High-damping organic silicon pressure-sensitive adhesive and preparation method thereof

Abstract

The invention belongs to the technical field of organic materials, and particularly relates to an organic silicon pressure-sensitive adhesive capable of achieving high damping and high stripping force. The organic silicon pressure-sensitive adhesive has the advantages that a mixture containing boron-oxygen-silicon bonds and having good damping performance is well compatible and dispersed with a system; a multi-stage network structure is formed through molecular design, a mixture containing boron-oxygen-silicon bonds is limited within a certain range, cohesion is promoted, anchor-shaped molecular chains and methyl hydroxyl MQ in the network structure can further synergistically enhance the damping performance, the stripping force is stable after a film is formed through coating of the colloid, and ghosting residual glue does not occur.

Description

Technical Field

[0001] The invention belongs to the technical field of organic materials, and in particular relates to a high-damping organic silicon pressure-sensitive adhesive and a preparation method thereof. Background Art

[0002] In modern industrial equipment, shock and vibration problems are common. The use of damping materials is an effective way to convert mechanical energy such as vibration and shock into heat energy dissipation.

[0003] High-performance damping rubber materials are usually obtained by rubber copolymerization, blending or interpenetrating polymer network technology of two or more polymers. The key point is to enhance the internal friction between molecular chains by controlling the viscoelasticity of the polymer. Although the interpenetrating polymer network technology can synergistically combine different polymers to form a new type of polymer material with high damping, its process is complicated and the cost is high, which limits its use. In addition, damping materials can also be prepared by dynamic covalent bonds such as hydrogen bonds, ionic bonds, and metal coordination bonds. These non-covalent bonds can reversibly break and regenerate, absorb external energy, thereby causing the movement of molecular chains and increasing internal friction. Usually, this type of material is mostly gel-like, and it is also necessary to add substances that can form a cross-linked network structure to increase cohesion. Patent CN 116694300 uses polyborosiloxane prepolymers to obtain impact-resistant silicone pressure-sensitive adhesives for flexible display screens. The poor dispersibility of the prepolymer may cause the pressure-sensitive adhesive to have low cohesion and residual glue when peeling. Patent CN108048031A uses covalent bonds between hydrogenated silicone and vinyl polysiloxane to obtain a pressure-sensitive adhesive with higher cohesive strength, but limits the mobility of the molecular network and greatly reduces the damping performance.

[0004] It can be seen that it is particularly important to provide a silicone pressure-sensitive adhesive that can achieve both high damping and high peeling force. The advantage of the present invention is that the mixture containing boron-oxygen-silicon bonds with good damping properties is well compatible and dispersed with the system, and the mixture containing boron-oxygen-silicon bonds is limited to a certain range by forming a multi-level network structure through molecular design, which is not only conducive to the improvement of cohesive force, but also the anchor-like molecular chain and methyl hydroxyl MQ in the network structure can further synergistically enhance the damping performance. After the colloid is coated and formed into a film, the peeling force is stable, and no ghost residual glue appears. Summary of the invention

[0005] In order to solve the above-mentioned deficiencies in the art, an organic silicone pressure-sensitive adhesive that can achieve both high damping and high peeling force has been invented.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0007] The present invention provides a high-damping organic silicon pressure-sensitive adhesive, the components of which include, by weight:

[0008]

[0009] Wherein, the mixture containing boron-oxygen-silicon bonds includes components of the following structure:

[0010]

[0011]

[0012] Wherein, Q1 and Q2 are a combination of one or more of -CH=CH2, -CH3, and -OH.

[0013] As a preferred technical solution of the present invention, the preparation method of the mixture containing boron-oxygen-silicon bonds is as follows: side chain vinyl polydimethylsiloxane, hydroxy vinyl polysiloxane, hydroxy polysiloxane, and boric acid are added into a reaction kettle in a weight ratio of (20-50): (40-70): (30-80): (4-16), D70 solvent is added to assist dissolution, and after rapid and uniform dispersion, negative pressure is turned on to remove the D70 solvent, and the temperature is raised and maintained at 150-180° C., and the mixture is stirred and reacted for 3-4 hours;

[0014] The side chain vinyl polydimethylsiloxane is an alkenyl-containing polydimethylsiloxane having at least two vinyl groups bonded to silicon atoms in one molecular chain and an average degree of polymerization of more than 5000. The side chain vinyl polydimethylsiloxane has a molecular weight of 400,000 to 600,000, a vinyl content of 0.012% to 0.15%, a molecular weight of preferably 450,000 to 550,000, and a vinyl content of preferably 0.03% to 0.12%;

[0015] The hydroxy vinyl polysiloxane has two hydroxyl groups bonded to silicon atoms on one molecular chain and at least one vinyl group bonded to silicon atoms on the molecular chain, a viscosity of 300 to 800 cps, a vinyl content of 2% to 4%, and a hydroxyl content of 2% to 4.5%;

[0016] The hydroxy polysiloxane has at least two hydroxyl groups bonded to silicon atoms in one molecular chain, a viscosity of 200-600 cps, and a hydroxyl content of 2%-4%.

