CN111875769A - High-solid-content aqueous polyurethane composite emulsion and preparation method thereof - Google Patents

High-solid-content aqueous polyurethane composite emulsion and preparation method thereof Download PDF

Info

Publication number
CN111875769A
CN111875769A CN202010846243.2A CN202010846243A CN111875769A CN 111875769 A CN111875769 A CN 111875769A CN 202010846243 A CN202010846243 A CN 202010846243A CN 111875769 A CN111875769 A CN 111875769A
Authority
CN
China
Prior art keywords
emulsion
water
temperature
added
acrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010846243.2A
Other languages
Chinese (zh)
Other versions
CN111875769B (en
Inventor
李萍
吴建兵
刘伟
马小龙
梁庆丰
郝静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi Kejing New Materials Co ltd
Shanxi Institute Of Applied Chemistry (ltd)
Original Assignee
Shanxi Kejing New Materials Co ltd
Shanxi Institute Of Applied Chemistry (ltd)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanxi Kejing New Materials Co ltd, Shanxi Institute Of Applied Chemistry (ltd) filed Critical Shanxi Kejing New Materials Co ltd
Priority to CN202010846243.2A priority Critical patent/CN111875769B/en
Publication of CN111875769A publication Critical patent/CN111875769A/en
Application granted granted Critical
Publication of CN111875769B publication Critical patent/CN111875769B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a high-solid content aqueous polyurethane composite emulsion and a preparation method thereof, and the high-solid content aqueous polyurethane composite emulsion is prepared by the steps of preparing a high-solid content aqueous polyurethane composite emulsion containing-OH and-NH2Or a silane functional acrylic emulsion; preparing a polyurethane prepolymer containing-NCO through the reaction of raw materials comprising polymer dihydric alcohol, diisocyanate, a hydrophilic chain extender, a micromolecular chain extender and a neutralizing agent; and (3) the acrylic emulsion replaces part of water to be added into the polyurethane prepolymer in the step two to emulsify and disperse the polyurethane prepolymer, so that the chemically cross-linked and modified high-solid-content waterborne polyurethane is obtained. According to the invention, the acrylic emulsion containing active functional groups replaces part of water to emulsify and chain extend the polyurethane prepolymer, and the high-solid content acrylic polyurethane composite emulsion is realized through chemical crosslinking and different particle size distributions, wherein the solid content is more than or equal to 55%.

