Long-chain alkyl silicone resin, method for producing the same, silicone composition, and method for producing and use thereof

Abstract

The application provides a long-chain alkyl silicone resin and a preparation method thereof, a silicone composition and a preparation method and application thereof, which are prepared by mixing a long-chain alkyl-containing silicone resin, a vinyl phenyl silicone resin, a hydrogen-containing phenyl silicone resin, an inhibitor, a platinum catalyst and the like, the silicone composition has a rapid recovery capability, can ensure that dispensing can be directly formed after high-speed shearing, has a relatively low viscosity before and after encapsulation and curing, facilitates the realization of the glue spraying process, and avoids the generation of bubbles, solves the problem that the silicone composition in the prior art is difficult to balance high thixotropy and low viscosity, and slow glue recovery speed can cause the glue to flow amorphously, thus causing inevitable bad effects in actual use.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of silicone materials, in particular to a silicone composition with high thixotropy, low viscosity, and rapid viscosity recovery after high shear thinning, and a preparation method and application thereof. BACKGROUND

[0002] In the prior art, in order to improve the thixotropy of optical materials, fumed silica with a surface containing hydroxyl groups is generally added as a thixotropic agent. However, the addition of fillers will cause the consistency coefficient of the product to increase sharply, and it is difficult to balance high thixotropy and low viscosity. In addition, under the existing sizing process conditions, the fluid will be thinned under the action of the ball needle of the dispensing machine, and if the viscosity recovery speed of the glue is slow, the glue will flow amorphously, resulting in inconsistent height-diameter ratios after solidification, and the chip position being difficult to be located at the center, thereby causing the light path of the chip to be inconsistent, the luminous efficiency to be poor, and the visual effect to be affected. Therefore, it is urgent to develop a silicone optical glue with high shear and rapid recovery thixotropy for packaging in the current high-definition display technology field.

[0003] Patent CN110055027A discloses an LED packaging silicone rubber material composed of component A and component B. Component A contains methylphenyl vinyl silicone resin with a refractive index of 1.46-1.50, methylphenyl vinyl silicone oil with a refractive index of 1.48-1.52, platinum catalyst, inhibitor, modified nano-silicon dioxide; component B contains methylphenyl hydrogen-containing silicone oil with a refractive index of 1.46-1.50, methylphenyl vinyl silicone resin with a refractive index of 1.46-1.50, methyl hydrogen-containing silicone resin, tackifier, and concentrated crosslinking agent. The prepared LED packaging silicone rubber material with a medium refractive index has ultrahigh transparency and light transmittance, good heat resistance, high mechanical properties, good yellowing resistance, and moderate thixotropy, but the viscosity is still large (≥15000 mPa·s).

[0004] Therefore, with the development of technology, especially in the field of ultra-high-definition display, the development of packaging technology puts forward higher requirements for silicone packaging glue: (1) the silicone packaging material has high thixotropy and low viscosity, so as to facilitate the realization of the sizing process and avoid problems such as air bubbles and stringing; (2) the viscosity of the packaging glue can be quickly recovered after high shear thinning, so as to ensure that the dispensing can be directly formed after high-speed shearing, and the shape remains basically unchanged before and after packaging and solidification. SUMMARY

[0005] The present application provides a long-chain alkyl silicone resin and a preparation method thereof, and a high-shear quick-recovery silicone composition containing the long-chain alkyl silicone resin, a vinyl silicone resin and a hydrogen-containing silicone resin, fumed silica, an inhibitor and a platinum catalyst, which has a relatively low viscosity and a high thixotropy, and in particular, after high-speed shearing during sizing, the viscosity can be quickly recovered, so that the high-aspect-ratio consistency and high light transmittance of the sizing before and after curing are maintained, thereby leading to consistent light paths of packaged chips and high luminous efficiency.

[0006] The silicone composition, by weight, consists of the following components:

[0007]

[0008] The silicone polymer includes a hydrogen-containing phenyl silicone resin and a vinyl phenyl silicone resin without long-chain structure. Preferably, the hydrogen-containing phenyl silicone resin can be a mixture of a high-viscosity hydrogen-containing phenyl silicone resin and a low-viscosity hydrogen-containing phenyl silicone resin.

[0009] Preferably, the vinyl phenyl silicone resin has a vinyl content of 1.5-12%, a phenyl content of 5-30% and a viscosity of 640000-660000 mPa·s; more preferably, a vinyl content of 5.71%, a phenyl content of 16.28% and a viscosity of 650000 mPa·s are selected.

[0010] Preferably, the high-viscosity hydrogen-containing phenyl silicone resin has a hydrogen content of 0.3-0.4%, a phenyl content of 10-20% and a viscosity of 5000-7000 mPa·s; more preferably, a hydrogen content of 0.32%, a phenyl content of 20% and a viscosity of 6000 mPa·s are selected.

[0011] Preferably, the low-viscosity hydrogen-containing phenyl silicone resin has a hydrogen content of 0.1-1.0%, a phenyl content of 5-30% and a viscosity of 400-600 mPa·s; more preferably, a hydrogen content of 0.91%, a phenyl content of 23.28% and a viscosity of 500 mPa·s are selected.

[0012] Preferably, the fumed silica has a specific surface area of 300-500 m 2 / g, preferably fumed silica with a specific surface area of 300 m 2 / g.

[0013] The inhibitor is at least one of 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 3-methylbutynol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-buten-2-ol; more preferably, the inhibitor is 1-ethynylcyclohexanol. Other adjuvants, such as tackifiers, diluents, can of course be added as appropriate.

[0014] Preferably, the platinum catalyst comprises at least one of platinum black, platinum halide, platinum-alkene complex, platinum-alcohol complex, platinum-hydrocarbyloxy complex, platinum-ether complex, platinum-aldehyde complex, platinum-ketone complex, platinum-vinylsiloxane complex, bis(gamma-methyl-pyridyl)-dichloroplatinum, trimethylenedipyridyl-dichloroplatinum, dicyclopentadienyl-dichloroplatinum, cyclooctadiene-dichloroplatinum, cyclopentadiene-dichloroplatinum, bis(alkynyl)bis(triphenylphosphine)- platinum complex, bis(alkynyl)(cyclooctadiene)-platinum complex; more preferably, the platinum halide comprises at least one of PtCl4, H2PtCl6.6H2O, Na2PtCl6.4H2O, H2PtCl6.6H2O.