[0017] As a preferred technical solution of the present invention, the polymethylvinylsiloxane includes one or two of terminal vinyl polymethylvinylsiloxane and side chain vinyl polydimethylsiloxane, wherein the terminal vinyl polymethylvinylsiloxane is a polymethylvinylsiloxane having at least 3 vinyl groups bonded to silicon atoms at both ends and in the side chain of one molecule and an average degree of polymerization of more than 5000; the molecular weight of the terminal vinyl polymethylvinylsiloxane is 350,000 to 650,000, and the alkenyl content is 0.12% to 0.3%;

[0018] The side chain vinyl polydimethylsiloxane is an alkenyl-containing polydimethylsiloxane having at least two vinyl groups bonded to silicon atoms in one molecular chain and an average degree of polymerization of more than 5000. The molecular weight of the side chain vinyl polydimethylsiloxane is 400,000 to 600,000, the vinyl content is 0.012% to 0.15%, the molecular weight is preferably 450,000 to 550,000, and the vinyl content is preferably 0.03% to 0.12%.

[0019] As a preferred technical solution of the present invention, the MQ silicone resin includes one or both of methyl vinyl MQ and methyl hydroxyl MQ, and the methyl vinyl MQ is compounded by methyl MQ silicone resin and methyl hydroxyl MQ silicone resin in a mass ratio of (4-6): (0.5-1.5), the M / Q value of the methyl vinyl MQ is 0.6-0.9, the vinyl content is 0.3%-0.8%, and the relative molecular mass is 4500-6000g / mol; the M / Q value of the methyl hydroxyl MQ is 0.6-0.9, the relative molecular mass is 3500-4500g / mol, and the hydroxyl content is 0.2%-0.5%. Preferably, the M / Q value of the methyl vinyl MQ silicone resin is 0.7-0.8, the relative molecular mass is 4500-5600g / mol; the M / Q value of the methyl hydroxyl MQ silicone resin is 0.6-0.8, and the relative molecular mass is 4000-4500g / mol.

[0020] As a preferred technical solution of the present invention, the first solvent is toluene or xylene.

[0021] As a preferred technical solution of the present invention, the hydrogen-containing silicone oil includes one, two or three of single-end hydrogen-terminated polydimethylsiloxane, double-end hydrogen-terminated polydimethylsiloxane and side-chain multi-hydrogen-terminated polydimethylsiloxane, wherein the single-end hydrogen-terminated polydimethylsiloxane is an organic hydrogen polysiloxane having one hydrogen atom bonded to a silicon atom in one molecule; the organic hydrogen polysiloxane has an active hydrogen content of 0.01 to 0.06% and a viscosity of 50 to 150 mm 2 / s, and preferably the active hydrogen content is 0.01 to 0.03%, and the viscosity is 80 to 100 mm 2 / s;

[0022] The double-end hydrogen-terminated polydimethylsiloxane is an organic hydrogen polysiloxane having two hydrogen atoms bonded to silicon atoms in one molecule; the organic hydrogen polysiloxane has an active hydrogen content of 0.02 to 0.08% and a viscosity of 40 to 100 mm 2 / s, further, preferably the active hydrogen content is 0.04-0.06%, the viscosity is 50-70mm 2 / s;

[0023] The side chain polyhydrogen-terminated polydimethylsiloxane is an organohydrogen polysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule, and the organohydrogen polysiloxane has an active hydrogen content of 0.8 to 1.8% and a viscosity of 12 to 34 mm 2 / s, further preferably, the active hydrogen content is 1 to 1.6%, and the viscosity is 16 to 28 mm 2 / s.

[0024] As a preferred technical solution of the present invention, the platinum catalyst is one of platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, platinum (0)-1,3-dimethyl-1,3-diphenyl-1,3-divinyldisiloxane complex, platinum (0)-1,3-divinyltetramethyldisiloxane complex, or a mixture of any of them.

[0025] As a preferred technical solution of the present invention, the anchoring agent is one or more of the siloxane adhesive anchoring agents ADD28, ADD38, ADD29, ADD109 produced by Elkem Silicones (Guangdong) Co., Ltd., preferably ADD28.

[0026] As a preferred technical solution of the present invention, the inhibitor is one of 2-methyl-3-butynol, 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol and 3-methyl-1-dodecyn-3-ol or a mixture of any of them.

[0027] As a preferred technical solution of the present invention, the second solvent includes one or more of toluene, xylene, ethyl acetate, butyl acetate, acetone, and D70 solvent.