Description

High-solid-content aqueous polyurethane composite emulsion and preparation method thereof
Technical Field
The invention relates to a polymer emulsion and a preparation method thereof, in particular to a preparation method of chemical crosslinking modification of a waterborne polyurethane-acrylic emulsion.
Background
The waterborne polyurethane has the advantages of good flexibility, non-inflammability, corrosion resistance, weather resistance, good bonding performance and the like, but most waterborne polyurethane coating films have performance deviation of water resistance, solvent resistance and the like, so that the application range of the waterborne polyurethane coating films is limited. Therefore, it is necessary to introduce other structural and performance components to modify them to improve the overall performance. The waterborne polyurethane and the acrylate have strong complementarity in performance, and most acrylate monomers are cheap and easily available, so that the production cost is reduced, the waterborne polyurethane and the acrylate are organically combined, the waterborne composite material which is cheap and excellent in quality, high in tensile strength, impact strength and chemical resistance, good in adhesive force, high in hardness and good in glossiness can be prepared, and the application prospect is very wide.
The most typical modification methods are physical blending modification and copolymerization modification. The physical mixing method is relatively simple, but the intersolubility between the two is poor, the film is formed to be opaque, the mechanical property is not obviously improved, and the stability of the system is poor. For example, the invention patent with publication number CN103059230B discloses modified waterborne polyurethane, which is prepared by first preparing waterborne polyurethane, and then modifying the waterborne polyurethane dispersion with styrene and acrylic acid to obtain acrylic acid modified waterborne polyurethane with interpenetrating network structure, wherein the interpenetrating network forms a topological bond rather than a real covalent bond, and belongs to physical modification. Compared with a physical modification method, the chemical copolymerization method has great advantages in solving the compatibility of PU and PA and improving the comprehensive performance of the emulsion. The invention patent with publication number CN101906192B provides a preparation method of aqueous polyurethane-acrylate composite emulsion, which is characterized in that unsaturated polyurethane monomer with double bonds and acrylate monomer are synthesized for copolymerization, no additional solvent and emulsifier are needed, but the problems of long reaction time, low grafting ratio of polyurethane and acrylate monomer, easy residual monomer retention and low solid content of the product exist.
Disclosure of Invention
The invention aims to solve the technical problem of providing the high-solid-content aqueous polyurethane composite emulsion and the preparation method thereof, and at least achieving the purpose of high solid content of the polyurethane composite emulsion.
In order to solve the above technical problems, according to an aspect of the present invention, there is provided a method for preparing a high solid content aqueous polyurethane composite emulsion, comprising:
step one, preparing a catalyst containing-OH and-NH2Or a silane functional acrylic emulsion;
reacting raw materials including polymer dihydric alcohol, diisocyanate, a hydrophilic chain extender, a micromolecular chain extender and a neutralizing agent to prepare a polyurethane prepolymer containing-NCO;
and step three, adding the acrylic emulsion and water in the step one into the polyurethane prepolymer in the step two, emulsifying and dispersing the polyurethane prepolymer to obtain the chemically cross-linked and modified high-solid-content waterborne polyurethane.
Further, in the first step, a seed emulsion polymerization method is adopted to prepare the acrylic emulsion;
firstly, mixing a water-based emulsifier, deionized water, an acrylate monomer and a crosslinking monomer to prepare a pre-emulsion, mixing 8-12% of the pre-emulsion with the water-based emulsifier, the deionized water and a water-soluble initiator, stirring and heating in a nitrogen protective atmosphere until the system is stable, heating to 80-90 ℃, then simultaneously dropwise adding the rest initiator and the pre-emulsion, preserving heat after dropwise adding is finished, fully reacting the system, then reducing the temperature of the system to 45-55 ℃, adjusting the pH of the system to 7-8 with ammonia water, cooling to room temperature, filtering by a filter screen, and discharging to obtain the acrylic emulsion.
Further, in the first step, an acrylic emulsion containing silane coupling agents KH550 and KH570 is prepared by the following method;
firstly, mixing an aqueous emulsifier, deionized water, an acrylate monomer and a crosslinking monomer gamma-methacryloxypropyltrimethoxysilane (KH 570) to prepare a pre-emulsion, mixing 8-12% of the pre-emulsion with the aqueous emulsifier, the deionized water and a water-soluble initiator, stirring and heating in a nitrogen protective atmosphere until the system is stable, heating to 80-90 ℃, simultaneously dropwise adding the rest initiator and the pre-emulsion, adding gamma-aminopropyltriethoxysilane (KH 550) when the pre-emulsion is left 1/4, preserving heat after dropwise adding is finished, fully reacting the system, reducing the temperature of the system to 44-55 ℃, adjusting the pH of the system to 7-8 by using ammonia water, reducing the temperature to room temperature, filtering by using a filter screen, and discharging to obtain the acrylic emulsion.
Further, in the first step, the acrylic emulsion containing the silane coupling agent KH570 is prepared by adopting the following method;
firstly, mixing a water-based emulsifier, deionized water, an acrylate monomer and a crosslinking monomer gamma-methacryloxypropyltrimethoxysilane (KH 570) to prepare a pre-emulsion, taking 8-12% of the pre-emulsion, the water-based emulsifier, the deionized water and a water-soluble initiator, stirring and heating in a nitrogen protective atmosphere until the system is stable, heating to 80-90 ℃, simultaneously dropwise adding the rest initiator and the pre-emulsion, keeping the temperature after dropwise adding is finished, fully reacting the system, reducing the temperature of the system to 44-55 ℃, adjusting the pH of the system to 7-8 by using ammonia water, cooling to room temperature, filtering by using a filter screen, and discharging to obtain the acrylic emulsion.
Further, in the second step, the polymer diol is dehydrated in vacuum at the temperature of 115-125 ℃, then the hydrophilic chain extender is added and continuously heated until the polymer diol is completely dissolved, the temperature is reduced to 75-85 ℃, the diisocyanate is added for reaction, then the micromolecule chain extender is added for reaction, the temperature is reduced to 45-55 ℃, and the neutralizer is added for reaction, so that the polyurethane prepolymer is obtained.
Further, in the second step, the polymer diol is dehydrated in vacuum at the temperature of 115-125 ℃, then the hydrophilic chain extender is added and continuously heated until the polymer diol is completely dissolved, the temperature is reduced to 75-85 ℃, the diisocyanate is added for reaction, then the micromolecule chain extender is added for reaction, the temperature is reduced to 45-55 ℃, the gamma-aminopropyltriethoxysilane is added for reaction, and then the neutralizer is added for reaction, so that the polyurethane prepolymer is obtained.
Further, the acrylate is specifically at least one of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isooctyl methacrylate; the water-based emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, octyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and salt thereof, and fatty alcohol ether phosphate and salt thereof; the crosslinking monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, gamma-aminopropyltriethoxysilane (KH 550), gamma-methacryloxypropyltrimethoxysilane (KH 570), hydroxyethyl methacrylate and hydroxypropyl methacrylate; the functional monomer is at least one of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid; the water-soluble initiator is one of potassium persulfate, sodium persulfate and ammonium persulfate.
In the second step, the polymer diol is one or two of polybutylene adipate (PBA), polypropylene glycol (PPG) or polytetrahydrofuran glycol (PTMEG) with the molecular weight of 1000; the diisocyanate is one or a mixture of Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI); the hydrophilic chain extender is one or a mixture of two of dimethylolpropionic acid (DMPA) and dimethylolbutyric acid (DMBA); the micromolecular chain extender is one or a mixture of two of 1, 4-Butanediol (BDO), diethylene glycol (DEG) and Trimethylolpropane (TMP).
Further, in the first step or the second step, the neutralizing agent is one or more of ammonia water, ethanolamine, triethylamine and N, N-dimethylethanolamine.
According to another aspect of the present invention, there is provided a high solid content aqueous polyurethane composite emulsion obtained by the above-described method.
The invention provides an acrylic emulsion containing active functional groups to replace partial water to emulsify and chain extend a polyurethane prepolymer, and the high-solid content acrylic polyurethane composite emulsion is realized through chemical crosslinking and different particle size distribution. Compared with the prior art, the method has the advantages that the method forms a chemical bond by synthesizing the acrylic emulsion with the active functional group and the polyurethane emulsion containing-NCO through chemical crosslinking modification, is copolymerization modification, has more advantages in the aspects of compatibility and comprehensive performance, improves the solid content (more than or equal to 55%) of the waterborne polyurethane, can be used as a main resin for waterborne coatings and adhesives, and meets the requirements of quick drying, high gloss, high saturation, high adhesive force and the like.
Detailed Description
