Long-chain alkyl organic silicon resin and preparation method thereof, organic silicon composition and preparation method and application thereof

Abstract

The invention provides long-chain alkyl organic silicon resin and a preparation method thereof, an organic silicon composition and a preparation method and application of the organic silicon composition, and the organic silicon composition is prepared by mixing organic silicon resin containing long-chain alkyl, vinyl phenyl silicon resin, hydrogen-containing phenyl silicon resin, an inhibitor, a platinum catalyst and the like. According to the present invention, the silicone composition can be directly formed after the high-speed shearing, the shape is substantially unchanged before and after the packaging curing, and the low viscosity is provided so as to easily achieve the glue spraying process and avoid the generation of the bubbles, such that the problems that the silicone composition in the prior art is difficult to achieve the balance of the high thixotropy and the low viscosity, and cannot easily achieve the high thixotropy and the low viscosity are solved; and the slow recovery speed of the colloid can cause the colloid to flow and be amorphous, so that inevitable bad influence is caused in actual use.

Description

Technical Field

[0001] The present application relates to the technical field of organic silicon materials, and specifically to an organic silicon composition having high thixotropy, relatively low viscosity, and the viscosity of which can be quickly restored after high shear thinning, as well as a preparation method and application thereof. Background Art In the prior art, in order to improve the thixotropic properties of optical materials, fumed silica containing hydroxyl groups on the surface is generally added as a thixotropic agent. However, the increase in fillers will cause a sharp increase in the consistency coefficient of the product, making it difficult to achieve a balance between high thixotropy and low viscosity. In addition, under the existing sizing process conditions, the fluid becomes thinner under the rapid shearing action of the ball needle of the dispensing machine. If the colloid viscosity recovers slowly, the colloid will flow amorphously, resulting in difficulty in making its height-to-diameter ratio consistent after curing, making it difficult for the chip to be located at the center of the circle, resulting in inconsistent chip optical paths, poor luminous efficiency, and affected visual effects. Therefore, it is urgent to develop a silicone high-shear fast-recovery thixotropic optical adhesive that can meet the packaging needs of the current high-definition display technology field.

[0002] Patent CN110055027A discloses a LED encapsulation 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, and modified nano-silicon dioxide; component B contains methylphenyl hydrogenated 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 hydrogenated silicone resin, tackifier, and concentrated cross-linking agent. The prepared medium refractive index LED encapsulation silicone rubber material has ultra-high transparency and transmittance, good heat resistance, high mechanical properties, good yellowing resistance, moderate thixotropy, and high viscosity (≥15000mPa·s) Therefore, with the development of technology, especially in the field of ultra-high-definition display, the development of packaging technology has put forward more stringent requirements for silicone encapsulants: (1) Silicone encapsulation materials have high thixotropy and low viscosity to facilitate the implementation of the gluing process and avoid problems such as bubbles and drawing; (2) The viscosity of the encapsulation glue can be quickly restored after high shear thinning to ensure that the dispensing can be directly formed after high-speed shearing, and the shape remains basically unchanged before and after the encapsulation is cured. Summary of the invention

[0003] In order to solve the above technical problems, the present application provides a long-chain alkyl silicone resin and a preparation method thereof, and a high-shear fast-recovery silicone composition, wherein the composition contains a long-chain alkyl silicone resin, a vinyl silicone resin and a hydrogenated silicone resin, fumed silica, an inhibitor and a platinum catalyst. The composition has a relatively low viscosity and a high thixotropy, and in particular, after high-speed shear during sizing, the viscosity can be quickly restored, so as to help the colloid maintain a high consistency in height-to-diameter ratio and a high transmittance before and after curing, thereby resulting in a consistent optical path of the packaged chip and high luminous efficiency.

[0004] The organosilicon composition is composed of the following components in parts by weight:

[0005] The organic silicon polymer includes hydrogenated phenyl silicone resin and vinyl phenyl silicone resin without long chain structure. Preferably, the hydrogenated phenyl silicone resin can be a mixture of high viscosity hydrogenated phenyl silicone resin and low viscosity hydrogenated phenyl silicone resin.

[0006] Preferably, the vinyl content of the vinylphenyl silicone resin is 1.5-12%, the phenyl content is 5-30%, and the viscosity is 640000-660000 mPa·s; more preferably, the vinyl mass content is 5.71%, the phenyl content is 16.28%, and the viscosity is 650000 mPa·s.

[0007] Preferably, the high-viscosity hydrogenated 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 hydrogenated silicone resin with a hydrogen content of 0.32%, a phenyl content of 20%, and a viscosity of 6000 mPa·s is selected.

[0008] Preferably, the low-viscosity hydrogenated phenyl silicone resin may have 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 hydrogenated phenyl silicone resin with a hydrogen content of 0.91%, a phenyl content of 23.28%, and a viscosity of 500 mPa·s is selected.