[0028] On the other hand, the present invention provides a method for preparing the above-mentioned high damping organosilicon pressure-sensitive adhesive:

[0029] Firstly, a mixture containing boron-oxygen-silicon bonds is prepared by reacting side chain vinyl polydimethylsiloxane, hydroxy vinyl polysiloxane, hydroxy polysiloxane and boric acid in a weight ratio of (20-50):(40-70):(30-80):(4-16);

[0030] The mixture containing boron-oxygen-silicon bonds, polymethylvinylsiloxane, MQ silicone resin, inhibitor and the first solvent are placed in a reaction kettle, sealed with nitrogen, stirred to make the materials uniformly mixed and dissolved, stirred for 8 to 12 hours, and cooled to room temperature to obtain an addition-type organic silicone pressure-sensitive adhesive main agent with a solid content of 65 to 80% and a viscosity of 30,000 to 50,000 mPa.s;

[0031] A second solvent is added to the main agent of the organic silicone pressure-sensitive adhesive to dilute it to a solid content of 30-45%, hydrogenated silicone oil, an anchoring agent, and a platinum catalyst are added and stirred evenly, a film preparation device is used to scrape the adhesive evenly on the PET film, and then it is baked and dried at a temperature of 100-150° C. to obtain the high damping organic silicone pressure-sensitive adhesive.

[0032] By adopting the above technical solution, the beneficial effects of the present invention are:

[0033] 1. The present invention uses a mixture containing boron-oxygen-silicon bonds. The introduction of a macromolecular main chain during preparation can be well interspersed in the newly generated boron-oxygen-silicon bond mixture. Its beneficial effect is that the silicon-oxygen-boron mixture can be quickly dispersed in the pressure-sensitive adhesive system, and then the prepolymer can be confined in the designed cross-linked network through addition reaction, which is conducive to improving cohesion and achieving high peeling force;

[0034] 2. The introduction of a small amount of methyl hydroxyl MQ can form new non-covalent bonds with boron oxide silicon in a local area, enhance the absorption and dissipation of external energy, increase adhesion and reinforcement, and improve damping performance.

[0035] 3. The single-end hydrogen-terminated polydimethylsiloxane used is used as a graft with the main molecular chain to form a molecular anchor chain, the double-end hydrogen-terminated polydimethylsiloxane is used as a chain extension crosslinker, and the side chain multi-hydrogen-terminated polydimethylsiloxane network crosslinker forms a multi-level network structure with the main chain to synergistically enhance the damping performance. DETAILED DESCRIPTION

[0036] It should be noted that the following detailed descriptions are all illustrative and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0037] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0038] The present invention is further illustrated below in conjunction with embodiments and comparative examples.

[0039] Example 1

[0040] The raw materials include (the following parts are all by weight):

[0041] 21 parts of a mixture containing boron-oxygen-silicon bonds

[0042] 44 parts of polymethylvinylsiloxane

[0043]

[0044] The preparation steps include:

[0045] 1) Preparation of a mixture containing boron-oxygen-silicon bonds

[0046] 32 parts of side chain vinyl polydimethylsiloxane, 48 parts of hydroxy vinyl polysiloxane, 57 parts of hydroxy polysiloxane and 7 parts of boric acid are put into a reaction kettle, 38 parts of D70 solvent is added for dissolution, and after rapid and uniform dispersion, negative pressure is turned on to remove the D70 solvent, the temperature is raised and maintained at 150-180° C., and the mixture is stirred and reacted for 3-4 hours to obtain a mixture containing boron-oxygen-silicon bonds, wherein the side chain vinyl polydimethylsiloxane has a molecular weight of 400,000 and a vinyl content of 0.06%; the hydroxy vinyl polysiloxane has a viscosity of 400 cps, a vinyl content of 3%, and a hydroxyl content of 3%; the hydroxy polysiloxane has a viscosity of 300 cps and a hydroxyl content of 3%.

[0047] 2) Preparation of high damping silicone pressure-sensitive adhesive

[0048] The mixture containing boron-oxygen-silicon bonds, polymethylvinylsiloxane, MQ silicone resin, inhibitor and the first solvent are placed in a reaction kettle, sealed with nitrogen, stirred to make the materials uniformly mixed and dissolved, stirred for 8 to 12 hours, and cooled to room temperature to obtain an addition-type organic silicone pressure-sensitive adhesive main agent with a solid content of 65 to 80% and a viscosity of 30,000 to 50,000 mPa.s;

[0049] A second solvent is added to the main agent of the organic silicone pressure-sensitive adhesive to dilute it to a solid content of 30-45%, hydrogenated silicone oil, an anchoring agent, and a platinum catalyst are added and stirred evenly, a film preparation device is used to scrape the adhesive evenly on the PET film, and then it is baked and dried at a temperature of 100-150° C. to obtain the high damping organic silicone pressure-sensitive adhesive.

