Curable organopolysiloxane composition and preparation method thereof

Abstract

According to the curable organopolysiloxane composition, synthesis raw materials are easy to obtain, the cost is low, organopolysiloxane resin with trace methoxyl groups and hydroxyl groups is synthesized at low temperature by adopting a large amount of water, the organopolysiloxane resin with different molecular weights is matched with methyl phenyl silicone oil with certain flexibility, and the curable organopolysiloxane composition is prepared. And through interaction of a hydrosilylation reaction catalyst, an inhibitor and a tackifier, the curable organopolysiloxane composition has excellent aging resistance, moisture resistance and cold and hot impact resistance on an organic resin substrate. The invention also provides a preparation method of the curable organopolysiloxane composition.

Description

[Technical field]

[0001] The invention belongs to the technical field of organosilicon materials, and in particular relates to a curable organopolysiloxane composition and a preparation method thereof. [Background technology]

[0002] Curable organopolysiloxane compositions, as a high-performance organosilicon material, are often used as sealing materials or protective coating materials for optical semiconductor elements in packaged optical semiconductor devices such as light emitting diodes (LEDs).

[0003] However, in practical applications, the cured products of curable organopolysiloxane compositions face many environmental challenges, which significantly affect their long-term performance and reliability. For example, ultraviolet rays in the natural environment will trigger photochemical reactions of the organopolysiloxane composition, causing aging of the material, such as color change, which may cause a decrease in luminous efficiency and shortened life; corrosive gases in the air (such as sulfides, hydroxides, etc.) will react chemically with the organopolysiloxane composition, causing corrosion of the material surface and degradation of performance, and may further cause corrosion of the silver material on the LED substrate; and temperature fluctuations in the natural environment will trigger thermal expansion and contraction of the organopolysiloxane composition, resulting in changes in internal stress of the material, which may cause problems such as material cracking and bonding failure, thereby affecting the normal operation of the LED. [Summary of the invention]

[0004] In order to solve the problems of the curable organopolysiloxane composition in the prior art, the present invention provides a curable organopolysiloxane composition with excellent anti-aging performance, moisture-proof performance and thermal shock resistance.

[0005] The present invention is achieved by the following technical solutions:

[0006] A curable organopolysiloxane composition comprising the following components:

[0007] The organopolysiloxane A is represented by the following average unit formula:

[0008] (Me2ViSiO 0.5 ) a (PhSiO 1.5 ) b

[0009] The organopolysiloxane A has at least two alkenyl groups in the molecule and has a very small amount of methoxy and hydroxyl groups;

[0010] The organopolysiloxane B is represented by the following average unit formula:

[0011] (Me2ViSiO 0.5 ) c(PhSiO 1.5 ) d

[0012] The organopolysiloxane B has at least two alkenyl groups in the molecule and has a very small amount of methoxy and hydroxyl groups;

[0013] The organopolysiloxane C is represented by the following average unit formula:

[0014] (HMe2SiO 0.5 ) e (MePhSiO 1.0 ) f

[0015] The organopolysiloxane C molecule has at least two silicon-bonded hydrogen atoms;

[0016] Hydrosilylation reaction catalyst;

[0017] Inhibitors;

[0018] Tackifier.

[0019] The curable organopolysiloxane composition of the present invention has excellent anti-aging performance, moisture resistance and resistance to cold and hot shock. First, a cross-linked network structure is formed by a silylation reaction between the alkenyl groups of organopolysiloxanes A and B with different molecular weights and the silylation bonds of an organopolysiloxane C with certain flexibility, thereby achieving the curing of the organopolysiloxane composition. Secondly, by combining a silylation reaction catalyst with an inhibitor, the reaction rate can be controlled to prevent the composition from curing too quickly during the preparation process and the application process, thereby improving the process operability. Finally, by using a tackifier, the adhesion of the composition to an organic resin substrate (such as an LED packaging material) can be enhanced, ensuring that the composition is tightly combined with the substrate, thereby improving the reliability and durability of the product.

[0020] Preferably, the ratio of the molar amount of the silicon-bonded hydrogen atoms to the molar amount of the total alkenyl groups of the curable organopolysiloxane composition is (0.5-2):1.

