Organic silicon tackifier as well as preparation method and application thereof

Abstract

The invention provides an organic silicon tackifier as well as a preparation method and application thereof. The preparation method comprises the following steps: (1) stirring and mixing phenyl siloxane and vinyl double-end socket, then dropwise adding a mixed solution of a strong acid catalyst and water, and carrying out reflux reaction to obtain a first mixture; (2) heating and evaporating the first mixture prepared in the step (1) to remove water and alcohol to obtain a second mixture; (3) mixing the second mixture prepared in the step (2) with an inactive solvent, a base catalyst and a methacryloyloxy siloxane compound, and adding water for reaction to obtain a third mixture; (4) heating and evaporating the third mixture prepared in the step (3) to remove water and alcohol, and carrying out reflux water separation reaction to obtain a fourth mixture; and (5) mixing the fourth mixture prepared in the step (4) with a neutralizer, washing with water, and filtering to obtain the organic silicon tackifier. By adding the organic silicon tackifier provided by the invention, the adhesive property of organic silica gel can be improved, and the light transmittance can be maintained.

Description

Technical Field

[0001] The invention belongs to the technical field of tackifiers, and specifically relates to an organosilicon tackifier and a preparation method and application thereof. Background Art

[0002] As a new generation of semiconductor solid-state light-emitting devices, light-emitting diodes (LEDs) are widely used in various lighting and display fields due to their advantages such as high luminous efficiency and long service life. As key supporting and protective materials, chip packaging materials directly affect the reliability, luminous performance and service life of LEDs. Among them, organic silicone is widely used as an encapsulation material for LEDs due to its good heat resistance, weather resistance, electrical insulation and other properties. However, the molecular polarity of organic silicone is relatively small, and it is highly saturated after curing, but its surface energy is relatively low, resulting in its weak adhesion to the substrate.

[0003] To solve this problem, conventional techniques usually add a tackifier to organic silicone to improve the bonding performance between the organic silicone and the substrate. However, existing tackifiers have some problems, such as poor tackifying effect and low refractive index, which can affect the transparency and curing effect of LED products.

[0004] CN116836392A discloses an organosilicon tackifier and a preparation method thereof, wherein the preparation method of the organosilicon tackifier comprises the following steps: step S1, mixing phenyltrimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, methylvinyldiethoxysilane and hexamethyldisiloxane to obtain a mixture, dripping potassium hydroxide aqueous solution into the mixture at an oil temperature of 40 to 45°C and a rotation speed of 200 to 250 r / min; Liquid, react for 1 hour after dripping, then continue to react for 2 hours under the condition of oil temperature of 60-65℃ and rotation speed of 200-250r / min to obtain a crude product; step S2, add water and n-heptane to the crude product obtained in step S1, stir for 28-32 minutes under the condition of rotation speed of 200-250r / min, let it stand, remove the water layer, wash with water until the pH value is 6-7, then remove the low boiling point solvent by reduced pressure distillation under 110℃ / -0.098MPa to obtain the organosilicon tackifier. The technical solution is simple in process, but the prepared organosilicon tackifier has a low refractive index of only 1.47-1.48, and the bonding strength is not high.

[0005] CN111072712A discloses an organosilicon tackifier and a preparation method thereof and a highly transparent self-adhesive addition-type organosilicon rubber composition. The organosilicon tackifier has a structure of formula I:

[0006]

[0007] In Formula I, R1, R2 and R3 are independently selected from Formula 101, Formula 102 or Formula 103:

[0008]

[0009] The silicone rubber composition prepared from the silicone tackifier provided by the technical solution and vinyl polysiloxane, hydrogen-containing crosslinking agent, platinum catalyst and inhibitor can be quickly cured under ultraviolet radiation and has high adhesion to electronic component housings and circuit boards, but the light transmittance is still low and needs to be further improved.

[0010] Therefore, it is necessary to develop a silicone tackifier to improve the bonding performance of silicone and maintain a high light transmittance. Summary of the invention

[0011] In view of the shortcomings of the prior art, the present invention aims to provide an organosilicon tackifier and a preparation method and application thereof. Adding the organosilicon tackifier can improve the adhesion performance and high temperature aging resistance of the organosilicon and maintain a high light transmittance.

[0012] To achieve this object, the present invention adopts the following technical solutions:

[0013] In a first aspect, the present invention provides a method for preparing a silicone tackifier, the preparation method comprising the following steps:

[0014] (1) stirring and mixing phenylsiloxane and vinyl double-capped silicone rubber, then dropping a mixed solution of a strong acid catalyst and water, and performing a reflux reaction to obtain a first mixture;

[0015] (2) heating the first mixture obtained in step (1) to evaporate and remove water and alcohol to obtain a second mixture;

[0016] (3) mixing the second mixture obtained in step (2) with an inactive solvent, a base catalyst and a methacryloxysiloxane compound, and adding water to react to obtain a third mixture;

[0017] (4) heating the third mixture obtained in step (3) to evaporate water and alcohol, and refluxing to separate water to obtain a fourth mixture;

[0018] (5) Mixing the fourth mixture obtained in step (4) with a neutralizer to obtain the organosilicon tackifier.

