Phenyl-sulfydryl-hydrogen-containing organic silicone oil as well as preparation method and application thereof

Abstract

The invention relates to the technical field of optical materials, in particular to phenyl-sulfydryl-hydrogen-containing organic silicone oil as well as a preparation method and application thereof. The preparation method of the phenyl-sulfydryl-hydrogen-containing organic silicone oil comprises the following steps: under the irradiation of ultraviolet rays, reacting a compound with a structure as shown in a formula II with a disulfydryl-containing high-refractive index monomer in a first solvent to obtain the phenyl-sulfydryl-hydrogen-containing organic silicone oil, wherein x is an integer greater than 1. According to the invention, the phenyl group and the sulfur-containing group with high refractive index are combined into the same molecular structure, so that the refractive index is improved, and the transparency is kept good. The OCR liquid optical cement prepared from the phenyl-sulfydryl-hydrogen-containing organic silicone oil prepared by the preparation method disclosed by the invention is relatively excellent in transparency, refractive index, bonding strength and weather resistance after being cured, and is suitable for bonding various materials. The OCR liquid optical cement is composed of two components, a certain operation time is provided after the two components are fully mixed, and the curing temperature is low.

Description

Technical Field

[0001] The present invention relates to the technical field of optical materials, and in particular to a phenyl-mercapto-hydrogen-containing organic silicone oil, a preparation method and application thereof. Background Art

[0002] Optical adhesives are specialized adhesives with optical properties, used to bond glass cover plates, touch screens, and LCD modules, providing a seamless bond. Currently, the adhesives used in the industry are divided into two main categories: solid OCA (Optically Clear Adhesive) and liquid OCR / LOCA (Liquid Optical Clear Adhesive). OCA adhesives must be tailored to the appropriate size based on the screen being bonded. With the rapid development of ultra-large, flexible, curved, and customized displays, the shortcomings of solid OCA adhesives are becoming increasingly apparent, including inconvenient handling, prone to bubbles, poor stability, and poor adhesion to curved surfaces. Liquid OCR adhesives, on the other hand, offer advantages such as high fluidity, excellent gap-filling properties, minimal cure shrinkage, and resistance to yellowing. They are widely used for bonding large screens, curved surfaces, and complex structures, playing a crucial role in advanced smart displays such as flexible foldable and curved screens and in-vehicle interactive screens.

[0003] There are two types of liquid OCR optical adhesives currently in widespread use on the market, categorized by material: acrylic and silicone. Acrylic adhesives are primarily composed of polyurethane or rubber-modified acrylates, while silicone adhesives are primarily composed of polydimethylsiloxane. Acrylic adhesives typically use UV curing, which transforms the initial intermolecular forces from van der Waals forces to covalent bonds after the reaction. This reduces the intermolecular distance by at least half, causing volume shrinkage. Furthermore, the curing time is only a dozen seconds, too fast for the polymer chains to relax. These two factors contribute to a high cure shrinkage rate, ranging from 1% to 4%. Silicone adhesives, on the other hand, typically use heat curing, curing through a hydrosilylation reaction between Si-H bond compounds and unsaturated organic compounds. This relatively long cure time allows the polymer chains to reach equilibrium, resulting in a lower cure shrinkage rate of less than 0.5%. This effectively prevents the forces generated by the adhesive's curing shrinkage, which can cause uneven display and MURA (mud-like spots) on LCD screens.

[0004] Xianpeng Fan(Fan X,Cao X,Shang X,et al.A transparent cyclo-linearpolyphenylsiloxane elastomer integrating high refractive index,thermalstability and flexibility[J].Polymer Chemistry, 2021, 12(36): 5149-5158) A new type of cyclic linear structure high phenyl content silicone elastomer was prepared by a "one-pot" hydrosilylation reaction using the reactivity difference of cyclic-diphenyl polysiloxane crosslinkers. The cyclic linear structure was prepared by the hydrosilylation reaction of 1,5-dimethyl-1,5-divinyl-3,3,7,7-tetraphenylcyclotetrasiloxane (ViPh-Cyclo) and α, ω-bis(dimethylsiloxy)polydiphenylsiloxane oligomer (H-Ph-Linear), and then reacted with α, ω-bis(methyldivinylsiloxy)poly(methylvinylsiloxane-diphenylsiloxane) (ethylene-phenyl crosslinker) to form a high polymerization degree cyclic linear high phenyl polysiloxane elastomer (Ph-CLS-Es). Ph-CLS-Es is a transparent elastomer with a refractive index ≥1.58, a Td 5wt% ≥437°C, and a maximum elongation at break of 189%. Its flexibility increases with the content of cyclic linear units, achieving a combination of high refractive index, excellent flexibility, and thermal stability, achieving both hardness and flexibility. However, this material is more suitable for packaging materials, with a transparency of around 83%. However, this transparency is far from sufficient for optical adhesives, and due to its high viscosity, the processing temperature reaches 200°C, which is not suitable for bonding optical materials. Furthermore, after curing, it becomes a permanent solid elastomer, losing the "liquid coating-solid bonding" characteristics of traditional optical adhesives. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a phenyl-mercapto-hydrogen-containing silicone oil, a preparation method and application thereof. The OCR liquid optical adhesive prepared by the phenyl-mercapto-hydrogen-containing silicone oil prepared by the present invention has better transparency, refractive index, bonding strength and weather resistance after curing.

[0006] The present invention provides a method for preparing a phenyl-mercapto-hydrogen-containing organosilicon oil, comprising the following steps:

[0007] Under ultraviolet irradiation, a compound having a structure shown in Formula II is reacted with a high refractive index monomer containing a dithiol group in a first solvent to obtain a phenyl-thiol-hydrogen-containing organic silicone oil;

[0008]

[0009] Here, x is an integer greater than 1.

[0010] Preferably, the refractive index of the high-refractive-index monomer containing a dithiol group is greater than 1.5;

[0011] The high refractive index monomer containing a dithiol group is selected from 4,4-dimercaptodiphenyl sulfide, 4,4'-[dithiobis(4,1-phenylthio)]bis-benzenethiol, 2,5-dimethylmercapto-1,4-dithiane, 1,6-dimercapto-3-hexyl sulfide, 2-mercaptoethyl sulfide, 2,2'-[1,2-ethylenediylbis(thio)]bisethanethiol or 4,4'-[1,4-phenylenebis(thio)]bis-benzenethiol.

[0012] Preferably, the method for preparing the compound having the structure shown in Formula II comprises the following steps:

[0013] Mixing the compound having the structure represented by Formula IV and a bisvinylmethylsiloxane end-capping agent to obtain a mixed solution;

[0014] Add dilute hydrochloric acid dropwise to the mixture while stirring, and react at 60-80° C. to obtain a compound having the structure shown in Formula II;

[0015]

[0016] Here, x is an integer greater than 1.

