Organosilicon polymer as well as preparation method and application thereof

Abstract

The invention relates to an organic silicon polymer and a preparation method and application thereof, the organic silicon polymer is an organic silicon polymer containing double bonds or other active functional groups obtained by imidization of an organic silicon raw material containing primary amine, and the organic silicon polymer is not easy to block due to the fact that amino groups are blocked. The catalyst can be applied to a hydrosilylation curing system; meanwhile, closed amino groups are protected during aging, serious yellowing cannot be caused, many polar functional groups are brought, the adhesive force of an organic compound system to an optical base material is greatly improved, and an organic silicon adhesive or coating capable of being subjected to multiple curing is generated through secondary reaction.

Description

Technical Field

[0001] The present application relates to the technical field of organosilicon materials, and in particular to an organosilicon polymer and a preparation method and application thereof. Background Art

[0002] The optical silicone adhesives on the market are mainly composed of vinyl silicone oil, vinyl silicone resin, hydrogenated silicone oil, platinum catalyst and additives. Due to its high transparency, resistance to aging and yellowing, it can still maintain excellent performance under a wide range of operating temperatures and is widely used in large-size and automotive touch screens. However, its overall low adhesion makes its adhesion on certain optical plastic substrates (PC, PMMA) low, limiting its application.

[0003] The modified products in the related technologies still have defects. For example, the Chinese patent with patent application number 202311332449.3 discloses that silicone is modified by epoxy / organoboron to increase adhesion while ensuring optical properties, but the hardness is above 50 (Shore D), which cannot be used for flexible materials such as display screens; and its curing temperature is as high as above 100°C, which cannot be used on some sensitive substrates. For example, the Chinese patent with patent application number 202310744565.X discloses that phenolic resin is modified by silicone, but the reaction only produces polyamide, and there is no further reaction to become polyimide, and the phenolic resin has non-optical properties. Therefore, it is urgent to develop silicone materials that are suitable for optical plastic substrates and can maintain good adhesion. Summary of the invention

[0004] The embodiments of the present application provide a silicone polymer and a preparation method and application thereof, which can achieve the property of maintaining a relatively high adhesive force on an optical substrate.

[0005] In order to achieve the above object, according to the first aspect of the present application, there is provided an organosilicon polymer, including a polymer as shown in Formula I: Formula I; In formula I, at least one of R1, R2, R3 and R4 is independently selected from a functional group formed by imidization of an anhydride and an amino group; The value range of m and n is 50 to 50000.

[0006] Optionally, in some embodiments of the present application, at least one of R1, R2, R3 and R4 is independently selected from a combination of a functional group formed by imidization of the acid anhydride and the amino group and one or more of methyl, ethyl, propyl, hydroxyl and phenyl.

[0007] Optionally, in some embodiments of the present application, the functional group formed by imidization of the acid anhydride and the amino group comprises a chemical formula as shown in Formula II and / or Formula III: Formula II; Formula III; In formula II, R5 is independently selected from the residual group of anhydride and amino group after imidization; a ranges from 1 to 10; In formula III, R6 is a hydrogen atom, or a functional group containing one or more of acryloyloxy, methacryloyloxy, epoxy, acrylonitrile, cyclopentadiene, and siloxane; and the value of a ranges from 1 to 10.

[0008] Optionally, in some embodiments of the present application, the acid anhydride includes a monobasic acid anhydride or a dibasic acid anhydride.

[0009] Optionally, in some embodiments of the present application, the acid anhydride includes one or more of methyltetrahydrophthalic anhydride, cyclobutanetetracarboxylic dianhydride, bicyclo[2.2.1]-heptane-2-methylcarboxylic acid-3,5,6-tricarboxy-2,3,5,6-dianhydride, difluorophthalic anhydride, hexafluorodianhydride, and pyromellitic dianhydride.

[0010] Optionally, in some embodiments of the present application, the value range of m and n is 1000 to 20000.

[0011] Optionally, in some embodiments of the present application, the value range of m and n is 2000 to 10000.

