Search

CN-122011290-A - Double-component aqueous polyurethane adhesive containing modified polyurethane emulsion, and preparation method and application thereof

CN122011290ACN 122011290 ACN122011290 ACN 122011290ACN-122011290-A

Abstract

The invention discloses a double-component aqueous polyurethane adhesive containing modified polyurethane emulsion, and a preparation method and application thereof. The adhesive consists of 60-100 parts by weight of a waterborne polyurethane emulsion, 0-30 parts by weight of pigment and filler, 0.05-2 parts by weight of wetting agent, 0.05-2 parts by weight of defoamer and 0.5-3 parts by weight of thickener, wherein the mass ratio of the waterborne polyurethane emulsion to the curing agent is 100:1-10, the waterborne polyurethane emulsion is obtained by copolymerization reaction of the waterborne polyurethane emulsion and a mixed monomer containing an initiator, and the mixed monomer is an acrylic acid monomer containing epoxy groups or nitrile groups. The adhesive has excellent initial adhesion, high bonding strength, good high temperature resistance, long operable time and storage stability, is suitable for the fields with high requirements on environmental protection and high performance, and has wide application prospects in automobile manufacturing.

Inventors

  • LIU LIN
  • KONG YUNJIE
  • Hui Lanping
  • NI BOWEN

Assignees

  • 江苏美境新材料有限公司

Dates

Publication Date
20260512
Application Date
20260310

Claims (10)

  1. 1. A modified polyurethane emulsion is characterized in that the emulsion is obtained by copolymerization of aqueous polyurethane emulsion and a mixed monomer containing an initiator, wherein the aqueous polyurethane emulsion is a polyurethane prepolymer formed by polyalcohol, carboxylic acid type hydrophilic functional monomer, a chain extender and a curing agent, and is obtained by adding a polymerization inhibitor, a hydroxyl-containing acrylic acid monomer and a catalyst to neutralize and emulsify, and the mixed monomer is an acrylic acid monomer containing epoxy groups or nitrile groups.
  2. 2. The modified polyurethane emulsion according to claim 1, wherein the mixed monomer is added in an amount of 20 to 50wt% based on the mass of the polyol.
  3. 3. The modified polyurethane emulsion of claim 1, wherein the epoxy-containing or nitrile-containing acrylic monomer comprises at least one of methyl methacrylate, acrylonitrile, glycidyl acrylate, glycidyl methacrylate.
  4. 4. The modified polyurethane emulsion according to claim 1, wherein the initiator comprises at least one of azobisisobutyronitrile or dibenzoyl peroxide, and the initiator is added in an amount of 0.01 to 1wt% of the mixed monomer.
  5. 5. The modified polyurethane emulsion of claim 1, wherein the polyol comprises one or more of a polyester polyol, a polyether polyol and a polycarbonate polyol, and specifically comprises at least one of a polyethylene glycol adipate glycol, a polybutylene glycol adipate glycol, a polyhexamethylene glycol adipate glycol, a polyethylene glycol adipate glycol, a polybutylene glycol phthalate glycol, a1, 6-hexanediol carbonate glycol, a polyoxyethylene ether glycol and a polytetrahydrofuran glycol, the molecular weight is 1000-8000, the carboxylic acid type hydrophilic functional monomer is at least one of dimethylolpropionic acid (DMAP) and dimethylolbutyric acid (DMBA) in an amount of 1-15wt% based on the mass of the polyol, the chain extender is at least one of ethylene glycol, 1, 4-butanediol, diethylene glycol, neopentyl glycol and 1,6 hexanediol in an amount of 1-3wt% based on the mass of the polyol, the curing agent is Toluene Diisocyanate (TDI), diphenyl Methane Diisocyanate (MDI), isophorone diisocyanate (IPDI) and Hexamethylene Diisocyanate (HDI) in an amount of 1-3wt% based on the mass of the polyol, and the catalyst is at least one of 1.01% based on the mass of the polyol is at least one of the catalyst of 1.0.0 wt% based on the mass of the polyol, and the catalyst is at least one of 1.01% based on the mass of the polyol is at least one of 1.0% of the catalyst.
  6. 6. A process for preparing the modified polyurethane emulsion of any one of claims 1 to 5, comprising the steps of: (1) The polyol is decompressed and dehydrated, and carboxylic acid type hydrophilic functional monomers, a chain extender, a solvent and a curing agent are sequentially added under the protection of inert gas to react to obtain polyurethane prepolymer; (2) Adding a polymerization inhibitor, a hydroxyl-containing acrylic monomer and a catalyst into the polyurethane prepolymer obtained in the step (1) for modification reaction, and then adding a neutralizer for reaction to obtain aqueous polyurethane emulsion; (3) And (3) dropwise adding a mixed monomer containing an initiator into the aqueous polyurethane emulsion obtained in the step (2) for reaction to obtain a modified polyurethane emulsion.
  7. 7. The double-component aqueous polyurethane adhesive containing the modified polyurethane emulsion of claim 1 is characterized by comprising an aqueous polyurethane main agent and an isocyanate curing agent, wherein the mass ratio of the aqueous polyurethane main agent to the isocyanate curing agent is 100 (1-10), and the aqueous polyurethane main agent comprises, by weight, 60-100 parts of the modified polyurethane emulsion, 0-30 parts of pigment and filler, 0.05-2 parts of wetting agent, 0.05-2 parts of defoaming agent and 0.5-3 parts of thickening agent.
  8. 8. The two-component aqueous polyurethane adhesive of claim 7, wherein the pigment filler is at least one of zinc oxide, fumed silica, iron oxide red, iron oxide black, and carbon black, the wetting agent is at least one of polyether modified silicones, particularly BYK-346, BYK349, and Tego Wet 270, the defoamer is at least one of silicone or mineral oils, particularly BYK-019, BYK020, BYK093, and Tego foam 8420, the thickener is at least one of celluloses, alkali-swellable, or polyurethane associative, particularly hydroxymethyl cellulose, BYK-7610, BYK-7650, BYK-7670, and BYK-HV 80, and the isocyanate curing agent comprises an adduct of toluene diisocyanate and trimethylolpropane (TDI-TMP), hexamethylene diisocyanate trimer (HDI trimer), isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), diphenylmethane diisocyanate (TDI), hexamethylene Diisocyanate (HDI), and a hydroxyl group of di-isocyanate (MDI) and a hydroxyl group of 1/n (OH) mole ratio of 1.
  9. 9. A method for preparing the two-component aqueous polyurethane adhesive according to claim 7, which is characterized by comprising the following steps: (1) Mixing and stirring the modified polyurethane emulsion, pigment and filler, wetting agent, defoaming agent and thickening agent to prepare a water-based polyurethane main agent; (2) And mixing the aqueous polyurethane main agent with an isocyanate curing agent to prepare the two-component aqueous polyurethane adhesive.
  10. 10. Use of the two-component aqueous polyurethane adhesive according to claim 7 in the field of automobile and material manufacturing.