[0017] Preferably, the bisvinylmethylsiloxane end-capping agent is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

[0018] Preferably, the method for preparing the compound having the structure represented by Formula IV comprises the following steps:

[0019] Diphenylsilanediol and methyldichlorosilane are reacted in a second solvent under a catalyst, filtered, and the resulting solution is washed to neutrality. The product is precipitated with ethanol and recrystallized to obtain a compound having the structure shown in Formula VI;

[0020] During the recrystallization separation process, the first separated liquid is collected, and the separated liquid is placed at 0-4° C. for 22-26 hours, and the precipitate is removed to obtain a compound having the structure shown in Formula IV;

[0021]

[0022] Preferably, the catalyst is selected from diethylamine, dimethylamine or tetramethylammonium hydroxide;

[0023] The second solvent is selected from toluene, hexane, acetone, dichloromethane or tetrahydrofuran;

[0024] The molar ratio of the diphenylsilanediol to methyldichlorosilane is 1:0.5-2.

[0025] Preferably, the molar ratio of the compound having the structure shown in Formula IV to the bisvinylmethylsiloxane end-capping agent is 3 to 5:1;

[0026] The reaction time is 3 to 5 hours;

[0027] After the reaction, the method further comprises:

[0028] The mixture was washed with deionized water until neutral, dried, and rotary evaporated to obtain an oily product containing a divinyl end-capping group, namely, a compound having the structure shown in Formula II.

[0029] Preferably, the first solvent is selected from toluene, hexane, acetone, dichloromethane or tetrahydrofuran;

[0030] The reaction is carried out under protective gas conditions;

[0031] After the reaction, the method further comprises:

[0032] The product is precipitated in methanol, excess by-products are washed away, and the product is vacuum dried to obtain phenyl-mercapto-hydrogen-containing organosilicon oil.

[0033] The present invention also provides a phenyl-mercapto-hydrogen-containing organic silicone oil prepared by the preparation method described above.

[0034] The present invention also provides an OCR optical adhesive, which is prepared from raw materials including component A and component B;

[0035] The component A comprises a polysiloxane containing Si-CH=CH2;

[0036] The component B includes phenyl-mercapto-hydrogen-containing organosilicon oil; the phenyl-mercapto-hydrogen-containing organosilicon oil is the phenyl-mercapto-hydrogen-containing organosilicon oil described above.

[0037] Preferably, the component A comprises, by weight:

[0038] 30-80 parts of vinyl-terminated methylphenyl vinyl silicone oil;

[0039] 30-60 parts of vinyl-terminated phenyl vinyl silicone oil;

[0040] 0.2-0.5 parts of platinum catalyst;

[0041] The viscosity of the vinyl-terminated methylphenyl vinyl silicone oil is 500 to 2000 MPa·s;

[0042] The platinum catalyst is a tetramethyldivinylsilane complex of chloroplatinic acid;

[0043] The component B comprises, by weight fraction:

[0044] End vinyl methyl phenyl vinyl silicone oil 20-60 parts;

[0045] Phenyl-mercapto-hydrogen-containing silicone oil 5-15 parts;

[0046] End hydrogen-containing methyl phenyl hydrogen-containing silicone oil 5-15 parts;

[0047] The viscosity of the end vinyl methyl phenyl vinyl silicone oil is 500-2000 Mpa·s;

[0048] The viscosity of the end hydrogen-containing methyl phenyl hydrogen-containing silicone oil is 100-300 Mpa·s.

[0049] The application also provides a preparation method of the above-mentioned OCR optical glue, comprising the following steps:

[0050] The glue solution after mixing component A and component B is placed on a glass cover plate, scraped flat, and placed to remove bubbles, another glass cover plate is laid on the glue solution after removing bubbles, and heated and cured.

[0051] Preferably, the mass ratio of the component A and the component B is 90-100: 90-100.

[0052] The application comprises designing a synthesis method, combining a high refractive phenyl group and a sulfur-containing group into the same molecular structure, realizing the combination of organic silicon material and sulfur-containing material in the current optical glue field, and achieving the effect of mutual benefit; designing and synthesizing a random macromolecular organic silicon polymer with organic silicon as the main chain segment, sulfur group, benzene ring or aromatic ring coexisting; starting from raw materials, synthesizing a monomer with high refractive index and good transparency, determining the optimal ratio of phenyl and sulfur content, and reducing the occurrence of dispersion phenomenon. While ensuring the high refractive index of the optical glue, the balance between the viscosity and the bonding performance is adjusted to adapt to the bonding of large-size, special-shaped structure screens, and the optical glue with certain flow performance and gap filling property is obtained.

[0053] The application combines a high refractive phenyl group and a sulfur-containing group into the same molecular structure, the refractive index is no longer blindly dependent on the increase of the phenyl content, the introduction of S-containing substances also increases the refractive index, and the refractive index is improved while maintaining good transparency. The OCR liquid optical glue prepared by using the phenyl-mercapto-hydrogen-containing silicone oil prepared by the application has good transparency, refractive index, bonding strength and weather resistance after curing, and is suitable for pasting various materials. The OCR liquid optical glue is two components, has a certain operation time after mixing, and has a low curing temperature. BRIEF DESCRIPTION OF DRAWINGS

[0054] Figure 1 This is the H NMR spectrum of the phenyl-mercapto-hydrogen-containing silicone oil of Example 1 of the present invention. DETAILED DESCRIPTION

[0055] The following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0056] The present invention provides a method for preparing a phenyl-mercapto-hydrogen-containing organosilicon oil, comprising the following steps:

[0057] Under ultraviolet irradiation, a compound having a structure shown in Formula II is reacted with a high refractive index monomer containing a dithiol group in a first solvent to obtain a phenyl-thiol-hydrogen-containing organic silicone oil;

[0058]

[0059] Here, x is an integer greater than 1.

[0060] In some embodiments of the present invention, the refractive index of the high-refractive-index monomer containing a dithiol group is greater than 1.5. It can be 4,4-dimercaptodiphenyl sulfide having the structure shown in Formula III-1, 4,4′-[dithiobis(4,1-phenylthio)]bis-benzenethiol having the structure shown in Formula III-2, 2,5-dimethylmercapto-1,4-dithiane having the structure shown in Formula III-3, 1,6-dimercapto-3-hexyl sulfide having the structure shown in Formula III-4, 2-mercaptoethyl sulfide having the structure shown in Formula III-5, 2,2′-[1,2-ethanediylbis(thio)]bisethanethiol having the structure shown in Formula III-6, or 4,4′-[1,4-phenylenebis(thio)]bis-benzenethiol having the structure shown in Formula III-7.

