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CN-121975089-A - Low-temperature-resistant toughness epoxy resin and preparation method thereof

CN121975089ACN 121975089 ACN121975089 ACN 121975089ACN-121975089-A

Abstract

The invention provides a low temperature resistant toughness epoxy resin and a preparation method thereof, the low temperature resistant toughness epoxy resin has a structure shown in a formula 1, multi-functionality unsaturated double bonds are introduced into the low temperature resistant epoxy resin structure, and through Michael addition reaction with amine curing agents, interpenetrating macromolecule crosslinking anchor points are formed, so that the mechanical property of the epoxy resin is improved, the castor oil component of a polyalkyl chain is introduced, the flexible chain segment structure of the epoxy resin is increased, and the low temperature resistance of the epoxy resin is greatly improved. The low-temperature-resistant toughening resin is formed by grafting and modifying bisphenol A epoxy resin, has excellent compatibility with bisphenol A epoxy resin, and increases the free volume of a crosslinked network formed after curing, so that a molecular chain cannot be completely frozen at low temperature, thereby having excellent toughness.

Inventors

  • ZHANG HONGMING
  • WANG XIANHONG

Assignees

  • 中国科学院长春应用化学研究所

Dates

Publication Date
20260505
Application Date
20260327

Claims (10)

  1. 1. A low temperature resistant tough epoxy resin having a structure represented by formula 1: Formula 1; in the formula 1, R 1 is a structure shown in any one of the formulas 2 to 6: the method comprises the steps of (2), The number of the components in the liquid crystal display is 3, The method comprises the steps of (1) setting a first time period (4), The number of the components is 5, Formula 6; r 2 has the structure shown in formula 7: Formula 7.
  2. 2. A preparation method of low-temperature-resistant toughness epoxy resin comprises the following steps: a) Mixing castor oil, partial diisocyanate and a catalyst to obtain a prepolymer; b) Mixing the prepolymer with bisphenol A epoxy resin, reacting, adding the rest diisocyanate, pentaerythritol triacrylate and polymerization inhibitor, and continuing reacting to obtain the low-temperature-resistant toughness epoxy resin.
  3. 3. The preparation method according to claim 2, wherein the mass ratio of castor oil, total diisocyanate, catalyst, bisphenol A epoxy resin, pentaerythritol triacrylate and polymerization inhibitor is (179-294): (789-1337): (0.3-1.8): (610-4561): (305-486): (10-27).
  4. 4. The preparation method according to claim 2, wherein the mass of the diisocyanate used in the step a) is 71.1 to 75.6% of the total mass of all the diisocyanates.
  5. 5. The method according to claim 2, wherein the diisocyanate comprises one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, bis (isocyanatomethyl) cyclohexane, toluene diisocyanate, and 4,4' -diphenylmethane diisocyanate.
  6. 6. The preparation method according to claim 2, wherein the catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, dibutyltin dichloride and dibutyltin diacetate.
  7. 7. The method according to claim 2, wherein the temperature of the mixing in step a) is 80 to 90 ℃, and the time of the mixing in step a) is 1 to 3 hours.
  8. 8. The preparation method according to claim 2, wherein the reaction temperature of the prepolymer and the bisphenol a epoxy resin in the step B) is 85 to 95 ℃, and the reaction time of the prepolymer and the bisphenol a epoxy resin in the step B) is 1 to 3 hours.
  9. 9. The preparation method according to claim 2, wherein in the step B), after adding the remaining diisocyanate, pentaerythritol triacrylate and polymerization inhibitor, the reaction is continued for 0.5 to 2 hours at a temperature of 85 to 95 ℃.
  10. 10. The process of claim 2 wherein the castor oil is dehydrated and then mixed with a portion of the diisocyanate and the catalyst; The temperature of the water removal is 100-120 ℃, and the pressure of the water removal is 1800-2200Pa.