One exemplary embodiment of the present invention provides a method for preparing a high solid content aqueous polyurethane composite emulsion, which includes the following steps.
Step one, preparing a catalyst containing-OH and-NH2Or a silane functional acrylic emulsion;
reacting raw materials including polymer dihydric alcohol, diisocyanate, a hydrophilic chain extender, a micromolecular chain extender and a neutralizing agent to prepare a polyurethane prepolymer containing-NCO;
and step three, adding the acrylic emulsion and the substitute part of water into the polyurethane prepolymer in the step two, replacing part of water with the acrylic emulsion, emulsifying and dispersing the polyurethane prepolymer, and obtaining the chemically cross-linked and modified high-solid-content waterborne polyurethane.
The preparation of the acrylic emulsion modified waterborne polyurethane composite emulsion is realized by synthesizing the acrylic emulsion containing the active functional group and the polyurethane prepolymer containing the unreacted isocyanate group and chemically crosslinking the acrylic emulsion and the polyurethane prepolymer. According to the principle of an emulsion particle accumulation model, the integral number of a closest-packed masonry body of emulsion particles with binary particle size distribution is obviously higher than that of emulsion with monodisperse particle size distribution, acrylic emulsion and polyurethane emulsion have different particle sizes, and when the acrylic emulsion and the polyurethane emulsion are compounded, small particles are dispersed among large particles, so that the space utilization rate of the emulsion particles can be improved, and the solid content of a polymer is improved. After the waterborne polyurethane and the acrylic emulsion are compounded, the advantages can be complemented, and the solid content of the compounded polymer can be further improved by changing the particle size distribution of the waterborne polyurethane and the acrylic emulsion.
For the preparation method of the acrylic emulsion in the step one, a seed emulsion polymerization method is generally adopted. Mixing a water-based emulsifier, deionized water, an acrylate monomer and a crosslinking monomer to prepare a pre-emulsion, mixing 8-12% of the pre-emulsion with the water-based emulsifier, the deionized water and a water-soluble initiator, stirring and heating in a nitrogen protective atmosphere until the system is stable, heating to 80-90 ℃, then simultaneously dropwise adding the rest initiator and the pre-emulsion, preserving heat after dropwise adding is finished, fully reacting the system, then reducing the temperature of the system to 45-55 ℃, adjusting the pH of the system to 7-8 with ammonia water, cooling to room temperature, filtering by a filter screen, and discharging to obtain the acrylic emulsion.
In order to obtain better performance of the product, and particularly to be beneficial for further providing solid content, the preparation method of the acrylic emulsion is preferably as follows: firstly, mixing a water-based emulsifier, deionized water, an acrylate monomer and a crosslinking monomer, carrying out high shear to prepare a pre-emulsion, mixing 10% of the pre-emulsion with the water-based emulsifier, the deionized water and a water-soluble initiator, stirring and heating in a nitrogen protective atmosphere until the system is stable, heating to 85 ℃, then simultaneously dropwise adding the rest initiator and the pre-emulsion, carrying out heat preservation after dropwise adding is finished, after the system fully reacts, reducing the temperature of the system to 50 ℃, adjusting the pH of the system to 7-8 with ammonia water, cooling to room temperature, filtering by a filter screen, and discharging to obtain the acrylic emulsion.
On the basis of the step one, the polyurethane prepolymer is prepared by two methods relatively concretely.
In the first step, the polymer diol is dehydrated in vacuum at the temperature of 115-125 ℃, then the hydrophilic chain extender is added and continuously heated until the polymer diol is completely dissolved, the temperature is reduced to 75-85 ℃, the diisocyanate is added for reaction, then the micromolecular chain extender is added for reaction, the temperature is reduced to 45-55 ℃, and the neutralizer is added for reaction, so that the polyurethane prepolymer is obtained. Preferably: and (2) dehydrating the polymer diol at 120 ℃ in vacuum, adding a hydrophilic chain extender, continuously heating until the polymer diol is completely dissolved, cooling to 80 ℃, adding diisocyanate for reaction, adding a small molecular chain extender for reaction, cooling to 50 ℃, and adding a neutralizer for reaction to obtain the polyurethane prepolymer.
And in the second step, the polymer diol is dehydrated in vacuum at the temperature of 115-125 ℃, then the hydrophilic chain extender is added and continuously heated until the polymer diol is completely dissolved, the temperature is reduced to 75-85 ℃, the diisocyanate is added for reaction, then the micromolecule chain extender is added for reaction, the temperature is reduced to 45-55 ℃, the gamma-aminopropyl triethoxysilane (KH 550) is added for reaction, and then the neutralizer is added for reaction, so that the polyurethane prepolymer is obtained. Preferably: and (2) dehydrating the polymer diol in vacuum at 120 ℃, adding a hydrophilic chain extender, continuously heating until the polymer diol is completely dissolved, cooling to 80 ℃, adding diisocyanate for reaction, adding a small-molecular chain extender for reaction, cooling to 50 ℃, adding 1 gamma-aminopropyltriethoxysilane (KH 550) for reaction, and adding a neutralizer for reaction to obtain the polyurethane prepolymer.
As the acrylic emulsion containing a silane coupling agent, there are two types, the first is a cross-linking monomer containing a silane coupling agent, gamma-methacryloxypropyltrimethoxysilane (KH 570); the second is a silane coupling agent containing gamma-aminopropyltriethoxysilane (KH 550) and gamma-methacryloxypropyltrimethoxysilane (KH 570).
The acrylic emulsion modified polyurethane composite emulsion is prepared by two process methods according to the principle that KH570 can be hydrolyzed to form silanol groups and then subjected to chemical condensation, wherein the first process method comprises the steps of receiving KH570 into acrylic emulsion, grafting amino into the acrylic emulsion through hydrolytic condensation and KH550 reaction, and then carrying out crosslinking reaction with a polyurethane prepolymer containing-NCO to synthesize the acrylic modified polyurethane composite emulsion. The second method is to polymerize the silane coupling agent KH570 into the acrylic emulsion, graft the silane coupling agent KH550 onto the polyurethane prepolymer, and synthesize the acrylic modified polyurethane composite emulsion by hydrolysis and condensation.
Aiming at the first method, in the first step, the acrylic emulsion containing silane coupling agents KH550 and KH570 is prepared by adopting the following method;
firstly, mixing an aqueous emulsifier, deionized water, an acrylate monomer and a crosslinking monomer gamma-methacryloxypropyltrimethoxysilane (KH 570) to prepare a pre-emulsion, mixing 8-12% of the pre-emulsion with the aqueous emulsifier, the deionized water and a water-soluble initiator, stirring and heating in a nitrogen protective atmosphere until the system is stable, heating to 80-90 ℃, simultaneously dropwise adding the rest initiator and the pre-emulsion, adding gamma-aminopropyltriethoxysilane (KH 550) when the pre-emulsion is left 1/4, preserving heat after dropwise adding is finished, fully reacting the system, reducing the temperature of the system to 44-55 ℃, adjusting the pH of the system to 7-8 by using ammonia water, reducing the temperature to room temperature, filtering by using a filter screen, and discharging to obtain the acrylic emulsion.
Preferably, the acrylic emulsion is prepared by mixing an aqueous emulsifier, deionized water, an acrylate monomer and a crosslinking monomer gamma-methacryloxypropyltrimethoxysilane (KH 570), mixing 10% of the pre-emulsion with the aqueous emulsifier, the deionized water and a water-soluble initiator, stirring and heating in a nitrogen protective atmosphere until the system is stable, heating to 85 ℃, simultaneously dropwise adding the rest initiator and the pre-emulsion, adding gamma-aminopropyltriethoxysilane (KH 550) when the pre-emulsion is left 1/4, preserving heat after dropwise adding is finished, fully reacting the system, reducing the temperature of the system to 50 ℃, adjusting the pH of the system to 7-8 with ammonia water, reducing the temperature to room temperature, filtering with a filter screen, and discharging.
And in the second step, the polymer diol is dehydrated in vacuum at the temperature of 115-125 ℃, then the hydrophilic chain extender is added and continuously heated until the polymer diol is completely dissolved, the temperature is reduced to 75-85 ℃, the diisocyanate is added for reaction, then the micromolecule chain extender is added for reaction, the temperature is reduced to 45-55 ℃, and the neutralizer is added for reaction, so that the polyurethane prepolymer is obtained.
Preferably: and (2) dehydrating the polymer diol at 120 ℃ in vacuum, adding a hydrophilic chain extender, continuously heating until the polymer diol is completely dissolved, cooling to 80 ℃, adding diisocyanate for reaction, adding a small molecular chain extender for reaction, cooling to 50 ℃, and adding a neutralizer for reaction to obtain the polyurethane prepolymer.
Aiming at the second method, in the first step, the acrylic emulsion containing the silane coupling agent KH570 is prepared by adopting the following method;
firstly, mixing a water-based emulsifier, deionized water, an acrylate monomer and a crosslinking monomer gamma-methacryloxypropyltrimethoxysilane (KH 570) to prepare a pre-emulsion, taking 8-12% of the pre-emulsion, the water-based emulsifier, the deionized water and a water-soluble initiator, stirring and heating in a nitrogen protective atmosphere until the system is stable, heating to 80-90 ℃, simultaneously dropwise adding the rest initiator and the pre-emulsion, keeping the temperature after dropwise adding is finished, fully reacting the system, reducing the temperature of the system to 44-55 ℃, adjusting the pH of the system to 7-8 by using ammonia water, cooling to room temperature, filtering by using a filter screen, and discharging to obtain the acrylic emulsion.
