Search

CN-121975463-A - Preparation method of heat-resistant, high-adhesion and high-conductivity acrylic resin adhesive

CN121975463ACN 121975463 ACN121975463 ACN 121975463ACN-121975463-A

Abstract

The invention relates to a preparation method of heat-resistant high-adhesiveness high-conductivity acrylic resin adhesive, and relates to the technical field of conductive adhesive. The preparation method comprises the steps of mixing acrylate resin, carbon nanotube dispersion liquid, epoxy resin dispersion, diethylenetriamine, 2-ethyl-4-methylimidazole and acetone uniformly, stirring and mixing to obtain a mixture A, adding an antioxidant, conductive silver powder and a coupling agent into the mixture A, stirring uniformly to obtain a mixture B, defoaming the mixture B for 10min under the vacuum degree of minus 0.095MPa to obtain the heat-resistant, high-dispersivity, self-repairing and high-adhesiveness conductive adhesive, wherein the mass loss rate of the obtained conductive adhesive is lower than 6.65%, the peeling strength is higher than 3.82N/cm, the volume resistivity is lower than 6.35 multiplied by 10 ‑5 ohm cm, and the heat resistance, the adhesiveness and the lower volume resistivity are good.

Inventors

  • DUAN BAORONG
  • DUAN XUCHAO
  • FENG LIANXIANG
  • WANG QUANJIE
  • WANG SHUNPING
  • YANG CHENGYU
  • Pan Xinrui
  • WANG YANQING
  • LI MINGYU
  • CAO JINYAN
  • SONG YUEHAI
  • Shang Changjian
  • WENG YONGGEN
  • SUN LIBO
  • NIU RUIYI
  • XU KE

Assignees

  • 烟台大学

Dates

Publication Date
20260505
Application Date
20260403

Claims (10)