[0019] In the present invention, phenylsiloxane is sequentially reacted with a vinyl double-capped siloxane compound and a methacryloxysiloxane compound through a sequential polymerization method, and vinyl and methacryloxy groups are sequentially introduced into the polymer main chain; in step (1), a method of co-feeding a strong acid catalyst and water is used to dropwisely add the catalyst, so that the hydrolysis activity and the temperature rise of the reaction system are controllable, and the accuracy of catalyst metering and the process safety are improved; in step (2), the remaining water and the generated by-product alcohol in the reaction of step (1) are evaporated and removed, so that the residual water and alcohol are prevented from interfering with the reaction of the methacryloxysiloxane compound into the polymer chain segment, and the generation of by-products is reduced, so that the organic silica gel added with the organic silicone tackifier has the advantages of good anti-cracking performance, high bonding strength and the like, and can be applied to the field of LED chip solid crystal and packaging.

[0020] It should be noted that the dripping method of the mixed solution of the strong acid catalyst and water is not particularly limited in the present invention, and those skilled in the art can adjust it according to the actual situation. For example, uniform dripping, non-uniform dripping and staged uniform dripping, etc., the staged uniform dripping can be to drip 1 / 2 of the mixed solution of the strong acid catalyst and water at a uniform speed of 1 drop / s, and the remaining mixed solution of the strong acid catalyst and water is accelerated to drip at 2 to 3 drops / s.

[0021] Preferably, the stirring and mixing in step (1) is carried out at a temperature of 25 to 80°C (e.g., 30°C, 40°C, 50°C, 60°C or 70°C, etc.), and the time is 0.1 to 1.0 h (e.g., 0.2 h, 0.3 h, 0.4 h, 0.5 h, 0.6 h, 0.7 h, 0.8 h or 0.9 h, etc.).

[0022] Preferably, the dripping in step (1) is uniform dripping, and the frequency of dripping is 0.5 to 3 drops / s, such as 1 drop / s, 1.5 drops / s, 2 drops / s or 2.5 drops / s.

[0023] Preferably, the temperature of the reflux reaction in step (1) is 40-75°C (e.g., 45°C, 50°C, 55°C, 60°C, 65°C or 70°C, etc.), and the time is 2-6h (e.g., 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 5.5h, etc.).

[0024] Preferably, the temperature of the heating evaporation in steps (2) and (4) is independently 85-102°C (for example, 87°C, 89°C, 91°C, 93°C, 95°C, 97°C, 99°C or 101°C, etc.), and the time of the heating evaporation is independently 1-4h (for example, 1.5h, 2h, 2.5h, 3h or 3.5h, etc.).

[0025] Preferably, the water is added in step (3) by uniformly dropping water, and the frequency of dropping water is 0.5 to 3 drops / s, such as 1 drop / s, 1.5 drops / s, 2 drops / s or 2.5 drops / s.

[0026] Preferably, the temperature of the reflux water separation reaction in step (4) is 110-125°C (for example, 112°C, 114°C, 116°C, 118°C, 120°C, 122°C or 124°C, etc.), and the time is 2-8h (for example, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h or 7.5h, etc.).

[0027] Preferably, step (5) further comprises the steps of washing with water until neutrality and filtering after mixing.

[0028] Preferably, the phenylsiloxane includes any one of phenyltrimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, methylphenyldiethoxysilane, dimethylphenylmethoxysilane or dimethylphenylethoxysilane, or a combination of at least two thereof, preferably phenyltrimethoxysilane and / or diphenyldimethoxysilane.

[0029] Preferably, the strong acid catalyst comprises any one of hydrochloric acid, sulfuric acid, acetic acid or trifluoromethanesulfonic acid, or a combination of at least two thereof.

[0030] Preferably, the inactive solvent includes any one of toluene, xylene or acetone, or a combination of at least two of them.

[0031] Preferably, the base catalyst includes any one of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide pentahydrate or lithium hydroxide, or a combination of at least two thereof.

[0032] Preferably, the methacryloxysiloxane compound includes 3-(methacryloxy)propyltrimethoxysilane (KH570) and / or 3-acryloxypropylmethyldimethoxysilane.

[0033] Preferably, the neutralizing agent includes any one of ammonium bicarbonate, ammonium carbonate, sodium bicarbonate or acetic acid, or a combination of at least two thereof.

[0034] Preferably, in step (1), the mass ratio of phenylsiloxane to vinyl double head is (40-65):10, for example, 43:10, 46:10, 49:10, 52:10, 55:10, 58:10, 61:10 or 64:10, etc.

[0035] Preferably, in step (1), the mass ratio of the vinyl double end cap to the strong acid catalyst is 10:(0.01-0.07), for example, 10:0.02, 10:0.03, 10:0.04, 10:0.05 or 10:0.06.

[0036] Preferably, in step (1), the mass ratio of the vinyl double head to water is 10:(10-20), for example, 10:11, 10:12, 10:13, 10:14, 10:15, 10:16, 10:17, 10:18 or 10:19, etc.

[0037] Preferably, the mass ratio of the vinyl double head in step (1) to the inactive solvent in step (3) is 10:(20-80), for example, 10:25, 10:30, 10:35, 10:40, 10:45, 10:50, 10:55, 10:60, 10:65, 10:70 or 10:75, etc.