[0061]

[0062] In some embodiments of the present invention, the method for preparing the compound having the structure shown in Formula II comprises the following steps:

[0063] Mixing a compound having a structure represented by Formula IV, a bisvinylmethylsiloxane end-capping agent, and a second catalyst to obtain a mixed solution;

[0064] Add dilute hydrochloric acid dropwise to the mixture while stirring, and react at 60-80° C. to obtain a compound having the structure shown in Formula II;

[0065]

[0066] Here, x is an integer greater than 1.

[0067] In some embodiments of the present invention, the bisvinylmethylsiloxane end-capping agent is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane having the structure shown in Formula V;

[0068]

[0069] In some embodiments of the present invention, the method for preparing the compound having the structure represented by Formula IV comprises the following steps:

[0070] In the presence of a catalyst, diphenylsilanediol and methyldichlorosilane are reacted in a second solvent, filtered, and the resulting solution is washed until neutral. The product is precipitated with ethanol and recrystallized to obtain a white crystalline powder, i.e., a compound having the structure represented by Formula VI (product a);

[0071] During the recrystallization separation process, the first separated liquid is collected and placed at 0-4° C. for 22-26 hours, and the precipitate is removed to obtain a transparent oil-like product, i.e., a compound having the structure shown in Formula IV (product b);

[0072]

[0073] The structure of the diphenylsilanediol is shown in Formula VII; the structure of the methyldichlorosilane is shown in Formula VIII;

[0074]

[0075] In some embodiments of the present invention, the catalyst is selected from diethylamine, dimethylamine or tetramethylammonium hydroxide;

[0076] In some embodiments of the present invention, the second solvent is selected from toluene, hexane, acetone, dichloromethane or tetrahydrofuran.

[0077] In some embodiments of the present invention, the molar ratio of diphenylsilanediol to methyldichlorosilane is 1:0.5-2, such as 1:1.

[0078] In some embodiments of the present invention, the reaction temperature of the diphenylsilanediol and methyldichlorosilane in the solvent is room temperature, such as 25° C., and the reaction time is 22 to 26 hours, such as 24 hours. The reaction is a stirring reaction.

[0079] After obtaining the compound having the structure shown in Formula IV, the compound having the structure shown in Formula IV and a bisvinylmethylsiloxane end-capping agent are mixed to obtain a mixed solution;

[0080] Dilute hydrochloric acid is added dropwise to the mixed solution while stirring, and the reaction is carried out at 60-80° C. to obtain a compound having the structure shown in Formula II.

[0081] In some embodiments of the present invention, the molar ratio of the compound having the structure represented by Formula IV to the bisvinylmethylsiloxane end-capping agent is 3 to 5:1, such as 4.4:1.

[0082] In some embodiments of the present invention, dilute hydrochloric acid acts as an acidic catalyst to promote the condensation reaction and control the direction of the reaction. The dilute hydrochloric acid is obtained by diluting concentrated hydrochloric acid with THF; the concentration of the dilute hydrochloric acid is 0.2 to 0.4 mol / L, such as 0.3 mol / L.

[0083] In some embodiments of the present invention, the reaction temperature is 75° C. and the reaction time is 3 to 5 hours, such as 4 hours.

[0084] In some embodiments of the present invention, after the reaction, the method further comprises:

[0085] The mixture was washed with deionized water until neutral, dried, and rotary evaporated to obtain an oily product containing a divinyl end cap, namely, a compound having the structure shown in Formula II (product c).

[0086] After obtaining the compound having the structure shown in formula II, the compound having the structure shown in formula II is reacted with a high refractive index monomer containing a dithiol group in a first solvent under ultraviolet irradiation to obtain phenyl-thiol-hydrogen-containing organic silicone oil.

[0087] The reaction does not require a catalyst and is a thiol-ene click reaction, wherein ultraviolet light initiates the addition of thiol radicals (S·) to vinyl groups (C═C) to form C—S bonds (no additional photoinitiator is required).

[0088] In some embodiments of the present invention, the first solvent is selected from toluene, hexane, acetone, dichloromethane or tetrahydrofuran.

[0089] In some embodiments of the present invention, the ultraviolet light has a wave number of 365 nm and a power of 120 W.

[0090] In some embodiments of the present invention, the reaction is carried out under protective gas conditions; the protective gas may be nitrogen.

[0091] In some embodiments of the present invention, the reaction is carried out under stirring. The initial stirring rate of the reaction is 300 to 500 rpm, such as 400 rpm. As the reaction proceeds, the viscosity of the system increases, and the stirring rate needs to be reduced to 100 to 200 rpm, such as 150 rpm.

[0092] In some embodiments of the present invention, the reaction temperature is room temperature, such as 25° C., and the reaction time is 30 to 60 minutes, such as 50 minutes.

[0093] In some embodiments of the present invention, after the reaction, the method further comprises:

[0094] The product is precipitated in methanol, excess by-products are washed away, and the product is vacuum dried to obtain phenyl-mercapto-hydrogen-containing organosilicon oil.

[0095] The vacuum degree of the vacuum drying is -0.12 to -0.08 MPa, for example -0.1 MPa.

[0096] The vacuum drying temperature is 90-110° C., such as 100° C.; and the time is 8-12 hours, such as 12 hours.

[0097] The present invention also provides a phenyl-mercapto-hydrogen-containing organic silicone oil prepared by the preparation method described above.

[0098] In some embodiments of the present invention, the phenyl-mercapto-hydrogen-containing organosilicon oil has a structure shown in Formula I-1 or Formula I-2;

[0099]

[0100]

[0101] Wherein, y is an integer greater than 1; Z is an integer greater than 1.

[0102] The present invention also provides an OCR optical adhesive, which is prepared from raw materials including component A and component B;

[0103] The component A includes a polysiloxane containing Si-CH=CH2; the component B includes a polysiloxane containing a Si-H bond;

[0104] The component B includes phenyl-mercapto-hydrogen-containing silicone oil;

[0105] The component A and component B are stored separately.

[0106] In some embodiments of the present invention, component A includes a high-refractive-index vinyl silicone oil containing Si-CH=CH2, with a refractive index ≥1.500, and the vinyl group may be in the side chain or at both ends, with a number ≥1, and may also contain a phenyl group, with a number ≥1.

[0107] In some embodiments of the present invention, the component A comprises at least one of formula A-1, A-2, A-3 and a platinum (Pt) catalyst;

[0108]

[0109]

[0110] wherein m and n are each an integer greater than 1.

[0111] In some embodiments of the present application, the component A comprises, by weight fraction:

[0112] vinyl terminated methyl phenyl vinyl silicone oil 30-80 parts;

[0113] vinyl terminated methyl phenyl vinyl silicone oil 30-60 parts;

[0114] platinum catalyst 0.2-0.5 parts.