Description

Low-temperature-resistant toughness epoxy resin and preparation method thereof Technical Field The invention belongs to the technical field of epoxy resin, and particularly relates to low-temperature-resistant toughness epoxy resin and a preparation method thereof. Background The epoxy resin is an important thermosetting resin, mainly comprises several epoxy resins with aliphatic, alicyclic and aromatic structures, and the thermosetting polymer is prepared by the chemical reaction of two or more epoxy groups contained in the molecular structure, anhydride and amine curing agent, and has been widely applied to the fields of adhesives and coatings. Bisphenol A aromatic epoxy resin is most widely applied, however, a large amount of benzene ring rigid groups and high reactivity of the benzene ring rigid groups in the resin structure lead to overlarge crosslinking density and large volume deformation after the resin is cured, so that the material has great brittleness in a low-temperature environment of-5 ℃, and particularly when the material is used in the application field of paint, paint films fall off in the low-temperature application scene, and quality problems are caused. Epoxy resin toughening has been studied in a great deal in recent years, and methods such as rubber elastomer toughening, thermoplastic polymer toughening and inorganic nano material toughening of epoxy resin are mainly included at present, and have been proved to be capable of effectively relieving the problem of low-temperature brittleness of the epoxy resin, however, the mechanical properties of the material are greatly reduced while the toughness of the epoxy resin is improved, and the improvement of the performance in use at low temperature (-40 ℃) is very limited. Disclosure of Invention The invention aims to provide low-temperature-resistant toughness epoxy resin and a preparation method thereof, wherein the low-temperature-resistant toughness epoxy resin has excellent toughness at a low temperature of-40 ℃ and has excellent mechanical properties. The invention provides low-temperature-resistant toughness epoxy resin, which has a structure shown in formula 1: Formula 1; in the formula 1, R 1 is a structure shown in any one of the formulas 2 to 6: the method comprises the steps of (2), The number of the components in the liquid crystal display is 3, The method comprises the steps of (1) setting a first time period (4),The number of the components is 5, Formula 6; r 2 has the structure shown in formula 7: Formula 7. The invention provides a preparation method of low-temperature-resistant toughness epoxy resin, which comprises the following steps: a) Mixing castor oil, partial diisocyanate and a catalyst to obtain a prepolymer; b) Mixing the prepolymer with bisphenol A epoxy resin, reacting, adding the rest diisocyanate, pentaerythritol triacrylate and polymerization inhibitor, and continuing reacting to obtain the low-temperature-resistant toughness epoxy resin. Preferably, the mass ratio of the castor oil to the total diisocyanate to the catalyst to the bisphenol A epoxy resin to the pentaerythritol triacrylate to the polymerization inhibitor is (179-294): (789-1337): (0.3-1.8): (610-4561): (305-486): (10-27). Preferably, the mass of the diisocyanate used in the step A) accounts for 71.1-75.6% of the total mass of all the diisocyanate. Preferably, the diisocyanate comprises one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, bis (isocyanatomethyl) cyclohexane, toluene diisocyanate and 4,4' -diphenylmethane diisocyanate. Preferably, the catalyst comprises one or more of dibutyl tin dilaurate, stannous octoate, dibutyl tin dichloride and dibutyl tin diacetate. Preferably, the temperature of the mixing in the step A) is 80-90 ℃, and the mixing time in the step A) is 1-3 hours. Preferably, the reaction temperature of the prepolymer and the bisphenol A epoxy resin in the step B) is 85-95 ℃, and the reaction time of the prepolymer and the bisphenol A epoxy resin in the step B) is 1-3 hours. Preferably, in the step B), after adding the rest of diisocyanate, pentaerythritol triacrylate and polymerization inhibitor, the reaction is continued for 0.5-2 hours at a temperature of 85-95 ℃. Preferably, the castor oil is dehydrated firstly and then mixed with part of diisocyanate and a catalyst; The temperature of the water removal is 100-120 ℃, and the pressure of the water removal is 1800-2200Pa. The invention provides low temperature resistant toughness epoxy resin, which has a structure shown in a formula 1, wherein the low temperature resistant epoxy resin structure introduces multi-functionality unsaturated double bonds, and through Michael addition reaction with amine curing agents, interpenetrating macromolecule crosslinking anchor points are formed, so that the mechanical property of the epoxy resin is improved, the castor oil component of a polyalkyl chain is introduced, the flexibl