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CN-121991320-A - Epoxy vinyl ester resin and preparation method thereof

CN121991320ACN 121991320 ACN121991320 ACN 121991320ACN-121991320-A

Abstract

The invention discloses an epoxy vinyl ester resin and a preparation method thereof, wherein the epoxy vinyl ester resin comprises, by mass, 4% -36% of an unsaturated epoxy oligomer, 4% -36% of a crosslinking monomer, 0.1% -5.0% of a catalyst 1#, 5% -15% of an organic unsaturated carboxylic acid, 0.2% -2.0% of a catalyst 2#, 0.01% -0.05% of a polymerization inhibitor, 10.0% -25.0% of an anhydride and 15% -25% of a diluent, wherein the catalyst 1# comprises an azo compound and/or a persulfate, and the catalyst 2# comprises one or more of imidazole, an imidazole derivative and an imidazole-metal salt complex. According to the invention, the reaction temperature of the synthesis process is reduced by optimizing the proportion of raw material components, improving the preparation process and selecting the adaptive catalyst, and the temperature in the preparation process is always lower than 90 ℃, so that the reaction process is easier to control. The casting body of the epoxy vinyl ester resin prepared by the method has high toughness, high hardness and high thermal stability, and meanwhile, the wear resistance is excellent, and the epoxy vinyl ester resin can work for a long time in a high-temperature environment.

Inventors

  • MAO LINGFENG
  • WU FANGZHI
  • LIU SHIQIANG
  • WU BING

Assignees

  • 华东理工大学华昌聚合物有限公司

Dates

Publication Date
20260508
Application Date
20241106

Claims (10)

  1. 1. The epoxy vinyl ester resin is characterized by comprising the following raw materials in percentage by mass: The catalyst 1# comprises azo compounds and/or persulfates; and/or the catalyst 2# is selected from an anionic catalyst, wherein the catalyst 2# comprises one or more of imidazole, imidazole compounds and imidazole-metal salt complexes.
  2. 2. An epoxy vinyl ester resin according to claim 1, wherein the mass ratio of unsaturated epoxy oligomer to crosslinking monomer is 1:9-9:1, preferably the mass ratio of unsaturated epoxy oligomer to crosslinking monomer is 1:5-5:1.
  3. 3. An epoxy vinyl ester resin according to claim 1, wherein the unsaturated epoxy oligomer comprises carbon-carbon unsaturated double bonds and epoxy groups in the structure, and wherein the unsaturated epoxy oligomer comprises one or more of allyl glycidyl ether, glycidyl acrylate, and glycidyl methacrylate.
  4. 4. An epoxyvinyl ester resin according to claim 1, wherein said crosslinking monomer comprises one or more of styrene, methyl styrene, divinylbenzene, chlorostyrene, t-butylstyrene, methyl acrylate, methyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate and pentaerythritol triacrylate.
  5. 5. An epoxyvinyl ester resin according to claim 1, wherein said catalyst 1# comprises one or more of azobisisobutyronitrile, sodium persulfate and potassium persulfate; And/or the catalyst 2# comprises one or more of 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole and copper-imidazole coordination compound.
  6. 6. An epoxyvinyl ester resin according to claim 1, wherein said anhydride comprises one or more of maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, chlorendic anhydride, pyromellitic dianhydride, ethylene glycol bis-trimellitic anhydride, methylcyclohexenyl tetracarboxylic dianhydride, and trimellitic anhydride.
  7. 7. An epoxyvinyl ester resin according to claim 1, wherein said organic unsaturated carboxylic acid comprises an unsaturated monobasic acid; and/or the polymerization inhibitor comprises one or more of tert-butylhydroquinone, tert-butylcatechol, p-benzoquinone, hydroquinone and methyl hydroquinone; and/or the diluent comprises an acetate compound and/or a polyol alkyl ether acetate compound.
  8. 8. An epoxyvinyl ester resin according to claim 7, wherein said organic unsaturated carboxylic acid comprises one or more of acrylic acid, methacrylic acid and butenoic acid; and/or the polymerization inhibitor comprises one or more of tert-butylhydroquinone, tert-butylcatechol, hydroquinone and methyl hydroquinone; and/or the diluent comprises one or more of ethyl acetate, ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate.
  9. 9. The method for producing an epoxy vinyl ester resin according to any one of claims 1 to 8, comprising the steps of: (1) Uniformly mixing an unsaturated epoxy oligomer and a crosslinking monomer; (2) Pre-reacting, namely adding a catalyst 1#, uniformly mixing in an inert atmosphere, gradually heating to 40-80 ℃, and performing pre-reacting, wherein the viscosity is controlled to be 10-25 Pa.s; (3) Ring-opening esterification, namely adding organic unsaturated carboxylic acid, catalyst No. 2 and polymerization inhibitor, fully mixing, and reacting at 60-90 ℃ until the acid value is less than 10mgKOH/g; (4) Esterification chain extension reaction, namely controlling the temperature of a system to 40-60 ℃, adding anhydride, and carrying out heat preservation reaction until the acid value is 50-100 mgKOH/g; (5) Diluting and filtering, namely adding a diluent, fully mixing, cooling, and filtering to obtain the epoxy vinyl ester resin.
  10. 10. The method according to claim 10, wherein in the step (2), the pre-reaction is performed for 1 to 3 hours; And/or in the step (3), the reaction time at 60-90 ℃ is 1-2 hours; And/or, in the step (4), the time of the heat preservation reaction is 0.5-1 hour.