[0038] Preferably, the mass ratio of the vinyl double head in step (1) to the alkaline catalyst in step (3) is 10:(0.05-0.1), for example, 10:0.0055, 10:0.006, 10:0.0065, 10:0.007, 10:0.0075, 10:0.008, 10:0.0085, 10:0.009 or 10:0.0095, etc.

[0039] Preferably, the mass ratio of the vinyl double head in step (1) to the methacryloxysiloxane compound in step (3) is 10:(15-40), for example, 10:18, 10:21, 10:24, 10:27, 10:30, 10:33, 10:36 or 10:39, etc.

[0040] Preferably, the mass ratio of the vinyl double head in step (1) to the water in step (3) is 10:(10-20), for example, 10:11, 10:12, 10:13, 10:14, 10:15, 10:16, 10:17, 10:18 or 10:19, etc.

[0041] Preferably, the mass ratio of the vinyl double head in step (1) to the neutralizer in step (5) is 10:(0.05-0.1), for example, 10:0.055, 10:0.06, 10:0.065, 10:0.07, 10:0.075, 10:0.08, 10:0.085, 10:0.09 or 10:0.095, etc.

[0042] In a second aspect, the present invention provides an organosilicon tackifier, which is prepared by the preparation method described in the first aspect. Preferably, the organosilicon tackifier has a general formula as shown in Formula I: M 1 a M 2 b M 3 c .

[0043] Among them, M 1 ViMe2SiO 1 / 2 , Vi is vinyl, and Me is methyl.

[0044] M 2 For R 1 SiO 3 / 2 and / or R 2 MeSiO 2 / 2 , R 1 is 3-(methacryloyloxy)propyl, R 2 is 3-acryloxypropyl, and Me is methyl.

[0045] M 3 For R 3 SiO 3 / 2 , R 3 2SiO 2 / 2 , R 3 MeSiO 2 / 2 or R 3 Me2SiO 1 / 1 Any one or a combination of at least two of 3 is phenyl, and Me is methyl.

[0046] a+b+c=100, 5≤a≤25 (for example, 7, 9, 11, 13, 15, 17, 19, 21 or 23, etc.), 15≤b≤35 (for example, 17, 19, 21, 23, 25, 27, 29, 31 or 33, etc.), 40≤c≤65 (for example, 43, 46, 49, 52, 55, 58, 61 or 64, etc.).

[0047] In a third aspect, the present invention provides an organic silica gel, wherein the organic silica gel includes the organic silica gel viscosity enhancer as described in the second aspect.

[0048] Preferably, the organic silica gel comprises the following components: phenyl vinyl silicone resin, phenyl hydrogen silicone oil, phenyl vinyl silicone oil, the organic silicone adhesion promoter and inhibitor as claimed in claim 8.

[0049] In the present invention, a methacryloxysiloxane compound with a specific structure is used to carry out a hydrolysis condensation reaction to prepare an organic silicone tackifier, and the organic silicone tackifier has good compatibility with phenyl vinyl silicone resin, thereby greatly improving the bonding performance of organic silicone.

[0050] Preferably, the organic silica gel comprises the following components in parts by weight: 60-70 parts (e.g., 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts or 69 parts, etc.) of phenyl vinyl silicone resin, 15-25 parts (e.g., 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts or 24 parts, etc.) of phenyl hydrogen silicone oil, 10-20 parts (e.g., 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts or 19 parts, etc.) of phenyl vinyl silicone oil. ), 1 to 2 parts (e.g. 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8 or 1.9 parts, etc.) of the organosilicon adhesion promoter as described in the second aspect, 0.1 to 1 part (e.g. 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9 parts, etc.) of the inhibitor, and 0.1 to 0.5 part (e.g. 0.15, 0.2, 0.25, 0.3, 0.35, 0.4 or 0.45 parts, etc.) of the Pt catalyst diluent.

[0051] Preferably, the mass percentage of the Pt catalyst in the Pt catalyst dilution solution is 0.04% to 0.1%, for example, 0.05%, 0.06%, 0.07%, 0.08% or 0.09%.

[0052] Compared with the prior art, the present invention has the following beneficial effects:

[0053] In the present invention, phenyl siloxane is sequentially reacted with vinyl double caps and methacryloxysiloxane compounds by a sequential polymerization method, and vinyl and methacryloxy groups are sequentially introduced into the polymer main chain; and the remaining water and the byproduct alcohol produced by the reaction of step (1) are evaporated and removed by step (2), so as to avoid the residual water and alcohol interfering with the reaction of the methacryloxysiloxane compound into the polymer segment, reduce the generation of byproducts, and make the organic silica gel added with the organic silica gel tackifier have the advantages of good crack resistance and high bonding strength, so that it can be applied to the field of LED chip solid crystal and packaging. The chip thrust of the organic silica gel at 25°C is ≥3.3kgf, the chip thrust at 260°C is ≥0.3kgf, the light transmittance of the organic silica gel after curing with a thickness of 2mm is ≥99.1%, and it does not crack after high temperature aging. DETAILED DESCRIPTION

[0054] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0055] The sources of some raw materials in the following examples and comparative examples are as follows.