[0115] The viscosity of the vinyl terminated methyl phenyl vinyl silicone oil (Formula A-1) is 500-2000 Mpa·s; such as 500-1000 Mpa·s, 1000-2000 mpa·s.

[0116] The vinyl terminated methyl phenyl vinyl silicone oil has a structure shown in Formula A-3.

[0117] The platinum catalyst can be tetramethyldivinyldisilane chloroplatinic acid complex.

[0118] The component B comprises, by weight fraction:

[0119] vinyl terminated methyl phenyl vinyl silicone oil 20-60 parts;

[0120] phenyl-mercapto-hydrogen-containing silicone oil 5-15 parts;

[0121] hydrogen terminated methyl phenyl hydrogen silicone oil 5-15 parts;

[0122] The phenyl-mercapto-hydrogen-containing silicone oil is the phenyl-mercapto-hydrogen-containing silicone oil described above, or the phenyl-mercapto-hydrogen-containing silicone oil prepared by the preparation method described above;

[0123] The viscosity of the vinyl terminated methyl phenyl vinyl silicone oil is 500-2000 Mpa·s; such as 500-1000 Mpa·s, 1000-2000 mpa·s.

[0124] The viscosity of the hydrogen terminated methyl phenyl hydrogen silicone oil is 100-300 Mpa·s.

[0125] The present application does not have special restrictions on the preparation method of the components A and B, and the components can be mixed uniformly to obtain.

[0126] The present application also provides a preparation method of an OCR optical adhesive, comprising the following steps:

[0127] Place the glue solution after mixing component A and component B on a glass cover plate, scrape it flat, let it stand to remove bubbles, place another glass cover plate on the glue solution after removing bubbles, and heat to cure.

[0128] In some embodiments of the present invention, the mass ratio of component A to component B is 90-100:90-100, such as 100:95.

[0129] In some embodiments of the present invention, prior to placement on the glass cover plate, vacuum degassing is further performed to remove air bubbles. The vacuum degassing time can be 3 to 7 minutes, for example, 5 minutes. After vacuum degassing, a tape can be applied around the glass cover plate to regularize the adhesive solution.

[0130] In some embodiments of the present invention, after being scraped and leveled, the thickness of the glue on the glass cover is controlled to be 0.4-0.6 mm, for example, 0.5 mm.

[0131] In some embodiments of the present invention, the time for standing to remove bubbles is 5 to 10 minutes, such as 7 minutes.

[0132] In some embodiments of the present invention, the temperature for heating and curing is 55-65° C., such as 60° C., and the time is 10-50 minutes.

[0133] In the present invention, during the heat curing process, the principle of the reaction between component A and component B is that a hydrosilylation reaction occurs under the catalytic action of the Pt catalyst.

[0134] The present invention has no particular limitation on the sources of the raw materials used above, and they can be generally commercially available.

[0135] The present invention adopts a mercapto-ene click reaction to successfully react a high-refractive index compound containing a phenyl group and a sulfur element to generate a novel polymer containing Si-H bonds in which organic silicon-oxygen chain segments and sulfur-benzene chain segments are alternately distributed.

[0136] Through molecular structure design and hydrosilylation reaction, a polymer containing alternating distributions of organic siloxane chains and thiobenzene chains is cross-linked with a benzene-containing silyl vinyl polymer to achieve the effect of alternating distribution of long and short chains, so that phenyl groups are distributed in small quantities and multiple locations on the main chain and side chain of the organic siloxane chain, achieving a double leap in high refractive index and low viscosity.

[0137] The silicone liquid OCR optical adhesive synthesized by this scheme is a transparent elastomer that is both flexible and hard. It also has properties such as bendability, foldability, and stretchability, bringing new application possibilities to wearable materials, flexible display technology and other fields.

[0138] The refractive index of the optical adhesive used for full bonding on the market is generally low, about 1.42, which is a certain distance away from the 1.5-1.6 of the glass cover. The resulting refraction and reflection of light can lead to energy loss, screen frame loss, dizziness, and damage to the human eye. The present invention increases the refractive index of the optical adhesive as a whole by increasing the refractive index of a single component, thereby alleviating eye fatigue.

[0139] In previous studies, most of them relied on increasing the content of phenyl monomers to increase the refractive index of optical adhesives. However, the reactivity of phenyl monomers is poor. If too much is introduced, the product will become opaque and the viscosity will be too high. This study does not rely solely on phenyl to increase the refractive index, but introduces S elements and phenyl at the same time, and the content and viscosity are controllable, breaking the traditional limitation that the viscosity increases when the refractive index is high.

[0140] The method for synthesizing component A is highly versatile, has non-critical reaction conditions, and is applicable to reactions of various high-refractive-index monomers.

[0141] To further illustrate the present invention, the following detailed description of a phenyl-mercapto-hydrogen-containing organosilicone oil, its preparation method and application provided by the present invention is provided in conjunction with examples. However, these examples should not be construed as limiting the scope of protection of the present invention.

[0142] Example 1

[0143] 1) Preparation of phenyl-mercapto-hydrogen-containing silicone oil:

[0144] 1-1) 0.2 mol of diphenylsilanediol, 0.2 mol of methyldichlorosilane, and 400 mL of toluene were added to a 1000 mL flask and mixed. A mixture of 100 mL of toluene and 0.8 mol of NH(CH2CH3)2 was then added dropwise to the flask at room temperature. The mixture was then stirred at room temperature (25°C) for 24 hours, the ammonium salt was removed by filtration, and the resulting solution was washed until neutral. The product was dissolved in ethanol and recrystallized to obtain a white crystalline powder, i.e., the compound having the structure represented by Formula VI (Product a). During the recrystallization separation process, the first separated liquid was collected and refrigerated at 0-4°C for 24 hours. The precipitate was then removed to obtain a transparent, oil-like product, i.e., the compound having the structure represented by Formula IV (Product b).

[0145] 1-2) A mixture of 0.035 mol of product b and 0.008 mol of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added to a 25 mL flask. Dilute hydrochloric acid (6.0 mL, 0.3 mol / L, diluted with THF) was added dropwise to the flask with stirring. The mixed solution was reacted at 75°C for 4 hours, washed with deionized water until neutral, dried, and rotary evaporated to obtain a compound having the structure of Formula II (product c), where x is a positive integer from 1 to 50.