[0015] The long chain alkyl silicone resin is a long chain alkyl containing silicone resin, preferably an alkenyl group and long chain alkyl containing silicone resin or a long chain alkyl and hydrogen group containing silicone resin or a mixture of both; wherein the structure of the long chain alkyl containing silicone resin can be represented as follows:

[0016] (R1R2R3SiO 0.5 ) a (R2R3R4SiO 0.5 ) b (R5R6SiO) c (R7SiO 1.5 ) d (R8SiO 1.5 ) e (R9SiO 1.5 ) f (SiO2) g ;

[0017] wherein R1~R9are groups connecting silicon atoms, R1, R2, R3are alkyl groups with carbon atom number of 1~6; R4is an alkenyl group or hydrogen group, preferably vinyl group; R5, R6are methyl or phenyl groups, R7is methyl group; R8is phenyl group; R9is long chain alkyl group with carbon atom number of 6~18; wherein 0≤g≤0.2, a, b, c, d, e, f are independently selected from numbers greater than or equal to zero and less than 1, and a+b+c+d+e+f+g=1; more preferably, wherein 0

[0018] More preferably, the a:b:c:d:e:f:g=0~0.1:0.1~0.5:0~0.5:0~0.8:0~0.5:0~0.5:0~0.2; further preferably, 0.23≤e≤0.36.

[0019] The silicone composition, wherein the ratio of total moles of alkenyl groups to total moles of hydrogen groups is 1:0.8~1:1.2; the inventor surprisingly found that when the long-chain alkyl silicone resin contains long-chain alkyl groups and phenyl groups in a molar ratio N of 0.5~1.3, the silicone composition has a faster viscosity recovery after high-shear rapid sizing and the cured product has better light transmittance. In particular, when N is 0.7~1.2, the above properties are better.

[0020] Preferably, the preparation method of the long-chain alkyl silicone resin comprises the following steps:

[0021] 1) Proportionally add siloxane I with the structure R7Si(OR 10 )3, siloxane II with the structure R8Si(OR 11 )3, siloxane III with the structure R9Si(OR 12 )3, siloxane monomer IV with the structure Si(OR 13 )4, siloxane monomer V with the structure R5R6Si(OR 14 )2, end-capping agent VI, 5~15wt% of anhydrous ethanol, and end-capping agent VII into a reaction vessel, slowly drop 0.2wt% trifluoromethanesulfonic acid aqueous solution at a constant oil temperature of 20~50℃, heat to 50~80℃, and react for 3~5h to obtain semi-finished product A.

[0022] 2) Heat semi-finished product A in step 1) to 80~100℃ to evaporate the reaction by-products, add toluene and anhydrous sodium carbonate, stir for 20~30min, add 0.05~0.2wt% potassium hydroxide after overnight, and react at 110-135℃ and 200r / min for 5~6h to promote the condensation reaction. After the reaction is completed, wash the obtained product with water to pH 7~8, remove the solvent and low-boiling substances under reduced pressure, and obtain the long-chain alkyl silicone resin after no bubbles come out.

[0023] wherein R 10 , R 11 , R 12 , R 13 , R 14 are alkyl groups with 1~6 carbon atoms, preferably methyl or ethyl or propyl; preferably, the siloxane monomer I with the structure R7Si(OR 10 )3 is at least one of methyltrimethoxysilane or methyltriethoxysilane;

[0024] the siloxane II having the structure R8Si(OR 11 )3 is at least one of phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane;

[0025] the siloxane monomer III having the structure R9Si(OR 12 )3 is at least one of hexyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, octyltriethoxysilane, dodecyltriethoxysilane;

[0026] the siloxane IV having the structure Si(OR 13 )4 is at least one of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate;

[0027] the siloxane V having the structure R5R6Si(OR 14 )2 is at least one of diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane;

[0028] the end-capping agent VI is at least one of hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane;

[0029] the end-capping agent VII is at least one of 1,3-divinyltetramethyldisiloxane, 1,3-divinyltetraphenyldisiloxane, 1,3-tetravinyl dimethyldisiloxane, hexavinyl disiloxane.

[0030] In another aspect, the present application also provides a preparation method of the above-mentioned organosilicon composition, comprising the following steps:

[0031] After weighing, the long-chain alkyl organosilicon resin, the organosilicon polymer, the fumed silica, the inhibitor and the platinum catalyst are fully mixed and uniformly taken out for vacuum degassing for 5-20 min, to obtain the organosilicon composition.

[0032] The present application also provides an application of the organosilicon composition in Mini / Micro LED display panel packaging.

[0033] Compared with the prior art, the present application has the following beneficial effects:

[0034] The application provides a long-chain alkyl silicone resin and a preparation method thereof, and further provides a silicone composition and a preparation method and application thereof, the silicone composition containing a long-chain alkyl silicone resin, a vinyl silicone resin and a hydrogen-containing silicone resin, fumed silica, an auxiliary inhibitor and a platinum catalyst, the silicone composition having a rapid recovery capability to ensure that dispensing can be directly formed after high-speed shearing, and the shape remains basically unchanged before and after encapsulation and curing; the silicone composition has a relatively low viscosity to facilitate the realization of the glue spraying process and avoid the generation of bubbles. DETAILED DESCRIPTION

[0035] The application is further described below in combination with examples:

[0036] (1) Preparation of long-chain alkyl silicone resin

[0037] Preparation Example 1:

[0038] Synthesis of long-chain alkyl type vinyl long-chain alkyl silicone resin 61

[0039] 0.34 mol of phenyl trimethoxysilane, 0.44 mol of hexyl trimethoxysilane, 0.44 mol of methyl trimethoxysilane, 0.20 mol of vinyl bis-capped, 0.04 mol of methyl bis-capped and 0.30 mol of anhydrous ethanol are added to a 500 ml four-necked flask, and the oil temperature is set to 40°C; then a constant-pressure dropping funnel is used to slowly drop a 0.2 wt% concentrated triflic acid aqueous solution, wherein the content of triflic acid is 0.005 mol; after the dropping is completed, the constant temperature reaction is carried out at 60°C for 3 h; the alcohol-water mixture is distilled off at 90°C; 200 g of toluene and 0.86 g of anhydrous sodium carbonate are added and stirred for 20 min; then 0.1 wt% of potassium hydroxide is added, and the reaction is carried out at 120°C for 5 h to promote the condensation reaction; then water washing is carried out until the pH value is 7-8; the product is transferred to a round-bottom flask, and the solvent and low-boiling substances are removed by distillation under reduced pressure; after no bubbles are generated, the product with a phenyl content of 13.71%, N of 1.29 and a vinyl content of 5.71% is obtained.