Preferably, mixing an aqueous emulsifier, deionized water, an acrylate monomer and a crosslinking monomer gamma-methacryloxypropyltrimethoxysilane (KH 570) to prepare a pre-emulsion, taking 10% of the pre-emulsion, the aqueous emulsifier, the deionized water and a water-soluble initiator, stirring and heating the pre-emulsion, the aqueous emulsifier, the deionized water and the water-soluble initiator to 85 ℃ in a nitrogen protective atmosphere, simultaneously dropwise adding the rest initiator and the pre-emulsion after heating the pre-emulsion to 85 ℃, keeping the temperature after dropwise adding is finished, fully reacting the system, reducing the temperature of the system to 50 ℃, adjusting the pH of the system to 7-8 by using ammonia water, cooling the system to room temperature, filtering the system by using a filter.
And in the second step, the polymer diol is dehydrated in vacuum at the temperature of 115-125 ℃, then the hydrophilic chain extender is added and continuously heated until the polymer diol is completely dissolved, the temperature is reduced to 75-85 ℃, the diisocyanate is firstly added for reaction, then the micromolecular chain extender is added for reaction, the temperature is reduced to 45-55 ℃, the 1 gamma-aminopropyltriethoxysilane is added for reaction, and then the neutralizer is added for reaction, so that the polyurethane prepolymer is obtained. Preferably: and (2) dehydrating the polymer diol in vacuum at 120 ℃, adding a hydrophilic chain extender, continuously heating until the polymer diol is completely dissolved, cooling to 80 ℃, adding diisocyanate for reaction, adding a small molecular chain extender for reaction, cooling to 50 ℃, adding 1 gamma-aminopropyltriethoxysilane for reaction, and adding a neutralizer for reaction to obtain the polyurethane prepolymer.
In the above embodiment, the acrylate is specifically at least one of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isooctyl methacrylate; the water-based emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, octyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and salt thereof, and fatty alcohol ether phosphate and salt thereof; the crosslinking monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, gamma-aminopropyltriethoxysilane (KH 550), gamma-methacryloxypropyltrimethoxysilane (KH 570), hydroxyethyl methacrylate and hydroxypropyl methacrylate; the functional monomer is at least one of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid; the water-soluble initiator is one of potassium persulfate, sodium persulfate and ammonium persulfate.
In the above embodiment, in the second step, the polymer diol is one or a mixture of two of polybutylene adipate (PBA), polypropylene glycol (PPG) or polytetrahydrofuran glycol (PTMEG) with a molecular weight of 1000; the diisocyanate is one or a mixture of Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI); the hydrophilic chain extender is one or a mixture of two of dimethylolpropionic acid (DMPA) and dimethylolbutyric acid (DMBA); the micromolecular chain extender is one or a mixture of two of 1, 4-Butanediol (BDO), diethylene glycol (DEG) and Trimethylolpropane (TMP).
In the above embodiment, in the first step or the second step, the neutralizing agent is one or more of ammonia, ethanolamine, triethylamine and N, N-dimethylethanolamine.
In the first step, the addition amount of each raw material is selected from the following components in parts by mass: 85-95 parts of acrylate monomers, 5-10 parts of crosslinking monomers, 1-3 parts of functional monomers, 1-6 parts of water-based emulsifiers, 0.2-0.4 part of buffering agents, 0.4-1 part of water-soluble initiators, 1-3 parts of neutralizing agents and 200-300 parts of water.
In the second step, the addition amount of each raw material is selected from the following components in parts by mass: 50-60 parts of polymer diol, 7-9 parts of hydrophilic chain extender, 25-30 parts of diisocyanate, 3-5 parts of neutralizer and 0.5-1 part of micromolecular chain extender.
The claimed solution is further illustrated by the following examples. However, the examples and comparative examples are intended to illustrate the embodiments of the present invention without departing from the scope of the subject matter of the present invention, and the scope of the present invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Example 1
Step one, 0.8g of sodium dodecyl sulfate, 0.4g of OP-10 (octylphenol polyoxyethylene ether), 40g of deionized water, 40g of methyl methacrylate, 18g of ethyl acrylate, 40g of butyl acrylate, 2g of acrylic acid and 2g of gamma-methacryloxypropyltrimethoxysilane (KH 570) are sequentially weighed and mixed to prepare a pre-emulsion through high shearing for 15 minutes, 10 percent of the pre-emulsion is taken out and added into a 500mL four-neck flask, 1.2g of sodium dodecyl sulfate, 0.6g of OP-10, 100g of deionized water and 0.2g of ammonium persulfate are simultaneously added into the four-neck flask, nitrogen is opened for protection, the pre-emulsion is heated to 85 ℃ under stirring till the system is in a uniform blue phase and is stable, the rest initiator solution (0.25 g of ammonium persulfate and 10g of water) and the pre-emulsion are respectively and simultaneously dripped, 3g of gamma-aminopropyltriethoxysilane (KH 550) are added when 1/4 of the pre-emulsion remains, the dropwise addition was continued for 3 h. And (4) after the dropwise addition, keeping the temperature for 1h to ensure that the system fully reacts, then reducing the temperature of the system to 50 ℃, and adjusting the pH of the system to 7-8 by using ammonia water. Cooling to room temperature, filtering by a filter screen, and discharging to obtain the acrylic emulsion.
And step two, placing 60g of PBA (Mn = 1000) and 40g of PPG (Mn = 1000) in a 500mL four-mouth bottle, dehydrating for 1h under vacuum at 120 ℃, stopping vacuum, adding 13.32g of DMBA, continuously heating until the PBA is completely dissolved, cooling to 80 ℃, adding 53.28g of IPDI, reacting for 2h under stirring, adding 3.6g of BDO, reacting for 1h, cooling to 50 ℃, adding 7.7g of TEA, and reacting for 20min to obtain the polyurethane prepolymer.
And step three, adding 250g of acrylic emulsion and 60g of deionized water into the polyurethane prepolymer, stirring at a high speed, and reacting for 30min to obtain the polyurethane acrylic composite emulsion. The composite emulsion obtained in example 1 has a solid content of 55%, a viscosity of 200cp, a film tensile strength of 14Mpa and an elongation at break of 710%.
Example 2
Step one, 0.8g of sodium dodecyl benzene sulfonate, 0.4g of AEO-9 (fatty alcohol polyoxyethylene ether), 40g of deionized water, 20g of methyl acrylate, 20g of methyl methacrylate, 15g of ethyl acrylate, 40g of butyl acrylate, 3g of methacrylic acid and 2g of gamma-methacryloxypropyl trimethoxysilane (KH 570) are sequentially weighed and mixed for high shear for 15 minutes to prepare a pre-emulsion, 10% of the pre-emulsion is taken out and added into a 500mL four-neck flask, 1.2g of sodium dodecyl sulfate, 0.6g of AEO-9, 100g of deionized water and 0.2g of potassium persulfate are simultaneously added into the four-neck flask, nitrogen protection is performed, the pre-emulsion is heated to 85 ℃ under stirring till the system is in a uniform blue phase and is stable, and then the temperature is raised to 85 ℃, and the residual initiator solution (0.25 g of potassium persulfate and 10g of water) and the pre-emulsion are respectively and simultaneously added, wherein. And (4) after the dropwise addition, keeping the temperature for 1h to ensure that the system fully reacts, then reducing the temperature of the system to 50 ℃, and adjusting the pH of the system to 7-8 by using ammonia water. Cooling to room temperature, filtering by a filter screen, and discharging to obtain the acrylic emulsion.
Step two, 100g of PTMEG (Mn = 1000) is placed in a 500mL four-mouth bottle, vacuum dehydration is carried out for 1h at 120 ℃, vacuum stopping is carried out, 12g of DMPA is added and continuously heated until the PTMEG is completely dissolved, the temperature is reduced to 80 ℃, 45g of HDI is added and stirred for reaction for 2h, 6.3g of BDO is added and reacted for 1h, the temperature is reduced to 50 ℃, 1.8g of gamma-aminopropyltriethoxysilane (KH 550) is added, 7.7g of TEA is added after reaction for 30min, and reaction is carried out for 20min, so that a polyurethane prepolymer is obtained.
And step three, adding 250g of acrylic emulsion and 30g of deionized water into the polyurethane prepolymer, stirring at a high speed, and reacting for 30min to obtain the polyurethane acrylic composite emulsion. The composite emulsion obtained in example 2 has a solid content of 56%, a viscosity of 220cp, a film tensile strength of 17Mpa, and an elongation at break of 650%.
Example 3
Step one, 0.8g of sodium dodecyl sulfate, 0.4g of OP-10 (octylphenol polyoxyethylene ether), 40g of deionized water, 20g of methyl methacrylate, 45g of methyl acrylate, 28g of isooctyl acrylate, 2g of acrylic acid and 5g of hydroxyethyl methacrylate are sequentially weighed and mixed to prepare a pre-emulsion through high shearing for 15 minutes, 10 percent of the pre-emulsion is taken out and added into a 500mL four-neck flask, 1.2g of sodium dodecyl sulfate, 0.6g of OP-10, 100g of deionized water and 0.2g of ammonium persulfate are simultaneously added into the four-neck flask, nitrogen protection is performed, the mixture is heated under stirring until the system is in a uniform blue phase and is stable, the temperature is increased to 85 ℃, and the rest initiator solution (0.25 g of ammonium persulfate and 10g of water) and the pre-emulsion are respectively and simultaneously dripped, and the dripping time is 3 hours. And (4) after the dropwise addition, keeping the temperature for 1h to ensure that the system fully reacts, then reducing the temperature of the system to 50 ℃, and adjusting the pH of the system to 7-8 by using ammonia water. Cooling to room temperature, filtering by a filter screen, and discharging to obtain the acrylic emulsion.