[0146] 1-3) To a solution of product c (1.0 g) in toluene (30 mL) was added 4,4-dithiodiphenyl sulfide (having the structure shown in Formula III-1), resulting in a solution with a mass concentration of 1.5% 4,4-dithiodiphenyl sulfide. The mixture was irradiated with a 120 W UV lamp at a wave number of 365 nm at 25°C, and nitrogen was continuously purged to remove excess oxygen. The initial stirring speed was set at 400 rpm. As the reaction proceeded and the viscosity of the system increased, the stirring speed was reduced to 150 rpm. After 50 minutes, the UV lamp was turned off to terminate the reaction. The product was precipitated in methanol, and excess byproducts were washed off. The product was dried at -0.1 MPa and 100°C for 12 hours to obtain a phenyl-mercapto-hydrogen silicone oil having the structure shown in Formula I-1. Wherein, y is a positive integer from 1 to 50; and z is a positive integer from 1 to 50. Figure 1 This is the H NMR spectrum of the phenyl-mercapto-hydrogen-containing organosilicon oil of Example 1 of the present invention, proving that the present invention synthesized the phenyl-mercapto-hydrogen-containing organosilicon oil having the structure shown in Formula Ⅰ-1.

[0147] 2) Preparation of OCR optical adhesive:

[0148] Prepare component A: Measure, by weight, 80 parts of 500-1000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil; 30 parts of vinyl-terminated phenyl vinyl silicone oil; and 0.2 parts of a platinum catalyst (tetramethyldisiloxane chloroplatinate complex). Mix all components thoroughly and set aside.

[0149] Prepare component B: Measure, by weight, 60 parts of a 500-1000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil; 7 parts of the phenyl-mercapto-hydrogenated organosilicon oil; and 6 parts of a 100-300 MPa·s hydrogenated methylphenyl hydrogenated silicone oil. Mix all components thoroughly and set aside.

[0150] Preparation of OCR optical adhesive:

[0151] After evenly mixing component A and component B in a mass ratio of 100:95, vacuum degas for 5 minutes to remove bubbles; then use tape to stick a circle on the glass cover with a thickness of 0.5mm, pour the treated glue onto the glass cover, scrape it flat, let it stand for 7 minutes to remove bubbles, then place another glass cover on it and heat cure at 60℃ for 15 minutes.

[0152] Example 2

[0153] 1) Preparation of phenyl-mercapto-hydrogen-containing silicone oil:

[0154] Same as Example 1.

[0155] 2) Preparation of OCR optical adhesive:

[0156] Prepare component A: Measure, by weight, 50 parts of 500-1000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil, 40 parts of vinyl-terminated phenyl vinyl silicone oil, and 0.4 parts of platinum catalyst (tetramethyldisiloxane chloroplatinate complex). Mix all components thoroughly and set aside.

[0157] Prepare component B: Measure, by weight, 40 parts of a 500-1000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil; 9 parts of the phenyl-mercapto-hydrogenated organosilicon oil; and 9 parts of a 100-300 MPa·s hydrogenated methylphenyl hydrogenated silicone oil. Mix all components thoroughly and set aside.

[0158] Preparation of OCR optical adhesive:

[0159] After evenly mixing component A and component B in a mass ratio of 100:95, vacuum degas for 5 minutes to remove bubbles; then use tape to stick a circle on the glass cover with a thickness of 0.5mm, pour the treated glue onto the glass cover, scrape it flat, let it stand for 7 minutes to remove bubbles, then place another glass cover on it and heat cure at 60℃ for 15 minutes.

[0160] Example 3

[0161] 1) Preparation of phenyl-mercapto-hydrogen-containing silicone oil:

[0162] 1-1) 0.2 mol of diphenylsilanediol, 0.2 mol of methyldichlorosilane, and 400 mL of toluene were added to a 1000 mL flask and mixed. A mixture of 100 mL of toluene and 0.8 mol of NH(CH2CH3)2 was then added dropwise to the flask at room temperature. The mixture was then stirred at room temperature (25°C) for 24 hours, the ammonium salt was removed by filtration, and the resulting solution was washed until neutral. The product was dissolved in ethanol and recrystallized to obtain a white crystalline powder, i.e., the compound having the structure represented by Formula VI (Product a). During the recrystallization separation process, the first separated liquid was collected and refrigerated at 0-4°C for 24 hours. The precipitate was then removed to obtain a transparent, oil-like product, i.e., the compound having the structure represented by Formula IV (Product b).

[0163] 1-2) A mixture of 0.035 mol of product b and 0.008 mol of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added to a 25 mL flask. Dilute hydrochloric acid (6.0 mL, 0.3 mol / L, diluted with THF) was added dropwise to the flask with stirring. The mixed solution was reacted at 75°C for 4 hours, washed with deionized water until neutral, dried, and rotary evaporated to obtain a compound having the structure of Formula II (product c), where x is a positive integer from 1 to 50.

[0164] 1-3) In a solution of product c (1.0 g) in toluene (30 mL), 2,2'-[1,2-ethanediylbis(thiol)]bisethanethiol (having a structure shown in formula III-6) was added to obtain a solution with a mass concentration of 1.5% of 2,2'-[1,2-ethanediylbis(thiol)]bisethanethiol, and the solution was irradiated with an ultraviolet lamp with a wave number of 365 nm and 120 W at 25°C, and the mixture was continuously purged with nitrogen to eliminate excess oxygen. The initial stirring speed was set to 400 rpm, and as the viscosity of the system increased during the reaction, the stirring rate was reduced to 150 rpm. After 50 min, the ultraviolet lamp was turned off to stop the reaction. The product was precipitated in methanol, and the excess byproduct was washed away. The product was dried at -0.1 MPa and 100°C for 12 h to obtain a phenyl-mercapto-hydrogen-containing silicone oil having a structure shown in formula I-3. Wherein y is a positive integer of 1-50; Z is a positive integer of 1-50.

[0165] 2) Preparation of OCR optical adhesive:

[0166] Preparation of component A: metered by weight parts. 500-1000 Mpa.s of vinyl-terminated methyl phenyl vinyl silicone oil, 35 parts; vinyl-terminated phenyl vinyl silicone oil, 40 parts; platinum catalyst (tetramethyl divinyl disilane complex of chloroplatinic acid) 0.3 parts; mix the components uniformly and reserve.

[0167] Preparation of component B: metered by weight parts. 500-1000 Mpa.s of vinyl-terminated methyl phenyl vinyl silicone oil, 40 parts; the phenyl-mercapto-hydrogen-containing silicone oil, 9 parts; 100-300 Mpa.s of hydrogen-terminated methyl phenyl hydrogen-containing silicone oil, 9 parts; mix the components uniformly and reserve.

[0168] Preparation of OCR optical adhesive:

[0169] After mixing component A and component B uniformly according to a mass ratio of 100:95, vacuum degassing for 5 min to remove bubbles; then use adhesive tape to paste a circle on the glass cover plate, with a thickness of 0.5 mm, pour the treated adhesive onto the glass cover plate, scrape it flat, stand for 7 min to remove bubbles, and then lay another glass cover plate on it, and heat and cure at 60°C for 15 min.