[0009] Preferably, the specific surface area of ​​the fumed silica is 300 to 500 m 2 / g, preferably with a specific surface area of ​​300m 2 / g of gas silicon.

[0010] 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-butyn-2-ol; more preferably, the inhibitor is 1-ethynylcyclohexanol. Of course, other additives such as tackifiers and diluents can be added depending on the specific situation.

[0011] Preferably, the platinum catalyst includes at least one of platinum black, platinum halide, platinum-olefin complex, platinum-alcohol complex, platinum-hydrocarbon oxide complex, platinum-ether complex, platinum-aldehyde complex, platinum-ketone complex, platinum-vinylsiloxane complex, bis(γ-methyl-pyridyl)-platinum dichloride, trimethylenedipyridyl-platinum dichloride, dicyclopentadienyl-platinum dichloride, cyclooctadiene-platinum dichloride, cyclopentadiene-platinum dichloride, bis(alkynyl)bis(triphenylphosphine)-platinum complex, and bis(alkynyl)(cyclooctadiene)-platinum complex; more preferably, the platinum halide includes at least one of PtCl4, H2PtCl6·6H2O, Na2PtCl6·4H2O, and H2PtCl6·6H2O.

[0012] The long-chain alkyl silicone resin is a silicone resin containing a long-chain alkyl group, preferably a silicone resin containing an alkenyl group and a long-chain alkyl group, or a silicone resin containing a long-chain alkyl group and a hydrogen group, or a mixture of the two; wherein the structural formula of the silicone resin containing a long-chain alkyl group can be expressed as follows: (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 to R9 are groups connected to silicon atoms, R1, R2, and R3 are alkyl groups with 1 to 6 carbon atoms; R4 is an alkenyl group or a hydrogen group, preferably a vinyl group; R5 and R6 are methyl or phenyl groups, R7 is a methyl group; R8 is a phenyl group; R9 is a long-chain alkyl group with 6 to 18 carbon atoms; Wherein 0≤g≤0.2, a, b, c, d, e, and 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, where 0<e<0.5, and 0<f<0.5; More preferably, 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.

[0013] The organic silicon composition, wherein the ratio of the total molar amount of alkenyl groups to the total molar amount of hydrogen groups is 1:0.8 to 1:1.2; the inventor unexpectedly discovered that when the molar ratio N of the long-chain alkyl group to the phenyl group contained in the long-chain alkyl organic silicon resin is 0.5 to 1.3, the viscosity of the organic silicon composition has a faster recovery after high shear rapid sizing and the light transmittance of the cured product is better. In particular, when the N value is 0.7 to 1.2, the above performance is better.

[0014] Preferably, the method for preparing the long-chain alkyl silicone resin comprises the following steps: 1) Proportionally convert the structure R7Si(OR 10 )3 siloxane I, having the structure R8Si(OR 11 )3 siloxane II, having the structure R9Si(OR 12 )3 Siloxane III, having the structure Si(OR 13 )4 siloxane monomer IV, having the structure R5R6Si(OR 14 )2 siloxane monomer V, end-capping agent VI, 5-15wt% anhydrous ethanol and end-capping agent VII are added into a reaction container, and under the condition of a constant oil temperature of 20-50°C, a 0.2wt% trifluoromethanesulfonic acid aqueous solution is slowly dripped into it, and the temperature is raised to 50-80°C for reaction for 3-5h to obtain a semi-finished product A.

[0015] 2) The semi-finished product A in step 1) is heated to 80-100° C. to evaporate the reaction by-products, toluene and anhydrous sodium carbonate are added and stirred for 20-30 minutes, and 0.05-0.2 wt% potassium hydroxide is added overnight to react at 110-135° C. and 200 r / min for 5-6 hours to promote the condensation reaction. After the reaction is completed, the obtained product is washed with water to a pH value of 7-8, and the solvent and low-boiling substances are removed under reduced pressure. After no bubbles emerge, a long-chain alkyl silicone resin is obtained.

[0016] Among them, R 10 , R 11 , R 12 , R 13 , R 14 is an alkyl group with 1 to 6 carbon atoms, preferably a methyl group, an ethyl group or a propyl group; preferably, the group having the structure R7Si(OR 10 ) The siloxane monomer I of 3 is at least one of methyltrimethoxysilane and methyltriethoxysilane; The structure R8Si(OR11 ) Siloxane II of 3 is at least one of phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane and methyltriethoxysilane; The structure R9Si(OR 12 ) The siloxane monomer III of 3 is at least one of hexyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane and dodecyltriethoxysilane; The Si(OR 13 ) Siloxane IV of 4 is at least one of tetramethyl silicate, tetraethyl silicate and tetrapropyl silicate; The structure R5R6Si(OR 14 ) Siloxane V in 2 is at least one of diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, dimethyldimethoxysilane and dimethyldiethoxysilane; The end-capping agent VI is at least one of hexamethyldisiloxane, hexaethyldisiloxane, and hexapropyldisiloxane; The end-capping agent VII is at least one of 1,3-divinyltetramethyldisiloxane, 1,3-divinyltetraphenyldisiloxane, 1,3-tetravinyldimethyldisiloxane, and hexavinyldisiloxane.