[0050] Specifically, the polymethylvinylsiloxane is a vinyl-terminated polymethylvinylsiloxane with a molecular weight of 350,000 and an olefin content of 0.18%. The MQ silicone resin includes 40.5 parts of methylvinylMQ and 10.1 parts of methylhydroxyMQ, wherein the M / Q value of the methylvinylMQ is 0.8, the vinyl content is 0.12%, and the relative molecular mass is 4500 g / mol; the M / Q value of the methylhydroxyMQ is 0.8, the relative molecular mass is 3600 g / mol, and the hydroxyl content is 0.3%.

[0051] Specifically, the first solvent is xylene.

[0052] Specifically, the hydrogen-containing silicone oil includes 0.5 parts of single-end hydrogen-terminated polydimethylsiloxane, 0.2 parts of double-end hydrogen-terminated polydimethylsiloxane, and 1.8 parts of side-chain multi-hydrogen-terminated polydimethylsiloxane, wherein the active hydrogen content of the single-end hydrogen-terminated polydimethylsiloxane is 0.03% and the viscosity is 60 mm 2 / s; the active hydrogen content of the double-terminal hydrogen-terminated polydimethylsiloxane is 0.05%, and the viscosity is 50mm 2 / s; the active hydrogen content of the side chain polyhydrogen-terminated polydimethylsiloxane is 1.4%, and the viscosity is 16mm 2 / s.

[0053] Specifically, the anchoring agent includes 1.2 parts of ADD38 and 0.2 parts of ADD28;

[0054] Specifically, the platinum catalyst is a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.

[0055] Specifically, the inhibitor is 0.2 parts of ethynylcyclohexanol;

[0056] Specifically, the second solvent includes 150 parts of ethyl acetate and 50 parts of butyl acetate.

[0057] Similarly, Examples 2 to 5 and Comparative Examples 1 and 2 were prepared respectively. Since the preparation methods were similar and the only difference was the raw material components, only the components and amounts were provided below:

[0058] Example 2

[0059]

[0060] The polymethylvinylsiloxane is specifically a vinyl-terminated polymethylvinylsiloxane with a molecular weight of 400,000 and an olefin content of 0.16%. The MQ silicone resin includes 41.8 parts of methylvinylMQ and 8.8 parts of methylhydroxyMQ, wherein the M / Q value of the methylvinylMQ is 0.8, the vinyl content is 0.14%, and the relative molecular mass is 4000 g / mol; the M / Q value of the methylhydroxyMQ is 0.8, the relative molecular mass is 4500 g / mol, and the hydroxyl content is 0.3%.

[0061] Specifically, the first solvent is xylene.

[0062] Specifically, the hydrogen-containing silicone oil includes 0.7 parts of single-end hydrogen-terminated polydimethylsiloxane, 0.3 parts of double-end hydrogen-terminated polydimethylsiloxane, and 2 parts of side-chain multi-hydrogen-terminated polydimethylsiloxane, wherein the active hydrogen content of the single-end hydrogen-terminated polydimethylsiloxane is 0.02% and the viscosity is 80 mm 2 / s; the active hydrogen content of the double-terminal hydrogen-terminated polydimethylsiloxane is 0.04%, and the viscosity is 70mm 2 / s; the active hydrogen content of the side chain multi-hydrogen-terminated polydimethylsiloxane is 1.4%, and the viscosity is 18mm 2 / s.

[0063] Specifically, the anchoring agent includes 1.0 parts of ADD109, 0.6 parts of ADD38;

[0064] Specifically, the platinum catalyst is a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.

[0065] Specifically, the inhibitor is 3-methyl-1-dodecyne-3-ol;

[0066] Specifically, the second solvent includes 200 parts of xylene.

[0067] The raw materials of the mixture containing boron-oxygen-silicon bonds include: 24 parts of side chain vinyl polydimethylsiloxane, 42 parts of hydroxy vinyl polysiloxane, 62 parts of hydroxy polysiloxane, 8 parts of boric acid, and 40 parts of D70 solvent, wherein the molecular weight of the side chain vinyl polydimethylsiloxane is 450,000 and the vinyl content is 0.08%; the viscosity of the hydroxy vinyl polysiloxane is 300cps, the vinyl content is 3%, and the hydroxyl content is 4%; the viscosity of the hydroxy polysiloxane is 350cps, and the hydroxyl content is 4%.

[0068] Example 3

[0069]

[0070]

[0071] The polymethylvinylsiloxane is specifically a vinyl-terminated polymethylvinylsiloxane with a molecular weight of 450,000 and an olefin content of 0.16%. The MQ silicone resin includes 42.4 parts of methylvinylMQ and 8.5 parts of methylhydroxyMQ, wherein the M / Q value of the methylvinylMQ is 0.9, the vinyl content is 0.16%, and the relative molecular mass is 4000 g / mol; the M / Q value of the methylhydroxyMQ is 0.7, the relative molecular mass is 4000 g / mol, and the hydroxyl content is 0.5%.

[0072] Specifically, the first solvent is xylene.