[0170] Example 4

[0171] 1) Preparation of phenyl-mercapto-hydrogen-containing silicone oil:

[0172] 1-1) 0.2 mol of diphenylsilanediol, 0.2 mol of methyldichlorosilane, and 400 mL of toluene were added to a 1000 mL flask and mixed. A mixture of 100 mL of toluene and 0.8 mol of NH(CH2CH3)2 was then added dropwise to the flask at room temperature. The mixture was then stirred at room temperature (25°C) for 24 hours, the ammonium salt was removed by filtration, and the resulting solution was washed until neutral. The product was dissolved in ethanol and recrystallized to obtain a white crystalline powder, i.e., the compound having the structure represented by Formula VI (Product a). During the recrystallization separation process, the first separated liquid was collected and refrigerated at 0-4°C for 24 hours. The precipitate was then removed to obtain a transparent, oil-like product, i.e., the compound having the structure represented by Formula IV (Product b).

[0173] 1-2) A mixture of 0.035 mol of product b and 0.008 mol of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added to a 25 mL flask. Dilute hydrochloric acid (6.0 mL, 0.3 mol / L, diluted with THF) was added dropwise to the flask with stirring. The mixed solution was reacted at 75°C for 4 hours, washed with deionized water until neutral, dried, and rotary evaporated to obtain a compound having the structure of Formula II (product c), where x is a positive integer from 1 to 50.

[0174] 1-3) To a solution of product c (1.0 g) in toluene (30 mL) was added 4,4′-[dithiobis(4,1-phenylthio)]bis-benzenethiol (having the structure shown in Formula III-2), resulting in a 1.5% mass concentration of 4,4′-[dithiobis(4,1-phenylthio)]bis-benzenethiol. The mixture was irradiated with a 120 W UV lamp at 365 nm at 25°C, while nitrogen was continuously purged to remove excess oxygen. The initial stirring speed was set at 400 rpm. As the reaction proceeded and the viscosity of the system increased, the stirring speed was reduced to 150 rpm. After 50 minutes, the UV lamp was turned off to terminate the reaction. The product was precipitated in methanol, and excess byproducts were washed off. The product was dried at -0.1 MPa and 100°C for 12 hours to obtain a phenyl-mercapto-hydrogen silicone oil having the structure shown in Formula I-2. Wherein, y is a positive integer from 1 to 50; Z is a positive integer from 1 to 50.

[0175] 2) Preparation of OCR optical adhesive:

[0176] Prepare component A: Measure, by weight, 50 parts of 500-1000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil, 40 parts of vinyl-terminated phenyl vinyl silicone oil, and 0.4 parts of platinum catalyst (tetramethyldisiloxane chloroplatinate complex). Mix all components thoroughly and set aside.

[0177] Prepare component B: Measure, by weight, 40 parts of a 500-1000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil; 9 parts of the phenyl-mercapto-hydrogenated organosilicon oil; and 9 parts of a 100-300 MPa·s hydrogenated methylphenyl hydrogenated silicone oil. Mix all components thoroughly and set aside.

[0178] Preparation of OCR optical adhesive:

[0179] After evenly mixing component A and component B in a mass ratio of 100:95, vacuum degas for 5 minutes to remove bubbles; then use tape to stick a circle on the glass cover with a thickness of 0.5mm, pour the treated glue onto the glass cover, scrape it flat, let it stand for 7 minutes to remove bubbles, then place another glass cover on it and heat cure at 60℃ for 15 minutes.

[0180] Example 5

[0181] The difference from Example 4 is that the viscosity of the vinyl-terminated methylphenyl vinyl silicone oil used in component A and component B is different.

[0182] Step 2) is:

[0183] Preparation of OCR optical adhesive:

[0184] Prepare component A: Measure, by weight, 50 parts of 1000-2000 mPa·s vinyl-terminated methylphenyl vinyl silicone oil, 40 parts of vinyl-terminated phenyl vinyl silicone oil, and 0.4 parts of platinum catalyst (tetramethyldisiloxane chloroplatinate complex). Mix all components thoroughly and set aside.

[0185] Prepare component B: Measure, by weight, 40 parts of a 1000-2000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil; 9 parts of the phenyl-mercapto-hydrogenated organosilicon oil; and 9 parts of a 100-300 MPa·s hydrogenated methylphenyl hydrogenated silicone oil. Mix all components thoroughly and set aside.

[0186] Preparation of OCR optical adhesive:

[0187] After evenly mixing component A and component B in a mass ratio of 100:95, vacuum degas for 5 minutes to remove bubbles; then use tape to stick a circle on the glass cover with a thickness of 0.5mm, pour the treated glue onto the glass cover, scrape it flat, let it stand for 7 minutes to remove bubbles, then place another glass cover on it and heat cure at 60℃ for 15 minutes.

[0188] Example 6

[0189] The difference from Example 4 is that the high refractive index monomer containing a dithiol group is different, and the monomer used is 2,5-dimethylmercapto-1,4-dithiane (having the structure shown in Formula III-3). The viscosity of the vinyl-terminated methylphenyl vinyl silicone oil used in component A and component B is different.

[0190] 1) Preparation of phenyl-mercapto-hydrogen-containing silicone oil:

[0191] 1-1) 0.2 mol of diphenylsilanediol, 0.2 mol of methyldichlorosilane, and 400 mL of toluene were added to a 1000 mL flask and mixed. A mixture of 100 mL of toluene and 0.8 mol of NH(CH2CH3)2 was then added dropwise to the flask at room temperature. The mixture was then stirred at room temperature (25°C) for 24 hours, the ammonium salt was removed by filtration, and the resulting solution was washed until neutral. The product was dissolved in ethanol and recrystallized to obtain a white crystalline powder, i.e., the compound having the structure represented by Formula VI (Product a). During the recrystallization separation process, the first separated liquid was collected and refrigerated at 0-4°C for 24 hours. The precipitate was then removed to obtain a transparent, oil-like product, i.e., the compound having the structure represented by Formula IV (Product b).

[0192] 1-2) A mixture of 0.035 mol of product b and 0.008 mol of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was added to a 25 mL flask. Dilute hydrochloric acid (6.0 mL, 0.3 mol / L, diluted with THF) was added dropwise to the flask with stirring. The mixed solution was reacted at 75°C for 4 hours, washed with deionized water until neutral, dried, and rotary evaporated to obtain a compound having the structure of Formula II (product c), where x is a positive integer from 1 to 50.