[0017] On the other hand, the present application also provides a method for preparing the above-mentioned organosilicon composition, comprising the following steps: The weighed long-chain alkyl silicone resin, silicone polymer, fumed silica, inhibitor and platinum catalyst are fully mixed and taken out for vacuum degassing for 5-20 minutes to obtain the silicone composition.

[0018] The present application also provides an application of a silicone composition in Mini / Micro LED display panel packaging.

[0019] Compared with the prior art, the present invention has the following beneficial effects: The present application provides a long-chain alkyl silicone resin and a preparation method thereof, and also provides an organosilicon composition and a preparation method and application thereof, wherein the composition contains 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, and the organosilicon composition has the ability to recover quickly to ensure that dispensing can be directly molded after high-speed shearing, and the shape remains basically unchanged before and after encapsulation and curing; the organosilicon composition has a relatively low viscosity to facilitate the implementation of the spraying process and avoid the generation of bubbles. DETAILED DESCRIPTION

[0020] The present invention will be further described below in conjunction with embodiments: (1) Preparation of long-chain alkyl silicone resin Preparation Example 1: Synthesis of long-chain alkyl vinyl long-chain alkyl silicone resin 61 0.34 mol of phenyltrimethoxysilane, 0.44 mol of hexyltrimethoxysilane, 0.44 mol of methyltrimethoxysilane, 0.20 mol of vinyl double-end cap, 0.04 mol of methyl double-end cap and 0.30 mol of anhydrous ethanol were added to a 500 ml four-necked flask, and the oil temperature was set to 40°C; then a 0.2 wt% aqueous solution of trifluoromethanesulfonic acid was slowly dripped into the flask using a constant pressure dropping funnel, wherein the content of trifluoromethanesulfonic acid was 0.005 mol; after the addition was completed, After completion, the reaction was carried out at a constant temperature of 60°C for 3 hours; at 90°C, the alcohol-water mixture was evaporated; 200g toluene and 0.86g anhydrous sodium carbonate were added and stirred for 20min; then 0.1wt% potassium hydroxide was added and reacted at 120°C for 5h to promote the condensation reaction; then washed with water 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 vacuum distillation. After no bubbles emerged, the phenyl content was 13.71%, N was 1.29, and the vinyl content was 5.71%.

[0021] The general structural formula of long-chain alkyl vinyl long-chain alkyl silicone resin 61 is: (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 .

[0022] Preparation Example 2: Synthesis of Long-chain Alkyl Vinyl Long-chain Alkyl Silicone Resin 121 0.42 mol of phenyltrimethoxysilane, 0.48 mol of dodecyltrimethoxysilane, 0.48 mol of methyltrimethoxysilane, 0.23 mol of vinyl double-end cap, 0.05 mol of methyl double-end cap and 0.35 mol of anhydrous ethanol were added into a 500 ml four-necked flask, and the oil temperature was set to 40°C; then a 0.2 wt% aqueous solution of trifluoromethanesulfonic acid was slowly dripped into the flask using a constant pressure dropping funnel, wherein the content of trifluoromethanesulfonic acid was 0.007 mol; and After completion, the reaction was carried out at a constant temperature of 60°C for 3 hours; at 90°C, the alcohol-water mixture was evaporated; 200g toluene and 1.04g anhydrous sodium carbonate were added and stirred for 20min; then 0.1wt% potassium hydroxide was added and reacted at 120°C for 5h to promote the condensation reaction; then washed with water 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 vacuum distillation. After no bubbles emerged, the phenyl content was 13.71%, N was 1.14, and the vinyl content was 5.05%.

[0023] The general structural formula of long-chain alkyl vinyl long-chain alkyl silicone resin 121 is: (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 .

[0024] Preparation Example 3: Synthesis of Long-chain Alkyl Vinyl Alkyl Silicone Resin 181 0.34 mol of phenyltrimethoxysilane, 0.34 mol of octadecyltrimethoxysilane, 0.34 mol of methyltrimethoxysilane, 0.17 mol of vinyl double-end cap, 0.03 mol of methyl double-end cap and 0.26 mol of anhydrous ethanol were added to a 500 ml four-necked flask, and the oil temperature was set to 40°C; then a 0.2 wt% aqueous solution of trifluoromethanesulfonic acid was slowly dripped into the flask using a constant pressure dropping funnel, wherein the content of trifluoromethanesulfonic acid was 0.005 mol; after the addition was completed, After completion, react at a constant temperature of 60°C for 3 hours; at 90°C, evaporate the alcohol-water mixture; add 200g toluene and 0.80g anhydrous sodium carbonate and stir for 20min; add 0.1wt% potassium hydroxide overnight and react at 120°C for 5h to promote the condensation reaction; then wash with water until the pH value is 7-8; transfer the product to a round-bottom flask, and distill under reduced pressure to remove the solvent and low-boiling substances. After no bubbles emerge, the phenyl content is 13.19%, N is 1.0, and the vinyl content is 4.63%.