[0021] By controlling the molar ratio of silicon-hydrogen bonds to alkenyl groups, the amounts of components of the composition are adjusted to control the reaction rate and ensure that the alkenyl groups can react with silicon-hydrogen bonds to form stable silicon-carbon bonds, thereby achieving complete crosslinking and curing.

[0022] Preferably, the values ​​of subscripts a and b in the average unit formula of the organopolysiloxane A are 0.01≤a<0.3, 0.3≤b<1, and a+b=1.

[0023] Preferably, the values ​​of subscripts c and d in the average unit formula of the organopolysiloxane B are 0.3≤c<1, 0.3≤d<1, and c+d=1.

[0024] By adjusting the ratio of a to b, and c to d, the reactive active sites can be adjusted, the compatibility between the organopolysiloxanes A and B can be optimized, and the optical properties of the organopolysiloxanes A and B can be adjusted.

[0025] Preferably, the values ​​of subscripts e and f in the average unit formula of the organopolysiloxane C are 0.01≤e≤5, 1≤f≤50.

[0026] By adjusting the ratio of e and f, the density of the silicon-hydrogen bond can be controlled, the reaction rate of the silicon-hydrogen addition reaction can be adjusted, and at the same time, the mechanical properties of the composition, such as flexibility and strength, can be optimized, and the adhesion of the composition to different substrates can be improved.

[0027] Preferably, the hydrosilylation catalyst is a Custer catalyst having a platinum content of 1-1000 ppm.

[0028] The Custer catalyst has high catalytic activity and can significantly accelerate the hydrosilylation reaction, allowing the composition to cure quickly at a lower temperature. Secondly, the catalyst is highly selective for the hydrosilylation reaction, which can effectively avoid the occurrence of side reactions and ensure the purity and performance of the reaction product. In addition, by controlling the platinum content of the catalyst, the amount of catalyst used is low, thereby reducing production costs, reducing the potential impact of the catalyst on the human body and the environment, and improving the purity and safety of the product.

[0029] Preferably, the inhibitor is an alkynol compound. More preferably, the alkynol compound is one of methylpentynol and ethynylcyclohexanol.

[0030] The inhibitor can inhibit the hydrosilylation reaction caused by the catalyst at room temperature, thereby extending the operating time of the composition at room temperature, improving the flexibility and operability of the preparation process, and further improving product quality and optimizing product performance.

[0031] Another object of the present invention is to provide a method for preparing the curable organopolysiloxane composition, including a method for preparing the organopolysiloxane A and the organopolysiloxane B, comprising the following steps:

[0032] S11, hydrolysis condensation: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, toluene, water and concentrated sulfuric acid are added into a reaction container, and phenyltrimethoxysilane is added dropwise at low temperature to obtain a mixed solution, which is stirred;

[0033] S12, deacidification: after the mixed solution in step S1 is cooled to room temperature, toluene is added, and then water is added for washing to obtain an organopolysiloxane resin prepolymer;

[0034] S13, neutralization and fractionation: adding potassium hydroxide and water to the organopolysiloxane resin prepolymer in step S2, fractionating with a water separator, cooling to room temperature after fractionation, adding glacial acetic acid, stirring, and obtaining an organopolysiloxane resin fraction;

[0035] S14, product purification: cooling the organopolysiloxane resin fraction in step S3 to room temperature, washing the organic phase with water for multiple times, and removing the solvent under negative pressure to obtain the organopolysiloxane resin.

[0036] By using a large amount of water to synthesize an organic polysiloxane resin with trace amounts of methoxy and hydroxyl groups at low temperature, and then inlaying and combining organic polysiloxane resins of different molecular weights to form a dense cross-linked network structure, it can effectively block the penetration of water vapor, thereby improving the moisture-proof performance of the composition.

[0037] Preferably, the amount of water used in step S11 is 5-50 times the amount of water required for hydrolyzing the methoxy groups.

[0038] By using a large amount of water, the hydrolysis rate of the alkoxy group is accelerated in the form of water-in-oil, and the hydrolysis reaction and condensation reaction of the organic siloxane are positively guided and balanced, thereby regulating the content of methoxy and hydroxyl groups.

[0039] Specifically, as the content of methoxy and hydroxyl groups increases, in natural environmental conditions, ultraviolet rays, water vapor, alternating hot and cold conditions, etc., the methoxy and hydroxyl groups will further react, and at the same time "bite back" the silicon material skeleton, producing methanol, water and low molecular weight polysiloxane, causing the material to lose weight, turn yellow and age. Therefore, by inlaying and stacking resins of different molecular weights, it can resist the penetration of water vapor and improve moisture resistance. At the same time, with methylphenyl silicone oil with a certain degree of softness, it can improve the resistance to cold and heat shock.