[0040] Structural general formula of long-chain alkyl type vinyl long-chain alkyl silicone resin 61:

[0041] (Me3SiO 0.5 ) 0.04 (Me2ViSiO 0.5 ) 0.20 (C6H 17 SiO 1.5 ) 0.26 (MeSiO 1.5 ) 0.25 (PhSiO 1.5 ) 0.21 .

[0042] Preparation Example 2

[0043] Synthesis of long-chain alkyl type vinyl long-chain alkyl silicone resin 121

[0044] 0.42 mol of phenyltrimethoxysilane, 0.48 mol of dodecyltrimethoxysilane, 0.48 mol of methyltrimethoxysilane, 0.23 mol of vinyl bis-capped, 0.05 mol of methyl bis-capped, and 0.35 mol of anhydrous ethanol were added to a 500 ml four-necked flask, and the oil temperature was set to 40°C; then a constant pressure dropping funnel was used to slowly drop in a 0.2 wt% concentration of a triflic acid aqueous solution, wherein the triflic acid content was 0.007 mol; after the dropping was completed, the reaction was carried out at 60°C for 3 h; at 90°C, the alcohol-water mixture was distilled off; 200 g of toluene and 1.04 g of anhydrous sodium carbonate were added and stirred for 20 min; then 0.1 wt% of potassium hydroxide was added, and the reaction was carried out at 120°C for 5 h to promote the condensation reaction; then water was washed until the pH value was 7-8; the product was transferred to a round-bottom flask, and the solvent and low-boiling substances were removed by distillation under reduced pressure; after no bubbles were generated, the phenyl content was 13.71%, N was 1.14, and the vinyl content was 5.05%.

[0045] Structural general formula of long-chain alkyl type vinyl long-chain alkyl silicone resin 121

[0046] (Me3SiO 0.5 ) 0.05 (Me2ViSiO 0.5 ) 0.25 (C 12 H 25 SiO 1.5 ) 0.34 (MeSiO 1.5 ) 0.34 (PhSiO 1.5 ) 0.31 .

[0047] Preparation Example 3

[0048] Synthesis of long-chain alkyl type vinyl long-chain alkyl silicone resin 181

[0049] Into a 500ml four-necked flask, 0.34mol phenyltrimethoxysilane, 0.34mol octadecyltrimethoxysilane, 0.34mol methyltrimethoxysilane, 0.17mol vinyl bishead, 0.03mol methyl bishead and 0.26mol anhydrous ethanol were added, and the oil temperature was set at 40℃; then a constant pressure dropping funnel was used to slowly drop in a 0.2wt% trifluoromethanesulfonic acid aqueous solution, wherein the trifluoromethanesulfonic acid content was 0.005mol; after the dropping was completed, the reaction was carried out at 60℃ for 3h; at 90℃, the alcohol-water mixture was distilled off; 200g of toluene and 0.80g of anhydrous sodium carbonate were added and stirred for 20min; after overnight, 0.1wt% potassium hydroxide was added and the condensation reaction was promoted by reacting at 120℃ for 5h; then water washing was carried out until the pH value was 7~8; the product was transferred into a round-bottom flask, and the solvent and low-boiling substances were removed by distillation under reduced pressure; after no bubbles were generated, a phenyl content of 13.19%, N of 1.0 and a vinyl content of 4.63% were obtained.

[0050] Structural general formula of long-chain alkyl type vinyl long-chain alkyl silicone resin 181:

[0051] (Me3SiO 0.5 ) 0.04 (Me2ViSiO 0.5 ) 0.19 (C 18 H 32 SiO 1.5 ) 0.26 (MeSiO 1.5 ) 0.26 (PhSiO 1.5 ) 0.25 .

[0052] Preparation Example 4

[0053] Synthesis of long-chain alkyl type vinyl long-chain alkyl silicone resin 62

[0054] Into a 500 ml four-necked flask, 0.17 mol of diphenyl dimethoxysilane, 0.38 mol of hexyl trimethoxysilane, 0.38 mol of methyl trimethoxysilane, 0.17 mol of vinyl bishead, 0.03 mol of methyl bishead and 0.28 mol of anhydrous ethanol were added, and the oil temperature was set to 40°C; then a constant pressure dropping funnel was used to slowly drop in a 0.2 wt% triflic acid aqueous solution, wherein the content of triflic acid was 0.009 mol; after the dropping was completed, the reaction was carried out at 60°C for 3 h; at 90°C, the alcohol-water mixture was distilled off; 150 g of toluene and 0.63 g of anhydrous sodium carbonate were added and stirred for 20 min; then 0.1 wt% of potassium hydroxide was added, and the reaction was carried out at 120°C for 5 h to promote the condensation reaction; then water was washed until the pH value was 7-8; the product was transferred to a round-bottom flask, and the solvent and low-boiling substances were removed by distillation under reduced pressure; after no bubbles were generated, a phenyl content of 17.81%, N of 1.12 and a vinyl content of 6.24% were obtained.

[0055] Structural general formula of the long-chain alkyl type vinyl long-chain alkyl silicone resin 62:

[0056] (Me3SiO 0.5 ) 0.04 (Me2ViSiO 0.5 ) 0.25 (C6H 25 SiO 1.5 ) 0.29 (MeSiO 1.5 ) 0.29 (Ph2SiO) 0.13 .