[0073] Specifically, the hydrogen-containing silicone oil includes 0.6 parts of single-end hydrogen-terminated polydimethylsiloxane, 0.3 parts of double-end hydrogen-terminated polydimethylsiloxane, and 2.2 parts of side-chain multi-hydrogen-terminated polydimethylsiloxane, wherein the active hydrogen content of the single-end hydrogen-terminated polydimethylsiloxane is 0.03% and the viscosity is 100 mm2 / s; the active hydrogen content of the double-terminal hydrogen-terminated polydimethylsiloxane is 0.04%, and the viscosity is 1000mm 2 / s; the active hydrogen content of the side chain polyhydrogen-terminated polydimethylsiloxane is 1.2%, and the viscosity is 25mm 2 / s.

[0074] Specifically, the anchoring agent includes 0.6 parts of ADD109, 0.7 parts of ADD38;

[0075] Specifically, the platinum catalyst is a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.

[0076] Specifically, the inhibitor is 0.1 parts of ethynylcyclohexanol, 0.06 parts of 3-methyl-1-dodecyne-3-ol;

[0077] Specifically, the second solvent is butyl acetate.

[0078] The raw materials of the mixture containing boron-oxygen-silicon bonds include: 26 parts of side chain vinyl polydimethylsiloxane, 42 parts of hydroxy vinyl polysiloxane, 62 parts of hydroxy polysiloxane, 11 parts of boric acid, and 44 parts of D70 solvent, wherein the molecular weight of the side chain vinyl polydimethylsiloxane is 500,000 and the vinyl content is 0.06%; the viscosity of the hydroxy vinyl polysiloxane is 400cps, the vinyl content is 3%, and the hydroxyl content is 3%; the viscosity of the hydroxy polysiloxane is 300cps, and the hydroxyl content is 3%.

[0079] Example 4

[0080]

[0081]

[0082] The polymethylvinylsiloxane is specifically a vinyl-terminated polymethylvinylsiloxane, with a molecular weight of 400,000 and an olefin content of 0.16%. The MQ silicone resin includes 45.4 parts of methylvinylMQ and 9.4 parts of methylhydroxyMQ, wherein the M / Q value of the methylvinylMQ is 0.8, the vinyl content is 0.12%, and the relative molecular mass is 5000 g / mol; the M / Q value of the methylhydroxyMQ is 0.8, the relative molecular mass is 4500 g / mol, and the hydroxyl content is 0.3%.

[0083] Specifically, the first solvent is toluene.

[0084] Specifically, the hydrogen-containing silicone oil includes 0.8 parts of single-end hydrogen-terminated polydimethylsiloxane, 0.5 parts of double-end hydrogen-terminated polydimethylsiloxane, and 2.3 parts of side chain multi-hydrogen-terminated polydimethylsiloxane, wherein the active hydrogen content of the single-end hydrogen-terminated polydimethylsiloxane is 0.02% and the viscosity is 80 mm 2 / s; the active hydrogen content of the double-terminal hydrogen-terminated polydimethylsiloxane is 0.05%, and the viscosity is 50mm 2 / s; the active hydrogen content of the side chain polyhydrogen-terminated polydimethylsiloxane is 1.2%, and the viscosity is 25mm 2 / s.

[0085] Specifically, the anchoring agent includes 1.4 parts of ADD38, 0.2 parts of ADD28;

[0086] Specifically, the platinum catalyst is a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.

[0087] Specifically, the inhibitor is 0.2 parts of ethynylcyclohexanol;

[0088] Specifically, the second solvent includes 50 parts of ethyl acetate and 150 parts of butyl acetate.

[0089] The raw materials of the mixture containing boron-oxygen-silicon bonds include: 23 parts of side chain vinyl polydimethylsiloxane, 44 parts of hydroxy vinyl polysiloxane, 60 parts of hydroxy polysiloxane, 14 parts of boric acid, and 39 parts of D70 solvent, wherein the molecular weight of the side chain vinyl polydimethylsiloxane is 550,000 and the vinyl content is 0.06%; the viscosity of the hydroxy vinyl polysiloxane is 400cps, the vinyl content is 3%, and the hydroxyl content is 3%; the viscosity of the hydroxy polysiloxane is 400cps, and the hydroxyl content is 4%.

[0090] Example 5

[0091]

[0092] The polymethylvinylsiloxane is specifically a vinyl-terminated polymethylvinylsiloxane with a molecular weight of 350,000 and an olefin content of 0.2%. The MQ silicone resin includes 42.9 parts of methylvinylMQ and 9 parts of methylhydroxyMQ, wherein the M / Q value of the methylvinylMQ is 0.8, the vinyl content is 0.12%, and the relative molecular mass is 4500 g / mol; the M / Q value of the methylhydroxyMQ is 0.8, the relative molecular mass is 4500 g / mol, and the hydroxyl content is 0.4%.

[0093] Specifically, the first solvent is toluene.