Description

Epoxy vinyl ester resin and preparation method thereof Technical Field The invention belongs to the field of high polymer materials, and particularly relates to epoxy vinyl ester resin and a preparation method thereof. Background The epoxy vinyl ester resin is resin with unsaturated acid and epoxy resin as main material and through heating reaction under the action of catalyst and other assistants to obtain molecular end group or side group containing unsaturated double bond. Epoxy vinyl ester resin is one of the resin varieties with larger usage amount in composite materials, has the characteristics of low viscosity, moderate price, convenient processing, but also has the defects of large brittleness after solidification, poor impact performance and the like. The resin toughening technology is mainly characterized in that a rubber elastomer comprising active elastomer and other disperse phases is added into a resin matrix to form an interpenetrating or semi-interpenetrating network structure, and rigid particles, especially nano toughening reinforcement, chemical structure modification toughening and the like are adopted. The toughness of the existing resin is improved, the impact strength and the bending strength of the composite material are improved, but the glass transition temperature of the product is reduced, and the heat resistance is reduced. The reaction temperature in the existing epoxy vinyl ester resin synthesis process is high and is generally higher than 100 ℃. Chinese patent CN105694000A discloses a vinyl ester resin and a preparation method thereof, wherein an epoxy resin and a4, 4-dihydroxydiphenyl compound are subjected to addition polymerization under the action of a specific catalytic system to obtain an intermediate A, the intermediate A and unsaturated carboxylic acid are subjected to ring-opening addition reaction, and a final addition product is diluted in a reactive diluent to obtain the vinyl ester resin, wherein the reaction condition of the addition polymerization is 120-160 ℃ for 0.5-4 hours, and the reaction condition of the ring-opening addition reaction is 100-140 ℃ for 1-6 hours. Chinese patent CN116143997a discloses an epoxy vinyl ester resin with enhanced mechanical properties, wherein the chain extension reaction is carried out at 100-150 ℃ and the ring opening reaction is carried out at 100-120 ℃. At high temperature, the reaction in the epoxy vinyl ester resin synthesis process is difficult to control, and side reactions are extremely easy to generate. Disclosure of Invention Aiming at the problems that the epoxy vinyl ester resin has high reaction temperature, the reaction is difficult to control, the prepared epoxy vinyl ester resin cannot have toughness, heat resistance and the like in order to overcome the defects in the prior art, the invention aims to provide the epoxy vinyl ester resin and the preparation method thereof, and the reaction temperature of the epoxy vinyl ester resin synthesis process is reduced, the reaction time is shortened and the reaction process is easy to control by optimizing the component proportion, improving the preparation process and adopting a specific catalyst system to catalyze the reaction. And the casting body of the epoxy vinyl ester resin prepared by the medium-temperature synthesis process has high toughness and high hardness, and has excellent heat resistance and wear resistance. The epoxy vinyl ester resin can be designed to have reactivity and crosslinking density according to the requirements, and is suitable for the fields of printing ink, coating, adhesive and the like. The epoxy vinyl ester resin is synthesized by pre-reacting unsaturated epoxy oligomer with crosslinking monomer, then opening a ring with organic unsaturated carboxylic acid, and then esterifying and chain extending by anhydride. The object of the invention is achieved by at least one of the following technical solutions. The invention provides an epoxy vinyl ester resin, which comprises the following raw materials in percentage by mass: The catalyst 1# comprises azo compounds and/or persulfates; The catalyst 2# is selected from an anionic catalyst, and the catalyst 2# comprises one or more of imidazole, imidazole compounds and imidazole-metal salt complexes. Further, the catalyst 1# comprises one or more of azobisisobutyronitrile, sodium persulfate and potassium persulfate. Further, the catalyst 2# comprises one or more of 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole and copper-imidazole complex compounds. Further, the mass ratio of the unsaturated epoxy oligomer to the crosslinking monomer is 1:9-9:1. Further, the mass ratio of the unsaturated epoxy oligomer to the crosslinking monomer is 1:5-5:1. Further, the epoxy vinyl ester resin raw material comprises the following components in percentage by mass: further, the unsaturated epoxy oligomer structure contains carbon-carbon unsaturated double bonds and epoxy groups. Still further, the