[0056] Phenyltrimethoxysilane, brand name SICO-P13, manufacturer is Shandong SICO New Materials Co., Ltd.;

[0057] Diphenyldimethoxysilane, brand name SICO-P212, manufacturer is Shandong SICO New Materials Co., Ltd.

[0058] Vinyl double head, the manufacturer is Xinyaqiang Silicon Chemical Co., Ltd.;

[0059] Strong acid catalyst: trifluoromethanesulfonic acid, manufactured by Hangzhou Bangyi Chemical Co., Ltd.

[0060] Water: deionized water, the manufacturer is Hangzhou Bangyi Chemical Co., Ltd.;

[0061] 3-(Methacryloyloxy)propyltrimethoxysilane, CAS: 2530-85-0, manufactured by Shanghai MacLean;

[0062] Epoxy siloxane compound: KH560, manufactured by Shanghai MacLean;

[0063] Alkaline catalyst: potassium hydroxide, manufactured by Sinopharm Group;

[0064] Neutralizing agent: acetic acid, manufactured by Sinopharm Group;

[0065] Inactive solvent: toluene, manufactured by Hangzhou Bangyi Chemical Co., Ltd.

[0066] Phenyl hydrogenated silicone oil 1, brand name IOTA232, manufacturer Anhui Aiyota Silicone Oil;

[0067] Phenyl hydrogenated silicone oil 2, brand name IOTA235, manufacturer Anhui IOTA Silicone Oil;

[0068] Phenyl vinyl silicone oil, brand name IOTA252-5000Vi, manufacturer Anhui Aiyota Silicone Oil;

[0069] Inhibitor: 1-ethynyl-1-cyclohexanol, manufactured by Changzhou Xudong Chemical;

[0070] Phenyl vinyl silicone resin is prepared by the following method:

[0071] (1) 186.04 g of phenyltrimethoxysilane (SICO-P13), 22.1 g of diphenyldimethoxysilane (SICO-P212) and 28.15 g of vinyl double-end capped reactor were added, heated and stirred at 50° C. for 0.15 h to obtain a reaction substrate;

[0072] (2) adding an aqueous solution prepared from 0.4 g of a strong acid catalyst (trifluoromethanesulfonic acid) and 66.3 g of deionized water to the reaction substrate obtained in step (1) at a uniform rate of 2 drops / s, and after all the addition is completed, reflux at 78° C. for 3.5 h to obtain a crude hydrolysis product of phenyl vinyl silicone resin; heating to 92° C., evaporating for 2.5 h, removing water and alcohol fractions, and obtaining a phenyl vinyl silicone resin precursor;

[0073] (3) The phenyl vinyl silicone resin precursor obtained in step (2) is cooled to room temperature, 230 g of toluene and 1.5 g of an alkali catalyst (potassium hydroxide) are added, and the mixture is refluxed at 121° C. for 8 h to obtain a phenyl vinyl silicone resin solution. The phenyl vinyl silicone resin solution is neutralized with a neutralizing agent (sodium bicarbonate), washed with water several times until neutral, filtered and desolventized, and the phenyl vinyl silicone resin is obtained.

[0074] The Pt catalyst dilution was prepared by the following method:

[0075] A 20% concentration of Heraeus Karstedt Pt catalyst and phenyl vinyl silicone oil (IOTA 252-5000Vi) were mixed to prepare a Pt catalyst dilution solution, wherein the mass percentage concentration of the Karstedt Pt catalyst in the Pt catalyst dilution solution was 0.05%.

[0076] Example 1

[0077] This embodiment provides an organic silicon tackifier and a preparation method thereof and organic silicon gel. The organic silicon tackifier is prepared by the following method:

[0078] (1) 132.3 g (0.667 mol) of phenyltrimethoxysilane and 31.7 g (0.170 mol) of vinyl double-end capped reactor were added to a stirred reactor, stirred at room temperature (25° C.) for 0.5 h, and then an aqueous solution prepared by adding 0.1 g (0.0007 mol) of trifluoromethanesulfonic acid and 35.1 g (1.950 mol) of deionized water was added dropwise at a uniform rate of 1 drop / s. After all the additions were completed, the mixture was refluxed at 65° C. for 3 h to obtain a first mixture;

[0079] (2) heating the first mixture obtained in step (1) to 90° C. and evaporating for 2.5 hours to remove water and alcohol to obtain a second mixture;

[0080] (3) The second mixture obtained in step (2) was cooled to room temperature (25° C.), and then mixed with 92 g (0.998 mol) of toluene, 0.2 g (0.004 mol) of potassium hydroxide and 78 g (0.314 mol) of 3-(methacryloyloxy)propyltrimethoxysilane, and 32.3 g (1.79 mol) of deionized water was slowly added dropwise at a frequency of 1 drop / s to obtain a third mixture;

[0081] (4) evaporating the third mixture obtained in step (3) at 90° C. for 2 h to remove water and alcohol, and refluxing and separating water at 115° C. for 4 h to obtain a fourth mixture;

[0082] (5) The fourth mixture obtained in step (4) is mixed with 0.2 g (0.003 mol) of acetic acid, washed with water for multiple times until neutral, and filtered to obtain the organosilicon tackifier.