[0012] According to the second aspect of the present application, there is also provided a method for preparing an organosilicon polymer, comprising the following steps: The organic silicon raw material containing primary amine is imidized to obtain an anhydride-terminated organic silicon polymer.

[0013] Optionally, in some embodiments of the present application, the anhydride-terminated silicone polymer is reacted with a reactive group containing a hydroxyl / epoxy functional group to obtain the silicone polymer.

[0014] Optionally, in some embodiments of the present application, the reactive group containing hydroxyl / epoxy functional groups includes one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, glycidyl methacrylate, and cyclohexane-1,2-dicarboxylic acid diglycidyl ester.

[0015] According to a third aspect of the present application, a composition is also provided, comprising the aforementioned organosilicon polymer.

[0016] Optionally, in some embodiments of the present application, the composition includes the following components in parts by weight: 5-70 parts of the aforementioned organosilicon polymer, 5-70 parts of silicone oil containing vinyl functional groups, 1-15 parts of silicone resin containing vinyl functional groups, 5-70 parts of hydrogen-containing silicone oil, 0-10 parts of platinum catalyst and additives, wherein the platinum catalyst is calculated as 2-50ppm according to the platinum content.

[0017] Optionally, in some embodiments of the present application, the composition includes the following components in parts by weight: 10-90 parts of the aforementioned organosilicon polymer, 0-5 parts of initiator, 5-70 parts of active diluent, 0-5 parts of catalyst and 0-10 parts of auxiliary agent.

[0018] According to a fourth aspect of the present application, there is also provided a use of the aforementioned organosilicon polymer or the aforementioned composition in an adhesive or a coating.

[0019] The organosilicon polymer of the embodiment of the present application is an organosilicon polymer containing double bonds or other active functional groups obtained by imidizing an organosilicon material containing primary amines. Since the amino group is blocked, the organosilicon polymer can be applied to a hydrosilylation curing system. At the same time, the blocked amino group is protected during aging and will not cause severe yellowing. At the same time, it brings many polar functional groups, greatly improving the adhesion of the organic compound system to the optical substrate, and through a secondary reaction, a functional organosilicon adhesive / coating that can be cured by ultraviolet light is generated. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present application, and those skilled in the art can obtain other drawings based on these drawings without creative work.

[0021] Figure 1 is the chemical reaction structure diagram of S100 in Example 1 of the present application; Figure 2 is a chemical reaction structure diagram of S200 in Example 1 of the present application; Figure 3 is the chemical reaction structure diagram of S100 in Example 2 of the present application; Figure 4 is the chemical reaction structure diagram of S200 in Example 2 of the present application; Figure 5 It is a chemical reaction structure diagram of S400 in Example 2 of the present application. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application.

[0023] The optical silicone adhesives on the market are mainly composed of vinyl silicone oil, vinyl silicone resin, hydrogenated silicone oil, platinum catalyst, additives, etc. As optical silicone adhesives have the characteristics of high transparency, aging resistance and yellowing resistance, they can still maintain good bonding properties at a wide range of operating temperatures and are widely used in the field of large-size and automotive touch screens.

[0024] However, optical silicone adhesives have the characteristic of low adhesion, especially on certain optical plastic substrates (PC, PMMA), which limits their application.

[0025] The embodiments of the present application provide an organosilicon polymer and a preparation method and application thereof.

[0026] In a first aspect, an organosilicon polymer is provided, comprising a polymer as shown in formula I: Formula I.

[0027] In some embodiments of the present application, in Formula I, at least one of R1, R2, R3 and R4 is independently selected from a functional group formed by imidization of anhydride and an amino group.

[0028] In some embodiments of the present application, at least one of R1, R2, R3 and R4 is independently selected from a combination of a functional group formed by imidization of anhydride and an amino group and one or more of methyl, ethyl, propyl, hydroxyl and phenyl.