And step two, placing 100g of PBA (Mn = 1000) in a 500mL four-mouth bottle, dehydrating for 1h in vacuum at 120 ℃, stopping vacuum, adding 12.06g of DMPA, continuously heating until the PBA is completely dissolved, cooling to 80 ℃, adding 62.16g of IPDI, reacting for 2h under stirring, adding 4.5g of BDO, reacting for 1h, cooling to 50 ℃, adding 7.7g of TEA, and reacting for 20min to obtain the polyurethane prepolymer.
And step three, adding 250gA of acrylic emulsion and 40g of deionized water into the polyurethane prepolymer, stirring at a high speed, and reacting for 30min to obtain the polyurethane acrylic composite emulsion. The composite emulsion obtained in example 3 has a solid content of 56%, a viscosity of 230cp, a film tensile strength of 16Mpa and an elongation at break of 680%.
Example 4
Step one, 0.8g of sodium dodecyl benzene sulfonate, 0.4g of AEO-9 (fatty alcohol-polyoxyethylene ether), 40g of deionized water, 45g of methyl methacrylate, 43g of butyl acrylate, 3g of methacrylic acid and 9g of hydroxypropyl methacrylate are sequentially weighed and mixed to prepare a pre-emulsion through high shear for 15 minutes, 10% of the pre-emulsion is taken out and added into a 500mL four-neck flask, 1.2g of sodium dodecyl sulfate, 0.6g of AEO-9, 100g of deionized water and 0.2g of potassium persulfate are simultaneously added into the four-neck flask, nitrogen protection is performed, the mixture is heated under stirring until the system is in a uniform blue phase and is stable, the temperature is raised to 85 ℃, and the rest initiator solution (0.25 g of potassium persulfate and 10g of water) and the pre-emulsion are respectively and simultaneously dripped for 3 hours. And (4) after the dropwise addition, keeping the temperature for 1h to ensure that the system fully reacts, then reducing the temperature of the system to 50 ℃, and adjusting the pH of the system to 7-8 by using ammonia water. Cooling to room temperature, filtering by a filter screen, and discharging to obtain the acrylic emulsion.
Step two, putting 100g of PTMEG (Mn = 1000) into a 500mL four-mouth bottle, dehydrating for 1h under vacuum at 120 ℃, stopping vacuum, adding 13.4g of DMPA, continuously heating until the mixture is completely dissolved, cooling to 80 ℃, adding 47.04g of HDI, reacting for 2h under stirring, adding 3.6g of BDO, reacting for 1h, cooling to 50 ℃, adding 1.8g of gamma-aminopropyltriethoxysilane (KH 550), reacting for 30min, adding 8.6g of TEA, and reacting for 20min to obtain the polyurethane prepolymer.
And step three, adding 250g of acrylic emulsion and 30g of deionized water into the polyurethane prepolymer, stirring at a high speed, and reacting for 30min to obtain the polyurethane acrylic composite emulsion. The composite emulsion obtained in example 4 has a solid content of 55%, a viscosity of 250cp, a film tensile strength of 12Mpa, and an elongation at break of 820%.
Example 5
Step one, 0.8g of sodium dodecyl sulfate, 0.4g of OP-10 (octylphenol polyoxyethylene ether), 40g of deionized water, 44g of methyl methacrylate, 46g of butyl acrylate, 2g of acrylic acid and 8g of hydroxyethyl acrylate are sequentially weighed and mixed to prepare a pre-emulsion through high shearing for 15 minutes, 10% of the pre-emulsion is taken out and added into a 500mL four-neck flask, 1.2g of sodium dodecyl sulfate, 0.6g of OP-10, 100g of deionized water and 0.2g of ammonium persulfate are simultaneously added into the four-neck flask, nitrogen protection is performed, the mixture is heated under stirring until the system is in a uniform blue phase and is stable, the temperature is raised to 85 ℃, and then the rest initiator solution (0.25 g of ammonium persulfate and 10g of water) and the pre-emulsion are respectively and simultaneously dripped at the beginning time of 3 hours. And (4) after the dropwise addition, keeping the temperature for 1h to ensure that the system fully reacts, then reducing the temperature of the system to 50 ℃, and adjusting the pH of the system to 7-8 by using ammonia water. Cooling to room temperature, filtering by a filter screen, and discharging to obtain the acrylic emulsion.
And step two, placing 100g of PPA (Mn = 1000) into a 500mL four-mouth bottle, dehydrating for 1h in vacuum at 120 ℃, stopping vacuum, adding 14.8g of DMBA, continuously heating until the PPA is completely dissolved, cooling to 80 ℃, adding 57.72g of IPDI, reacting for 2h under stirring, adding 1.8g of BDO, reacting for 1h, cooling to 50 ℃, adding 8.6g of TEA, and reacting for 20min to obtain the polyurethane prepolymer.
And step three, adding 250gA of acrylic emulsion and 35g of deionized water into the polyurethane prepolymer, stirring at a high speed, and reacting for 30min to obtain the polyurethane acrylic composite emulsion. The composite emulsion obtained in example 5 has a solid content of 56%, a viscosity of 240cp, a film tensile strength of 15Mpa, and an elongation at break of 680%.
Example 6
This example differs from example 1 only in that: in the first step, 0.8g of sodium dodecyl sulfate, 0.4gOP-10 (octylphenol polyoxyethylene ether), 40g of deionized water, 40g of methyl methacrylate, 18g of ethyl acrylate, 40g of butyl acrylate, 2g of acrylic acid, 2g of gamma-methacryloxypropyltrimethoxysilane (KH 570) are sequentially weighed and mixed to prepare a pre-emulsion through high shear for 15 minutes, 8 percent of the pre-emulsion is taken out and added into a 500mL four-neck flask, 1.2g of sodium dodecyl sulfate, 0.6g of OP-10, 100g of deionized water and 0.2g of ammonium persulfate are simultaneously added into the four-neck flask, nitrogen is opened for protection, the pre-emulsion is heated to 80 ℃ under stirring till the system is in a uniform blue phase and is stable, the rest initiator solution (0.25 g of ammonium persulfate and 10g of water) and the pre-emulsion are respectively and dropwise added at the same time, when the pre-emulsion is in rest 1/4, 3g of gamma-aminopropyltriethoxysilane (KH 550, the dropwise addition was continued for 3 h. And (4) after the dropwise addition, keeping the temperature for 1h to ensure that the system fully reacts, then reducing the temperature of the system to 45 ℃, and adjusting the pH of the system to 7-8 by using ammonia water. Cooling to room temperature, filtering by a filter screen, and discharging to obtain the acrylic emulsion.
Example 7
This example differs from example 2 only in that: step one, 0.8g of sodium dodecyl benzene sulfonate, 0.4g of AEO-9 (fatty alcohol polyoxyethylene ether), 40g of deionized water, 20g of methyl acrylate, 20g of methyl methacrylate, 15g of ethyl acrylate, 40g of butyl acrylate, 3g of methacrylic acid and 2g of gamma-methacryloxypropyl trimethoxysilane (KH 570) are sequentially weighed and mixed for high shear for 15 minutes to prepare a pre-emulsion, 12% of the pre-emulsion is taken out and added into a 500mL four-neck flask, 1.2g of sodium dodecyl benzene sulfonate, 0.6g of AEO-9, 100g of deionized water and 0.2g of potassium persulfate are simultaneously added into the four-neck flask, nitrogen protection is started, the pre-emulsion is heated to 90 ℃ under stirring until a uniform blue phase is formed and the system is stable, and then the residual initiator solution (0.25 g of potassium persulfate and 10g of water) and the pre-emulsion are respectively and simultaneously added into the pre-emulsion for 3 hours after the. And (4) after the dropwise addition, keeping the temperature for 1h to ensure that the system is fully reacted, reducing the temperature of the system to 55 ℃, and adjusting the pH of the system to 7-8 by using ammonia water. Cooling to room temperature, filtering by a filter screen, and discharging to obtain the acrylic emulsion.
Example 8
This example differs from example 3 only in that: and step two, placing 100g of PBA (Mn = 1000) in a 500mL four-mouth bottle, dehydrating for 1h in vacuum at 115 ℃, stopping vacuum, adding 12.06g of DMPA, continuously heating until the PBA is completely dissolved, cooling to 75 ℃, adding 62.16g of IPDI, reacting for 2h under stirring, adding 4.5g of BDO, reacting for 1h, cooling to 45 ℃, adding 7.7g of TEA, and reacting for 20min to obtain the polyurethane prepolymer.
Example 9
This example differs from example 4 only in that: step two, putting 100g of PTMEG (Mn = 1000) into a 500mL four-mouth bottle, dehydrating for 1h under vacuum at 125 ℃, stopping vacuum, adding 13.4g of DMPA, continuously heating until the mixture is completely dissolved, cooling to 85 ℃, adding 47.04g of HDI, reacting for 2h under stirring, adding 3.6g of BDO, reacting for 1h, cooling to 55 ℃, adding 1.8g of gamma-aminopropyltriethoxysilane (KH 550), reacting for 30min, adding 8.6g of TEA, and reacting for 20min to obtain the polyurethane prepolymer.
Comparative example 1
Putting 60g of PBA (Mn = 1000) and 40g of PPG (Mn = 1000) into a 500mL four-mouth bottle, dehydrating in vacuum at 120 ℃ for 1h, stopping vacuum, adding 13.32g of DMBA, continuously heating until all the DMBA is dissolved, cooling to 80 ℃, adding 53.28g of IPDI, reacting for 2h under stirring, adding 3.6g of BDO, reacting for 1h, cooling to 50 ℃, adding 7.7g of TEA, reacting for 20min, adding 130g of deionized water, stirring at high speed, and reacting for 30min to obtain the polyurethane acrylic composite emulsion.
Comparative examples 2 and 3 the same raw material ratios as in examples 2 and 3, water was used in total and 130g was used for emulsification. Examples 1, 2, 3 and comparative examples 1, 2, 3 were simultaneously formulated as waterborne coatings, and the test results were as follows:
example 1 Comparative example 1 Example 2 Comparative example 2 Example 3 Comparative example 3
Viscosity/cp 200 300 220 310 230 330
Tensile strength/MPa 14 19 17 20 16 18
Elongation at break/% 710 484 650 425 680 507
Degree of fullness Good taste In general Good taste In general Good taste In general
Gloss/60 ° 60 40 55 42 58 45
Adhesion force Level 1 Level 1 Level 1 Level 1 Level 1 Level 1
Drying time/min 20 40 18 36 21 35
The comparison shows that the modified composite emulsion has slightly reduced tensile strength but enhanced toughness and elasticity, which shows that the modified composite emulsion realizes the complementary advantages of acrylic acid and polyurethane and has the characteristics of high solid content and low viscosity. The water paint prepared by the modified composite emulsion has obvious improvement on fullness, drying time and glossiness.

