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CN-122011339-A - Special epoxy resin for copper-clad plate with low dielectric loss and synthesis process thereof

CN122011339ACN 122011339 ACN122011339 ACN 122011339ACN-122011339-A

Abstract

The invention relates to the technical field of epoxy resin materials, in particular to a special epoxy resin with low dielectric loss for a copper-clad plate and a synthesis process thereof, wherein the special epoxy resin is synthesized by the following components of low-viscosity liquid epoxy resin, a composite chain extension modifier, a high-efficiency selective compound catalyst, an antioxidant, a diluent and a catalyst regulator; according to the technical scheme, the signal attenuation of the copper-clad plate in a high-frequency signal transmission scene is obviously reduced, the transmission rate and the stability are greatly improved, and the use requirements of advanced electronic equipment such as 5G communication and high-frequency radars can be better met. Meanwhile, the material has good viscosity stability and processing suitability, reduces the coating difficulty and rejection rate in the production process of the copper-clad plate, and is beneficial to improving the production efficiency and reducing the production cost.

Inventors

  • Zhong Gaozhong
  • WU RUNHUI
  • LU HONGBIN

Assignees

  • 铜陵圣创新材料有限公司

Dates

Publication Date
20260512
Application Date
20260320

Claims (10)

  1. 1. The special epoxy resin for the copper-clad plate with low dielectric loss is characterized by being prepared from the following components, by weight, 46-54 parts of low-viscosity liquid epoxy resin, 20-28 parts of a composite chain extension modifier, 0.8-1.3 parts of a high-efficiency selective compound catalyst, 0.4-0.7 part of an antioxidant, 3-6 parts of a diluent and 0.1-0.2 part of a catalyst regulator; the low-viscosity liquid epoxy resin is bisphenol F type epoxy resin EP-4400, and the epoxy value is 0.51-0.55eq/100g; the diluent is active diluent butyl glycidyl ether; The catalyst regulator is dimethylformamide; The composite chain extension modifier is a pre-crosslinked compound of bisphenol A, resorcinol type epoxy resin, hydrolysis modified KH-560 and a crosslinking accelerator triallyl isocyanurate, the addition amount of the triallyl isocyanurate is 0.35-0.55% of the total weight of the composite chain extension modifier, the pre-crosslinking reaction temperature is 96-104 ℃, the pre-crosslinking reaction time is 1.5-1.9h, the pre-crosslinking reaction stirring rate is 320-430r/min, and the pre-crosslinking reaction end point is based on the system viscosity reaching 800-1000 mPa.s; Resorcinol type epoxy resin RE-180 with epoxy value of 0.62-0.66eq/100g.
  2. 2. The epoxy resin special for the low-dielectric-loss copper-clad plate according to claim 1, wherein the weight ratio of bisphenol A to resorcinol-type epoxy resin to hydrolysis-modified KH-560 in the composite chain-extending modifier is 10:6.5:4.8.
  3. 3. The epoxy resin special for the copper-clad plate with low dielectric loss according to claim 2 is characterized in that the preparation method comprises the steps of adding KH-560 into deionized water, controlling the weight ratio of KH-560 to deionized water to be 1:2-2.5, controlling the reaction temperature to be 32-38 ℃, stirring at 220-280r/min, dropwise adding 0.14-0.26mol/L hydrochloric acid to adjust the pH of a system to 4.7-5.3, carrying out hydrolysis reaction for 1.5-2.0h, wherein the end point of the hydrolysis reaction is based on oil-free layering of the system and is uniform transparent liquid, adding 34-46% absolute ethyl alcohol by weight of KH-560 after the reaction is ended, and stirring for 30min to obtain the hydrolysis modified KH-560.
  4. 4. The epoxy resin special for the low-dielectric-loss copper-clad plate, which is disclosed in claim 1, is characterized in that the efficient and selective compound catalyst is formed by compounding tetrabutylammonium bromide and triphenylphosphine according to a weight ratio of 2-3:1.