[0029] In some embodiments of the present application, the functional group formed by imidization of the acid anhydride and the amino group comprises a chemical formula as shown in Formula II and / or Formula III: Formula II; Formula III; In formula II, R5 is independently selected from the residual group of anhydride and amino group after imidization; a ranges from 1 to 10; In formula III, R6 is a hydrogen atom, or a functional group containing one or more of acryloyloxy, methacryloyloxy, epoxy, acrylonitrile, cyclopentadiene, and siloxane; and the value of a ranges from 1 to 10.

[0030] In some embodiments of the present application, the acid anhydride includes a monobasic acid anhydride or a dibasic acid anhydride.

[0031] In some embodiments of the present application, the monoacid anhydride includes, but is not limited to, one or more of acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, salicylic anhydride, succinic anhydride, oxalic anhydride, and phosphoric anhydride.

[0032] In some embodiments of the present application, the dibasic acid anhydride includes but is not limited to one or more of maleic anhydride, fumaric anhydride, succinic anhydride, glutamic anhydride, adipic anhydride, phthalic anhydride, terephthalic anhydride, isocyanic anhydride, and trifluoroacetic anhydride.

[0033] In some embodiments of the present application, the acid anhydride includes one or more of methyltetrahydrophthalic anhydride, cyclobutanetetracarboxylic dianhydride, bicyclo[2.2.1]-heptane-2-methylcarboxylic acid-3,5,6-tricarboxy-2,3,5,6-dianhydride, difluorophthalic anhydride, hexafluorodianhydride, and pyromellitic dianhydride.

[0034] It should be noted that if it is necessary to prepare a highly transparent organosilicon polymer, hexafluorodianhydride can be selected.

[0035] In some embodiments of the present application, the value range of m and n is 50 to 50,000.

[0036] In some embodiments of the present application, the value range of m and n is 1000 to 20000.

[0037] In some embodiments of the present application, the value range of m and n is 2000 to 10000.

[0038] It should be noted that if the values ​​of m and n are too small, the molecular chain will be too short and the flexibility will be poor; if the values ​​of m and n are too large, the molecular chain will be too long and the viscosity will be too high to be suitable for use.

[0039] In a second aspect, a method for preparing an organosilicon polymer is provided, comprising the following steps: The organic silicon raw material containing primary amine is imidized to obtain an anhydride-terminated organic silicon polymer.

[0040] In some embodiments of the present application, the method for preparing the organosilicon polymer comprises the following steps: Add the acid anhydride and the solvent into a flask respectively, stir for 20-30 minutes at -10-10°C to fully dissolve them; under vacuum conditions (argon is introduced to remove oxygen in the reaction device), dropwise add the organosilicon raw material containing the primary amine, react at -10-10°C for 1-5 hours, then heat to room temperature and react for 12-48 hours to obtain a transparent amide acid modified intermediate; Acetic anhydride and triethylamine are added to the transparent amide acid modified intermediate, and the reaction is continued. After precipitation and separation, an anhydride-terminated organic silicon polymer is obtained.

[0041] In some embodiments of the present application, the organic silicon raw material may be aminopropyl silicone oil or aminopropyl terminated silicone oil, etc.

[0042] In some embodiments of the present application, an anhydride-terminated silicone polymer is reacted with a reactive group containing a hydroxyl / epoxy functional group to obtain a silicone polymer.

[0043] In some embodiments of the present application, the reactive group includes an active reactive group or an inactive reactive group.

[0044] In some embodiments of the present application, the active reaction groups include active groups such as double bonds and epoxy bonds.

[0045] In some embodiments of the present application, the inactive reactive groups include carboxyl groups, anhydride bonds and the like.

[0046] In some embodiments of the present application, if the organosilicon polymer does not contain active groups such as double bonds and epoxy bonds, a secondary reaction is required.

[0047] In some embodiments of the present application, the secondary reaction process is: S300, taking a certain amount of organosilicon polymer, adding solvent, catalyst and reactive groups containing hydroxyl or epoxy functional groups, and reacting at 100-150°C for 0.5-24h; S400, removing the solvent under vacuum at 60-120° C. to obtain an organosilicon polymer.