[0040] In addition, the organopolysiloxanes A and B both have very small amounts of methoxy and hydroxy groups, that is, no characteristic absorption peaks of methoxy and hydroxy groups are observed in the infrared spectra of the two.

[0041] Preferably, a method for preparing the curable organopolysiloxane composition further includes a method for preparing the organopolysiloxane C, comprising the following steps:

[0042] S21, hydrolysis condensation: adding methylphenyldimethoxysilane, trifluoromethanesulfonic acid and glacial acetic acid into a reaction container, reacting at a certain temperature, evaporating the mixture, adding 1,1,3,3-tetramethyldisiloxane, and then adding acetic acid dropwise, and after the addition of acetic acid is completed, continuing the reaction to obtain a first organopolysiloxane resin pre-product;

[0043] S22, esterification: adding acetic anhydride dropwise to the first organopolysiloxane resin pre-product by water bath heating, and continuing the reaction after the addition of the acetic anhydride is completed to obtain a second organopolysiloxane resin pre-product;

[0044] S23, product purification: cool the second organopolysiloxane resin pre-product in step S22 to room temperature, add toluene, wash the organic phase with water for multiple times, remove the solvent under negative pressure, and obtain the organopolysiloxane resin.

[0045] Compared with phenyl silicone oil, by selecting methylphenyl silicone oil as the raw material, the chain links in the silicone oil skeleton have better flexibility, thereby optimizing the mechanical properties of the composition, so that it exhibits better durability and stability when facing temperature changes and mechanical stress.

[0046] The beneficial effects of the present invention are as follows:

[0047] The present invention provides a curable organopolysiloxane composition. First, a cross-linked network structure is formed by a silylation reaction between alkenyl groups of organopolysiloxanes A and B with different molecular weights and a silylation bond of an organopolysiloxane C with certain flexibility, thereby achieving the curing of the organopolysiloxane composition. Secondly, by combining a silylation reaction catalyst with an inhibitor, the reaction rate can be controlled, and the composition is prevented from curing too quickly during the preparation process and the application process, thereby improving the process operability. Finally, by using a tackifier, the adhesion of the composition to an organic resin substrate (such as an LED packaging material) can be enhanced, ensuring that the composition is tightly combined with the substrate, thereby improving the reliability and durability of the product.

[0048] The present invention also provides a method for preparing a curable organopolysiloxane composition. The synthetic raw materials are easy to obtain and the cost is low. A large amount of water is used to synthesize an organopolysiloxane resin having trace amounts of methoxy groups and hydroxy groups. Organopolysiloxane resins of different molecular weights are inlaid and combined, and then matched with methylphenyl silicone oil with a certain degree of flexibility, so that the curable organopolysiloxane composition has excellent anti-aging performance, moisture resistance and resistance to cold and heat shock on an organic resin substrate.

Brief Description of the Drawings

[0049] Figure 1 is a schematic diagram of an optical semiconductor device of the present invention;

[0050] 1-optical semiconductor element; 2-lead frame; 3-lead frame; 4-bonding wire; 5-frame material; 6-cured product of the curable organopolysiloxane composition. [Specific implementation method]

[0051] The specific technical scheme of the present invention is described below in conjunction with Examples 1-2:

[0052] Example 1

[0053] A method for preparing the curable organopolysiloxane composition comprises:

[0054] The preparation method of the organopolysiloxane A-1 comprises the following steps:

[0055] S11, hydrolysis condensation: 27.96 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 200 g of toluene, 540 g of water and 4.53 g of concentrated sulfuric acid were added into a reaction container, 198.29 g of phenyltrimethoxysilane was added dropwise at 0-5° C. to obtain a mixed solution, and the solution was stirred at 75° C. for 2 h;

[0056] S12, deacidification: after the mixed solution in step S1 is cooled to room temperature, 100 g of toluene is added, and then water is added for washing to obtain an organopolysiloxane resin prepolymer;