[0083] The structural formula of the organosilicon tackifier is as follows:

[0084] (ViMe2SiO 1 / 2 ) 15 (R 1 SiO 3 / 2 ) 27 (R 3 SiO 3 / 2 ) 58

[0085] Among them, R 1 is 3-(methacryloyloxy)propyl, R 3 It is phenyl.

[0086] The organic silica gel is prepared by the following method:

[0087] 63 parts by weight of phenyl vinyl silicone resin, 17.9 parts by weight of phenyl hydrogen silicone oil 1, 2 parts by weight of phenyl hydrogen silicone oil 2, 15.2 parts by weight of phenyl vinyl silicone oil, 1 part by weight of the above-mentioned silicone thickener and 0.4 part by weight of inhibitor were added into a planetary mixer, stirred at 1500 r / min for 5 minutes, scraped the sides halfway, cooled to 25°C, added with 0.5 parts by weight of Pt catalyst diluent, stirred at 800 r / min for 3 minutes, and vacuum degassed to obtain the silicone gel.

[0088] Example 2

[0089] This embodiment provides an organic silicon tackifier and a preparation method thereof and organic silicon gel. The organic silicon tackifier is prepared by the following method:

[0090] (1) 130.6 g (0.659 mol) of phenyltrimethoxysilane and 21.1 g (0.113 mol) of vinyl double-end capped reactor were added to a stirred reactor, stirred at 40° C. for 0.5 h, and then an aqueous solution prepared by adding 0.13 g (0.0009) of trifluoromethanesulfonic acid and 36.2 g (2.011 mol) of deionized water was added dropwise at a uniform rate of 2 drops / s. After all the additions were completed, the mixture was refluxed at 50° C. for 4 h to obtain a first mixture;

[0091] (2) heating the first mixture obtained in step (1) to 85° C. and evaporating for 3 h to remove water and alcohol to obtain a second mixture;

[0092] (3) The second mixture obtained in step (2) was cooled to room temperature (25° C.), then mixed with 84 g (0.912 mol) of toluene, 0.15 g (0.003 mol) of potassium hydroxide and 79 g (0.318 mol) of 3-(methacryloyloxy)propyltrimethoxysilane, and 33.23 g (1.85 mol) of deionized water was slowly added dropwise at a frequency of 2 drops / s to obtain a third mixture;

[0093] (4) evaporating the third mixture obtained in step (3) at 88° C. for 2.8 h to remove water and alcohol, and refluxing at 114° C. for 6 h to obtain a fourth mixture;

[0094] (5) The fourth mixture obtained in step (4) is mixed with 0.2 g (0.003 mol) of acetic acid, washed with water for multiple times until neutral, and filtered to obtain the organosilicon tackifier.

[0095] The structural formula of the organosilicon tackifier is as follows:

[0096] (ViMe2SiO 1 / 2 ) 10 (R 1 SiO 3 / 2 ) 29 (R 3 SiO 3 / 2 ) 61

[0097] Among them, R 1 is 3-(methacryloyloxy)propyl, R 3 It is phenyl.

[0098] The organic silica gel is prepared by the following method:

[0099] 63 parts by weight of phenyl vinyl silicone resin, 17.9 parts by weight of phenyl hydrogen silicone oil 1, 2 parts by weight of phenyl hydrogen silicone oil 2, 15.2 parts by weight of phenyl vinyl silicone oil, 1 part by weight of the above-mentioned silicone thickener and 0.4 part by weight of inhibitor were added into a planetary mixer, stirred at 1500 r / min for 5 minutes, scraped the sides halfway, cooled to 25°C, added with 0.5 parts by weight of Pt catalyst diluent, stirred at 800 r / min for 3 minutes, and vacuum degassed to obtain the silicone gel.

[0100] Example 3

[0101] This embodiment provides an organic silicon tackifier, a preparation method thereof, and organic silicon gel, which differs from Embodiment 1 only in that phenyltrimethoxysilane is replaced with the same molar amount of diphenyldimethoxysilane, 163.0 g (0.667 mol).

[0102] The structural formula of the organosilicon tackifier is as follows:

[0103] (ViMe2SiO 1 / 2 ) 15 (R 1 SiO 3 / 2 ) 27 (R 3 2SiO 2 / 2 ) 58

[0104] Among them, R 1 is 3-(methacryloyloxy)propyl, R 3 It is phenyl.

[0105] Other conditions are the same as in Example 1.

[0106] Example 4

[0107] This embodiment provides an organic silicone tackifier, a preparation method thereof, and an organic silicone gel, which differs from Embodiment 1 only in that 3-(methacryloyloxy)propyltrimethoxysilane is replaced with the same molar amount of 3-acryloxypropylmethyldimethoxysilane, 68.6 g (0.314 mol).

[0108] The structural formula of the organosilicon tackifier is as follows:

[0109] (ViMe2SiO 1 / 2 ) 15 (R 2 MeSiO 2 / 2 ) 27 (R 3 MeSiO) 58

[0110] Among them, R 1 is 3-(methacryloyloxy)propyl, R 3 It is phenyl.

[0111] Other conditions are the same as in Example 1.

