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CN-121975090-A - Modified epoxy curing agent based on KH-560 distillation residue, and preparation method and application thereof

CN121975090ACN 121975090 ACN121975090 ACN 121975090ACN-121975090-A

Abstract

The invention discloses a modified epoxy curing agent based on KH-560 distillation residues, a preparation method and application thereof, wherein the preparation method comprises the steps of A, putting a polyamine compound into a stirring kettle for stirring; adding an accelerator into a stirring kettle, stirring the accelerator and the polyamine compound to obtain a mixed solution, introducing nitrogen into the stirring kettle and replacing air in the kettle after uniformly mixing, adding KH-560 distillation residue into a storage tank, introducing nitrogen into the storage tank and replacing air in the tank, heating the mixed solution in the stirring kettle to a reaction temperature, metering and dripping KH-560 distillation residue into the stirring kettle according to theoretical equivalent, reacting, and after the dripping is finished, preserving the temperature of the liquid in the stirring kettle at the reaction temperature, continuously stirring, and discharging to obtain the modified epoxy curing agent. According to the scheme, KH-560 distillation residues can be safely and efficiently converted into the modified epoxy curing agent, the recycling of epoxy values in the KH-560 distillation residues is realized, and meanwhile, the environmental-friendly disposal cost is reduced.

Inventors

  • DENG CHAO
  • OUYANG WEI
  • REN BIYE
  • HE ZHIGANG

Assignees

  • 佛山市桐立新材料科技有限公司

Dates

Publication Date
20260505
Application Date
20260115

Claims (8)

  1. 1. The preparation method of the modified epoxy curing agent based on KH-560 distillation residues is characterized by comprising the following steps: A. adding the polyamine compound into a stirring kettle for stirring; B. Adding an accelerator into a stirring kettle, stirring the accelerator and the polyamine compound to obtain a mixed solution, introducing nitrogen into the stirring kettle after uniformly mixing, replacing air in the stirring kettle, and sealing the stirring kettle; C. adding KH-560 distillation residue into a storage tank, introducing nitrogen into the storage tank, replacing air in the storage tank, and sealing the storage tank; D. Heating the mixed solution in the stirring kettle to a reaction temperature, metering and dripping KH-560 distillation residue in the storage tank into the stirring kettle according to theoretical equivalent, and reacting, wherein the liquid in the stirring kettle is maintained at the reaction temperature in the reaction process; E. after the dripping is completed, preserving the temperature of the liquid in the stirring kettle at the reaction temperature, continuously stirring in the preserving process, and discharging to obtain the modified epoxy curing agent; in the step C, the epoxy value of the KH-560 distillation residue is 0.1-0.3 mol/100g.
  2. 2. The method for preparing a modified epoxy hardener based on KH-560 distillation residues according to claim 1, wherein said polyamine compound comprises any one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, aminoethylpiperazine, dipropylenetriamine, m-xylylenediamine, polyetheramine D230 and 1.3-cyclohexanedimethylamine.
  3. 3. The method for preparing a modified epoxy hardener based on KH-560 distillation residues according to claim 1, wherein the accelerator comprises any one or more of benzyl alcohol, dodecylphenol, nonylphenol, bisphenol A, and p-tert-butylphenol.
  4. 4. The method for preparing the modified epoxy curing agent based on KH-560 distillation residues according to claim 1, wherein the reaction temperature is 80-90 ℃.
  5. 5. The method for preparing the modified epoxy hardener based on KH-560 distillation residues of claim 1, wherein in the step E, the stirring time of continuous stirring is 2-3 h.
  6. 6. The method for preparing a modified epoxy hardener based on KH-560 distillation residues according to claim 1, wherein in step D, the dropping time of the dropping is less than or equal to 2 hours.
  7. 7. The modified epoxy curing agent based on KH-560 distillation residues is characterized in that the modified epoxy curing agent is prepared by the preparation method of the modified epoxy curing agent based on KH-560 distillation residues according to any one of claims 1-6, wherein the amine value of the modified epoxy curing agent is 350-600 mg KOH/g, and the viscosity is 600-2000 mpa.s.
  8. 8. Use of a modified epoxy hardener based on KH-560 distillation residue for the preparation of an epoxy cured product, characterized in that it comprises an epoxy resin and a modified epoxy hardener based on KH-560 distillation residue according to claim 7.