[0057] S13, neutralization and fractionation: add 0.1 g potassium hydroxide and 1 g water to the organopolysiloxane resin prepolymer in step S2, perform fractionation at 130° C. for 2 h using a water separator, cool to room temperature after fractionation, add 0.12 g glacial acetic acid, stir for 1 h, and obtain an organopolysiloxane resin fraction;

[0058] S14, product purification: Cool the organopolysiloxane resin fraction in step S3 to room temperature, wash the organic phase with water for 3 times, and remove the solvent under negative pressure to obtain organopolysiloxane resin A-1, whose average unit formula is: (Me2ViSiO 0.5 ) 0.3 (PhSiO 1.5 ) 1.0

[0059] The preparation method of the organopolysiloxane B-1 comprises the following steps:

[0060] S11, hydrolysis condensation: 55.92 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 200 g of toluene, 540 g of water and 4.53 g of concentrated sulfuric acid were added into a reaction container, 198.29 g of phenyltrimethoxysilane was added dropwise at 0-5° C. to obtain a mixed solution, and the solution was stirred at 75° C. for 2 h;

[0061] S12, deacidification: after the mixed solution in step S1 is cooled to room temperature, 100 g of toluene is added, and then water is added for washing to obtain an organopolysiloxane resin prepolymer;

[0062] S13, neutralization and fractionation: add 0.1 g potassium hydroxide and 1 g water to the organopolysiloxane resin prepolymer in step S2, perform fractionation at 130° C. for 2 h using a water separator, cool to room temperature after fractionation, add 0.12 g glacial acetic acid, stir for 1 h, and obtain an organopolysiloxane resin fraction;

[0063] S14, product purification: The organopolysiloxane resin fraction of step S3 is cooled to room temperature, the organic phase is washed with water for 3 times, and the solvent is removed under negative pressure to obtain an organopolysiloxane resin B-1, the average unit formula of which is: (Me2ViSiO 0.5 ) 0.6 (PhSiO 1.5 ) 1.0

[0064] The preparation method of the organopolysiloxane C-1 comprises the following steps:

[0065] S21, hydrolysis condensation: 364.58 g of methylphenyldimethoxysilane, 1.497 g of trifluoromethanesulfonic acid and 60.05 g of glacial acetic acid were added to a reaction container, reacted at 50° C. for 0.5 h, the mixture was evaporated, 160.8 g of 1,1,3,3-tetramethyldisiloxane was added, and 120.1 g of acetic acid was added dropwise at 50° C. After the addition of the acetic acid was completed, the reaction was continued for 0.5 h to obtain a first organopolysiloxane resin pre-product;

[0066] S22, esterification: adding 102.09 g of acetic anhydride dropwise to the first organopolysiloxane resin pre-product at 48-55° C. by water bath heating, and after the addition of the acetic anhydride is completed, continuing the reaction at 50° C. for 1 hour to obtain a second organopolysiloxane resin pre-product;

[0067] S23, product purification: The second organopolysiloxane resin pre-product of step S22 was cooled to room temperature, 500 g of toluene was added, the organic phase was washed with water for 3 times, and the solvent was removed under negative pressure to obtain an organopolysiloxane resin C-1, the average unit formula of which is: (HMe2SiO 0.5 )2(MePhSiO)2

[0068] According to Table 1, the organopolysiloxane resin A-1, the organopolysiloxane resin B-1, the organopolysiloxane resin C-1, a hydrosilylation reaction catalyst, an inhibitor and a tackifier were mixed to obtain a curable organopolysiloxane composition.

[0069] Example 2

[0070] A method for preparing the curable organopolysiloxane composition comprises:

[0071] The preparation method of the organopolysiloxane A-2 comprises the following steps:

[0072] S11, hydrolysis condensation: 24.23 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 200 g of toluene, 540 g of water and 4.53 g of concentrated sulfuric acid were added into a reaction container, 198.29 g of phenyltrimethoxysilane was added dropwise at 0-5° C. to obtain a mixed solution, and the solution was stirred at 75° C. for 2 h;

[0073] S12, deacidification: after the mixed solution in step S1 is cooled to room temperature, 100 g of toluene is added, and then water is added for washing to obtain an organopolysiloxane resin prepolymer;

[0074] S13, neutralization and fractionation: add 0.1 g potassium hydroxide and 1 g water to the organopolysiloxane resin prepolymer in step S2, perform fractionation at 130° C. for 2 h using a water separator, cool to room temperature after fractionation, add 0.12 g glacial acetic acid, stir for 1 h, and obtain an organopolysiloxane resin fraction;