[0112] Example 5

[0113] This embodiment provides an organic silicone tackifier, a preparation method thereof, and an organic silicone gel, which differs from Embodiment 1 only in that the mass of 3-(methacryloyloxy)propyltrimethoxysilane in step (3) is adjusted to 99.34 g (0.4 mol).

[0114] The structural formula of the organosilicon tackifier is as follows:

[0115] (ViMe2SiO 1 / 2 ) 14 (R 1 SiO3 / 2 ) 32 (R 3 SiO 3 / 2 ) 54

[0116] Among them, R 1 is 3-(methacryloyloxy)propyl, R 3 It is phenyl.

[0117] Other conditions are the same as in Example 1.

[0118] Example 6

[0119] This embodiment provides an organic silicone tackifier, a preparation method thereof, and an organic silicone gel, which differs from Embodiment 1 only in that the mass of 3-(methacryloyloxy)propyltrimethoxysilane in step (3) is adjusted to 49.67 g (0.2 mol).

[0120] The structural formula of the organosilicon tackifier is as follows:

[0121] (ViMe2SiO 1 / 2 ) 16 (R 1 SiO 3 / 2 ) 19 (R 3 SiO 3 / 2 ) 64

[0122] Among them, R 1 is 3-(methacryloyloxy)propyl, R 3 It is phenyl.

[0123] Other conditions are the same as in Example 1.

[0124] Example 7

[0125] This embodiment provides an organic silicon tackifier and a preparation method thereof and organic silicon gel, which differs from Embodiment 1 only in that the organic silicon gel is prepared by the following method:

[0126] 65 parts by weight of phenyl vinyl silicone resin, 20 parts by weight of phenyl hydrogenated silicone oil 1, 1 part by weight of phenyl hydrogenated silicone oil 2, 10 parts by weight of phenyl vinyl silicone oil, 1.5 parts by weight of the above-mentioned organosilicon thickener and 0.2 parts by weight of inhibitor were mixed and added into a planetary mixer, stirred at 1500 r / min for 5 minutes, scraped the sides halfway, cooled to 25°C, added with 0.3 parts by weight of Pt catalyst diluent, stirred at 800 r / min for 3 minutes, and vacuum degassed to obtain the organosilicon gel.

[0127] Other conditions are the same as in Example 1.

[0128] Example 8

[0129] This embodiment provides an organic silicon tackifier and a preparation method thereof and organic silicon gel, which differs from Embodiment 1 only in that the organic silicon gel is prepared by the following method:

[0130] 68 parts by weight of phenyl vinyl silicone resin, 14 parts by weight of phenyl hydrogenated silicone oil 1, 3.4 parts by weight of phenyl hydrogenated silicone oil 2, 14.5 parts by weight of phenyl vinyl silicone oil, 2 parts by weight of the above-mentioned organosilicon thickener and 0.2 parts by weight of inhibitor were mixed and added into a planetary mixer, stirred at 1500 r / min for 5 minutes, scraped the sides halfway, cooled to 25°C, added with 0.3 parts by weight of Pt catalyst diluent, stirred at 800 r / min for 3 minutes, and vacuum degassed to obtain the organosilicon gel.

[0131] Other conditions are the same as in Example 1.

[0132] Comparative Example 1

[0133] This comparative example provides an organic silicone tackifier, a preparation method thereof, and an organic silicone gel, which differs from Example 1 only in that step (2) is not included, the second mixture in step (3) is replaced by the first mixture obtained in step (1), and other conditions are the same as those in Example 1.

[0134] Comparative Example 2

[0135] The present comparative example provides an organic silicone tackifier, a preparation method thereof and an organic silicone gel, which differs from Example 1 only in that step (1) is adjusted as follows: 132.3 g (0.667 mol) of phenyltrimethoxysilane, 31.7 g (0.170 mol) of vinyl double cap and 0.1 g (0.0007 mol) of trifluoromethanesulfonic acid are added into a stirred reactor, stirred at room temperature (25°C) for 0.5 h, and then 35.1 g (1.950 mol) of deionized water is added dropwise at a uniform rate of 1 drop / s. After all the addition is completed, the mixture is refluxed at 65°C for 3 h to obtain a first mixture.

[0136] Other conditions are the same as in Example 1.

[0137] Comparative Example 3

[0138] This comparative example provides an organic silicone tackifier, a preparation method thereof, and an organic silicone gel. The difference between the organic silicone tackifier and the comparative example 1 is that step (2) is adjusted to: washing the first mixture obtained in step (1) with water to remove trifluoromethanesulfonic acid and alcohol to obtain a second mixture. The other conditions are the same as those in Example 1.

[0139] Comparative Example 4

[0140] This comparative example provides an organic silicone tackifier, a preparation method thereof, and an organic silicone gel, which differs from Example 1 only in that 3-(methacryloyloxy)propyltrimethoxysilane in step (3) is replaced with an epoxysiloxane compound (KH560) of the same molar amount, and other conditions are the same as those in Example 1.

[0141] Comparative Example 5

[0142] This comparative example provides an organosilicon tackifier, a preparation method thereof, and an organic silica gel. The difference between this comparative example and Example 1 is that the organosilicon tackifier in the organic silica gel is replaced with KH560 of the same mass, and other conditions are the same as those in Example 1.