Description

Modified epoxy curing agent based on KH-560 distillation residue, and preparation method and application thereof Technical Field The invention relates to the technical field of curing agent preparation, in particular to a modified epoxy curing agent based on KH-560 distillation residues, and a preparation method and application thereof. Background Gamma-glycidoxypropyl trimethoxy silane (commercial name is KH-560) is an important epoxy functional group silane coupling agent, and is widely applied to the fields of composite materials, adhesives, coatings, electronic packaging and the like, and is used for improving the interfacial compatibility between inorganic fillers and organic resins. Commercially, KH-560 is generally synthesized by hydrosilylation reaction of allyl glycidyl ether and trimethoxy silane as raw materials with a platinum-based catalyst. Although the process is mature, side reactions inevitably occur in the actual production process. On one hand, the carbon-carbon double bond in the allyl glycidyl ether molecule can be self-polymerized or copolymerized under a catalytic system to generate an oligomeric or polymeric allyl polymerization byproduct, and on the other hand, the epoxy ring of the allyl glycidyl ether molecule is easy to undergo ring opening reaction under the conditions of trace water, acid or high temperature to form an epoxy ring opening byproduct with an alcohol, ether or polyalcohol structure. These byproducts differ from the target product KH-560 in physical properties, particularly in boiling point and density. Therefore, the industrial purification usually adopts a reduced pressure distillation mode to separate high-purity KH-560, and the residual high-boiling residue after distillation presents strong pungent smell and still has a certain epoxy value due to the components which are not fully reacted, polymers and substances with partial epoxy functional groups reserved. At present, the type of residue is classified as dangerous waste by most production enterprises due to complex components, poor stability, large smell and active functional groups, and needs to be entrusted with qualification units for incineration or chemical treatment, so that the environmental protection disposal cost is increased, and the resource waste is caused. Therefore, development of a technical scheme is needed to be developed, and KH-560 distillation residues can be safely and efficiently converted into products with practical values, so that process innovation of treating waste with waste and changing waste into valuable is realized. Disclosure of Invention The invention aims to provide a modified epoxy curing agent based on KH-560 distillation residues, and a preparation method and application thereof, which can safely and efficiently convert the KH-560 distillation residues into a modified epoxy curing agent with practical value, realize recycling of epoxy values in the KH-560 distillation residues, and simultaneously reduce environmental protection disposal cost so as to overcome the defects in the prior art. To achieve the purpose, the invention adopts the following technical scheme: a preparation method of a modified epoxy curing agent based on KH-560 distillation residues comprises the following steps: A. adding the polyamine compound into a stirring kettle for stirring; B. Adding an accelerator into a stirring kettle, stirring the accelerator and the polyamine compound to obtain a mixed solution, introducing nitrogen into the stirring kettle after uniformly mixing, replacing air in the stirring kettle, and sealing the stirring kettle; C. adding KH-560 distillation residue into a storage tank, introducing nitrogen into the storage tank, replacing air in the storage tank, and sealing the storage tank; D. Heating the mixed solution in the stirring kettle to a reaction temperature, metering and dripping KH-560 distillation residue in the storage tank into the stirring kettle according to theoretical equivalent, and reacting, wherein the liquid in the stirring kettle is maintained at the reaction temperature in the reaction process; E. after the dripping is completed, preserving the temperature of the liquid in the stirring kettle at the reaction temperature, continuously stirring in the preserving process, and discharging to obtain the modified epoxy curing agent; in the step C, the epoxy value of the KH-560 distillation residue is 0.1-0.3 mol/100g. Preferably, the polyamine compound includes any one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, aminoethylpiperazine, dipropylenetriamine, m-xylylenediamine, polyetheramine D230, and 1.3-cyclohexanedimethylamine. Preferably, the accelerator comprises any one or more of benzyl alcohol, dodecylphenol, nonylphenol, bisphenol A, and p-tert-butylphenol. Preferably, the reaction temperature is 80-90 ℃. Preferably, in the step E, the stirring time of the continuous stirring is 2-3 hours. Preferably, in the step D, the dripping