  1. 1. The preparation method of the heat-resistant, high-adhesiveness and high-conductivity acrylic resin adhesive is characterized by comprising the steps of (1) adding 25-30 parts of acrylic resin, 4-5 parts of carbon nano tube dispersion liquid, 5-8 parts of epoxy resin dispersion, 2.6-3.0 parts of diethylenetriamine, 0.7-0.9 part of 2-ethyl-4-methylimidazole and 16-25 parts of acetone into the mixture A, stirring, mixing and stirring uniformly to obtain a mixture A, (2) adding 0.3-0.7 part of antioxidant, 52-65 parts of conductive silver powder and 0.4-1.9 part of coupling agent into the mixture A, stirring uniformly to obtain a mixture B, and (3) defoaming the mixture B for 10min under vacuum degree of < -0.095MPa to obtain the heat-resistant, high-dispersibility, self-repairing and high-adhesiveness conductive adhesive; The preparation method of the acrylic resin comprises the following steps: (1) Preparing a core layer emulsion, namely adding 40-70 g of water, 12-18 g of an emulsifying agent A and 20-45 g of methacrylic acid into a reaction container, uniformly mixing and stirring, heating to 50-60 ℃, stirring and reacting for 45-60 min, adding A, DOPO 13.4.4-14.5 g of a monomer and 5.88-6.12 g of maleic anhydride, reacting for 30-40 min, heating to 65 ℃, introducing reflux water, continuously heating to 70-90 ℃, dropwise adding 1-1.5 g of an initiator potassium persulfate, and reacting for 0.5-1.0 h, thus obtaining the core layer emulsion; (2) Simultaneously dropwise adding 1-2 g of monomer B and 1-1.5 g of initiator potassium persulfate into the nuclear layer emulsion obtained in the step (1), carrying out heat preservation and stirring reaction for 1-1.5 g at 75-85 ℃, adding 7.9-8.1 g of diisopropanolamine and 0.32-g g of p-toluenesulfonic acid, carrying out reaction for 1-3H at 70-85 ℃, adding 36.5-37.6 g of tetrakis (hydroxymethyl) phosphonium sulfate and 2.8-3.1 g of diethyl thiophosphoryl chloride, carrying out stirring reaction for 1-2H at 70-80 ℃, adding 2.8-3.4 g of zirconium sulfate, 0.13-0.24 g of aspartic acid and 0.11-0.31 g of 1H-indole-2-formamide, cooling to 40 ℃, adding 14-21 g of emulsifier and 2.1-3.5 g of softener, carrying out reaction for 30-60 min, adding ammonia water to adjust the pH value to 7-8, and carrying out reduced pressure distillation until the solid content is 70%, thereby obtaining acrylic ester resin; The monomer A is prepared by mixing 33-60 g of ethyl acrylate, 22-38 g of methyl methacrylate, 5-7 g of styrene and 1-3 g of vinyl-terminated fluororubber; The monomer B is prepared by mixing 20-70 g of methyl methacrylate, 51-86 g of ethyl acrylate, 3-5 g of styrene and 1-3 g of vinyl-terminated fluororubber; the emulsifier A is formed by mixing sodium dodecyl benzene sulfonate and AEO-9 according to the weight ratio of 2.5:1.
  2. 2. The preparation method of the heat-resistant, high-adhesiveness and high-conductivity acrylic resin adhesive is characterized in that 0.2-0.4 g of chloroplatinic acid and 6-8 g of isopropanol are added into a four-neck flask, the temperature is raised to 70-80 ℃, 2.2 g g of hydrogen-terminated silicone oil and 25-36 g of allyl epoxy polyether are slowly added dropwise, the dropwise addition time is 1h, glacial acetic acid is added to maintain the pH of a system to be 5-6, the reaction is carried out for 2-4 hours at 90-100 ℃ to obtain an intermediate A, the polyether amine D400-13 g and the ethylboric acid 1.3-2.4 g are continuously added into the intermediate A, the pH of the system is maintained to be 5-6, the reaction is carried out for 2-5 hours at 75-90 ℃, and the softener is obtained after cooling.
  3. 3. The method for preparing the heat-resistant, high-adhesion and high-conductivity acrylic resin glue according to claim 1, wherein the method for preparing the vinyl-terminated fluororubber is as follows: (1) Adding 60 g vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer and 500-600 mL of acetone into a 2L three-neck flask, standing for 24-h at room temperature, stirring for 30-60 min under mechanical stirring of 200-300 r/min, controlling the temperature of the system to be 15 ℃, adding 2.28 g benzyl triethyl ammonium chloride, stirring for 5-10 min, adding 20-24 g of 30% hydrogen peroxide aqueous solution, stirring for reaction 5min, adding 10.8 mL concentration 16 mol/L potassium hydroxide aqueous solution, stirring for reaction 5min, placing the three-neck flask into a 24 ℃ oil bath, stirring for reaction 3-7 h, stopping the reaction, standing overnight, acidifying the reaction product, adding 5 times of deionized water, layering the system, wherein the upper layer is an aqueous phase, the lower layer is an organic phase, continuously small bubbles are upwards gushed into the aqueous phase, collecting the organic phase product after the small bubbles are completely disappeared, placing the organic phase product in a 60 ℃ vacuum oven for drying h, removing the system to obtain 35-yellow liquid with the moisture content of 2200 mol; (2) Placing AEF 10g obtained in the step (1) into a three-mouth bottle, adding 100mL acetone to dissolve the AEF, sequentially adding 0.8-1.0 g of silver carbonate, 1.7-2.1 g of allylphenylsulfone and 0.5-0.8 g of potassium persulfate into the three-mouth bottle after the AEF is completely dissolved, reacting for 2-4 h at 30-65 ℃ under mechanical stirring, collecting a product after the reaction is finished, washing and settling for 2-3 times with deionized water, and vacuum drying the product to constant weight at 65 ℃ to obtain the vinyl-terminated fluororubber.
  4. 4. The method for preparing the heat-resistant, high-adhesiveness and high-conductivity acrylic resin glue according to claim 1, wherein the method for preparing the epoxy resin dispersion is characterized in that 4-6 g of boron nitride is added into 23 g furfuryl alcohol glycidyl ether, uniformly dispersed boron nitride dispersion is obtained by ultrasonic treatment in an ice water bath for 1-1.5 hours, 110-130 g of epoxy resin E is added, and stirring is carried out for 0.5-1.5 hours at 500-1000 r/min, so that the epoxy resin dispersion is obtained.
  5. 5. The method for producing a heat-resistant, highly adhesive, highly conductive acrylic resin paste according to claim 4, wherein the particle size of the boron nitride is 1 to 10. Mu.m.
  6. 6. The method for preparing the heat-resistant, high-adhesiveness and high-conductivity acrylic resin glue according to claim 1, wherein the conductive silver powder consists of flake silver powder and spherical silver powder according to a weight ratio of 2.5:1-3.6:1.
  7. 7. The preparation method of the heat-resistant, high-adhesiveness and high-conductivity acrylic resin adhesive is characterized by comprising the steps of adding 1g carbon nanotubes, 0.1-0.6 g of ultra-long carbon nanotubes and 1.0-1.6 g of dispersing agent into 75 g deionized water, stirring at 500-1200 r/min to completely moisten the carbon nanotubes, adding 1.4-2.7 g of p-hydroxybenzaldehyde, further dispersing by using an ultrasonic cell pulverizer, outputting power of 600-700W for 10-50 min, and finally centrifuging the dispersion at a rotating speed of 900-1200 r/min for 15-30 min to obtain the carbon nanotube dispersion.
  8. 8. The method for preparing a heat-resistant, high-adhesiveness and high-conductivity acrylic resin glue according to claim 7, wherein the dispersing agent is prepared by mixing 1-1.5 parts by weight of sodium glycocholate, 0.3-0.5 part by weight of glycerol, dodecyl dimethyl betaine and 0.4-0.45 part by weight of aminoacetic acid.
  9. 9. The method for preparing a heat-resistant, high-adhesion and high-conductivity acrylic resin glue according to claim 1, wherein the coupling agent is any one of KH550, KH560, KH792 and KH570 or a mixture of the two.
  10. 10. The method for preparing a heat-resistant, high-adhesion and high-conductivity acrylic resin glue according to claim 1, wherein the antioxidant is any one of antioxidant 264 and para-hydroxyanisole or a mixture of the two in any proportion.