[0075] S14, product purification: Cool the organopolysiloxane resin fraction in step S3 to room temperature, wash the organic phase with water for 3 times, and remove the solvent under negative pressure to obtain organopolysiloxane resin A-2, the average unit formula of which is: (Me2ViSiO 0.5 ) 0.26 (PhSiO 1.5 ) 1.0

[0076] The preparation method of the organopolysiloxane B-2 comprises the following steps:

[0077] S11, hydrolysis condensation: 74.56 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 200 g of toluene, 540 g of water and 4.53 g of concentrated sulfuric acid were added into a reaction container, 198.29 g of phenyltrimethoxysilane was added dropwise at 0-5° C. to obtain a mixed solution, and the solution was stirred at 75° C. for 2 h;

[0078] S12, deacidification: after the mixed solution in step S1 is cooled to room temperature, 100 g of toluene is added, and then water is added for washing to obtain an organopolysiloxane resin prepolymer;

[0079] S13, neutralization and fractionation: add 0.1 g potassium hydroxide and 1 g water to the organopolysiloxane resin prepolymer in step S2, perform fractionation at 130° C. for 2 h using a water separator, cool to room temperature after fractionation, add 0.12 g glacial acetic acid, stir for 1 h, and obtain an organopolysiloxane resin fraction;

[0080] S14, product purification: The organopolysiloxane resin fraction of step S3 is cooled to room temperature, the organic phase is washed with water for 3 times, and the solvent is removed under negative pressure to obtain an organopolysiloxane resin B-2, the average unit formula of which is: (Me2ViSiO 0.5 ) 0.8 (PhSiO 1.5 ) 1.0

[0081] The preparation method of the organopolysiloxane C-2 comprises the following steps:

[0082] S21, hydrolysis condensation: 455.73 g of methylphenyldimethoxysilane, 1.497 g of trifluoromethanesulfonic acid and 90.08 g of glacial acetic acid were added to a reaction container, reacted at 50° C. for 0.5 h, the mixture was evaporated, 160.8 g of 1,1,3,3-tetramethyldisiloxane was added, 120.1 g of acetic acid was added dropwise at 50° C., after the addition of the acetic acid was completed, the reaction was continued for 0.5 h to obtain a first organopolysiloxane resin pre-product;

[0083] S22, esterification: adding 102.09 g of acetic anhydride dropwise to the first organopolysiloxane resin pre-product at 48-55° C. by water bath heating, and after the addition of the acetic anhydride is completed, continuing the reaction at 50° C. for 1 hour to obtain a second organopolysiloxane resin pre-product;

[0084] S23, product purification: The second organopolysiloxane resin pre-product of step S22 is cooled to room temperature, 500 g of toluene is added, the organic phase is washed with water for 3 times, and the solvent is removed under negative pressure to obtain an organopolysiloxane resin C-2, the average unit formula of which is: (HMe2SiO 0.5 )2(MePhSiO) 2.5

[0085] According to Table 1, the organopolysiloxane resin A-2, the organopolysiloxane resin B-2, the organopolysiloxane resin C-2, a hydrosilylation reaction catalyst, an inhibitor and a tackifier were mixed to obtain a curable organopolysiloxane composition.

[0086] Comparative Example 1

[0087] A method for preparing the curable organopolysiloxane composition comprises:

[0088] The preparation method of the organopolysiloxane A-3 comprises the following steps:

[0089] S11, hydrolysis condensation: 27.96 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 200 g of toluene, 54 g of water and 4.53 g of concentrated sulfuric acid were added to a reaction container, and 198.29 g of phenyltrimethoxysilane was added dropwise at room temperature to obtain a mixed solution, which was stirred under reflux for 2 h;

[0090] S12, deacidification: after the mixed solution in step S1 is cooled to room temperature, 100 g of toluene is added, and then water is added for washing to obtain an organopolysiloxane resin prepolymer;

[0091] S13, neutralization and fractionation: add 0.1 g potassium hydroxide and 1 g water to the organopolysiloxane resin prepolymer in step S2, perform fractionation at 130° C. for 2 h using a water separator, cool to room temperature after fractionation, add 0.12 g glacial acetic acid, stir for 1 h, and obtain an organopolysiloxane resin fraction;