Description

Double-component aqueous polyurethane adhesive containing modified polyurethane emulsion, and preparation method and application thereof Technical Field The invention relates to the technical field of adhesives, in particular to a two-component aqueous polyurethane adhesive containing modified polyurethane emulsion, and a preparation method and application thereof. Background In the manufacture of automotive interiors, components such as a door plate, an instrument desk, a seat back plate and the like are required to be compounded with a coating material through an adhesive, and the performance of the components directly affects the safety, the comfort and the durability of the automotive interiors. Solvent polyurethane adhesives are widely adopted in early industries, although the adhesives have certain bonding strength, the adhesives generally take solvents such as toluene, xylene and ethyl acetate as dispersion media, the content of Volatile Organic Compounds (VOC) is high, the air pollution in a vehicle is aggravated, the health of drivers and passengers is endangered, the related environmental protection requirements are not met, and the risks of inflammability and explosiveness exist in the production process, so that the double hidden hazards of environmental protection and safety exist. Along with the enhancement of global 'double carbon' target promotion and environmental protection consciousness, the upgrading of interior materials and the strict environmental protection standard form double driving. On one hand, the air quality requirement in the automobile is greatly improved, the traditional solvent adhesive replaces pressure due to an environment-friendly short-side surface, on the other hand, under the trend of light weight of interior trim, plastic base materials such as ABS, PC/ABS, modified PP and the like and coating materials such as fabrics, leather and the like are diversified, and the requirements on the base material suitability, the temperature resistance and the moist heat resistance of the adhesive are higher. Therefore, the aqueous polyurethane adhesive has the advantages of low VOC content, high adhesive force to multiple base materials, good film forming toughness and the like, can be suitable for various processes such as spraying, roller coating and the like, obviously improves weather resistance and temperature resistance after being crosslinked by isocyanate curing agents, and can meet the long-term use requirement of automobile interior trim. Disclosure of Invention The invention aims at providing a modified polyurethane emulsion containing nitrile groups, epoxy groups and partial acrylic acid monomers, a second aim of the invention is to provide a preparation method of the modified polyurethane emulsion, a third aim of the invention is to provide a double-component aqueous polyurethane adhesive with strong initial adhesiveness, good temperature resistance and long operation time, and a fourth aim of the invention is to provide a preparation method and application of the double-component aqueous polyurethane adhesive. The double-component aqueous polyurethane adhesive containing the modified polyurethane emulsion provided by the invention has the advantages of strong initial viscosity, good temperature resistance, long operable time and the like by introducing part of acrylic acid monomers, epoxy groups and nitrile groups, and has wide application prospect in the field of automobiles. The modified polyurethane emulsion is prepared by copolymerization reaction of aqueous polyurethane emulsion and mixed monomers containing an initiator, wherein the aqueous polyurethane emulsion is prepared by adding a polymerization inhibitor, a hydroxyl-containing acrylic acid monomer and a catalyst into a polyurethane prepolymer formed by a polyalcohol, a carboxylic acid type hydrophilic functional monomer, a chain extender and a curing agent, and neutralizing and emulsifying the mixture, and the mixed monomers are acrylic acid monomers containing epoxy groups or nitrile groups. Furthermore, the addition amount of the mixed monomer is 20-50wt% of the mass of the polyol, and the epoxy group and the nitrile group are introduced on the basis of the aqueous polyurethane emulsion, so that the temperature stability and the bonding strength of the adhesive are greatly improved, and the embedding of part of acrylic acid monomer effectively improves the water resistance and the weather resistance of the adhesive. Preferably, the acrylic monomer containing epoxy group or nitrile group comprises at least one of methyl methacrylate, acrylonitrile, glycidyl acrylate and glycidyl methacrylate. Preferably, the initiator comprises at least one of azobisisobutyronitrile or dibenzoyl peroxide. Further, the initiator is added in an amount of 0.01 to 1wt% of the acrylic monomer. Further, the polyol comprises one or more of polyester polyol, polyether polyol and polycarbonate polyol, and specifically comprises