Claims (10)

1. A preparation method of high-solid-content aqueous polyurethane composite emulsion is characterized by comprising the following steps:
step one, preparing a catalyst containing-OH and-NH2Or a silane functional acrylic emulsion;
reacting raw materials including polymer dihydric alcohol, diisocyanate, a hydrophilic chain extender, a micromolecular chain extender and a neutralizing agent to prepare a polyurethane prepolymer containing-NCO;
and step three, adding the acrylic emulsion and water in the step one into the polyurethane prepolymer in the step two, emulsifying and dispersing the polyurethane prepolymer to obtain the chemically cross-linked and modified high-solid-content waterborne polyurethane.
2. The method of claim 1, wherein: in the first step, preparing the acrylic emulsion by adopting a seed emulsion polymerization method;
firstly, mixing a water-based emulsifier, deionized water, an acrylate monomer and a crosslinking monomer to prepare a pre-emulsion, mixing 8-12% of the pre-emulsion with the water-based emulsifier, the deionized water and a water-soluble initiator, stirring and heating in a nitrogen protective atmosphere until the system is stable, heating to 80-90 ℃, then simultaneously dropwise adding the rest initiator and the pre-emulsion, preserving heat after dropwise adding is finished, fully reacting the system, then reducing the temperature of the system to 45-55 ℃, adjusting the pH of the system to 7-8 with ammonia water, cooling to room temperature, filtering by a filter screen, and discharging to obtain the acrylic emulsion.
3. The method of claim 1, wherein: in the first step, an acrylic emulsion containing silane coupling agents KH550 and KH570 is prepared by the following method;
firstly, mixing an aqueous emulsifier, deionized water, an acrylate monomer and a crosslinking monomer gamma-methacryloxypropyltrimethoxysilane (KH 570) to prepare a pre-emulsion, mixing 8-12% of the pre-emulsion with the aqueous emulsifier, the deionized water and a water-soluble initiator, stirring and heating in a nitrogen protective atmosphere until the system is stable, heating to 80-90 ℃, simultaneously dropwise adding the rest initiator and the pre-emulsion, adding gamma-aminopropyltriethoxysilane (KH 550) when the pre-emulsion is left 1/4, preserving heat after dropwise adding is finished, fully reacting the system, reducing the temperature of the system to 44-55 ℃, adjusting the pH of the system to 7-8 by using ammonia water, reducing the temperature to room temperature, filtering by using a filter screen, and discharging to obtain the acrylic emulsion.
4. The method of claim 1, wherein: in the first step, preparing acrylic emulsion containing a silane coupling agent KH570 by adopting the following method;
firstly, mixing a water-based emulsifier, deionized water, an acrylate monomer and a crosslinking monomer gamma-methacryloxypropyltrimethoxysilane (KH 570) to prepare a pre-emulsion, taking 8-12% of the pre-emulsion, the water-based emulsifier, the deionized water and a water-soluble initiator, stirring and heating in a nitrogen protective atmosphere until the system is stable, heating to 80-90 ℃, simultaneously dropwise adding the rest initiator and the pre-emulsion, keeping the temperature after dropwise adding is finished, fully reacting the system, reducing the temperature of the system to 44-55 ℃, adjusting the pH of the system to 7-8 by using ammonia water, cooling to room temperature, filtering by using a filter screen, and discharging to obtain the acrylic emulsion.
5. The method as claimed in claim 2 or 3, wherein in the second step, the polymer diol is dehydrated under vacuum at 115-125 ℃, then the hydrophilic chain extender is added and heated continuously until the polymer diol is completely dissolved, the temperature is reduced to 75-85 ℃, the diisocyanate is added for reaction, then the small molecular chain extender is added for reaction, the temperature is reduced to 45-55 ℃, the neutralizer is added for reaction, and the polyurethane prepolymer is obtained.
6. The method according to claim 2 or 4, characterized in that: and in the second step, the polymer diol is dehydrated in vacuum at the temperature of 115-125 ℃, then the hydrophilic chain extender is added and continuously heated until the polymer diol is completely dissolved, the temperature is reduced to 75-85 ℃, the diisocyanate is added for reaction, then the micromolecular chain extender is added for reaction, the temperature is reduced to 45-55 ℃, the gamma-aminopropyltriethoxysilane is added for reaction, and then the neutralizer is added for reaction, so that the polyurethane prepolymer is obtained.
7. The method according to claim 2 or 3 or 4, characterized in that: the acrylate is specifically at least one of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isooctyl methacrylate; the water-based emulsifier is at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, octyl phenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and salt thereof, and fatty alcohol ether phosphate and salt thereof; the crosslinking monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, gamma-aminopropyltriethoxysilane (KH 550), gamma-methacryloxypropyltrimethoxysilane (KH 570), hydroxyethyl methacrylate and hydroxypropyl methacrylate; the functional monomer is at least one of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid; the water-soluble initiator is one of potassium persulfate, sodium persulfate and ammonium persulfate.
8. The method according to claim 5 or 6, characterized in that: in the second step, the polymer diol is one or a mixture of two of polybutylene adipate (PBA), polypropylene glycol (PPG) or polytetrahydrofuran glycol (PTMEG) with the molecular weight of 1000; the diisocyanate is one or a mixture of Hexamethylene Diisocyanate (HDI), Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI); the hydrophilic chain extender is one or a mixture of two of dimethylolpropionic acid (DMPA) and dimethylolbutyric acid (DMBA); the micromolecular chain extender is one or a mixture of two of 1, 4-Butanediol (BDO), diethylene glycol (DEG) and Trimethylolpropane (TMP).
9. The method according to claim 5 or 6, characterized in that: in the first step or the second step, the neutralizing agent is one or more of ammonia water, ethanolamine, triethylamine and N, N-dimethylethanolamine.
10. A high-solid-content aqueous polyurethane composite emulsion is characterized in that: prepared by the process of any one of claims 1 to 9.
CN202010846243.2A 2020-08-21 2020-08-21 High-solid-content aqueous polyurethane composite emulsion and preparation method thereof Active CN111875769B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010846243.2A CN111875769B (en) 2020-08-21 2020-08-21 High-solid-content aqueous polyurethane composite emulsion and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010846243.2A CN111875769B (en) 2020-08-21 2020-08-21 High-solid-content aqueous polyurethane composite emulsion and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111875769A true CN111875769A (en) 2020-11-03
CN111875769B CN111875769B (en) 2022-03-22