[0092] S14, product purification: The organopolysiloxane resin fraction of step S3 is cooled to room temperature, the organic phase is washed with water for 3 times, and the solvent is removed under negative pressure to obtain an organopolysiloxane resin A-3, the average unit formula of which is: (Me2ViSiO 0.5 ) 0.3 (PhSiO 1.5 ) 1.0

[0093] The preparation method of the organopolysiloxane B-3 comprises the following steps:

[0094] S11, hydrolysis condensation: 55.92 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 200 g of toluene, 54 g of water and 4.53 g of concentrated sulfuric acid were added to a reaction container, and 198.29 g of phenyltrimethoxysilane was added dropwise at room temperature to obtain a mixed solution, which was stirred under reflux for 2 h;

[0095] S12, deacidification: after the mixed solution in step S1 is cooled to room temperature, 100 g of toluene is added, and then water is added for washing to obtain an organopolysiloxane resin prepolymer;

[0096] S13, neutralization and fractionation: add 0.1 g potassium hydroxide and 1 g water to the organopolysiloxane resin prepolymer in step S2, perform fractionation at 130° C. for 2 h using a water separator, cool to room temperature after fractionation, add 0.12 g glacial acetic acid, stir for 1 h, and obtain an organopolysiloxane resin fraction;

[0097] S14, product purification: The organopolysiloxane resin fraction of step S3 is cooled to room temperature, the organic phase is washed with water for 3 times, and the solvent is removed under negative pressure to obtain an organopolysiloxane resin B-3, the average unit formula of which is: (Me2ViSiO 0.5 ) 0.6 (PhSiO 1.5 ) 1.0

[0098] The preparation method of the organopolysiloxane C-3 comprises the following steps:

[0099] S21, hydrolysis condensation: 488.72 g of diphenyldimethoxysilane, 1.497 g of trifluoromethanesulfonic acid and 60.05 g of glacial acetic acid were added to a reaction container, reacted at 50° C. for 0.5 h, the mixture was evaporated, 160.8 g of 1,1,3,3-tetramethyldisiloxane was added, 120.1 g of acetic acid was added dropwise at 50° C., after the addition of the acetic acid was completed, the reaction was continued for 0.5 h to obtain a first organopolysiloxane resin pre-product;

[0100] S22, esterification: adding 102.09 g of acetic anhydride dropwise to the first organopolysiloxane resin pre-product at 48-55° C. by water bath heating, and after the addition of the acetic anhydride is completed, continuing the reaction at 50° C. for 1 hour to obtain a second organopolysiloxane resin pre-product;

[0101] S23, product purification: The second organopolysiloxane resin pre-product of step S22 is cooled to room temperature, 500 g of toluene is added, the organic phase is washed with water for 3 times, and the solvent is removed under negative pressure to obtain an organopolysiloxane resin C-3, the average unit formula of which is: (HMe2SiO 0.5 )2(PhSiO)2

[0102] According to Table 1, the organopolysiloxane resin A-3, the organopolysiloxane resin B-3, the organopolysiloxane resin C-3, a hydrosilylation reaction catalyst, an inhibitor and a tackifier were mixed to obtain a curable organopolysiloxane composition.

[0103] Comparative Example 2

[0104] The organopolysiloxane resin A-1, organopolysiloxane resin B-1, organopolysiloxane resin C-1 and organopolysiloxane resin A-3, organopolysiloxane resin B-3, organopolysiloxane resin C-3 prepared in the above Example 1 and Comparative Example 1 are used as components of a curable organopolysiloxane composition for later use.

[0105] According to Table 1, the organopolysiloxane resin A-3, the organopolysiloxane resin B-1, the organopolysiloxane resin C-1, a hydrosilylation reaction catalyst, an inhibitor and a tackifier were mixed to obtain a curable organopolysiloxane composition.

[0106] Comparative Example 3

[0107] The organopolysiloxane resin A-1, organopolysiloxane resin B-1, organopolysiloxane resin C-1 and organopolysiloxane resin A-3, organopolysiloxane resin B-3, organopolysiloxane resin C-3 prepared in the above Example 1 and Comparative Example 1 are used as components of a curable organopolysiloxane composition for later use.

[0108] According to Table 1, the organopolysiloxane resin A-1, the organopolysiloxane resin B-3, the organopolysiloxane resin C-1, a hydrosilylation reaction catalyst, an inhibitor and a tackifier were mixed to obtain a curable organopolysiloxane composition.