[0057] Preparation Example 5

[0058] Synthesis of long-chain alkyl type vinyl long-chain alkyl silicone resin 122

[0059] Into a 500ml four-necked flask, 0.13mol of diphenyl dimethoxysilane, 0.20mol of dodecyl trimethoxysilane, 0.20mol of methyl trimethoxysilane, 0.10mol of vinyl bishead, 0.02mol of methyl bishead and 0.16mol of anhydrous ethanol were added, and the oil temperature was set to 40℃; then a constant pressure dropping funnel was used to slowly drop in a 0.2wt% triflic acid aqueous solution, wherein the content of triflic acid was 0.009mol; after the dropping was completed, the reaction was carried out at 60℃ for 3h; at 90℃, the alcohol-water mixture was distilled off; 140g of toluene and 0.72g of anhydrous sodium carbonate were added and stirred for 20min; then 0.1wt% of potassium hydroxide was added, and the reaction was carried out at 120℃ for 5h to promote the condensation reaction; then water was washed until the pH value was 7~8; the product was transferred to a round-bottom flask, and the solvent and low-boiling substances were removed by distillation under reduced pressure; after no bubbles were generated, a phenyl content of 18.99%, N of 0.77 and a vinyl content of 5.12% were obtained.

[0060] Structural general formula of long-chain alkyl type vinyl long-chain alkyl silicone resin 122:

[0061] (Me3SiO 0.5 ) 0.04 (Me2ViSiO 0.5 ) 0.26 (C 12 H 25 SiO 1.5 ) 0.26 (MeSiO 1.5 ) 0.26 (Ph2SiO) 0.18 .

[0062] Preparation Example 6:

[0063] Synthesis of long-chain alkyl type vinyl long-chain alkyl silicone resin 182

[0064] Into a 500ml four-necked flask, 0.14mol of diphenyl dimethoxysilane, 0.18mol of octadecyl trimethoxysilane, 0.18mol of methyl trimethoxysilane, 0.10mol of vinyl bishead, 0.02mol of methyl bishead and 0.16mol of anhydrous ethanol were added, and the oil temperature was set to 40℃; then a constant pressure dropping funnel was used to slowly drop in a 0.2wt% trifluoromethanesulfonic acid aqueous solution, wherein the content of trifluoromethanesulfonic acid was 0.008mol; after the dropping was completed, the reaction was carried out at 60℃ for 3h; at 90℃, the alcohol-water mixture was distilled off; 200g of toluene and 0.72g of anhydrous sodium carbonate were added and stirred for 20min; after overnight, 0.1wt% of potassium hydroxide was added, and the reaction was carried out at 120℃ for 5h to promote the condensation reaction; then water was washed until the pH value was 7~8; the product was transferred to a round-bottom flask, and the solvent and low-boiling substances were removed by distillation under reduced pressure; after no bubbles were generated, a phenyl content of 18.46%, N of 0.75 and a vinyl content of 4.62% were obtained.

[0065] Structural general formula of long-chain alkyl type vinyl long-chain alkyl silicone resin 182:

[0066] (Me3SiO 0.5 ) 0.03 (Me2ViSiO 0.5 ) 0.27 (C 18 H 32 SiO 1.5 ) 0.25 (MeSiO 1.5 ) 0.25 (Ph2SiO) 0.20 .

[0067] Preparation Example 7

[0068] Synthesis of long-chain alkyl type vinyl long-chain alkyl silicone resin 63

[0069] Into a 500ml four-necked flask, 0.45mol phenyltrimethoxysilane, 0.30mol hexyltrimethoxysilane, 0.30mol methyltrimethoxysilane, 0.30mol tetraethyl silicate, 0.20mol vinyl bishead, 0.04mol methyl bishead and 0.40mol anhydrous ethanol were added, and the oil temperature was set at 40℃; then a constant pressure dropping funnel was used to slowly drop in a 0.2wt% trifluoromethanesulfonic acid aqueous solution, wherein the trifluoromethanesulfonic acid content was 0.005mol; after the dropping was completed, the reaction was carried out at 60℃ for 3h; at 90℃, the alcohol-water mixture was distilled off; 200g of toluene and 0.86g of anhydrous sodium carbonate were added and stirred for 20min; after overnight, 0.1wt% potassium hydroxide was added, and the reaction was carried out at 120℃ for 5h to promote the condensation reaction; then water washing was carried out until the pH value was 7~8; the product was transferred into a round-bottom flask, and the solvent and low-boiling substances were removed by distillation under reduced pressure; after no bubbles came out, a phenyl content of 16.14%, N of 0.67 and a vinyl content of 5.03% were obtained.

[0070] Structural general formula of long-chain alkyl type vinyl long-chain alkyl silicone resin 63:

[0071] (Me3SiO 0.5 ) 0.02 (Me2ViSiO 0.5 ) 0.22 (C6H 17 SiO 1.5 ) 0.17 (MeSiO 1.5 ) 0.17 (PhSiO 1.5 ) 0.25 (SiO2) 0.17 .

[0072] Preparation Example 8

[0073] Synthesis of long-chain alkyl type vinyl long-chain alkyl silicone resin 123

[0074] Into a 500ml four-necked flask, 0.50mol phenyltrimethoxysilane, 0.30mol dodecyltrimethoxysilane, 0.30mol methyltrimethoxysilane, 0.30mol tetraethyl silicate, 0.20mol vinyl bishead, 0.04mol methyl bishead and 0.30mol anhydrous ethanol were added, and the oil temperature was set at 40℃; then a constant pressure dropping funnel was used to slowly drop in a 0.2wt% trifluoromethanesulfonic acid aqueous solution, wherein the trifluoromethanesulfonic acid content was 0.005mol; after the dropping was completed, the reaction was carried out at 60℃ for 3h; at 90℃, the alcohol-water mixture was distilled off; 200g of toluene and 0.86g of anhydrous sodium carbonate were added and stirred for 20min; after overnight, 0.1wt% potassium hydroxide was added and the reaction was carried out at 120℃ for 5h to promote the condensation reaction; then water was washed until the pH value was 7~8; the product was transferred into a round-bottom flask, and the solvent and low-boiling substances were removed by distillation under reduced pressure; after no bubbles were generated, a phenyl content of 15.62%, N of 0.60 and a vinyl content of 4.38% were obtained.