  5. 5. The low dielectric loss epoxy resin special for copper-clad plates according to claim 1, wherein the antioxidant is a hindered phenol antioxidant and is selected from one of antioxidants 1010 and 1076.
  6. 6. A synthesis process of the low dielectric loss copper-clad plate special epoxy resin is characterized by adopting an improved catalytic two-step addition method, comprising a prepolymerization stage, a chain growth stage and a post-treatment stage, wherein the chain growth stage adopts a bisphenol A segmented feeding strategy, TAIC is added in the preparation process of the composite chain extension modifier for carrying out a pre-crosslinking reaction, and a temperature-catalyst cooperative regulation mechanism is adopted in the whole synthesis process.
  7. 7. The synthesis process according to claim 6, wherein the temperature-catalyst cooperative regulation mechanism is specifically a prepolymerization stage, the addition rate of the high-efficiency selective compound catalyst is 0.011-0.019g/min, the corresponding temperature range is 64-86 ℃, the end point of the prepolymerization stage is based on the condition that the epoxy value of the system is reduced to 0.35-0.40eq/100g, the addition rate of the catalyst is 0.008-0.01g/min at 90-100 ℃, the addition rate of the catalyst is 0.005-0.009g/min at 100-120 ℃, the temperature is raised to 127-133 ℃ for 1.0-1.5h before 30min in the chain growth stage, the catalyst regulator is added at one time, the stirring rate is adjusted to 350-400r/min, and the temperature is kept for a prescribed time after stirring for 10-15 min.
  8. 8. The synthesis process according to claim 6, wherein the prepolymerization stage adopts a sectional gradient heating, and the specific steps are as follows: Firstly, adding low-viscosity liquid epoxy resin into a reaction kettle, heating to 62-68 ℃, preserving heat for 22-28min, starting to add 1/2 dosage of high-efficiency selective compound catalyst at the rate of 0.011-0.019g/min, and maintaining the stirring rate at 320-380r/min in the adding process; And secondly, raising the temperature to 82-88 ℃ at a temperature raising rate of 1.2-1.8 ℃ per minute, and preserving the heat for 32-38min to perform a prepolymerization ring-opening reaction, wherein nitrogen is introduced in the whole prepolymerization process for protection, the nitrogen flow is 0.85-1.15L/min, and the prepolymerization end point is determined by reducing the epoxy value of the system to 0.35-0.40eq/100 g.
  9. 9. The synthesis process according to claim 6, wherein the specific steps of the chain extension stage are that the compound chain extension modifier after the pre-crosslinking reaction is added into the reaction system for 3 times, the feeding amount is equal each time, the temperature of the reaction system is stabilized at 92-98 ℃ before each feeding, the fluctuation of the reaction temperature is controlled to be not more than +/-1.6 ℃ in the feeding process, the feeding interval is 22-28min, the stirring rate in the feeding process is 400-500r/min, the temperature is raised to 112-118 ℃ at the heating rate of 0.5-1.0 ℃/min after the feeding is finished, the temperature is kept for 2-3h, the temperature is raised to 127-135 ℃ and the temperature is kept for 1.0-1.5h, the rest amount of efficient selective compound catalyst is added in the stage, and the end point of the chain extension stage is based on the system viscosity reaching 1500-1800 mPa.s and the epoxy value is reduced to 0.12-0.16eq/100 g.
  10. 10. The synthetic process according to claim 6, wherein the post-treatment stage comprises the specific steps of cooling the temperature in the reaction kettle to 92-98 ℃, adding an antioxidant and a diluent, adjusting the stirring speed to 300-350r/min, uniformly stirring, preserving heat for 32-38min, naturally cooling to below 50 ℃ at the speed of 0.34-0.46 ℃/min at the ambient temperature of 25-30 ℃, maintaining the stirring speed of 220-280r/min in the cooling process, filtering by adopting a 0.22 mu m organic filter membrane after cooling, controlling the filtering pressure to 0.1-0.15MPa, drying for 2-2.5h at the temperature of 82-88 ℃ and obtaining the finished product after drying.