Family

ID=73203074

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010846243.2A Active CN111875769B (en) 2020-08-21 2020-08-21 High-solid-content aqueous polyurethane composite emulsion and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111875769B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114163922A (en) * 2021-12-09 2022-03-11 常州艾肯智造科技有限公司 Water-based nano heat-insulating coating and preparation method thereof
CN114672237A (en) * 2022-02-14 2022-06-28 广东银洋环保新材料有限公司 Polyurethane modified acrylic resin, preparation method thereof and wood lacquer
CN115074061A (en) * 2022-07-05 2022-09-20 湖南林特科技有限公司 Surface coating adhesive for impregnated paper and preparation method thereof
CN117363186A (en) * 2023-10-17 2024-01-09 广东日东工具有限公司 Water-based non-stick paint and preparation method thereof

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ235161A (en) * 1989-10-06 1991-12-23 Basf Corp Water dispersible polyurethane-acrylic graft co-polymers
CN101429407A (en) * 2008-12-08 2009-05-13 广州市科霖水性材料有限公司 Watersoluble polyurethane acrylic acid composite coating agent and method of producing the same
CN101519479A (en) * 2009-01-22 2009-09-02 广东天银化工实业有限公司 Method for preparing self-cross linking type water-based fluorine-contained acrylic resin and polyurethane hybrid
CN102911633A (en) * 2012-10-18 2013-02-06 四川大学 Branched-structure polyurethane-silicious polyacrylate hot melt adhesive and preparation method thereof
CN103012714A (en) * 2012-12-26 2013-04-03 江苏柏鹤涂料有限公司 High-flexibility aqueous acrylic acid polyurethane elastic resin and coating thereof
CN103360561A (en) * 2013-07-02 2013-10-23 广东海顺新材料科技有限公司 Polyurethane modified acrylic emulsion, preparation method of acrylic emulsion and prepared artificial stone
CN104592462A (en) * 2014-12-26 2015-05-06 上海维凯光电新材料有限公司 Silica sol modified acrylic emulsion and preparation and application thereof
CN104893527A (en) * 2015-06-09 2015-09-09 浩力森涂料（上海）有限公司 Aqueous polyurethane coating with increased limiting film thickness and preparation method of aqueous polyurethane coating
KR20150117313A (en) * 2014-04-09 2015-10-20 수산고분자 주식회사 Acryl Modified Polyurethane Water Dispersion and the use thereof
CN105408435A (en) * 2013-07-16 2016-03-16 株式会社钟化 Active energy-ray-curable resin composition for coating organic or inorganic substrate
CN105859978A (en) * 2016-06-24 2016-08-17 安徽省思维新型建材有限公司 Preparation method of organosilicon/acrylic ester modified polyurethane
CN106543877A (en) * 2016-10-27 2017-03-29 中科院广州化学有限公司南雄材料生产基地 The modified polyurethane woodwork coating of water polyacrylic acid containing organosilicon and its preparation method and application
CN106589286A (en) * 2016-11-21 2017-04-26 万华化学集团股份有限公司 Silane modified polyurethane resin and preparation method thereof
CN106590385A (en) * 2016-12-13 2017-04-26 天长市银狐漆业有限公司 Self-cleaning antifouling organic-inorganic super-amphiphobic polymer coating
CN111057210A (en) * 2019-12-31 2020-04-24 阜阳欣奕华材料科技有限公司 Waterborne polyurethane coating agent and preparation method and application thereof