[0048] In some embodiments of the present application, the reactive group containing a hydroxyl or epoxy functional group includes at least one of acrylate, epoxy resin with a hydroxyl or epoxy functional group, silane coupling agent, cyanoacrylate, and cyclopentadiene.

[0049] In some embodiments of the present application, the reactive group containing hydroxyl / epoxy functional groups includes one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, glycidyl methacrylate, and cyclohexane-1,2-dicarboxylic acid diglycidyl ester.

[0050] In some embodiments of the present application, the organosilicon polymer is a colorless and transparent material and is used in the optical grade field.

[0051] In some embodiments of the present application, if the organosilicon polymer contains active groups such as double bonds and epoxy bonds, step S300 and step S400 are not performed.

[0052] It should be noted that imidization is an organic chemical reaction involving the reaction of anhydride with amine to form imide. Imide is a compound containing an imino group, which usually has high thermal stability and good chemical properties.

[0053] In a third aspect, a composition is also provided, comprising the aforementioned organosilicon polymer.

[0054] In some embodiments of the present application, the composition includes the following components in parts by weight: 5-70 parts of the aforementioned organosilicon polymer, 5-70 parts of silicone oil containing vinyl functional groups, 1-15 parts of silicone resin containing vinyl functional groups, 5-70 parts of hydrogen-containing silicone oil, 0-10 parts of platinum catalyst and additives, wherein the platinum catalyst is calculated as 2-50ppm according to the platinum content.

[0055] In some embodiments of the present application, the composition includes the following components in parts by weight: 10-90 parts of the aforementioned organosilicon polymer, 0-5 parts of initiator, 5-70 parts of active diluent, 0-5 parts of catalyst and 0-10 parts of auxiliary agent.

[0056] In some embodiments of the present application, the composition includes 5-70% of the aforementioned organosilicon polymer, 5-70% of vinyl silicone oil, 1-15% of vinyl MQ silicone resin, 15-70% of terminal hydrogen-containing silicone oil, 0-5% of side hydrogen-containing silicone oil, and 0-10% of platinum catalyst and agent; wherein the platinum catalyst is calculated as 2-50ppm according to the platinum content.

[0057] Specifically, the platinum catalyst uses a Custer platinum catalyst or an ultraviolet-activated platinum catalyst.

[0058] In a fourth aspect, there is also provided a use of the aforementioned organosilicon polymer or the aforementioned composition in an adhesive or a coating.

[0059] In some embodiments of the present application, a UV-curable organic silicone adhesive is provided, wherein the aforementioned organic silicone polymer is capped with an acrylate containing hydroxyl / epoxy functional groups or an epoxy resin containing hydroxyl / epoxy functional groups to obtain a modified material having a photoactive group, and then a photoinitiator, an active diluent and an auxiliary agent are added to obtain a UV-curable organic silicone adhesive.

[0060] In some embodiments of the present application, a UV-curable silicone coating is provided, wherein the aforementioned silicone polymer is end-capped with an acrylate containing hydroxyl / epoxy functional groups or an epoxy resin containing hydroxyl / epoxy functional groups to obtain a modified material having a photoactive group, and then a photoinitiator, an active diluent and an auxiliary agent are added to obtain a UV-curable silicone coating.

[0061] In some embodiments of the present application, the photoinitiator includes but is not limited to 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-1-[4-(methylthio)phenyl]-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester and one or more mixtures thereof.

[0062] In some embodiments of the present application, the active diluent includes, but is not limited to, a mixture of one or more of acrylates, methacrylates, vinyl ethers, alkoxy epoxy monomers, aromatic epoxy monomers, and the like.

[0063] In some embodiments of the present application, the auxiliary agent includes but is not limited to a mixture of one or more of silane coupling agents, leveling agents, defoaming agents, and antioxidants.