[0109] Comparative Example 4

[0110] The organopolysiloxane resin A-1, organopolysiloxane resin B-1, organopolysiloxane resin C-1 and organopolysiloxane resin A-3, organopolysiloxane resin B-3, organopolysiloxane resin C-3 prepared in the above Example 1 and Comparative Example 1 are used as components of a curable organopolysiloxane composition for later use.

[0111] According to Table 1, the organopolysiloxane resin A-3, the organopolysiloxane resin B-3, the organopolysiloxane resin C-1, a hydrosilylation reaction catalyst, an inhibitor and a tackifier were mixed to obtain a curable organopolysiloxane composition.

[0112] Comparative Example 5

[0113] The organopolysiloxane resin A-1, organopolysiloxane resin B-1, organopolysiloxane resin C-1 and organopolysiloxane resin A-3, organopolysiloxane resin B-3, organopolysiloxane resin C-3 prepared in the above Example 1 and Comparative Example 1 are used as components of a curable organopolysiloxane composition for later use.

[0114] According to Table 1, the organopolysiloxane resin A-1, the organopolysiloxane resin B-1, the organopolysiloxane resin C-3, a hydrosilylation reaction catalyst, an inhibitor and a tackifier were mixed to obtain a curable organopolysiloxane composition.

[0115] Table 1 Components of the curable composition of Example 2 and Comparative Examples 2-5 (by mass)

[0116]

[0117] Note: The inhibitor content is expressed as platinum metal relative to the content of the organopolysiloxane composition (ppm, in mass units); "H / Vi" represents the ratio of the molar amount of silicon-bonded hydrogen atoms in the organopolysiloxane resin (C) to the molar amount of the total alkenyl groups in the organopolysiloxane resin (A) and the organopolysiloxane resin (B).

[0118] The curable compositions of Examples 1-2 and Comparative Examples 1-5 were used to prepare Figure 1 The optical semiconductor device shown is subjected to a performance test. The test conditions are as follows and the test data are shown in Table 2.

[0119] Anti-aging property: The curable composition was cured by heating at 150°C for 3 hours, and the cured optical semiconductor device was placed in an oven at 150°C for 24 hours, and the weight change of the cured product was recorded. Among them, the weight loss of ≤0.2% was indicated by "√", and the weight loss of >0.2% was indicated by "×".

[0120] Moisture resistance: The optical semiconductor device was aged in the above manner and placed at 85°C and 85% for 12 hours. The appearance of the optical semiconductor device was observed using an electron microscope. Water vapor permeability of ≤1% was indicated by "√", and water vapor permeability of >1% was indicated by "×".

[0121] Thermal shock resistance: The optical semiconductor device is aged in the above manner, and subjected to 100 thermal shocks at -40-125°C, each shock lasting 15 minutes, and the thermal conversion time is ≤5 minutes. After the test, the appearance of the optical semiconductor device is observed using an electron microscope. Among them, the peeling situation of ≤1% is indicated by "√", and the peeling situation of >1% is indicated by "×".

[0122] Table 2 Test data of Examples 1-2 and Comparative Examples 1-5

[0123]

[0124] As shown in Table 2, compared with Comparative Examples 1-5, the organopolysiloxane compositions of Examples 1-2 all have better anti-aging properties, moisture resistance, and resistance to cold and heat shock.

[0125] Specifically, by inlaying and combining the organopolysiloxane resin A-1 and the organopolysiloxane resin B-1 of different molecular weights to form a dense cross-linked network structure, Example 1 has better anti-aging performance than Comparative Examples 2-4.

[0126] By adding methylphenyl silicone oil with certain flexibility, Example 1 has better resistance to cold and heat shock than Comparative Example 5.

[0127] By inlaying and combining the organopolysiloxane resin A-1 and the organopolysiloxane resin B-1 with different molecular weights, and then adding methylphenyl silicone oil with a certain flexibility, Example 1 has better anti-aging performance and resistance to cold and heat shock than Comparative Example 1.

[0128] The above examples are only used to further illustrate the technical content of the present invention, so that readers can understand it more easily, but it does not mean that the implementation of the present invention is limited to this. Any technical extension or re-creation made according to the present invention is protected by the present invention. The protection scope of the present invention shall be subject to the claims.