[0075] Structural general formula of long-chain alkyl type vinyl long-chain alkyl silicone resin 123:

[0076] (Me3SiO 0.5 ) 0.04 (Me2ViSiO 0.5 ) 0.22 (C 12 H 17 SiO 1.5 ) 0.16 (MeSiO 1.5 ) 0.16 (PhSiO 1.5 ) 0.26 (SiO2) 0.16 .

[0077] Preparation Example 9

[0078] Synthesis of long-chain alkyl type vinyl long-chain alkyl silicone resin 183

[0079] Into a 500ml four-necked flask, 0.60mol phenyltrimethoxysilane, 0.30mol octadecyltrimethoxysilane, 0.30mol methyltrimethoxysilane, 0.30mol tetraethyl silicate, 0.20mol vinyl bishead, 0.05mol methyl bishead and 0.50mol anhydrous ethanol were added, and the oil temperature was set at 40°C; then a constant pressure dropping funnel was used to slowly drop in a 0.2wt% trifluoromethanesulfonic acid aqueous solution, wherein the trifluoromethanesulfonic acid content was 0.005mol; after the dropping was completed, the reaction was carried out at 60°C for 3h; at 90°C, the alcohol-water mixture was distilled off; 200g of toluene and 0.86g of anhydrous sodium carbonate were added and stirred for 20min; after overnight, 0.1wt% potassium hydroxide was added and the reaction was carried out at 120°C for 5h to promote the condensation reaction; then water was washed until the pH value was 7-8; the product was transferred to a round-bottom flask, and the solvent and low-boiling substances were removed by distillation under reduced pressure; after no bubbles were generated, a phenyl content of 16.14%, N of 0.5 and a vinyl content of 3.77% were obtained.

[0080] Structural general formula of long-chain alkyl type vinyl long-chain alkyl silicone resin 183:

[0081] (Me3SiO 0.5 ) 0.05 (Me2ViSiO 0.5 ) 0.20 (C 18 H 17 SiO 1.5 ) 0.15 (MeSiO 1.5 ) 0.15 (PhSiO 1.5 ) 0.30 .

[0082] Preparation Example 10

[0083] Synthesis of long-chain alkyl type vinyl long-chain alkyl silicone resin 124

[0084] Into a 500 ml four-necked flask, 0.43 mol of phenyltrimethoxysilane, 0.09 mol of dodecyltrimethoxysilane, 0.09 mol of methyltrimethoxysilane, 0.10 mol of vinyl bis-capped, 0.02 mol of methyl bis-capped and 0.15 mol of anhydrous ethanol were added, and the oil temperature was set to 40°C; then a constant pressure dropping funnel was used to slowly drop in a 0.2 wt% aqueous solution of triflic acid, wherein the content of triflic acid was 0.003 mol; after the dropping was completed, the reaction was carried out at 60°C for 3 h; at 90°C, the alcohol-water mixture was distilled off; 150 g of toluene and 0.44 g of anhydrous sodium carbonate were added and stirred for 20 min; after overnight, 0.1 wt% of potassium hydroxide was added and the reaction was carried out at 120°C for 5 h to promote the condensation reaction; then water was washed until the pH value was 7-8; the product was transferred to a round-bottom flask, and the solvent and low-boiling substances were removed by distillation under reduced pressure; after no bubbles were generated, a phenyl content of 32.44%, N of 0.21 and a vinyl content of 5.23% were obtained.

[0085] Structural general formula of long-chain alkyl type vinyl long-chain alkyl silicone resin 124:

[0086] (Me3SiO 0.5 ) 0.05 (Me2ViSiO 0.5 ) 0.24 (C 12 H 17 SiO 1.5 ) 0.11 (MeSiO 1.5 ) 0.11 (PhSiO 1.5 ) 0.49 .

[0087] (2) Preparation of silicone composition

[0088] Example 1:

[0089] Take 20.3 g of long-chain alkyl modified long-chain alkyl silicone resin 61, 47.4 g of vinyl phenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.8 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 16.2 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), 5 g of fumed silica (specific surface area 300 m 20.1 g of 1-ethynylcyclohexanol and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration of 5000 ppm) were placed in a beaker and dispersed evenly using a high-speed disperser. The mixture was then degassed under vacuum for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 22.53%.

[0090] Example 2:

[0091] Take 20.5 g of long-chain alkyl-modified long-chain alkyl organosilicon resin 121, 47.9 g of vinylphenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.6 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 15.8 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), and 5 g of fumed silica (specific surface area 300 m²). 2 0.1 g of 1-ethynylcyclohexanol and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration of 5000 ppm) were placed in a beaker and dispersed evenly using a high-speed disperser. The mixture was then degassed under vacuum for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.24%.

[0092] Example 3:

[0093] Take 20.7 g of long-chain alkyl-modified long-chain alkyl organosilicon resin 181, 48.2 g of vinylphenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.4 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 15.6 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), and 5 g of fumed silica (specific surface area 300 m²). 2 0.1 g of 1-ethynylcyclohexanol and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration of 5000 ppm) were placed in a beaker and dispersed evenly using a high-speed disperser. The mixture was then degassed under vacuum for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.11%.

[0094] Example 4:

[0095] Take 33.9 g of long-chain alkyl-modified long-chain alkyl organosilicon resin 61, 33.9 g of vinylphenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.8 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 16.2 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), and 5 g of fumed silica (specific surface area 300 m²). 2 0.1 g of 1-ethynylcyclohexanol and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration of 5000 ppm) were placed in a beaker and dispersed evenly using a high-speed disperser. The mixture was then degassed under vacuum for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 15.92%.