[0193] 1-3) To a solution of product c (1.0 g) in toluene (30 mL) was added 2,5-dimethylmercapto-1,4-dithiane (having the structure shown in Formula III-3). The resulting solution had a mass concentration of 1.5% 4,4′-[dithiobis(4,1-phenylthio)]bis-benzenethiol. The mixture was irradiated with a 120 W UV lamp at 365 nm at 25°C, and nitrogen was continuously purged to remove excess oxygen. The initial stirring speed was set at 400 rpm. As the reaction proceeded and the viscosity of the system increased, the stirring speed was reduced to 150 rpm. After 50 minutes, the UV lamp was turned off to terminate the reaction. The product was precipitated in methanol, and excess byproducts were washed off. The product was dried at -0.1 MPa and 100°C for 12 hours to obtain a phenyl-mercapto-hydrogen silicone oil having the structure shown in Formula I-3. Wherein, y is a positive integer from 1 to 50; and z is a positive integer from 1 to 50.

[0194] 2) Preparation of OCR optical adhesive:

[0195] Prepare component A: Measure, by weight, 50 parts of 1000-2000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil, 40 parts of vinyl-terminated phenyl vinyl silicone oil, and 0.4 parts of platinum catalyst (tetramethyldisiloxane chloroplatinate complex). Mix all components thoroughly and set aside.

[0196] Prepare component B: Measure, by weight, 40 parts of a 1000-2000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil; 9 parts of the phenyl-mercapto-hydrogenated organosilicon oil; and 9 parts of a 100-300 MPa·s hydrogenated methylphenyl hydrogenated silicone oil. Mix all components thoroughly and set aside.

[0197] Preparation of OCR optical adhesive:

[0198] After evenly mixing component A and component B in a mass ratio of 100:95, vacuum degas for 5 minutes to remove bubbles; then use tape to stick a circle on the glass cover with a thickness of 0.5mm, pour the treated glue onto the glass cover, scrape it flat, let it stand for 7 minutes to remove bubbles, then place another glass cover on it and heat cure at 60℃ for 15 minutes.

[0199] Example 7

[0200] 1) Preparation of phenyl-mercapto-hydrogen-containing silicone oil:

[0201] Same as Example 1.

[0202] 2) Preparation of OCR optical adhesive:

[0203] Preparation of component A: Same as Example 1.

[0204] Prepare component B: Measure, by weight, 60 parts of a 500-1000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil; 5 parts of the phenyl-mercapto-hydrogenated organosilicon oil; and 6 parts of a 100-300 MPa·s hydrogenated methylphenyl hydrogenated silicone oil. Mix all components thoroughly and set aside.

[0205] 3) Preparation of OCR optical adhesive:

[0206] After evenly mixing component A and component B in a mass ratio of 100:95, vacuum degas for 5 minutes to remove bubbles; then use tape to stick a circle on the glass cover with a thickness of 0.5mm, pour the treated glue onto the glass cover, scrape it flat, let it stand for 7 minutes to remove bubbles, then place another glass cover on it and heat cure at 60℃ for 15 minutes.

[0207] Example 8

[0208] 1) Preparation of phenyl-mercapto-hydrogen-containing silicone oil:

[0209] The same as Example 2.

[0210] 2) Preparation of the OCR optical adhesive:

[0211] Preparation of Component A: The same as Example 2.

[0212] Preparation of Component B: The components were measured by weight parts. 500-1000 Mpa-s of end vinyl methyl phenyl vinyl silicone oil, 40 parts; the phenyl-mercapto-hydrogen-containing silicone oil, 5 parts; 100-300 Mpa-s of end hydrogen-containing methyl phenyl hydrogen-containing silicone oil, 9 parts; the components were mixed uniformly and reserved.

[0213] Preparation of the OCR optical adhesive:

[0214] After mixing Component A and Component B uniformly according to a mass ratio of 100:95, vacuum degassing was performed for 5 min to remove bubbles; then a circle of adhesive tape was pasted on a glass cover plate with a thickness of 0.5 mm, the treated adhesive was poured onto the glass cover plate, scraped flat, and left to stand for 7 min to remove bubbles, and then another glass cover plate was laid on it, and heating and curing were performed at 60°C for 15 min.

[0215] Example 9

[0216] 1) Preparation of the phenyl-mercapto-hydrogen-containing silicone oil:

[0217] The same as Example 3.

[0218] 2) Preparation of the OCR optical adhesive:

[0219] Preparation of Component A: The same as Example 3.

[0220] Preparation of Component B: The components were measured by weight parts. 500-1000 Mpa-s of end vinyl methyl phenyl vinyl silicone oil, 40 parts; the phenyl-mercapto-hydrogen-containing silicone oil, 5 parts; 100-300 Mpa-s of end hydrogen-containing methyl phenyl hydrogen-containing silicone oil, 9 parts; the components were mixed uniformly and reserved.

[0221] Preparation of the OCR optical adhesive:

[0222] After mixing Component A and Component B uniformly according to a mass ratio of 100:95, vacuum degassing was performed for 5 min to remove bubbles; then a circle of adhesive tape was pasted on a glass cover plate with a thickness of 0.5 mm, the treated adhesive was poured onto the glass cover plate, scraped flat, and left to stand for 7 min to remove bubbles, and then another glass cover plate was laid on it, and heating and curing were performed at 60°C for 15 min.

[0223] Comparative Example 1

[0224] Preparation of the OCR optical adhesive:

[0225] Preparation of component A: Same as Example 6.

[0226] Prepare component B: Measure, by weight, 49 parts of 1000-2000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil and 9 parts of 100-300 MPa·s hydrogen-terminated methylphenyl hydrogen silicone oil; mix the components evenly and set aside.

[0227] After evenly mixing component A and component B in a mass ratio of 100:95, vacuum degas for 5 minutes to remove bubbles; then use tape to stick a circle on the glass cover with a thickness of 0.5mm, pour the treated glue onto the glass cover, scrape it flat, let it stand for 7 minutes to remove bubbles, then place another glass cover on it and heat cure at 60℃ for 15 minutes.

[0228] Comparative Example 2

[0229] Preparation of OCR optical adhesive:

[0230] Preparation of component A: Same as Example 6.

[0231] Prepare component B: Measure, by weight, 40 parts of 1000-2000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil and 18 parts of 100-300 MPa·s hydrogen-terminated methylphenyl hydrogen silicone oil; mix the components evenly and set aside.

[0232] After evenly mixing component A and component B in a mass ratio of 100:95, vacuum degas for 5 minutes to remove bubbles; then use tape to stick a circle on the glass cover with a thickness of 0.5mm, pour the treated glue onto the glass cover, scrape it flat, let it stand for 7 minutes to remove bubbles, then place another glass cover on it and heat cure at 60℃ for 15 minutes.

[0233] Comparative Example 3

[0234] Preparation of OCR optical adhesive:

[0235] Prepare component A: Measure by weight: 90 parts of 1000-2000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil; 0.4 parts of platinum catalyst (tetramethyldisiloxane chloroplatinate complex); mix all components evenly and set aside.