[0143] Comparative Example 6

[0144] This comparative example provides an organosilicon tackifier, a preparation method thereof, and an organosilicon gel, which differs from Example 1 only in that the organosilicon tackifier in the organosilicon gel is replaced with 3-(methacryloyloxy)propyltrimethoxysilane of the same mass, and other conditions are the same as those in Example 1.

[0145] Comparative Example 7

[0146] This comparative example provides an organosilicon tackifier, a preparation method thereof, and an organic silica gel. The difference between this comparative example and Example 1 is that the organosilicon tackifier is not added to the organic silica gel, and other conditions are the same as those in Example 1.

[0147] The organic silica gel provided in the above examples and comparative examples was tested as follows.

[0148] Chip thrust: Tested in accordance with "HG / T 5912-2021 Conductive Adhesives", the silicon wafer size is 2mm×2mm; the substrate is a silver-plated copper sheet, and the curing condition is to cure in a 160℃ blast oven for 1.0h; the test equipment is a DAGE-4000P multi-function push-pull test machine, manufactured by Nordson DAGE Precision Engineering, USA, and the shear strength is the chip thrust size (in kgf); 10 samples of each organic silicone are tested and the average value is taken. When measuring the 260℃ high-temperature chip thrust, set the temperature on the temperature-controlled heating table, and stabilize for 5 minutes after reaching the target temperature before starting to measure the chip thrust.

[0149] Light transmittance: The organic silica gel was cured to form a 2 mm thick specimen in a 160°C forced air oven for 1.0 h. The light transmittance of the cured organic silica gel at a wavelength of 450 nm was tested using a UV-2601 ultraviolet-visible spectrophotometer produced by Beijing Beifen Rayleigh Analytical Instrument Co., Ltd.

[0150] High temperature aging test: The organic silicone was cured into 2 mm thick strips in a 160°C forced air oven for 1 h. The cured organic silicone was placed in a 200°C oven and baked to see if it cracked after 1000 h.

[0151] The test results are shown in Table 1 below.

[0152] Table 1

[0153]

[0154]

[0155] From the content of Table 1, it can be seen that the organic silica gel provided in Examples 1-8 has a chip thrust of ≥3.3 kgf at 25°C, a chip thrust of ≥0.3 kgf at 260°C, a light transmittance of ≥99.1%, and no cracking after high-temperature aging.

[0156] Compared with Example 1, if step (2) is not included (Comparative Example 1), the chip thrust and transmittance of the prepared silicone rubber are both reduced. The reason is that water and alcohol are not evaporated, and the residual water and alcohol in the sequential polymerization process will interfere with the reaction of the methacryloyloxysiloxane compound into the polymer chain segment, making the silicone rubber's bonding performance and transmittance both lower.

[0157] Compared with Example 1, if the strong acid catalyst is directly added at one time (Comparative Example 2), the chip thrust and transmittance of the prepared organic silica gel are reduced. The reason is that the stoichiometric accuracy and process safety of the strong acid catalyst in the preparation method provided in Comparative Example 2 are poor, the concentration of the strong acid catalyst is high at the initial stage of the reaction, and more oligomers are generated by the reaction, which affects the chip thrust and transmittance of the organic silica gel finally prepared.

[0158] Compared with Example 1, if trifluoromethanesulfonic acid and alcohol are removed by water washing (Comparative Example 3), the small amount of water dissolved after water washing also affects the reaction of the methacryloyloxysiloxane compound, and the organic silicone adhesive performance and light transmittance are lower than those of Example 1. Similarly, since Example 1 removes alcohol and most of the water, the organic silicone adhesive performance and light transmittance are better than those of Comparative Example 3.

[0159] Compared with Example 1, if 3-(methacryloyloxy)propyltrimethoxysilane is replaced with the same molar amount of epoxysiloxane compound (Comparative Example 4), the chip thrust and transmittance of the prepared silicone rubber are reduced. The reason is that compared with the epoxy group, the methacryloxy group has better bonding strength with the bonding substrate and better compatibility with the silicone material.

[0160] Compared with Example 1, if the organosilicon tackifier in the organic silica gel is replaced with the same mass of KH560 (Comparative Example 5) or the organosilicon tackifier in the organic silica gel is replaced with the same mass of 3-(methacryloyloxy)propyltrimethoxysilane (Comparative Example 6), the organic silica gel bonding performance and light transmittance are greatly reduced, and high temperature aging cracks. If the organosilicon tackifier is not added to the organic silica gel (Comparative Example 7), the organic silica gel bonding performance is greatly reduced, and high temperature aging cracks. It can be seen that adding the organic silica gel tackifier of the present invention can improve the bonding performance and high temperature aging resistance of the organic silica gel, and can maintain a high light transmittance.

[0161] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate a kind of organosilicon tackifier and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing an organosilicon tackifier, characterized in that: The preparation method comprises the following steps: (1) stirring and mixing phenylsiloxane and vinyl double-capped silicone rubber, then dropping a mixed solution of a strong acid catalyst and water, and performing a reflux reaction to obtain a first mixture; (2) heating the first mixture obtained in step (1) to evaporate and remove water and alcohol to obtain a second mixture; (3) mixing the second mixture obtained in step (2) with an inactive solvent, a base catalyst and a methacryloxysiloxane compound, and adding water to react to obtain a third mixture; (4) heating the third mixture obtained in step (3) to evaporate water and alcohol, and refluxing to separate water to obtain a fourth mixture; (5) Mixing the fourth mixture obtained in step (4) with a neutralizer to obtain the organosilicon tackifier.