[0096] Example 5:

[0097] Take 34.4 g of long-chain alkyl-modified long-chain alkyl organosilicon resin 121, 34.4 g of vinylphenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.4 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 15.6 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), and 5 g of fumed silica (specific surface area 300 m²). 2 0.1 g of 1-ethynylcyclohexanol and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration of 5000 ppm) were placed in a beaker and dispersed evenly using a high-speed disperser. The mixture was then degassed under vacuum for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 15.86%.

[0098] Example 6:

[0099] Take 34.8 g of long-chain alkyl-modified long-chain alkyl organosilicon resin 181, 34.8 g of vinylphenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.1 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 15.1 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), and 5 g of fumed silica (specific surface area 300 m²). 2Example 1: A mixture of 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 62, 60.8 g of vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 10.9 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 16.3 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 5 g of fumed silica (specific surface area 300 m2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration 5000 ppm) was uniformly dispersed in a beaker using a high-speed disperser, and vacuum degassing was performed for 10 min to obtain a silicone composition having a vinyl-to-hydrogen molar ratio of 1.05 and a phenyl content of 16.91%.

[0100] Example 7:

[0101] A mixture of 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 62, 60.8 g of vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 10.9 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 16.3 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 5 g of fumed silica (specific surface area 300 m 2 A mixture of 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 62, 60.8 g of vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 10.9 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 16.3 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 5 g of fumed silica (specific surface area 300 m

[0102] Example 8:

[0103] A mixture of 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 62, 60.8 g of vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 10.9 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 16.3 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 5 g of fumed silica (specific surface area 300 m 2 A mixture of 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 62, 60.8 g of vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 10.9 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 16.3 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 5 g of fumed silica (specific surface area 300 m

[0104] Example 9:

[0105] Take 6.8 g of long-chain alkyl-modified long-chain alkyl organosilicon resin 122, 61.2 g of vinylphenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.7 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 16.1 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), and 5 g of fumed silica (specific surface area 300 m²). 2 0.1 g of 1-ethynylcyclohexanol and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration of 5000 ppm) were placed in a beaker and dispersed evenly using a high-speed disperser. The mixture was then degassed under vacuum for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.97%.

[0106] Example 10:

[0107] Take 6.8 g of long-chain alkyl-modified long-chain alkyl organosilicon resin 123, 61.4 g of vinylphenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.6 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 16.0 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), and 5 g of fumed silica (specific surface area 300 m²). 2 0.1 g of 1-ethynylcyclohexanol and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration of 5000 ppm) were placed in a beaker and dispersed evenly using a high-speed disperser. The mixture was then degassed under vacuum for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.73%.

[0108] Example 11:

[0109] Take 6.8 g of long-chain alkyl-modified long-chain alkyl organosilicon resin 182, 61.3 g of vinylphenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.7 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 16.0 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), and 5 g of fumed silica (specific surface area 300 m²). 20.1 g of 1-ethynylcyclohexanol and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration of 5000 ppm) were placed in a beaker and dispersed evenly using a high-speed disperser. The mixture was then degassed under vacuum for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.93%.

[0110] Example 12:

[0111] Take 6.8 g of long-chain alkyl-modified long-chain alkyl organosilicon resin 183, 61.6 g of vinylphenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.6 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 15.8 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), and 5 g of fumed silica (specific surface area 300 m²). 2 0.1 g of 1-ethynylcyclohexanol and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration of 5000 ppm) were placed in a beaker and dispersed evenly using a high-speed disperser. The mixture was then degassed under vacuum for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.75%.

[0112] Example 13:

[0113] Take 26.0 g of long-chain alkyl-modified long-chain alkyl organosilicon resin 121, 48.0 g of vinylphenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.8 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 16.2 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), and 3 g of fumed silica (specific surface area 300 m²). 2 0.1 g of 1-ethynylcyclohexanol and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration of 5000 ppm) were placed in a beaker and dispersed evenly using a high-speed disperser. The mixture was then degassed under vacuum for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 17.14%.

[0114] Comparative Example 1:

[0115] Take 71.3 g of vinyl phenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 14.1 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 9.4 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration 5000 ppm) in a beaker, disperse uniformly using a high-speed disperser, vacuum degassing for 10 min, to obtain a silicone composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.77%.

[0116] Comparative Example 2:

[0117] Take 71.3 g of vinyl phenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 14.1 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 9.4 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration 5000 ppm) in a beaker, disperse uniformly using a high-speed disperser, vacuum degassing for 10 min, to obtain a silicone composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.77%.

[0118] Take 71.3 g of vinyl phenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 14.1 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 9.4 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 5 g of fumed silica (specific surface area 300 m 2Example 1: 66.3 g of a vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 10.6 g of a hydride phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 15.9 g of a hydride silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 7 g of fumed silica (specific surface area 300 m2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration 5000 ppm) were uniformly dispersed in a beaker using a high-speed disperser, and vacuum degassing was performed for 10 min to obtain a silicone composition having a vinyl-to-hydrogen molar ratio of 1.05 and a phenyl content of 16.44%.

[0119] Comparative Example 4:

[0120] Example 1: 66.3 g of a vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 10.6 g of a hydride phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 15.9 g of a hydride silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 7 g of fumed silica (specific surface area 300 m 2 Example 1: 66.3 g of a vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 10.6 g of a hydride phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 15.9 g of a hydride silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 7 g of fumed silica (specific surface area 300 m

[0121] Comparative Example 5:

[0122] Example 1: 66.3 g of a vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 10.6 g of a hydride phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 15.9 g of a hydride silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 7 g of fumed silica (specific surface area 300 m 2 Example 1: 66.3 g of a vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 10.6 g of a hydride phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 15.9 g of a hydride silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 7 g of fumed silica (specific surface area 300 m

[0123] Example 1: 7.2 g of long-chain alkyl-modified long-chain alkyl silicone resin 124, 50.4 g of vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 9.1 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 13.7 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration 5000 ppm) were taken in a beaker, dispersed uniformly using a high-speed disperser, and vacuum-deaerated for 10 minutes to obtain a silicone composition having a vinyl-to-hydrogen molar ratio of 1.05 and a phenyl content of 15.40%. 2 Example 2: 22.0 g of long-chain alkyl-modified long-chain alkyl silicone resin 121, 48.0 g of vinylphenyl silicone resin (vinyl mass content 5.71%, phenyl content 16.28%, viscosity 650000 mPa-s), 10.8 g of hydrogen-containing phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa-s), 16.2 g of hydrogen-containing silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa-s), 3 g of fumed silica (specific surface area 300 m -1 / g), 0.1 g of 1-ethynylcyclohexanol, 0.1 g of platinum(0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration 5000 ppm) were taken in a beaker, dispersed uniformly using a high-speed disperser, and vacuum-deaerated for 10 minutes to obtain a silicone composition having a vinyl-to-hydrogen molar ratio of 1.05 and a phenyl content of 16.59%.

[0124] Table 1: Amounts of main components of silicone compositions prepared in Examples 1-12 and Comparative Examples 1-6

[0125]

[0126] (3) Testing of silicone compositions obtained in Examples 1-12 and Comparative Examples 1-6

[0127] 1. Measurement of recovery percentage: A rheometer was used to perform a three-stage test using a flat plate rotor having a diameter of 50 mm, a gap setting of 0.1 mm, and a rotational time sweep mode to test at different temperatures of 25°C by setting a constant shear rate in three stages. Stage 1: shear rate 1 s -1 / 300 s -1 / 300 s-1 / 500s -1 Shearing time is 30s, phase three: shear rate is 1s -1 Shearing time is 120s. Recovery rate (RR) is the ratio of viscosity at a certain time in the third phase to the stable viscosity in the first phase, where RR1 is the recovery rate at 10s, and RR0 is the recovery rate after the viscosity in the third phase is stable;

[0128] 2. Measurement of light transmittance: The light transmittance of the film sample (30mm*20mm*0.2mm) cured at 100℃ for 30min was tested by ultraviolet-visible spectrophotometer, with air as blank control, test temperature: 25℃, test wavelength: 450nm light transmittance, test results are shown in Table 2.

[0129] Table 2: Test results of examples 1-12 and comparative examples 1-6

[0130]

[0131] From the test results in Table 2, compared with comparative example 1, the recovery rate RR of the product with long-chain alkyl silicone resin is improved to a certain extent, RR1 is improved by >10%, with the characteristics of rapid recovery. Not only that, but also with high transparency, adding about 5% of fumed silica, the recovery is ≥50% within 10s; the final recovery is ≥75%.

[0132] Compared with comparative example 2, the recovery rate of examples 1 and 4 does not increase significantly, and is relatively close, but the viscosity decreases with the increase of C61 content, indicating that the addition of C61 can make the RR remain relatively excellent while the viscosity also decreases.

[0133] Compared with comparative example 3, the recovery rate of examples 2 and 5 increases first and then decreases. Because the side chain length of the long-chain alkyl modified phenyl silicone resin in the system is longer than that of C61, the entanglement and disentanglement of the molecular chain movement process in the system are affected, and the recovery rate is also affected. But eventually it will reach a balance point of chain entanglement and disentanglement, so the recovery rate will not always be in an upward state with the increase of chain length and long-chain alkyl density. But the viscosity will still decrease with the increase of the content of long-chain alkyl modified phenyl silicone resin, because its viscosity is relatively low, it can also act as a diluent to reduce the viscosity of the system.

[0134] Compared with Comparative Example 4, the recovery rates of Examples 3 and 6 also show the trend of first increasing and then decreasing, and the transmittance also decreases, and the reason for the decrease in light transmittance is that the too long chain length leads to a decrease in compatibility with the original system, so that the colloid is not completely transparent and micro-turbid, and multiple liquid layers will be formed in the microstructure, and the internal friction and inertia of the system are also more obvious, resulting in the influence on the final viscosity recovery.

[0135] Compared with Comparative Examples 2-4, the viscosity of Examples 7-12 is different. The structure of the long-chain alkyl-modified phenyl silicone resin in Comparative Examples 2-4 is MT type silicone resin, the structure of the long-chain alkyl-modified phenyl silicone resin in Examples 7, 9 and 11 is MDT type silicone resin, and the structure of the long-chain alkyl-modified phenyl silicone resin in Examples 8, 10 and 12 is MQ type silicone resin. Compared with the high-shear fast-recovery transparent silicone composition prepared by the MT type silicone resin structure, the viscosity of the MDT type silicone resin structure is relatively low, and the viscosity of the MQ type structure is relatively high. The reason is that the D chain is linear structure, and the product prepared has low viscosity. The Q chain is a bulky structure, and the molecular network structure formed is large, and the structure of the system formed after mixing with other components is more complex, resulting in an increase in viscosity. In addition, the recovery rate also changes. When the N value is in the interval [0.7, 1.2], the recovery rate is excellent, RR1>60%, and RR0>85%.

[0136] Comparative Example 5 is a sample with a gas phase silica content of 7%, and its transmittance is 93.5% at 100 s -1 The recovery rate under shear for 10 s is 53.23%, and the final recovery rate is 86.77%. The recovery rate of Examples 7-12 and Comparative Examples 2-4 is RR1≥50% and RR0≥70% when the long-chain alkyl-modified silicone resin with a gas phase silica content of 5% and 10% is added, and the viscosity is about 6000 mPa·s. Compared with Comparative Example 5, the viscosity reduction rate is ≥55%.

[0137] Compared with Comparative Example 6, the light transmittance of the remaining examples is relatively high. The reason is that by accurately controlling the monomer content, e is in the interval [0.23, 0.36], and N is also in the interval [0.5, 1.3], so that the refractive index of the mixed resin matches the refractive index of the fumed silica, so that the light transmittance can be greater than 90% (450 nm @ 25°C).

[0138] Comparative Example 7, with 3% fumed silica and 21.57% C121, showed superior RR1 and RR0 values ​​compared to the sample without long-chain alkyl silicone resin C. Fumed silica contains hydrogen bonds, which significantly influence the shear recovery of the material. Due to the relatively low addition of long-chain alkyl groups, the change in hydrogen bond content is higher than that of long-chain alkyl groups. Therefore, the recovery rate of Example 2, with 20% C121 and 5% fumed silica, is relatively higher. Compared to Example 13, the recovery rate of Example 13 with 25% C121 and 3% fumed silica is comparable to that of Example 2 with 20% C121 and 5% fumed silica, but the viscosity of Example 13 is significantly lower.

[0139] The results of all tests show that the materials still have the ability to recover quickly after high-speed shearing, and they will have good application prospects in the face of even higher-speed sizing processes. At present, long-chain alkyl-modified phenyl silicone resin has excellent application potential in the field of ultra-high-definition display.

[0140] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A long chain alkyl silicone resin characterized by, The long-chain alkyl silicone resin is a silicone resin containing alkenyl groups and long-chain alkyl groups or a silicone resin containing long-chain alkyl groups and hydrogen groups or a mixture of both, and the general structure of the long-chain alkyl silicone resin is: (R1R2R3SiO 0.5 ) a (R2R3R4SiO 0.5 ) b (R5R6SiO) c (R7SiO 1.5 ) d (R8SiO 1.5 ) e (R9SiO 1.5 ) f (SiO2) g ; wherein R1-R9 are groups connected to silicon atoms, R1, R2, R3 are alkyl groups; R4 is an alkenyl group or a hydrogen group; R5, R6 are methyl or phenyl groups, R7 is a methyl group; R8 is a phenyl group; R9 is a long-chain alkyl group, wherein the number of carbon atoms is 6-18; wherein 0≤g≤0.2, a, b, c, d, e, f are independently selected from numbers greater than or equal to zero and less than 1, and a+b+c+d+e+f+g=1, the a:b:c:d:e:f:g=0~0.1:0.1~0.5:0~0.5:0~0.8:0~0.5:0~0.5:0~0.2, 0 The long-chain alkyl silicone resin has a molar ratio of long-chain alkyl groups to phenyl groups N of 0.5-1.

3.

2. The preparation method of the long-chain alkyl silicone resin according to claim 1, comprising the following steps: 1) proportionally adding siloxane I with structure R7Si(OR 10 )3, siloxane II with structure R8Si(OR 11 )3, siloxane III with structure R9Si(OR 12 )3, siloxane monomer IV with structure Si(OR 13 )4, siloxane monomer V with structure R5R6Si(OR 14 )2, end-capping agent VI, 5-15 wt% of anhydrous ethanol, and end-capping agent VII into a reaction vessel, slowly dropping in 0.2 wt% trifluoromethanesulfonic acid aqueous solution at a constant oil temperature of 20-50℃, warming to 50-80℃ for 3-5 h to obtain semi-finished product A, wherein R 10 , R 11 , R 12 , R 13 , R 14 are alkyl groups with 1-6 carbon atoms; 2) The semi-finished product A in step 1) is heated to 80-100℃ to evaporate the reaction by-products, toluene and anhydrous sodium carbonate are added and stirred for 20-30min, 0.05-0.2wt% of potassium hydroxide is added after overnight, and the condensation reaction is promoted at 110-135℃ for 5-6h, after the reaction is completed, the obtained product is washed with water to pH 7-8, the solvent and low-boiling substances are removed under reduced pressure, and after no bubbles are generated, the long-chain alkyl silicone resin is obtained.

3. The method of preparing long-chain alkyl silicone resins according to claim 2, characterized by: In step 1), the siloxane monomer I having the structure R7Si(OR 10 )3 is at least one of methyltrimethoxysilane, methyltriethoxysilane; and / or the siloxane II having the structure R8Si(OR 11 )3 is at least one of phenyltrimethoxysilane, phenyltriethoxysilane; and / or said siloxane monomer III having the structure R9Si(OR 12 )3 is at least one of hexyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, octyltriethoxysilane, dodecyltriethoxysilane; and / or said siloxane IV having the structure Si(OR 13 )4 is at least one of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate; and / or the siloxane V having the structure R5R6Si(OR 14 )2 is at least one of diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane; and / or The end-capping agent VI is at least one of hexamethyldisiloxane, hexaethyldisiloxane, and hexapropyldisiloxane; and / or The end-capping agent VII is 1,3-divinyltetramethyldisiloxane.

4. A silicone composition characterized in that, The silicone composition consists of the following components by weight fraction: The silicone polymer includes a hydrogen-containing phenyl silicone resin and a vinyl phenyl silicone resin without long-chain structure.

5. The silicone composition according to claim 4, characterized in that: The ratio of the total moles of alkenyl groups to the total moles of hydrogen groups in the silicone composition is 1:0.8-1:1.

2.

6. The silicone composition according to claim 4, characterized in that: The vinyl phenyl silicone resin without long-chain structure has a vinyl content of 1.5-12%, a phenyl content of 5-30%, and a viscosity of 640000-660000mPa·s.

7. The silicone composition according to claim 4, characterized in that: The hydrogen-containing phenyl silicone resin is a mixture of a high-viscosity hydrogen-containing phenyl silicone resin and / or a low-viscosity hydrogen-containing phenyl silicone resin; The high-viscosity hydrogen-containing phenyl silicone resin has a hydrogen content of 0.3-0.4%, a phenyl content of 10-20%, and a viscosity of 5000-7000mPa·s; The low-viscosity hydrogen-containing phenyl silicone resin has a hydrogen content of 0.1-1.0%, a phenyl content of 5-30%, and a viscosity of 400-600mPa·s.

8. The silicone composition according to claim 4, characterized in that: The specific surface area of the fumed silica is 300 to 500 m 2 / g; and / or The inhibitor is at least one of 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 3-methylbutynol, 3,5-dimethyl-1-hexyn-3-ol, and 2-phenyl-3-butyne-2-ol.

9. A process for the preparation of the silicone composition according to any one of claims 4 to 8, characterized in that, The method comprises the following steps: The weighed long-chain alkyl silicone resin, silicone polymer, fumed silica, inhibitor and platinum catalyst are mixed uniformly, and then taken out for vacuum degassing for 5-20 min to obtain the silicone composition.

10. Application of the silicone composition according to any one of claims 4-8 to encapsulation of a Mini / Micro LED display panel.

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