[0236] Prepare component B: Measure, by weight, 49 parts of 1000-2000 MPa·s vinyl-terminated methylphenyl vinyl silicone oil and 9 parts of 100-300 MPa·s hydrogen-terminated methylphenyl hydrogen silicone oil; mix the components evenly and set aside.

[0237] After evenly mixing component A and component B in a mass ratio of 100:95, vacuum degas for 5 minutes to remove bubbles; then use tape to stick a circle on the glass cover with a thickness of 0.5mm, pour the treated glue onto the glass cover, scrape it flat, let it stand for 7 minutes to remove bubbles, then place another glass cover on it and heat cure at 60℃ for 15 minutes.

[0238] The optical adhesives after curing of Examples 1 to 9 and the optical adhesives after curing of Comparative Examples 1 to 3 were subjected to performance testing, and the testing indicators and test standards are shown in Table 1.

[0239] Table 1 Detection indicators and test standards

[0240]

[0241]

[0242] Refractive index: measured using an Abbe refractometer at a wavelength of 589nm. Cut the fully bonded product with fishing line, then take a sample for refractive index testing.

[0243] Appearance: Visual inspection.

[0244] Bubbles: visual inspection.

[0245] Color: Visual inspection.

[0246] The test results are shown in Table 2.

[0247] Table 2 Test results

[0248]

[0249] Table 2 (Continued from Table 1)

[0250]

[0251]

[0252] The weather resistance test results of the cured optical adhesive are shown in Table 3.

[0253] Table 3 Weathering performance test results of cured optical adhesive

[0254]

[0255]

[0256] The above embodiments are intended only to facilitate understanding of the methods and core concepts of the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein, but is intended to be construed in the widest manner consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a phenyl-mercapto-hydrogen-containing organosilicon oil, comprising the following steps: Under ultraviolet irradiation, a compound having a structure shown in Formula II is reacted with a high refractive index monomer containing a dithiol group in a first solvent to obtain a phenyl-thiol-hydrogen-containing organic silicone oil; Here, x is an integer greater than 1.

2. The preparation method according to claim 1, characterized in that The refractive index of the high-refractive-index monomer containing a dithiol group is greater than 1.5; The high refractive index monomer containing a dithiol group is selected from 4,4-dimercaptodiphenyl sulfide, 4,4'-[dithiobis(4,1-phenylthio)]bis-benzenethiol, 2,5-dimethylmercapto-1,4-dithiane, 1,6-dimercapto-3-hexyl sulfide, 2-mercaptoethyl sulfide, 2,2'-[1,2-ethylenediylbis(thio)]bisethanethiol or 4,4'-[1,4-phenylenebis(thio)]bis-benzenethiol.

3. The preparation method according to claim 1, characterized in that The preparation method of the compound having the structure shown in Formula II comprises the following steps: Mixing the compound having the structure represented by Formula IV and a bisvinylmethylsiloxane end-capping agent to obtain a mixed solution; Add dilute hydrochloric acid dropwise to the mixture while stirring, and react at 60-80° C. to obtain a compound having the structure shown in Formula II; Here, x is an integer greater than 1.

4. The preparation method according to claim 3, characterized in that The divinylmethylsiloxane end-capping agent is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

5. The preparation method according to claim 3, characterized in that The method for preparing the compound having the structure shown in Formula IV comprises the following steps: Diphenylsilanediol and methyldichlorosilane are reacted in a second solvent under a catalyst, filtered, and the resulting solution is washed to neutrality. The product is precipitated with ethanol and recrystallized to obtain a compound having the structure shown in Formula VI; During the recrystallization separation process, the first separated liquid is collected, and the separated liquid is placed at 0-4° C. for 22-26 hours, and the precipitate is removed to obtain a compound having the structure shown in Formula IV; 6. The preparation method according to claim 5, characterized in that The catalyst is selected from diethylamine, dimethylamine or tetramethylammonium hydroxide; The second solvent is selected from toluene, hexane, acetone, dichloromethane or tetrahydrofuran; The molar ratio of the diphenylsilanediol to methyldichlorosilane is 1:0.5-2.

7. The preparation method according to claim 3, characterized in that The molar ratio of the compound having the structure shown in Formula IV to the bisvinylmethylsiloxane end-capping agent is 3 to 5:1; The reaction time is 3 to 5 hours; After the reaction, the present invention further comprises: The mixture was washed with deionized water until neutral, dried, and rotary evaporated to obtain an oily product containing a divinyl end cap, which is a compound having the structure shown in Formula II.

8. The preparation method according to claim 1, characterized in that The first solvent is selected from toluene, hexane, acetone, dichloromethane or tetrahydrofuran; The reaction is carried out under the condition of protective gas; After the reaction, the present invention further comprises: The product is precipitated in methanol, excess by-products are washed away, and the product is vacuum dried to obtain phenyl-mercapto-hydrogen-containing organosilicon oil.

9. Phenyl-mercapto-hydrogen-containing organosilicon oil prepared by the preparation method according to any one of claims 1 to 8.

10. An OCR optical adhesive prepared from raw materials including component A and component B; The component A comprises a polysiloxane containing Si-CH=CH2; The component B comprises phenyl-mercapto-hydrogen-containing organosilicon oil; the phenyl-mercapto-hydrogen-containing organosilicon oil is the phenyl-mercapto-hydrogen-containing organosilicon oil according to claim 9.

11. The OCR optical adhesive according to claim 10, characterized in that: The component A comprises, by weight: 30-80 parts of vinyl-terminated methylphenyl vinyl silicone oil; 30-60 parts of vinyl-terminated phenyl vinyl silicone oil; 0.2-0.5 parts of platinum catalyst; The viscosity of the vinyl-terminated methylphenyl vinyl silicone oil is 500 to 2000 MPa·s; The platinum catalyst is tetramethyl divinyl disilane chloroplatinate complex; The component B comprises, by weight: 20-60 parts of vinyl-terminated methylphenyl vinyl silicone oil; 5-15 parts of phenyl-mercapto-hydrogen-containing silicone oil; 5-15 parts of hydrogen-terminated methylphenyl hydrogen silicone oil; The viscosity of the vinyl-terminated methylphenyl vinyl silicone oil is 500 to 2000 MPa·s; The viscosity of the hydrogen-terminated methylphenyl hydrogen-containing silicone oil is 100-300 MPa·s.

12. The method for preparing the OCR optical adhesive according to any one of claims 10 to 11, comprising the following steps: Place the glue solution after mixing component A and component B on a glass cover plate, scrape it flat, let it stand to remove bubbles, place another glass cover plate on the glue solution after removing bubbles, and heat to cure.

13. The preparation method according to claim 12, characterized in that The mass ratio of component A to component B is 90-100:90-100.

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