[0094] Specifically, the hydrogen-containing silicone oil includes 0.5 parts of single-end hydrogen-terminated polydimethylsiloxane, 0.4 parts of double-end hydrogen-terminated polydimethylsiloxane, and 1.8 parts of side chain multi-hydrogen-terminated polydimethylsiloxane, wherein the active hydrogen content of the single-end hydrogen-terminated polydimethylsiloxane is 0.02% and the viscosity is 80 mm 2 / s; the active hydrogen content of the double-terminal hydrogen-terminated polydimethylsiloxane is 0.04%, and the viscosity is 70mm 2 / s; the active hydrogen content of the side chain multi-hydrogen-terminated polydimethylsiloxane is 1.4%, and the viscosity is 18mm 2 / s.

[0095] Specifically, the anchoring agent includes 1.3 parts of ADD109, 0.3 parts of ADD28;

[0096] Specifically, the platinum catalyst is a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.

[0097] Specifically, the inhibitor is 0.2 parts of ethynylcyclohexanol;

[0098] Specifically, the second solvent includes 200 parts of butyl acetate.

[0099] The raw materials of the mixture containing boron-oxygen-silicon bonds include: 36 parts of side chain vinyl polydimethylsiloxane, 37 parts of hydroxy vinyl polysiloxane, 65 parts of hydroxy polysiloxane, 12 parts of boric acid, and 46 parts of D70 solvent, wherein the molecular weight of the side chain vinyl polydimethylsiloxane is 450,000 and the vinyl content is 0.08%; the viscosity of the hydroxy vinyl polysiloxane is 350cps, the vinyl content is 3%, and the hydroxyl content is 3%; the viscosity of the hydroxy polysiloxane is 300cps, and the hydroxyl content is 3%.

[0100] Example 6

[0101]

[0102] The polymethylvinylsiloxane is specifically a vinyl-terminated polymethylvinylsiloxane with a molecular weight of 350,000 and an olefin content of 0.18%. The MQ silicone resin includes 46.2 parts of methylvinylMQ and 9.2 parts of methylhydroxyMQ, wherein the M / Q value of the methylvinylMQ is 0.8, the vinyl content is 0.14%, and the relative molecular mass is 5400 g / mol; the M / Q value of the methylhydroxyMQ is 0.7, the relative molecular mass is 4500 g / mol, and the hydroxyl content is 0.3%.

[0103] Specifically, the first solvent is toluene.

[0104] Specifically, the hydrogen-containing silicone oil includes 0.7 parts of single-end hydrogen-terminated polydimethylsiloxane, 0.3 parts of double-end hydrogen-terminated polydimethylsiloxane, and 2 parts of side-chain multi-hydrogen-terminated polydimethylsiloxane, wherein the active hydrogen content of the single-end hydrogen-terminated polydimethylsiloxane is 0.03% and the viscosity is 100 mm 2 / s; the active hydrogen content of the double-terminal hydrogen-terminated polydimethylsiloxane is 0.04%, and the viscosity is 70mm 2 / s; the active hydrogen content of the side chain multi-hydrogen-terminated polydimethylsiloxane is 1.4%, and the viscosity is 18mm 2 / s.

[0105] Specifically, the anchoring agent includes 1.0 parts of ADD109, 0.2 parts of ADD38, and 0.2 parts of ADD28;

[0106] Specifically, the platinum catalyst is a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.

[0107] Specifically, the inhibitor is 0.2 parts of ethynylcyclohexanol;

[0108] Specifically, the second solvent includes 200 parts of xylene.

[0109] The raw materials of the mixture containing boron-oxygen-silicon bonds include: 22 parts of side chain vinyl polydimethylsiloxane, 48 parts of hydroxy vinyl polysiloxane, 57 parts of hydroxy polysiloxane, 9 parts of boric acid, and 38 parts of D70 solvent, wherein the molecular weight of the side chain vinyl polydimethylsiloxane is 450,000 and the vinyl content is 0.08%; the viscosity of the hydroxy vinyl polysiloxane is 500cps, the vinyl content is 3%, and the hydroxyl content is 4.5%; the viscosity of the hydroxy polysiloxane is 300cps, and the hydroxyl content is 4%.

[0110] A comparative example was prepared without adding a mixture containing boron-oxygen-silicon bonds:

[0111] Comparative Example 1

[0112]

[0113] The polymethylvinylsiloxane is specifically a vinyl-terminated polymethylvinylsiloxane with a molecular weight of 350,000 and an olefin content of 0.18%. The MQ silicone resin includes 45.4 parts of methylvinylMQ and 9.4 parts of methylhydroxyMQ, wherein the M / Q value of the methylvinylMQ is 0.9, the vinyl content is 0.14%, and the relative molecular mass is 4000 g / mol; the M / Q value of the methylhydroxyMQ is 0.7, the relative molecular mass is 4000 g / mol, and the hydroxyl content is 0.3%.

[0114] Specifically, the first solvent is toluene.

[0115] Specifically, the hydrogen-containing silicone oil includes 2.4 parts of side chain polyhydrogen-terminated polydimethylsiloxane, the active hydrogen content of the side chain polyhydrogen-terminated polydimethylsiloxane is 1.4%, and the viscosity is 16 mm 2 / s.

[0116] Specifically, the anchoring agent includes 1.6 parts of ADD38;

[0117] Specifically, the platinum catalyst is a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.

[0118] Specifically, the inhibitor is ethynyl cyclohexanol

[0119] Specifically, the second solvent includes 200 parts of ethyl acetate.

[0120] Comparative Example 2

[0121]

[0122] The polymethylvinylsiloxane is specifically a side-chain vinyl polydimethylsiloxane with a molecular weight of 500,000 and an olefin content of 0.08%. The MQ silicone resin includes 54 parts of methylvinylMQ, wherein the M / Q value of the methylvinylMQ is 0.7, the vinyl content is 0.18%, and the relative molecular mass is 4200 g / mol.

[0123] Specifically, the first solvent is xylene.

[0124] Specifically, the hydrogen-containing silicone oil includes 2.6 parts of side chain polyhydrogen-terminated polydimethylsiloxane, the active hydrogen content of the side chain polyhydrogen-terminated polydimethylsiloxane is 1.2%, and the viscosity is 25 mm 2 / s.

[0125] Specifically, the anchoring agent includes 1.4 parts of ADD109 and 0.4 parts of ADD28.

[0126] Specifically, the platinum catalyst is a platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.

[0127] Specifically, the inhibitor is 2-methyl-3-butyn-ol.

[0128] Specifically, the second solvent includes 200 parts of butyl acetate.

[0129] The above-mentioned Examples 1 to 6 and Comparative Examples 1 and 2 were subjected to performance tests.

[0130] The test methods are:

[0131] Peel force gf / 25mm--film to steel plate: measured in accordance with GB / T 2792-2014 (at room temperature, the test rate is 300mm / min).

[0132] Adhesive residue test: Double 85 test is carried out according to GB / T 32368-2015, that is, the pressure-sensitive adhesive is pasted on a clean steel plate and placed under the conditions of temperature 85°C and humidity 85% for aging treatment for 72 hours. After that, the protective film is slowly removed and the surface condition of the adhered steel plate is observed.

[0133] Damping performance:

[0134] The damping performance is mainly measured by the loss factor (tanδ max )Distinguish the advantages and disadvantages of damping performance.

[0135]

[0136] In the damping performance evaluation, loss factor tanδ>0.3 is a key indicator. From the results, it can be seen that the loss factor of comparative examples 1-2 tested at a specific frequency is tanδ max <0.3, and Examples 1-6 are all greater than 0.3, which indicates that adding the prepared mixture containing boron oxygen silicon bonds can significantly improve the damping properties of the pressure-sensitive adhesive. The mixture containing boron oxygen silicon bonds used in Example 1 was not mixed with the side chain vinyl polydimethylsiloxane for reaction during preparation. The results show that the peeling force is relatively small. After the double 85 test, there is a trace amount of residual glue when the adhesive layer is removed. This may be because local gel is formed during the reaction process, thereby affecting the mechanical properties and aging of the pressure-sensitive adhesive.

[0137] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A high damping silicone pressure-sensitive adhesive, characterized in that: The components include by weight: Wherein, the mixture containing boron-oxygen-silicon bonds includes components of the following structure: Wherein, Q1 and Q2 are a combination of one or more of -CH=CH2, -CH3, and -OH.

2. The pressure-sensitive adhesive according to claim 1, characterized in that: The preparation method of the mixture containing boron-oxygen-silicon bonds is as follows: side chain vinyl polydimethylsiloxane, hydroxy vinyl polysiloxane, hydroxy polysiloxane and boric acid are added into a reaction kettle in a weight ratio of (20-50): (40-70): (30-80): (4-16), D70 solvent is added to assist dissolution, the D70 solvent is removed by negative pressure after rapid and uniform dispersion, and the temperature is raised and maintained at 150-180° C. to stir and mix for reaction for 3-4 hours; The side chain vinyl polydimethylsiloxane is an alkenyl-containing polydimethylsiloxane having at least two vinyl groups bonded to silicon atoms in one molecular chain and an average degree of polymerization of more than 5000. The molecular weight of the side chain vinyl polydimethylsiloxane is 400,000 to 600,000, and the vinyl content is 0.012% to 0.15%; The hydroxy vinyl polysiloxane has two hydroxyl groups bonded to silicon atoms on one molecular chain and at least one vinyl group bonded to silicon atoms on the molecular chain, a viscosity of 300 to 800 cps, a vinyl content of 2% to 4%, and a hydroxyl content of 2% to 4.5%; The hydroxy polysiloxane has two hydroxyl groups bonded to silicon atoms in one molecular chain, a viscosity of 200-600 cps, and a hydroxyl content of 2%-4%.

3. The pressure-sensitive adhesive according to claim 1, characterized in that: The polymethylvinylsiloxane comprises one or two of vinyl-terminated polymethylvinylsiloxane and side-chain vinyl polydimethylsiloxane. The vinyl-terminated polymethylvinylsiloxane is a polymethylvinylsiloxane having at least three vinyl groups bonded to silicon atoms at both ends and in the side chains of one molecule and an average degree of polymerization of more than 5,000. The molecular weight of the vinyl-terminated polymethylvinylsiloxane is 350,000 to 650,000, and the alkenyl content is 0.12% to 0.3%. The side chain vinyl polydimethylsiloxane is an alkenyl-containing polydimethylsiloxane having at least two vinyl groups bonded to silicon atoms in one molecular chain and an average polymerization degree of more than 5000. The molecular weight of the side chain vinyl polydimethylsiloxane is 400,000 to 600,000, and the vinyl content is 0.012% to 0.15%.

4. The pressure-sensitive adhesive according to claim 1, characterized in that: The MQ silicone resin comprises one or both of methyl vinyl MQ and methyl hydroxyl MQ. The methyl vinyl MQ is compounded by methyl MQ silicone resin and methyl hydroxyl MQ silicone resin in a mass ratio of (4-6):(0.5-1.5). The M / Q value of the methyl vinyl MQ is 0.6-0.9, the vinyl content is 0.1%-0.2%, and the relative molecular mass is 4500-6000g / mol; the M / Q value of the methyl hydroxyl MQ is 0.6-0.9, the relative molecular mass is 3500-4500g / mol, and the hydroxyl content is 0.2%-0.5%.

5. The pressure-sensitive adhesive according to claim 1, characterized in that: The first solvent is toluene or xylene.

6. The pressure-sensitive adhesive according to claim 1, characterized in that: The hydrogen-containing silicone oil comprises one, two or three of single-end hydrogen-terminated polydimethylsiloxane, double-end hydrogen-terminated polydimethylsiloxane and side-chain multi-hydrogen-terminated polydimethylsiloxane. The single-end hydrogen-terminated polydimethylsiloxane is an organic hydrogen polysiloxane having one hydrogen atom bonded to a silicon atom in one molecule. The organic hydrogen polysiloxane has an active hydrogen content of 0.01-0.06% and a viscosity of 50-150 mm 2 / s; The double-end hydrogen-terminated polydimethylsiloxane is an organic hydrogen polysiloxane having two hydrogen atoms bonded to silicon atoms in one molecule; the active hydrogen content of the organic hydrogen polysiloxane is 0.02-0.08% and the viscosity is 40-100 mm 2 / s; The side chain polyhydrogen-terminated polydimethylsiloxane is an organohydrogen polysiloxane having two or more hydrogen atoms bonded to silicon atoms in one molecule, and the organohydrogen polysiloxane has an active hydrogen content of 0.8 to 1.8% and a viscosity of 12 to 34 mm 2 / s.

7. The pressure-sensitive adhesive according to claim 1, characterized in that: The platinum catalyst is one of platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, platinum (0)-1,3-dimethyl-1,3-diphenyl-1,3-divinyldisiloxane complex, platinum (0)-1,3-divinyltetramethyldisiloxane complex or a mixture of any of them.

8. The pressure-sensitive adhesive according to claim 1, characterized in that: The inhibitor is one of 2-methyl-3-butynol, 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol and 3-methyl-1-dodecyn-3-ol or a mixture of any of them.

9. The pressure-sensitive adhesive according to claim 1, characterized in that: The second solvent includes one or more of toluene, xylene, ethyl acetate, butyl acetate, acetone, and D70 solvent.

10. A method for preparing the high damping organosilicon pressure-sensitive adhesive according to any one of claims 1 to 9, characterized in that: The preparation method is: Firstly, a mixture containing boron-oxygen-silicon bonds is prepared by reacting side chain vinyl polydimethylsiloxane, hydroxy vinyl polysiloxane, hydroxy polysiloxane and boric acid in a weight ratio of (20-50):(40-70):(30-80):(4-16); The boron-oxygen-silicon bond-containing mixture, polymethylvinylsiloxane, MQ silicone resin, inhibitor and the first solvent are placed in a reaction kettle, sealed with nitrogen, stirred to make the materials uniformly mixed and dissolved, stirred for 8 to 12 hours, and cooled to room temperature to obtain an addition-type organic silicone pressure-sensitive adhesive main agent with a solid content of 65 to 80% and a viscosity of 30,000 to 50,000 mPa.s; A second solvent is added to the main agent of the organic silicone pressure-sensitive adhesive to dilute it to a solid content of 30-45%, hydrogenated silicone oil, an anchoring agent, and a platinum catalyst are added and stirred evenly, a film preparation device is used to scrape the adhesive evenly on the PET film, and then it is baked and dried at a temperature of 100-150° C. to obtain the high damping organic silicone pressure-sensitive adhesive.

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