2. The preparation method according to claim 1, characterized in that: The stirring and mixing in step (1) is performed at a temperature of 25 to 80° C. for a time of 0.1 to 1.0 h; Preferably, the dripping in step (1) is performed at a uniform speed, and the frequency of dripping is 0.5 to 3 drops / s; Preferably, the temperature of the reflux reaction in step (1) is 40 to 75° C. and the time is 2 to 6 hours; Preferably, the heating evaporation temperatures in steps (2) and (4) are independently 85 to 102° C., and the heating evaporation times are independently 1 to 4 hours. Preferably, the water is added in step (3) by dripping water at a uniform speed, and the frequency of dripping is 0.5 to 3 drops / s; Preferably, the temperature of the reflux water separation reaction in step (4) is 110-125° C. and the time is 2-8 h; Preferably, step (5) further comprises the steps of washing with water until neutrality and filtering after mixing.

3. The preparation method according to claim 1 or 2, characterized in that: The phenylsiloxane includes any one of phenyltrimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, methylphenyldiethoxysilane, dimethylphenylmethoxysilane or dimethylphenylethoxysilane, or a combination of at least two thereof; Preferably, the strong acid catalyst comprises any one or a combination of at least two of hydrochloric acid, sulfuric acid, acetic acid or trifluoromethanesulfonic acid; Preferably, the inactive solvent comprises any one of toluene, xylene or acetone or a combination of at least two thereof; Preferably, the base catalyst includes any one of potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide pentahydrate or lithium hydroxide, or a combination of at least two thereof.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The methacryloxysiloxane compound includes 3-(methacryloxy)propyltrimethoxysilane and / or 3-acryloxypropylmethyldimethoxysilane; Preferably, the neutralizing agent includes any one of ammonium bicarbonate, ammonium carbonate, sodium bicarbonate or acetic acid, or a combination of at least two thereof.

5. The preparation method according to any one of claims 1 to 4, characterized in that: In the step (1), the mass ratio of phenylsiloxane to vinyl double end cap is (40-65):10; Preferably, in step (1), the mass ratio of the vinyl double end cap to the strong acid catalyst is 10:(0.01-0.07); Preferably, in step (1), the mass ratio of the vinyl double end cap to water is 10:(10-20); Preferably, the mass ratio of the vinyl double end cap in step (1) to the inactive solvent in step (3) is 10:(20-80); Preferably, the mass ratio of the vinyl double head in step (1) to the alkaline catalyst in step (3) is 10:(0.05-0.1).

6. The preparation method according to any one of claims 1 to 5, characterized in that: The mass ratio of the vinyl double head in step (1) to the methacryloxysiloxane compound in step (3) is 10:(15-40); Preferably, the mass ratio of the vinyl double head in step (1) to the water in step (3) is 10:(10-20).

7. The preparation method according to any one of claims 1 to 6, characterized in that: The mass ratio of the vinyl double head in step (1) to the neutralizing agent in step (5) is 10:(0.05-0.1).

8. An organosilicon tackifier, characterized in that: The organosilicon tackifier is prepared by the preparation method according to any one of claims 1 to 7.

9. The organosilicon tackifier according to claim 8, characterized in that: The organosilicon tackifier has the general formula as shown in Formula I: M 1 a M 2 b M 3 c ; Among them, M 1 ViMe2SiO 1 / 2 , Vi is vinyl, Me is methyl; M 2 For R 1 SiO 3 / 2 and / or R 2 MeSiO 2 / 2 , R 1 is 3-(methacryloyloxy)propyl, R 2 is 3-acryloxypropyl, Me is methyl; M 3 For R 3 SiO 3 / 2 , R 3 2SiO 2 / 2 , R 3 MeSiO 2 / 2 or R 3 Me2SiO 1 / 1 Any one or a combination of at least two of 3 is phenyl, Me is methyl; a+b+c=100, 5≤a≤25, 15≤b≤35, 40≤c≤65.

10. An organic silica gel, characterized in that: The organic silicone comprises the organic silicone tackifier as claimed in claim 8; Preferably, the organic silica gel comprises the following components: phenyl vinyl silicone resin, phenyl hydrogen silicone oil, phenyl vinyl silicone oil, the organic silicone adhesion promoter and inhibitor as described in claim 8 or 9; Preferably, the organic silica gel comprises the following components in parts by weight: 60-70 parts of phenyl vinyl silicone resin, 15-25 parts of phenyl hydrogen silicone oil, 10-20 parts of phenyl vinyl silicone oil, 1-2 parts of the organic silicon tackifier as claimed in claim 8 or 9, 0.1-1 parts of inhibitor and 0.1-0.5 parts of Pt catalyst diluent; Preferably, the mass percentage of the Pt catalyst in the Pt catalyst dilution solution is 0.04% to 0.1%.

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