Description

Preparation method of heat-resistant, high-adhesion and high-conductivity acrylic resin adhesive Technical Field The invention relates to a preparation method of conductive adhesive, in particular to a preparation method of heat-resistant, high-adhesiveness and high-conductivity acrylic resin adhesive. Background With the continuous development of electronic technology, especially in high-frequency, high-density, miniaturized electronic devices, conventional solder materials face many challenges. Although soldering tin is widely applied to electronic assembly, in the application with high requirements on high performance, vibration resistance and high-frequency stability, the soldering tin is easy to generate phenomena such as fatigue failure, thermal stress problem, conductivity decline and the like. The conductive adhesive is an adhesive which is cured or dried and has conductivity, and can connect various conductive materials together so as to form an electric path between the connected materials. In the electronics industry, conductive adhesives have become an indispensable key material. As a substitute for solder, conductive paste is becoming a core technology in high-performance electronic assembly due to its excellent conductivity, good temperature resistance and operational flexibility. The conductive adhesive can replace soldering tin and can effectively solve the problems of thermal damage, welding defects and the like in the welding process. The conductive adhesive is generally composed of a conductive filler, an adhesive matrix, a solvent, and the like. Wherein, the filler is mainly silver, copper, gold, nickel and carbon materials, silver powder is the most commonly used at present, the adhesive matrix is commonly used with epoxy resin, silicon rubber, polyurethane, acrylic ester and the like, the epoxy resin is the main at present, and the solvent is commonly used with water, alcohols, ketones, esters and the like. The epoxy resin matrix has higher adhesiveness and heat resistance, and is mainly used for precise chip bonding, printed circuit board element bonding, rigid connection of metal electrodes and conductive connection in a high-temperature environment. However, for the fields of flexibility/wearable electronics and the like, although the acrylate resin has excellent flexibility and a faster curing speed, the addition of the conductive filler increases the rigidity of the material while improving the conductivity, resulting in a decrease in flexibility and peel strength, and difficulty in combining high conductivity with high flexibility. In addition, the film-forming shrinkage rate of the conventional acrylic resin is high (about 5% -10%), which can destroy mechanical properties (such as adhesion and cracking resistance), electrical properties (such as conductive stability) and long-term reliability (such as aging resistance and migration resistance), and limit the application of the conventional acrylic resin in the scene of meeting the requirements of high conductivity and high flexibility. Meanwhile, the conventional acrylic ester conductive adhesive has poor heat resistance, is easy to decompose or has reduced performance at high temperature for a long time, and has relatively poor adhesive force of acrylic ester resin, so that improvement is needed. The patent CN116102989B discloses a quick-curing acrylic rubber which is prepared from the following raw materials, by weight, 13-17 parts of nitrile rubber of terminal methacrylate, 5-8 parts of urethane acrylate, 14-20 parts of monofunctional acrylate monomer, 7-13 parts of difunctional acrylate monomer, 1-3 parts of trifunctional acrylate monomer, 0.5-1.5 parts of peroxide, 0.01-0.04 parts of polymerization inhibitor and 0.5-0.7 part of coupling agent. The acrylic adhesive provided by the invention has the advantages of quick curing, low volume resistivity after silver powder is added for curing, good bonding strength and moderate elastic modulus, can be used for the photovoltaic shingle conductive silver adhesive, and has the minimum volume resistivity of 3.2 multiplied by 10 -4 omega cm, but does not relate to the improvement of heat resistance. The invention patent CN113231760B discloses a conductive adhesive film which is composed of, by mass, 0.1% -30% of a tin-based metal powder, 70% -99.9% of a soldering-aid adhesive, 30% -70% of a solvent, 45% -65% of a resin tackifier, 1% -5% of an organic acid active agent, 0.1% -1% of a surfactant, and 0.1% -0.5% of a peroxide initiator, 0.5% -5% of a curing agent and 94.5% -99% of a resin tackifier. Compared with the prior art, the content range of the tin-based metal powder in the patent is higher, and the influence of the oxide film on the surface of the tin-based metal powder on forming metallurgical connection is effectively balanced by adding the organic acid active agent into the soldering-aid adhesive, so that the metallurgical connection effect is improved. Although the patent us