Description

Special epoxy resin for copper-clad plate with low dielectric loss and synthesis process thereof Technical Field The invention relates to the technical field of epoxy resin materials, in particular to a special epoxy resin for a copper-clad plate with low dielectric loss and a synthesis process thereof. Background With the rapid development of electronic information technologies such as 5G communication and high-frequency radars, the requirements of electronic equipment on signal transmission rate and stability are continuously improved, and the performance of the copper-clad plate serving as a core base material of an electronic circuit directly influences the operation efficiency of the whole electronic system. In a high-frequency signal transmission scene, dielectric loss is a key factor for limiting signal transmission quality, and excessive dielectric loss not only can lead to signal attenuation and transmission delay, but also can influence the service life and reliability of electronic equipment due to heat. Therefore, developing epoxy resin special for copper-clad plates with low dielectric loss is an important direction of industry research. At present, epoxy resin for copper-clad plates on the market still has obvious defects in terms of dielectric properties. The traditional epoxy resin is prepared by adopting a conventional method, has higher polar group content in a molecular chain structure, is easy to generate polarization loss under the action of a high-frequency electric field, causes higher dielectric loss factor, and is difficult to meet the use requirement of high-frequency communication. Therefore, development of an epoxy resin special for copper-clad plates with reasonable formula and optimized process is needed, and good viscosity stability, mechanical property and processing suitability are simultaneously achieved while low dielectric loss is ensured, so as to solve a plurality of problems in the prior art. Disclosure of Invention The invention aims to provide epoxy resin special for a copper-clad plate with low dielectric loss and a synthesis process thereof. In order to achieve the above purpose, the present invention provides the following technical solutions: The special epoxy resin for the copper-clad plate with low dielectric loss is prepared from the following components, by weight, 46-54 parts of low-viscosity liquid epoxy resin, 20-28 parts of a composite chain extension modifier, 0.8-1.3 parts of a high-efficiency selective compound catalyst, 0.4-0.7 part of an antioxidant, 3-6 parts of a diluent and 0.1-0.2 part of a catalyst regulator; the low-viscosity liquid epoxy resin is bisphenol F type epoxy resin EP-4400, and the epoxy value is 0.51-0.55eq/100g; the diluent is active diluent butyl glycidyl ether; The catalyst regulator is dimethylformamide; The composite chain extension modifier is a pre-crosslinked compound of bisphenol A, resorcinol epoxy resin, hydrolysis modified KH-560 and a crosslinking accelerator triallyl isocyanurate, the addition amount of the triallyl isocyanurate is 0.35-0.55% of the total weight of the composite chain extension modifier, the pre-crosslinking reaction temperature is 96-104 ℃, the pre-crosslinking reaction time is 1.5-1.9h, the pre-crosslinking reaction stirring rate is 320-430r/min, and the pre-crosslinking reaction end point is based on the system viscosity reaching 800-1000 mPa.s (25 ℃); Resorcinol type epoxy resin RE-180 with epoxy value of 0.62-0.66eq/100g. As a further technical scheme, in the composite chain extension modifier, the weight ratio of bisphenol A to resorcinol-type epoxy resin to hydrolysis modified KH-560 is 10:6.5:4.8. The preparation method of the hydrolysis modified KH-560 comprises the steps of adding KH-560 into deionized water, controlling the weight ratio of KH-560 to deionized water to be 1:2-2.5, controlling the reaction temperature to be 32-38 ℃ and the stirring speed to be 220-280r/min, dropwise adding 0.14-0.26mol/L hydrochloric acid to adjust the pH of the system to be 4.7-5.3, carrying out hydrolysis reaction for 1.5-2.0h, wherein the end point of the hydrolysis reaction is based on the condition that the system is in oil-free layering and is uniform transparent liquid, adding 34-46% absolute ethyl alcohol by weight of KH-560 after the reaction is finished, and stirring for 30min to obtain the hydrolysis modified KH-560. As a further technical scheme, the efficient selective compound catalyst is prepared by compounding tetrabutylammonium bromide and triphenylphosphine according to a weight ratio of 2-3:1. As a further technical scheme, the antioxidant is a hindered phenol antioxidant and is selected from one of an antioxidant 1010 and an antioxidant 1076. The synthesis process of the special epoxy resin for the copper-clad plate with low dielectric loss adopts an improved catalytic two-step addition method, and comprises a prepolymerization stage, a chain growth stage and a post-treatment stage, wherein