[0064] In some embodiments of the present application, a heat-curing organic silicone adhesive is also provided, wherein the aforementioned organic silicone polymer is end-capped with an acrylate containing hydroxyl / epoxy functional groups or an epoxy resin containing hydroxyl / epoxy functional groups to obtain a modified material having active groups, and then a thermal initiator, an epoxy cross-linking agent, an active diluent and an auxiliary agent are added to obtain a heat-curing organic silicone adhesive.

[0065] In some embodiments of the present application, a heat-curing silicone coating is also provided, wherein the aforementioned silicone polymer is capped with an acrylate containing hydroxyl / epoxy functional groups or an epoxy resin containing hydroxyl / epoxy functional groups to obtain a modified material having active groups, and then a thermal initiator, an epoxy cross-linking agent, an active diluent and an auxiliary agent are added to obtain a heat-curing silicone coating.

[0066] In some embodiments of the present application, the thermal initiator includes but is not limited to a mixture of one or more of benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, tert-butyl perbenzoate, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, etc.

[0067] In some embodiments of the present application, the active diluent includes, but is not limited to, a mixture of one or more of acrylates, methacrylates, vinyl ethers, alkoxy epoxy monomers, aromatic epoxy monomers, and the like.

[0068] The present application is described in detail below by means of specific examples, which are only partial examples of the present application and are not intended to limit the present application. The raw materials used in the following examples are all commercially available products unless otherwise specified.

[0069] Example 1 An organic silicone adhesive is prepared by the following method: S100, 1,2,3,4-cyclobutanetetracarboxylic anhydride (2.9418 g, 0.015 mol), methyltetrahydrophthalic anhydride (2.6589 g, 0.016 mol) and solvent dimethylacetamide (150 g) were added to a flask respectively, and stirred at 0°C for 25 min to fully dissolve; after multiple vacuum-argon gas passes, the oxygen in the reaction device was removed, and then the side chain aminopropyl silicone oil (WACKER® FINISH WR 1300, 100 g, amino content 0.3 mmol / g) was slowly dripped in, and the dripping was completed in 1 hour, and the reaction was carried out at 0°C for 2 hours, and then at room temperature for 24 hours to obtain a transparent polyamic acid (PAAs) solution; S200, adding 26.7 g of acetic anhydride and 9.92 g of triethylamine to a transparent polyamic acid (PAAs) solution, removing oxygen in the reaction device by multiple vacuum-argon passes, continuing the reaction at room temperature for 12 h, slowly pouring the reaction mixture into ethanol, precipitating a white filamentous precipitate, filtering it, and drying it to obtain an imide-modified silicone polymer with an unsaturated double bond; S300, take 30g of the organic silicon polymer prepared by S200, 5g of MQ silicone resin (Andisil® VQM1040), 14g of vinyl silicone oil (Andisil® VS 2000), 1g of side chain vinyl silicone oil (Andisil® VDM500), and 10ppm of Custer catalyst, stir evenly to form component A. Take 40g of terminal hydrogen silicone oil (Andisil® CE500), 2g of side hydrogen silicone oil (Andisil® XL12), 8g of vinyl silicone oil (Andisil® VS 2000), and 50ppm of 1-ethynyl cyclohexanol to form component B. The ratio of A / B is 1:1 to obtain an organic silicon adhesive; The chemical reaction formula of S100 in this embodiment is shown in Figure 1 ; The chemical reaction formula of S200 in this embodiment is shown in Figure 2 .