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ235161A (en) * 1989-10-06 1991-12-23 Basf Corp Water dispersible polyurethane-acrylic graft co-polymers
CN101429407A (en) * 2008-12-08 2009-05-13 广州市科霖水性材料有限公司 Watersoluble polyurethane acrylic acid composite coating agent and method of producing the same
CN101519479A (en) * 2009-01-22 2009-09-02 广东天银化工实业有限公司 Method for preparing self-cross linking type water-based fluorine-contained acrylic resin and polyurethane hybrid
CN102911633A (en) * 2012-10-18 2013-02-06 四川大学 Branched-structure polyurethane-silicious polyacrylate hot melt adhesive and preparation method thereof
CN103012714A (en) * 2012-12-26 2013-04-03 江苏柏鹤涂料有限公司 High-flexibility aqueous acrylic acid polyurethane elastic resin and coating thereof
CN103360561A (en) * 2013-07-02 2013-10-23 广东海顺新材料科技有限公司 Polyurethane modified acrylic emulsion, preparation method of acrylic emulsion and prepared artificial stone
CN105408435A (en) * 2013-07-16 2016-03-16 株式会社钟化 Active energy-ray-curable resin composition for coating organic or inorganic substrate
KR20150117313A (en) * 2014-04-09 2015-10-20 수산고분자 주식회사 Acryl Modified Polyurethane Water Dispersion and the use thereof
CN104592462A (en) * 2014-12-26 2015-05-06 上海维凯光电新材料有限公司 Silica sol modified acrylic emulsion and preparation and application thereof
CN104893527A (en) * 2015-06-09 2015-09-09 浩力森涂料（上海）有限公司 Aqueous polyurethane coating with increased limiting film thickness and preparation method of aqueous polyurethane coating
CN105859978A (en) * 2016-06-24 2016-08-17 安徽省思维新型建材有限公司 Preparation method of organosilicon/acrylic ester modified polyurethane
CN106543877A (en) * 2016-10-27 2017-03-29 中科院广州化学有限公司南雄材料生产基地 The modified polyurethane woodwork coating of water polyacrylic acid containing organosilicon and its preparation method and application
CN106589286A (en) * 2016-11-21 2017-04-26 万华化学集团股份有限公司 Silane modified polyurethane resin and preparation method thereof
CN106590385A (en) * 2016-12-13 2017-04-26 天长市银狐漆业有限公司 Self-cleaning antifouling organic-inorganic super-amphiphobic polymer coating
CN111057210A (en) * 2019-12-31 2020-04-24 阜阳欣奕华材料科技有限公司 Waterborne polyurethane coating agent and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HAMID JAVAHERIANNAGHASH等: "Preparation and characterization of water-based polyurethane–acrylic hybrid nanocomposite emulsion based on a new silane-containing acrylic macromonomer", 《J. COAT. TECHNOL. RES.》 *
TINGFA YI等: "Polyurethane-acrylic hybrid emulsions with high acrylic/polyurethane ratios: Synthesis, characterization, and properties", 《J. APPL. POLYM. SCI.》 *
刘敏等: "丙烯酸改性聚氨酯的合成", 《山西化工》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114163922A (en) * 2021-12-09 2022-03-11 常州艾肯智造科技有限公司 Water-based nano heat-insulating coating and preparation method thereof
CN114672237A (en) * 2022-02-14 2022-06-28 广东银洋环保新材料有限公司 Polyurethane modified acrylic resin, preparation method thereof and wood lacquer
CN115074061A (en) * 2022-07-05 2022-09-20 湖南林特科技有限公司 Surface coating adhesive for impregnated paper and preparation method thereof
CN115074061B (en) * 2022-07-05 2024-04-12 湖南林特科技有限公司 Surface coating adhesive for impregnated paper and preparation method thereof
CN117363186A (en) * 2023-10-17 2024-01-09 广东日东工具有限公司 Water-based non-stick paint and preparation method thereof
CN117363186B (en) * 2023-10-17 2024-04-19 广东日东工具有限公司 Water-based non-stick paint and preparation method thereof

Also Published As

Publication number Publication date
CN111875769B (en) 2022-03-22

Similar Documents

Publication Publication Date Title
CN111875769B (en) High-solid-content aqueous polyurethane composite emulsion and preparation method thereof
CN101638464B (en) Method for preparing polyurethane-polyacrylic ester microemulsion
CN111662573B (en) Vegetable oil and organic silicon composite modified UV-curable nano silicon dioxide, preparation method and application thereof
CN101945906B (en) Aqueous coating composition comprising polyurethanes and vinyl polymers
TWI773891B (en) Method for preparing waterborne polyurethane dispersion
CN102977282A (en) Preparation method of anionic organic-solvent-free and emulsifier-free polyurethane microemulsion
CN108314770B (en) Carbon dioxide-based aqueous polyurethane dispersion, preparation method thereof and carbon dioxide-based aqueous polyurethane pressure-sensitive adhesive
JP2003508600A (en) Ultra high solid acrylic paint
CN110054722A (en) A kind of high richness Aqueous acrylic urethane coating composition and preparation method thereof including water-based hydroxyl acrylic acid dispersion resin
CN114891160B (en) Asparagus resin and epoxy resin modified water-based resin hydroxy acrylic resin and its preparation method and application
CN109293871B (en) Self-leveling water-based fluorine-containing polyurethane acrylic resin, preparation method thereof and water-based photocureable coating
EP0608274B1 (en) Vinyl polymer latex systems
CN109503738B (en) Phosphoric acid modified polyisoprene rubber, polyisoprene rubber modified acrylate resin dispersion, preparation method and application
CN108164650B (en) Alkenyl-terminated nonionic waterborne polyurethane modified acrylate emulsion and preparation method thereof
CN112409901B (en) Waterborne polyurethane coating and preparation method thereof
CN111675793B (en) Waterborne polyurethane modified acrylic resin and preparation method and application thereof
CN110423323B (en) Water-soluble blocked polyurethane curing agent and preparation method and application thereof
JP2000313735A (en) Preparative method for aqueous dispersion of polyurethane resin
EP1940884B1 (en) High temperature polymerization process for making branched acrylic polymers, caprolactone-modified branched acrylic polymers, and uses thereof
JP4826688B2 (en) Method for producing polyurethane resin aqueous dispersion
TWI811576B (en) Method for making waterborne polyurethane resin
CN112111191B (en) PET (polyethylene terephthalate) heat transfer water-based ink without release agent and preparation method thereof
CN102199374A (en) Ultraviolet light room temperature dual curing coating composition and preparation method thereof
CN112029067A (en) Photo-curing water-based acrylic acid dispersion and preparation method and application thereof
EP0808857A2 (en) A structured reactive latex

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant