CN-122011969-A - High-heat-conductivity solvent-free rubber-based adhesive and preparation method thereof

Abstract

The invention discloses a preparation method of a high-heat-conductivity solvent-free rubber-based adhesive, which is characterized in that the adhesive takes rubber as a matrix, terpene resin as a tackifier, tannic acid coated zinc oxide and carbon nano tubes are used for cooperatively constructing a heterogeneous heat-conducting network, and a peroxide cross-linking agent is used for cooperatively reinforcing a cross-linking structure. Firstly, under the assistance of ultrasonic dispersion force, taking Tannic Acid (TA) as an interface adhesive, uniformly, compactly and firmly coating zinc oxide (ZnO) particles on the surface of Carbon Nanotubes (CNTs) to form a unique heterostructure heat conduction filler (TA@CNTs@ZnO) of Core (CNTs) -shell (ZnO). And then the heterostructure filler, rubber and terpene resin are subjected to mixing and crosslinking processes to prepare the high-heat-conductivity composite material. In the hot press forming stage, core-shell fillers with one-dimensional characteristics are arranged directionally under the action of pressure, a continuous three-dimensional heat conduction network is constructed efficiently, directional heat transfer is greatly promoted, and meanwhile, terpene resin and tannic acid cooperatively play a role in adhesion. The rubber-based adhesive has excellent elastic recovery rate, heat conduction performance and bonding strength, and the preparation method is simple, solvent-free and environment-friendly, and is suitable for the fields of electronic device heat dissipation, thermal interface materials and the like.

Inventors

• ZHENG KAI
• LI CHENGJIE
• GUO CONG
• SUN HONGMIN
• WANG YING
• CAO SHUZHENG

Assignees

• 江苏海洋大学

Dates

Publication Date

20260512

Application Date

20260115

Claims (4)

1. 1. The high-heat-conductivity solvent-free rubber-based adhesive is characterized in that the main raw materials of the rubber-based adhesive material consist of the following components in parts by mass: 40-90 parts of raw rubber 10-60 Parts of terpene resin Tannic acid 0.6-6 parts 0.5-5 Parts of carbon nano tube Zinc oxide 0.5-5 parts Peroxide cross-linking agent 0.01-0.05 parts 0.01 To 0.03 part of auxiliary cross-linking agent Wherein the raw rubber is one or two of ethylene propylene diene monomer rubber, natural rubber and butadiene rubber; the terpene resin is natural terpene resin, and the softening point of the terpene resin is 80-120 ℃; The peroxide cross-linking agent is any one of cumene peroxide, dibenzoyl peroxide and 1, 4-di-tert-butyl peroxyisopropyl benzene; the auxiliary cross-linking agent is any one of triallyl cyanurate, zinc methacrylate, zinc diethyl dithiocarbamate and N-cyclohexyl-2-benzothiazole sulfenamide.
2. 2. The high thermal conductivity solvent-free rubber-based adhesive according to claim 1, wherein tannic acid modifies the surface of carbon nanotubes by Fe 3+ coordination to form tannic acid-Fe-CNTs heterostructure; the zinc oxide is further coated on the surface of the structure to form the core-shell heterogeneous heat conducting filler.
3. 3. A method of preparing a high thermal conductivity solvent-free rubber-based adhesive according to claim 1 or 2, comprising the steps of: s1 preparation of heterogeneous heat conduction filler Weighing 0.5-5 parts of carbon nano tubes in a beaker, adding 100 parts of distilled water, performing ultrasonic dispersion for 1h parts of tannic acid, uniformly stirring and pouring into a dispersion liquid, adding FeCl 3 ·6H 2 O into the dispersion liquid, dissolving in water, pouring into a mixed liquid, reacting in a water bath at 50-70 ℃ for 5-15 min, weighing 0.5-5 parts of ZnO, pouring into the mixed liquid, completely coating the carbon nano tubes under the ultrasonic dispersion effect, performing suction filtration, and drying at 50 ℃ to obtain heterogeneous heat conduction filler TA@CNTs@ZnO for later use; s2 preparation of rubber adhesive Mixing 10-60 parts of terpene resin and 40-90 parts of rubber on an open mill, sequentially adding stearic acid, heterogeneous heat conduction filler prepared in S1, 0.01-0.05 part of peroxide cross-linking agent and 0.01-0.03 part of auxiliary cross-linking agent, uniformly mixing, placing the mixed rubber in a mold, covering polytetrafluoroethylene molds on the upper side and the lower side, and hot-pressing for 10-30 min at 150-180 ℃ and 5-15 MPa to obtain the heat conduction rubber-based adhesive.
4. 4. The preparation method of claim 3, wherein the molar ratio of FeCl 3 ·6H 2 O to tannic acid in step S1 is 1:5-1:10.

Description

High-heat-conductivity solvent-free rubber-based adhesive and preparation method thereof Technical Field The invention relates to the technical field of heat-conducting rubber and adhesives, in particular to a high-heat-conducting solvent-free rubber-based adhesive and a preparation method thereof. Background Under the continuous driving of moore's law, the size of semiconductor chips has been developed over decades, shrinking from tens of micrometers to nanometers. This miniaturization, while bringing about high power densities, also poses significant heating challenges. If heat cannot be effectively conducted out in time, the performance of the device is attenuated or even damaged. Therefore, the heat dissipation efficiency of the power device is important. In recent years, the thermal interface bonding material can effectively remove the air gap between the heat source and the radiator due to the unique soft bullet and adhesion characteristics, and has excellent auxiliary heat dissipation capability, so that the thermal interface bonding material becomes a research hot spot. Traditional thermal interface adhesives such as silicone grease, epoxy glue and the like have certain thermal conductivity, but tend to have poor elasticity, are easy to age and contain harmful solvents, and are difficult to meet the requirements of modern electronic devices on flexibility, environmental protection and high reliability. Rubber materials which have excellent elasticity and thermal conductivity and are free of solvents are one of the ideal candidates for non-silicon-based thermal interface materials. However, the thermal conductivity of rubber materials is generally low (often less than 0.5W/(mK)). To improve the thermal conductivity, a high proportion of thermal conductive filler (such as alumina, boron nitride, carbon nanotubes, etc.) is usually added, but excessive filler can cause brittleness, reduced elasticity, and difficult processing. On the other hand, the traditional binder mostly adopts a solvent preparation process, a large amount of organic solvents are adopted in the preparation process, the problem of emission of Volatile Organic Compounds (VOC) exists, and the environment-friendly manufacturing trend is not met. At present, the natural rubber and styrene-butadiene rubber-based adhesive reported in the literature still exists a solid-phase rubber-based adhesive system which uses a large amount of organic solvent or emulsion solvent system, and is completely free of solvent. Therefore, the rubber-based adhesive which has high heat conductivity, strong adhesion and no solvent is developed, and has important research value and application prospect. Disclosure of Invention The invention aims to overcome the defects of the prior art and provides a preparation method of a high-heat-conductivity solvent-free rubber-based adhesive. The compatibility of the filler-matrix interface is obviously improved by coordination modification of tannic acid-Fe 3+ carbon nanotubes, the natural terpene resin is used as a tackifier, high bonding strength under the solvent-free condition is realized, and the elastic and heat conduction collaborative promotion is realized by combining with the design of a rubber crosslinked network. The preparation method is simple and convenient, has no solvent, can be prepared by a conventional rubber processing method, and is suitable for the severe requirements of high-efficiency heat dissipation and reliable interface contact in the field of high-end electronic device heat management. The aim of the invention is achieved by the following technical scheme, wherein the raw material fractions are mass fractions except for special descriptions. The main raw materials of the high-heat-conductivity solvent-free rubber-based adhesive consist of the following components: 40-90 parts of rubber 10-60 Parts of terpene resin Tannic acid 0.6-6 parts 0.5-5 Parts of carbon nano tube Zinc oxide 0.5-5 parts Peroxide cross-linking agent 0.01-0.05 parts 0.01 To 0.03 part of auxiliary cross-linking agent Wherein the rubber is any one or two of ethylene propylene diene monomer rubber, natural rubber and butadiene rubber; The terpene resin is natural terpene resin, has a softening point of 80-120 ℃, is environment-friendly and nontoxic, contains unsaturated bonds and polar groups in a molecular structure, can enhance the compatibility with rubber and provides a durable tackifying effect; The peroxide cross-linking agent is any one of cumene peroxide, dibenzoyl peroxide and 1, 4-di-tert-butyl peroxyisopropyl benzene; the auxiliary cross-linking agent is any one of triallyl cyanurate, zinc methacrylate, zinc diethyl dithiocarbamate and N-cyclohexyl-2-benzothiazole sulfenamide. The tannic acid modifies the surface of the carbon nano tube through Fe 3+ coordination to form a tannic acid-Fe-CNTs heterostructure; The zinc oxide is further coated on the surface of the structure to form a 'core-shell' heterogeneous heat