[0070] Example 2 A UV-curable adhesive is prepared by the following method: S100, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (0.8629 g, 0.0044 mol) and solvent dimethylacetamide (150 g) were added to a flask respectively, and stirred at 0°C for 20-30 min to fully dissolve; after multiple vacuum-argon gas passes, the oxygen in the reaction device was removed, and then aminopropyl-terminated silicone oil (20000 cps, 100 g, amino content 0.04 mmol / g) was slowly dripped in, and the dripping was completed in 1 hour, and the reaction was carried out at 0°C for 2 hours, and then at room temperature for 24 hours to obtain a transparent polyamic acid (PAAs) solution; S200, add appropriate amount of acetic anhydride 3.8g and triethylamine 1.5g to the polymerization system, remove oxygen in the reaction device by vacuum-passing argon several times, and continue the reaction at room temperature for 12h. Slowly pour the reaction mixture into ethanol to precipitate white filamentous precipitate, filter it out, and dry it to obtain an anhydride-terminated silicone resin; S300, adding an anhydride-terminated silicone resin into a four-necked flask, adding 100 g of dimethylacetamide, 0.01 g of p-toluenesulfonic acid and 0.51 g of hydroxyethyl acrylate, removing oxygen from the reaction device by multiple vacuum-argon passes, and reflux reaction at 115° C. for 4 h; S400, removing the solvent by vacuum at 60-120°C to obtain an acrylic acid-modified organosilicon polymer; S500, taking 72.5 g of the acrylic acid-modified silicone polymer prepared in S400, adding 15 g of isobornyl methacrylate, 5 g of hydroxyethyl acrylate, 0.5 g of 1,3,5-triacryloylhexahydro-1,3,5-triazine, 0.5 g of photoinitiator TPO-, 0.1 g of photoinitiator 811-, 0.4 g of triethyl phosphite, 3 g of antioxidant 1010-, and 3 g of 1,6-hexanedithiol, and mixing them thoroughly under argon conditions to obtain a UV-curable adhesive; The chemical reaction formula of S100 in this embodiment is shown in Figure 3 ; In this embodiment, the chemical reaction formula of S200 is shown in Figure 4 ; The chemical reaction formula of S400 in this embodiment is shown in Figure 5 .

[0071] Example 3 A silicone optical tape is prepared by the following method: S100, 1,2,3,4-cyclobutanetetracarboxylic anhydride (3.9224 g, 0.02 mol), methyltetrahydrophthalic anhydride (1.828 g, 0.011 mol) and solvent dimethylacetamide (150 g) were added to a flask respectively, and stirred at 0°C for 25 min to fully dissolve; after multiple vacuum-argon gas passes, the oxygen in the reaction device was removed, and then the side chain aminopropyl silicone oil (WACKER® FINISH WR 1300, 100 g, amino content 0.3 mmol / g) was slowly dripped in, and the dripping was completed in 1 hour, and the reaction was carried out at 0°C for 2 hours, and then at room temperature for 24 hours to obtain a transparent polyamic acid (PAAs) solution; S200, adding 26.7 g of acetic anhydride and 9.92 g of triethylamine to a transparent polyamic acid (PAAs) solution, removing oxygen in the reaction device by multiple vacuum-argon passes, continuing the reaction at room temperature for 12 h, slowly pouring the reaction mixture into ethanol, precipitating a white filamentous precipitate, filtering it, and drying it to obtain an imide-modified silicone polymer with an unsaturated double bond; S300, take 30g of imide-modified silicone polymer with unsaturated double bonds, 5g of MQ silicone resin (Andisil® VQM1040), 14.5g of vinyl silicone oil (Andisil® VS 2000), 0.5g of side-chain vinyl silicone oil (Andisil® VDM500), and 10ppm of Custer catalyst; component B: take 46g of terminal hydrogen silicone oil (Andisil® CE500), 4g of vinyl silicone oil (Andisil® VS 2000), and 50ppm of 1-ethynyl cyclohexanol to form component B. The ratio of A / B is 1:1, and after mixing evenly, apply it on the release film to cure, and then cover the surface of the adhesive layer with the release film and roll it up to make a silicone optical tape (OCA).