[0025] The general structural formula of long-chain alkyl vinyl long-chain alkyl silicone resin 181 is: (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 .

[0026] Preparation Example 4 Synthesis of long-chain alkyl vinyl long-chain alkyl silicone resin 62 0.17 mol of diphenyldimethoxysilane, 0.38 mol of hexyltrimethoxysilane, 0.38 mol of methyltrimethoxysilane, 0.17 mol of vinyl double-end cap, 0.03 mol of methyl double-end cap and 0.28 mol of anhydrous ethanol were added to a 500 ml four-necked flask, and the oil temperature was set to 40°C; then a 0.2 wt% aqueous solution of trifluoromethanesulfonic acid was slowly dripped into the flask using a constant pressure dropping funnel, wherein the content of trifluoromethanesulfonic acid was 0.009 mol; after the addition was completed, After completion, the mixture was reacted at a constant temperature of 60°C for 3 hours; at 90°C, the alcohol-water mixture was evaporated; 150g toluene and 0.63g anhydrous sodium carbonate were added and stirred for 20 minutes; then 0.1wt% potassium hydroxide was added and reacted at 120°C for 5 hours to promote the condensation reaction; then the mixture was washed with water 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 vacuum distillation. After no bubbles emerged, the phenyl content was 17.81%, N was 1.12, and the vinyl content was 6.24%.

[0027] The general structural formula of long-chain alkyl vinyl long-chain alkyl silicone resin 62 is: (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 .

[0028] Preparation Example 5 Synthesis of long-chain alkyl vinyl long-chain alkyl silicone resin 122 0.13 mol of diphenyldimethoxysilane, 0.20 mol of dodecyltrimethoxysilane, 0.20 mol of methyltrimethoxysilane, 0.10 mol of vinyl double-end cap, 0.02 mol of methyl double-end cap and 0.16 mol of anhydrous ethanol were added into a 500 ml four-necked flask, and the oil temperature was set to 40°C; then a 0.2 wt% aqueous solution of trifluoromethanesulfonic acid was slowly dripped into the flask using a constant pressure dropping funnel, wherein the content of trifluoromethanesulfonic acid was 0.009 mol; and After completion, the reaction was carried out at a constant temperature of 60°C for 3 hours; at 90°C, the alcohol-water mixture was evaporated; 140g of toluene and 0.72g of anhydrous sodium carbonate were added and stirred for 20 minutes; then 0.1wt% of potassium hydroxide was added and reacted at 120°C for 5 hours to promote the condensation reaction; then washed with water 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 vacuum distillation. After no bubbles emerged, the phenyl content was 18.99%, N was 0.77, and the vinyl content was 5.12%.

[0029] The general structural formula of long-chain alkyl vinyl long-chain alkyl silicone resin 122 is: (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 .

[0030] Preparation Example 6: Synthesis of Long-chain Alkyl Vinyl Alkyl Silicone Resin 182 0.14 mol of diphenyldimethoxysilane, 0.18 mol of octadecyltrimethoxysilane, 0.18 mol of methyltrimethoxysilane, 0.10 mol of vinyl double-end cap, 0.02 mol of methyl double-end cap and 0.16 mol of anhydrous ethanol were added into a 500 ml four-necked flask, and the oil temperature was set to 40°C; then a 0.2 wt% aqueous solution of trifluoromethanesulfonic acid was slowly dripped into the flask using a constant pressure dropping funnel, wherein the content of trifluoromethanesulfonic acid was 0.008 mol; and After completion, the reaction was carried out at a constant temperature of 60°C for 3 hours; at 90°C, the alcohol-water mixture was evaporated; 200g toluene and 0.72g anhydrous sodium carbonate were added and stirred for 20min; after overnight, 0.1wt% potassium hydroxide was added and reacted at 120°C for 5h to promote the condensation reaction; then washed with water 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 vacuum distillation. After no bubbles emerged, the phenyl content was 18.46%, N was 0.75, and the vinyl content was 4.62%.

[0031] The general structural formula of long-chain alkyl vinyl long-chain alkyl silicone resin 182 is: (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 .

