 0.1 wt%, 5 parts of a hydrogenated silicone resin having a hydrogen content of 0.9 wt%, 5 parts of an organosilicon compound (the organosilicon compounds prepared in Example 1, Example 2, Example 3, and Example 4 were used as the implementation application, and no organosilicon compound was added as a comparative example) and 0.02 parts of 1-ethynylcyclohexanol were placed in a mixer and mixed uniformly to obtain component B;

[0070] (3) When packaging and transporting, component A and component B should be packaged separately. When using, component A and component B should be mixed evenly in a mass ratio of 2:1, applied or potted to the required parts, and can be cured at room temperature or high temperature.

[0071] A packaging adhesive to which no organosilicon compound is added during the preparation process is used as a comparative example.

[0072] The performance test standards are:

[0073] Viscosity test standard: GB / T 22235-2008 rotational viscometer method;

[0074] Tensile strength and elongation at break test standard: GB / T 528-2009;

[0075] Shear strength test standard: GB / T 7124-2008;

[0076] Peel strength test standard: GB / T 2790-1995;

[0077] Transmittance test standard: GB / T 2410-2008 spectrophotometer method.

[0078] The performance test results are shown in Table 1.

[0079] Table 1: Performance test results of encapsulation adhesives prepared using the organosilicon compounds of Examples 1 to 4

[0080]

[0081] As can be seen from Table 1, the viscosity of component A and component B in the encapsulation glue samples prepared using the organosilicon compounds of Examples 1-4, the viscosity after A / B mixing and the 0.5 mm transmittance are not significantly different from those of the encapsulation glue of the comparative example, which indicates that the addition of the organosilicon compounds of the present application has no significant effect on the viscosity and transmittance of the encapsulation glue; and from the comparison of tensile strength, elongation at break, glass-glass shear strength and glass-TPT film glass strength, it can be found that the above properties of the encapsulation glue prepared using the organosilicon compounds of Examples 1-4 are significantly higher than those of the encapsulation glue of the comparative example, which shows that the addition of organosilicon compounds can significantly increase the mechanical properties of the encapsulation glue without increasing the viscosity of the glue.

[0082] In summary, adding the organosilicon compound provided in the present application to the organosilicon encapsulant can enable the encapsulant to maintain a relatively low viscosity while having good mechanical properties.

[0083] In the description of this specification, the description with reference to the terms "one embodiment / method", "some embodiments / methods", "example", "specific example" or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment / method or example are included in at least one embodiment / method or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment / method or example. Moreover, the specific features, structures, materials or characteristics described may be combined in a suitable manner in any one or more embodiments / methods or examples. In addition, those skilled in the art may combine and combine the different embodiments / methods or examples described in this specification and the features of the different embodiments / methods or examples, unless they are contradictory.

[0084] It should be noted that, in the present application, the terms "comprise", "include" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, an element defined by the sentence "comprises one ..." does not exclude the presence of other identical elements in the process, method, article or device including the element. In the present application, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically specified.

[0085] The above description is only a specific implementation of the present application, so that those skilled in the art can understand or implement the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein, but will conform to the widest range consistent with the principles and novel features applied for herein.

Claims

1. An organosilicon compound, characterized in that: The organosilicon compound is obtained by reacting an isocyanate prepolymer and a hydrogen-containing silane, and the isocyanate prepolymer is prepared by the following process: by weight, 10-300 parts of hydroxyl-containing siloxane, 20-700 parts of diisocyanate, 10-300 parts of hydroxyl acrylate, 10-1000 parts of organic solvent and 0.01-5 parts of catalyst are mixed, and heated under reflux reaction at 50-120° C. After the reaction is completed, the isocyanate prepolymer is distilled under reduced pressure, separated and purified to obtain the isocyanate prepolymer; The hydroxyl-containing siloxane is α,ω-dihydroxy polysiloxane; Method for preparing organosilicon compounds, The method comprises the following steps: mixing 10-500 parts by mass of isocyanate prepolymer, 10-500 parts by mass of hydrogen-containing silane, 10-100 parts by mass of hydrochloric acid and 10-100 parts by mass of water, heating under reflux reaction at 30-100°C, and after the reaction is completed, standing, washing and drying to obtain an organosilicon compound.

2. The organosilicon compound according to claim 1, characterized in that The viscosity of the organosilicon compound is 50-1000 cps, the vinyl content at the main chain end is 0.1-1 wt %, and the hydrogen content at the main chain end is 0.01-0.2 wt %.

3. The organosilicon compound according to claim 1, characterized in that The diisocyanate is any one of hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexyl dimethylene diisocyanate, and norbornane diisocyanate; the hydroxy acrylate is any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

4. The organosilicon compound according to claim 1, characterized in that The hydrogen-containing silane is any one of dimethyl monochlorosilane, dimethylethoxysilane and 1,1,3,3-tetramethyldisiloxane.

5. The method for preparing an organosilicon compound according to any one of claims 1 to 4, characterized in that: The following steps are involved: An isocyanate prepolymer, a hydrogen-containing silane, hydrochloric acid and water are mixed and heated to react at 30-100° C. After the reaction is completed, the mixture is allowed to stand, washed and dried to obtain an organosilicon compound. The isocyanate prepolymer is prepared by the following process: a hydroxy-containing siloxane, a diisocyanate, a hydroxy acrylate, an organic solvent and a catalyst are mixed and heated to reflux at 50-120° C. After the reaction is completed, the mixture is distilled under reduced pressure, separated and purified to obtain the isocyanate prepolymer. The catalyst is any one of dibutyltin dilaurate, stannous octoate, lead isooctanoate and tetrabutyl titanate.

6. The method for preparing an organosilicon compound according to claim 5, characterized in that: The mass fraction of the isocyanate prepolymer is 10-500 parts, the mass fraction of the hydrogen-containing silane is 10-500 parts, the mass fraction of the hydrochloric acid is 10-100 parts, and the mass fraction of water is 10-100 parts.

7. The method for preparing an organosilicon compound according to claim 6, characterized in that: The organic solvent is a mixture of one or more of acetone, xylene, N,N-dimethylformamide, ethyl acetate and butyl acetate.

8. The method for preparing an organosilicon compound according to claim 7, characterized in that: The mass fraction of hydroxyl-containing siloxane is 10-300 parts, the mass fraction of diisocyanate is 20-700 parts, the mass fraction of hydroxy acrylate is 10-300 parts, the mass fraction of organic solvent is 10-1000 parts and the mass fraction of catalyst is 0.01-5 parts.

9. The use of the organosilicon compound according to claim 1, characterized in that: The organosilicon compound is used for preparing packaging glue.

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