[0072] Comparative Example 1 An organic silicone adhesive, which is different from Example 1 in that no modification reaction is performed, and in its formula, a side vinyl silicone oil with the same functionality is used to replace the imide-modified organic silicone polymer with an unsaturated double bond; Take 30g of the above silicone polymer, 5g of MQ silicone resin (Andisil® VQM1040), 14g of vinyl silicone oil (Andisil® VS 2000), 1g of side chain vinyl silicone oil (Andisil® VDM500), and 10ppm of Custer catalyst, and stir evenly to form component A. Take 40g of terminal hydrogen silicone oil (Andisil® CE500), 2g of side hydrogen silicone oil (Andisil® XL12), 8g of vinyl silicone oil (Andisil® VS 2000), and 50ppm of 1-ethynyl cyclohexanol to form component B. The ratio of A / B is 1:1 to obtain a silicone adhesive.

[0073] Comparative Example 2 An adhesive, which is different from Example 2 in that aminopropyl terminated silicone oil (20000 cps, 100 g, amino content 0.04 mmol / g) is slowly added with isocyanoethyl methacrylate (0.6827 g, 0.0044 mol) at room temperature to finally prepare an amined silicone polymer containing an acryloxy group; Take 72.5 g of the above-mentioned silicone polymer, add 15 g of isobornyl methacrylate, 5 g of hydroxyethyl acrylate, 0.5 g of 1,3,5-triacryloylhexahydro-1,3,5-triazine, 0.5 g of photoinitiator TPO-, 0.1 g of photoinitiator 811-, 0.4 g of triethyl phosphite, 3 g of antioxidant 1010-, and 3 g of 1,6-hexanedithiol, and mix thoroughly under argon conditions to obtain an adhesive.

[0074] Comparative Example 3 An organic silicon optical adhesive tape, which is different from Example 3 in that the imide-modified organic silicon polymer with unsaturated double bonds is replaced with a common side-chain vinyl silicone oil (with equivalent vinyl content); Take 30g of the above silicone polymer, 5g of MQ silicone resin (Andisil® VQM1040), 14.5 parts of vinyl silicone oil (Andisil® VS 2000), 0.5g of side chain vinyl silicone oil (Andisil® VDM500), and 10ppm of Custer catalyst; component B: take 46g of terminal hydrogen silicone oil (Andisil® CE500), 4g of vinyl silicone oil (Andisil® VS 2000), and 50ppm of 1-ethynyl cyclohexanol to form component B. The ratio of A / B is 1:1, and after mixing evenly, apply it on the light release film to cure, and then cover the surface of the adhesive layer with the light release film and roll it up to make a silicone optical tape.

[0075] Detection methods: (1) b value test (Lab test): GB / T 3181-2008 "Paint Film Color Standard"; (2) Clarity test: GB / T 2410-2008 "Determination of light transmittance and haze of transparent plastics"; (3) Elastic modulus test: ASTM D5026 "Standard Test Methods for Plastics: Dynamic Mechanical Properties" sample size 8 mm diameter, tested using Anton Paar's MCR 702e; (4) Hardness test: GB / T 2411-2008 "Plastics and hard rubber - Determination of indentation hardness (Shore hardness) using a hardness tester"; (5) Shear force test: GB / T 7124-2008 "Determination of tensile shear strength (rigid material to rigid material)"; (6) Q-sun test: GB / T 16422.2-2014 "Plastics laboratory light source exposure test method Part 2: Xenon arc lamp".

[0076] Table 1

[0077] Combining the test results of Examples 1-3, Comparative Examples 1-3 and Table 1, it can be seen that at 25°C, the elastic modulus of Examples 1-3 and Comparative Examples 1-3 are not much different. This is because after modification, Examples 1-3 have more branches and are not easy to crystallize at low temperatures, so the elastic modulus does not change much. The Comparative Example uses ordinary vinyl silicone oil, which has higher symmetry, is easy to crystallize at low temperatures, and the elastic modulus increases sharply.

[0078] The modified silicone polymers of Examples 1-3 contain additional anhydride bonds, which can easily react with the hydroxyl groups on the surface of the substrate, greatly improving the adhesion to the substrate, so the shear strength G+G and shear strength PC+PC are significantly increased. However, Comparative Examples 1-3 do not have additional anhydride bonds and cannot continue to react with the hydroxyl groups on the surface of the substrate, so the shear strength decreases, especially the shear strength decreases significantly on the PC substrate.