[0032] Preparation Example 7 Synthesis of long-chain alkyl vinyl long-chain alkyl silicone resin 63 0.45 mol of phenyltrimethoxysilane, 0.30 mol of hexyltrimethoxysilane, 0.30 mol of methyltrimethoxysilane, 0.30 mol of tetraethyl silicate, 0.20 mol of vinyl double-end cap, 0.04 mol of methyl double-end cap and 0.40 mol of anhydrous ethanol were added into a 500 ml four-necked flask, and the oil temperature was set to 40 ° C; then a 0.2 wt% aqueous solution of trifluoromethanesulfonic acid was slowly dripped into the flask using a constant pressure dropping funnel, wherein the content of trifluoromethanesulfonic acid was 0.005 m ol; after the addition is completed, the reaction is carried out at a constant temperature of 60°C for 3 hours; at 90°C, the alcohol-water mixture is evaporated; 200g toluene and 0.86g anhydrous sodium carbonate are added and stirred for 20min; after overnight, 0.1wt% potassium hydroxide is added and reacted at 120°C for 5h to promote the condensation reaction; then washed with water 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 vacuum distillation. After no bubbles emerge, the phenyl content is 16.14%, N is 0.67, and the vinyl content is 5.03%.

[0033] The general structural formula of long-chain alkyl vinyl long-chain alkyl silicone resin 63 is: (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 .

[0034] Preparation Example 8 Synthesis of Long-chain Alkyl Vinyl Alkyl Silicone Resin 123 0.50 mol phenyltrimethoxysilane, 0.30 mol dodecyltrimethoxysilane, 0.30 mol methyltrimethoxysilane, 0.30 mol tetraethyl silicate, 0.20 mol vinyl double-end cap, 0.04 mol methyl double-end cap and 0.30 mol anhydrous ethanol were added into a 500 ml four-necked flask, and the oil temperature was set to 40 ° C; then a 0.2 wt% trifluoromethanesulfonic acid aqueous solution was slowly dripped into the flask using a constant pressure dropping funnel, wherein the trifluoromethanesulfonic acid content was 0.005 mol; after the addition is completed, react at a constant temperature of 60°C for 3h; at 90°C, evaporate the alcohol-water mixture; add 200g toluene and 0.86g anhydrous sodium carbonate and stir for 20min; after overnight, add 0.1wt% potassium hydroxide and react at 120°C for 5h to promote its condensation reaction; then wash with water until the pH value is 7-8; transfer the product to a round-bottom flask, and distill under reduced pressure to remove the solvent and low-boiling substances. After no bubbles emerge, the phenyl content is 15.62%, N is 0.60, and the vinyl content is 4.38%.

[0035] The general structural formula of long-chain alkyl vinyl long-chain alkyl silicone resin 123 is: (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 .

[0036] Preparation Example 9 Synthesis of Long-chain Alkyl Vinyl Alkyl Silicone Resin 183 0.60 mol phenyltrimethoxysilane, 0.30 mol octadecyltrimethoxysilane, 0.30 mol methyltrimethoxysilane, 0.30 mol tetraethyl silicate, 0.20 mol vinyl double-end cap, 0.05 mol methyl double-end cap and 0.50 mol anhydrous ethanol were added into a 500 ml four-necked flask, and the oil temperature was set to 40 ° C; then a 0.2 wt% trifluoromethanesulfonic acid aqueous solution was slowly dripped into the flask using a constant pressure dropping funnel, wherein the trifluoromethanesulfonic acid aqueous solution was 0.2 wt% and ... The sulfonic acid content is 0.005 mol; after the addition is completed, the reaction is carried out at a constant temperature of 60°C for 3 hours; at 90°C, the alcohol-water mixture is evaporated; 200g toluene and 0.86g anhydrous sodium carbonate are added and stirred for 20 minutes; after overnight, 0.1wt% potassium hydroxide is added and reacted at 120°C for 5 hours to promote the condensation reaction; then washed with water 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 vacuum distillation. After no bubbles emerge, the phenyl content is 16.14%, N is 0.5, and the vinyl content is 3.77%.

[0037] The general structural formula of long-chain alkyl vinyl long-chain alkyl silicone resin 183 is: (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 .

[0038] Preparation Example 10 Synthesis of long-chain alkyl vinyl long-chain alkyl silicone resin 124 0.43 mol of phenyltrimethoxysilane, 0.09 mol of dodecyltrimethoxysilane, 0.09 mol of methyltrimethoxysilane, 0.10 mol of vinyl double-end cap, 0.02 mol of methyl double-end cap and 0.15 mol of anhydrous ethanol were added to a 500 ml four-necked flask, and the oil temperature was set to 40°C; then a 0.2 wt% aqueous solution of trifluoromethanesulfonic acid was slowly dripped into the flask using a constant pressure dropping funnel, wherein the content of trifluoromethanesulfonic acid was 0.003 mol; after the addition was completed, After completion, the reaction was carried out at a constant temperature of 60°C for 3 hours; at 90°C, the alcohol-water mixture was evaporated; 150g toluene and 0.44g anhydrous sodium carbonate were added and stirred for 20min; after overnight, 0.1wt% potassium hydroxide was added and reacted at 120°C for 5h to promote the condensation reaction; then washed with water 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 vacuum distillation. After no bubbles emerged, the phenyl content was 32.44%, N was 0.21, and the vinyl content was 5.23%.

[0039] The general structural formula of long-chain alkyl vinyl long-chain alkyl silicone resin 124 is: (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 .

[0040] (2) Preparation of silicone composition Embodiment 1: Take 20.3 g of long-chain alkyl-modified long-chain alkyl silicone resin 61, 47.4 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed for 10 min to obtain an organic silicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 22.53%.

[0041] Embodiment 2: Take 20.5 g of long-chain alkyl-modified long-chain alkyl silicone resin 121, 47.9 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed 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%.

[0042] Embodiment 3: Take 20.7 g of long-chain alkyl-modified long-chain alkyl silicone resin 181, 48.2 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed 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%.

[0043] Embodiment 4: Take 33.9 g of long-chain alkyl-modified long-chain alkyl silicone resin 61, 33.9 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed 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%.

[0044] Embodiment 5: Take 34.4 g of long-chain alkyl-modified long-chain alkyl silicone resin 121, 34.4 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed for 10 min to obtain an organic silicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 15.86%.

[0045] Embodiment 6: Take 34.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 181, 34.8 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 15.63%.

[0046] Embodiment 7: Take 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 62, 60.8 g of vinyl phenyl silicone resin (vinyl 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 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.91%.

[0047] Embodiment 8: Take 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 63, 61.2 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.77%.

[0048] Embodiment 9: Take 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 122, 61.2 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed 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%.

[0049] Embodiment 10: Take 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 123, 61.4 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed 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%.

[0050] Embodiment 11: Take 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 182, 61.3 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed 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%.

[0051] Embodiment 12: Take 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 183, 61.6 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed 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%.

[0052] Embodiment 13: Take 26.0 g of long-chain alkyl-modified long-chain alkyl silicone resin 121, 48.0 g of vinyl phenyl 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), 3 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed 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%.

[0053] Comparative Example 1: Take 71.3 g of vinyl phenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 14.1 g of hydrogenated phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 9.4 g of hydrogenated 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, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed for 10 minutes to obtain an organic silicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.77%.

[0054] Comparative Example 2: Take 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 61, 61.0 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 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, dispersed evenly using a high-speed disperser, and vacuum degassed for 10 minutes to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.62%. Comparative Example 3: Take 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 121, 61.2 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.61%.

[0055] Comparative Example 4: Take 6.8 g of long-chain alkyl-modified long-chain alkyl silicone resin 181, 61.3 g of vinyl phenyl 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), 5 g of fumed silica (specific surface area 300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed for 10 min to obtain an organic silicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.57%.

[0056] Comparative Example 5: Take 66.3 g of vinyl phenyl silicone resin (vinyl content 5.71%, phenyl content 16.28%, viscosity 650000 mPa·s), 10.6 g of hydrogenated phenyl silicone resin (hydrogen content 0.91%, phenyl content 23.28%, viscosity 500 mPa·s), 15.9 g of hydrogenated silicone resin (hydrogen content 0.32%, phenyl content 20%, viscosity 6000 mPa·s), 7 g of fumed silica (specific surface area 300 m 2 / g), 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, dispersed evenly using a high-speed disperser, and vacuum degassed for 10 minutes to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.44%. Comparative Example 6: Take 7.2 g of long-chain alkyl-modified long-chain alkyl silicone resin 124, 50.4 g of vinyl phenyl silicone resin (vinyl 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 of 5000 ppm) in a beaker, use a high-speed disperser to disperse evenly, vacuum degassing for 10 minutes, and obtain a silicone composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 15.40%. Comparative Example 7: Take 22.0 g of long-chain alkyl modified long-chain alkyl silicone resin 121, 48.0 g of vinyl phenyl silicone resin (vinyl mass content of 5.71%, phenyl content of 16.28%, viscosity of 650000mPa·s), 10.8 g of hydrogen-containing phenyl silicone resin (hydrogen content of 0.91%, phenyl content of 23.28%, viscosity of 500mPa·s), 16.2 g of hydrogen-containing silicone resin (hydrogen content of 0.32%, phenyl content of 20%, viscosity of 6000mPa·s), 3 g of fumed silica (specific surface area of ​​300 m 2 / g), 0.1 g of 1-ethynylcyclohexanol, and 0.1 g of platinum (0)-divinyltetramethyldisiloxane complex (platinum atomic mass concentration is 5000 ppm) are placed in a beaker, dispersed evenly using a high-speed disperser, and vacuum degassed for 10 min to obtain an organosilicon composition with a vinyl to hydrogen molar ratio of 1.05 and a phenyl content of 16.59%.

[0057] Table 1: Amounts of main components of the organosilicon compositions prepared in Examples 1-12 and Comparative Examples 1-6

[0058] (3) The organosilicon compositions obtained in Examples 1-12 and Comparative Examples 1-6 were tested 1. Determination of recovery percentage: The sample was tested in three stages using a rheometer, using a flat rotor with a diameter of 50 mm and a gap setting of 0.1 mm. The test was conducted at different 25°C using a rotation time scanning mode with three fixed shear rates. Stage 1: The shear rate was 1 s -1 Shearing time is 120s, stage 2: shearing rate is 100s -1 / 300s -1 / 500s -1 Shear time is 30s, stage 3: shear rate is 1s -1 Shear time is 120 s. The recovery rate (RR) is the ratio of the viscosity at a certain moment in the third stage to the stable viscosity in the first stage, where RR1 is the recovery rate at 10 s and RR0 is the recovery rate after the viscosity in the third stage stabilizes; 2. Determination of light transmittance: The light transmittance of the film sample (30mm*20mm*0.2mm) heat-cured at 100℃ for 30min was tested by UV-visible spectrophotometer, with air as blank control. The test temperature was 25℃ and the test wavelength was 450nm. The test results are shown in Table 2.

[0059] Table 2: Test results of Examples 1-12 and Comparative Examples 1-6

[0060] From the test results in Table 2, it can be seen that compared with Comparative Example 1, the recovery rate RR of the product with the addition of long-chain alkyl silicone resin is improved to a certain extent, and RR1 is increased by >10%, which has the characteristics of rapid recovery. Not only that, it also has high transparency. Adding about 5% of gas phase dioxide can recover ≥50% within 10s; the final recovery is ≥75%.

[0061] Compared with Comparative Example 2, the recovery rates of Examples 1 and 4 did not increase significantly, but were relatively close. However, their viscosities decreased with the increase of C61 content, indicating that the addition of C61 can keep RR relatively excellent while reducing its viscosity. Compared with Comparative Example 3, the recovery rates of Examples 2 and 5 first increase and then decrease. Since 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 in the system are affected, and the recovery rate is also affected accordingly, but it will eventually reach a balance point between chain entanglement and disentanglement. Therefore, as the chain length and its long-chain alkyl density increase, the recovery rate will not always be in an upward state. However, its viscosity will still decrease due to the increase in the content of the long-chain alkyl-modified phenyl silicone resin. Because its own viscosity is relatively low, it can also be used as a diluent to reduce the viscosity of the system.

[0062] Compared with Comparative Example 4, the recovery rates of Examples 3 and 6 also increase first and then decrease, and the transmittance also decreases. The reason for the decrease in transmittance is that the chain length is too long, which leads to a decrease in compatibility with the original system, causing the colloid to be slightly turbid and not completely transparent, and multiple liquid layers will be formed in the microstructure. The internal friction and inertia of the system are also more obvious, resulting in the final viscosity recovery being affected.

[0063] Compared with Comparative Examples 2 to 4, the viscosity of Examples 7 to 12 is different. The structure of the long-chain alkyl-modified phenyl silicone resin in Comparative Examples 2 to 4 is MT-type silicone resin, while 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 large. The reason is that the D segment is a linear structure, and the product obtained has a low viscosity, and the Q segment is a body structure. The molecular network structure formed is huge, and the system structure formed after mixing with other components is more complex, resulting in an increase in viscosity. In addition, its recovery rate also changes. When the N value is in the range of [0.7, 1.2], the recovery rate is relatively excellent, RR1>60%, RR0>85%.

[0064] Comparative Example 5 is a sample with a 7% fumed silica content. -1 The recovery after 10s under shear was 53.23%, and the final recovery was 86.77%. In Examples 7 to 12 and Comparative Examples 2 to 4, RR1 ≥ 50%, RR0 ≥ 70% of the long-chain alkyl modified silicone resin with 5% and 10% gas silicon content were added, and the viscosity was about 6000 mPa·s. Compared with Comparative Example 5, the viscosity reduction rate was ≥ 55%.

[0065] Compared with Comparative Example 6, the transmittance of the remaining examples is relatively high. The reason is that by precisely controlling the reaction monomer content, e is in the range of [0.23, 0.36] and N is also in the range of [0.5, 1.3], so that the refractive index of the mixed resin matches the refractive index of the gas-phase silica, resulting in a transmittance greater than 90% (450nm@25°C).

[0066] Comparative Example 7 is a sample with a 3% fumed silica content and a C121 content of 21.57%. Its RR1 and RR0 values ​​are better than those without the addition of long-chain alkyl silicone resin C. The surface of the fumed silica contains hydrogen bonds, and the hydrogen bonding effect also has a significant impact on the shear recovery of the material. Since the amount of long-chain alkyl content added is relatively small, the change in hydrogen bonds is higher than that of the long-chain alkyl. Therefore, compared with Example 2 in which the C121 content is 20% and the fumed silica content is 5%, the recovery rate is relatively high. Compared with Example 13, when the long-chain alkyl silicone resin C121 content is 25% and the fumed silica content is 3%, its recovery rate is equivalent to that of Example 2 in which the C121 content is 20% and the fumed silica content is 5%, but the viscosity of Example 13 is significantly lower.

[0067] Combining all the test results, it can be seen that the materials after different high-speed shearing still have the ability to recover quickly, and will have good application prospects in the face of higher-speed sizing processes in the future. For now, long-chain alkyl-modified phenyl silicone resin has excellent application potential in the field of ultra-high-definition display.

[0068] 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 in the protection scope of the present invention.

Claims

1. A long-chain alkyl silicone resin, characterized in that: The long-chain alkyl silicone resin is a silicone resin containing an alkenyl group and a long-chain alkyl group, or a silicone resin containing a long-chain alkyl group and a hydrogen group, or a mixture of the two. The general structural formula 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, and R3 are alkyl groups; R4 is an alkenyl group or a hydrogen group; R5 and R6 are methyl groups or phenyl groups, and R7 is a methyl group; R8 is a phenyl group; R9 is a long-chain alkyl group with 6 to 18 carbon atoms; wherein 0≤g≤0.2, a, b, c, d, e, and 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.

2. The method for preparing a long-chain alkyl silicone resin according to claim 1, comprising the following steps: 1) Proportionally convert the structure R7Si(OR 10 )3 siloxane I, having the structure R8Si(OR 11 )3 siloxane II, having the structure R9Si(OR 12 )3 Siloxane III, having the structure Si(OR 13 )4 siloxane monomer IV, having the structure R5R6Si(OR 14 )2 siloxane monomer V, end-capping agent VI, 5-15wt% anhydrous ethanol and end-capping agent VII are added to a reaction container, and under the condition of a constant oil temperature of 20-50°C, a 0.2wt% trifluoromethanesulfonic acid aqueous solution is slowly dripped, and the temperature is raised to 50-80°C for reaction for 3-5h to obtain a semi-finished product A; 2) The semi-finished product A in step 1) is heated to 80-100° C. to evaporate the reaction by-products, toluene and anhydrous sodium carbonate are added and stirred for 20-30 minutes, and 0.05-0.2 wt% potassium hydroxide is added overnight to react at 110-135° C. for 5-6 hours to promote the condensation reaction. After the reaction is completed, the obtained product is washed with water to a pH value of 7-8, and the solvent and low-boiling substances are removed under reduced pressure. When no bubbles emerge, a long-chain alkyl silicone resin is obtained.

3. The method for preparing a long-chain alkyl silicone resin according to claim 2, characterized in that: In step 1), the 10 ) The siloxane monomer I of 3 is at least one of methyltrimethoxysilane and methyltriethoxysilane; and / or The structure R8Si(OR 11 ) Siloxane II of 3 is at least one of phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane and methyltriethoxysilane; and / or The structure R9Si(OR 12 ) The siloxane monomer III of 3 is at least one of hexyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane and dodecyltriethoxysilane; and / or The Si(OR 13 ) Siloxane IV of 4 is at least one of tetramethyl silicate, tetraethyl silicate and tetrapropyl silicate; and / or The structure R5R6Si(OR 14 ) 2 Siloxane V is at least one of diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, dimethyldimethoxysilane and 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 at least one of 1,3-divinyltetramethyldisiloxane, 1,3-divinyltetraphenyldisiloxane, 1,3-tetravinyldimethyldisiloxane, and hexavinyldisiloxane.

4. An organosilicon composition, characterized in that: The organosilicon composition is composed of the following components in parts by weight: The organic silicon polymer includes hydrogen-containing phenyl silicone resin and vinyl phenyl silicone resin without long-chain structure.

5. The organosilicon composition according to claim 4, characterized in that: The ratio of the total molar amount of alkenyl groups to the total molar amount of hydrogen groups in the organic silicon composition is 1:0.8 to 1:1.

2.

6. The organosilicon 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 640000-660000 mPa·s.

7. The organosilicon composition according to claim 4, characterized in that: The hydrogenated phenyl silicone resin is a mixture of a high-viscosity hydrogenated phenyl silicone resin and / or a low-viscosity hydrogenated phenyl silicone resin; The high-viscosity hydrogenated 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; The low-viscosity hydrogenated phenyl silicone resin may have a hydrogen group content of 0.1 to 1.0%, a phenyl group content of 5 to 30%, and a viscosity of 400 to 600 mPa·s.

8. The organosilicon composition according to claim 1 or 2, 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-butyn-2-ol.

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

10. Use of the organosilicon composition according to any one of claims 4 to 8 in Mini / Micro LED display panel packaging.

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