Claims

1. A curable organopolysiloxane composition, characterized in that: Contains the following ingredients: The organopolysiloxane A is represented by the following average unit formula: (Me2ViSiO 0.5 ) a (PhSiO 1.5 ) b The organopolysiloxane A has at least two alkenyl groups in the molecule and has a very small amount of methoxy and hydroxyl groups; The organopolysiloxane B is represented by the following average unit formula: (Me2ViSiO 0.5 ) c (PhSiO 1.5 ) d The organopolysiloxane B has at least two alkenyl groups in the molecule and has a very small amount of methoxy and hydroxyl groups; The organopolysiloxane C is represented by the following average unit formula: (HMe2SiO 0.5 ) e (MePhSiO 1.0 ) f The organopolysiloxane C molecule has at least two silicon-bonded hydrogen atoms; Hydrosilylation reaction catalyst; Inhibitors; Tackifier.

2. The curable organopolysiloxane composition according to claim 1, characterized in that: The ratio of the molar amount of the silicon-bonded hydrogen atoms to the molar amount of the total alkenyl groups of the curable organopolysiloxane composition is (0.5-2):

1.

3. The curable organopolysiloxane composition according to claim 1, characterized in that: The values ​​of subscripts a and b in the average unit formula of the organopolysiloxane A are 0.01≤a<0.3, 0.3≤b<1, and a+b=1.

4. The curable organopolysiloxane composition according to claim 1, characterized in that: The values ​​of subscripts c and d in the average unit formula of the organopolysiloxane B are 0.3≤c<1, 0.3≤d<1, and c+d=1.

5. The curable organopolysiloxane composition according to claim 1, characterized in that: The values ​​of subscripts e and f in the average unit formula of the organopolysiloxane C are 0.01≤e≤5, 1≤f≤50.

6. The curable organopolysiloxane composition according to claim 1, characterized in that: The hydrosilylation catalyst is a Custer catalyst, and its platinum content is 1-1000ppm.

7. The curable organopolysiloxane composition according to claim 1, characterized in that: The inhibitor is an alkynol compound.

8. A method for preparing a curable organopolysiloxane composition as claimed in claims 1 to 7, characterized in that: The preparation method of the organopolysiloxane A and the organopolysiloxane B comprises the following steps: S11, hydrolysis condensation: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, toluene, water and concentrated sulfuric acid are added into a reaction container, and phenyltrimethoxysilane is added dropwise at low temperature to obtain a mixed solution, which is stirred; S12, deacidification: after the mixed solution in step S1 is cooled to room temperature, toluene is added, and then water is added for washing to obtain an organopolysiloxane resin prepolymer; S13, neutralization and fractionation: adding potassium hydroxide and water to the organopolysiloxane resin prepolymer in step S2, fractionating with a water separator, cooling to room temperature after fractionation, adding glacial acetic acid, stirring, and obtaining an organopolysiloxane resin fraction; S14, product purification: cooling the organopolysiloxane resin fraction in step S3 to room temperature, washing the organic phase with water for multiple times, and removing the solvent under negative pressure to obtain the organopolysiloxane resin.

9. The method for preparing the curable organopolysiloxane composition according to claim 8, characterized in that: The amount of water used in step S11 is 5-50 times the amount of water required for hydrolyzing the methoxy groups.

10. The method for preparing the curable organopolysiloxane composition according to claim 8, characterized in that: Also included is a method for preparing the organopolysiloxane C, comprising the following steps: S21, hydrolysis condensation: adding methylphenyldimethoxysilane, trifluoromethanesulfonic acid and glacial acetic acid into a reaction container, reacting at a certain temperature, evaporating the mixture, adding 1,1,3,3-tetramethyldisiloxane, and then adding acetic acid dropwise, and after the addition of acetic acid is completed, continuing the reaction to obtain a first organopolysiloxane resin pre-product; S22, esterification: adding acetic anhydride dropwise to the first organopolysiloxane resin pre-product by water bath heating, and continuing the reaction after the addition of the acetic anhydride is completed to obtain a second organopolysiloxane resin pre-product; S23, product purification: cool the second organopolysiloxane resin pre-product in step S22 to room temperature, add toluene, wash the organic phase with water for multiple times, remove the solvent under negative pressure, and obtain the organopolysiloxane resin.

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