[0079] The above are only preferred embodiments of the present application and do not constitute any form of limitation to the present application. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present application without departing from the content of the technical solution of the present application are still within the scope of the technical solution of the present application.

Claims

1. An organosilicon polymer, characterized in that: Including a polymer as shown in formula I: Formula I; In formula I, at least one of R1, R2, R3 and R4 is independently selected from a functional group formed by imidization of an anhydride and an amino group; The value range of m and n is 50 to 50000.

2. The organosilicon polymer according to claim 1, characterized in that At least one of R1, R2, R3 and R4 is independently selected from a combination of a functional group formed by imidization of the acid anhydride and the amino group and one or more of methyl, ethyl, propyl, hydroxyl and phenyl.

3. The organosilicon polymer according to claim 1, characterized in that The functional group formed by imidization of the acid anhydride and the amino group includes the chemical formula shown in Formula II and / or Formula III: Formula II; Formula III; In formula II, R5 is independently selected from the residual group of anhydride and amino group after imidization; a ranges from 1 to 10; In formula III, R6 is independently selected from a hydrogen atom, or selected from one or more functional groups selected from the group consisting of an acryloyloxy group, a methacryloyloxy group, an epoxy group, an acrylonitrile group, a cyclopentadienyl group, and a siloxane group; and the value of a ranges from 1 to 10.

4. The organosilicon polymer according to claim 1, characterized in that The acid anhydride includes a monobasic acid anhydride or a dibasic acid anhydride.

5. The organosilicon polymer according to claim 4, characterized in that The acid anhydride includes one or more of methyltetrahydrophthalic anhydride, cyclobutanetetracarboxylic dianhydride, bicyclo[2.2.1]-heptane-2-methylcarboxylic acid-3,5,6-tricarboxy-2,3,5,6-dianhydride, difluorophthalic anhydride, hexafluorodianhydride, and pyromellitic dianhydride.

6. The organosilicon polymer according to claim 1, characterized in that The value range of m and n is 1000 to 20000.

7. The organosilicon polymer according to claim 6, characterized in that The value range of m and n is 2000 to 10000.

8. A method for preparing an organosilicon polymer according to any one of claims 1 to 7, characterized in that: The steps include: The organic silicon raw material containing primary amine is imidized to obtain an anhydride-terminated organic silicon polymer.

9. The method for preparing an organosilicon polymer according to claim 8, characterized in that: The following steps are also included: The anhydride terminated silicone polymer is reacted with a reactive group containing hydroxyl / epoxy functional groups to obtain a silicone polymer.

10. The method for preparing an organosilicon polymer according to claim 9, characterized in that: The reactive group containing hydroxyl / epoxy functional groups includes one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, glycidyl methacrylate, and cyclohexane-1,2-dicarboxylic acid diglycidyl ester.

11. A composition, characterized in that The organic silicon polymer comprises the organic silicon polymer described in any one of claims 1 to 7.

12. The composition according to claim 11, characterized in that The composition comprises the following components in parts by weight: 5-70 parts of the organosilicon polymer according to any one of claims 1-7, 5-70 parts of silicone oil containing vinyl functional groups, 1-15 parts of silicone resin containing vinyl functional groups, 5-70 parts of hydrogen-containing silicone oil, and 0-10 parts of platinum catalyst and additives, wherein the platinum catalyst is 2-50 ppm calculated according to the platinum content.

13. The composition according to claim 11, characterized in that The composition comprises the following components in parts by weight: 10-90 parts of the aforementioned organosilicon polymer, 0-5 parts of initiator, 5-70 parts of active diluent, 0-5 parts of catalyst and 0-10 parts of auxiliary agent.

14. Use of the organosilicon polymer according to any one of claims 1 to 7 or the composition according to any one of claims 11 to 13 in an adhesive or a coating.

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