CN113402695A - Waterborne polyurethane resin and low-temperature-resistant waterborne PVC primer - Google Patents

Waterborne polyurethane resin and low-temperature-resistant waterborne PVC primer Download PDF

Info

Publication number
CN113402695A
CN113402695A CN202110687338.9A CN202110687338A CN113402695A CN 113402695 A CN113402695 A CN 113402695A CN 202110687338 A CN202110687338 A CN 202110687338A CN 113402695 A CN113402695 A CN 113402695A
Authority
CN
China
Prior art keywords
parts
chain extender
polyurethane resin
neutralizer
organic solvent
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
CN202110687338.9A
Other languages
Chinese (zh)
Other versions
CN113402695B (en
Inventor
张国华
谢洋
黄华
李晋权
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.)
Guangzhou Haoyi New Material Technology Co ltd
Original Assignee
Guangzhou Foucs Carbon Synthetic Material Co 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 Guangzhou Foucs Carbon Synthetic Material Co ltd filed Critical Guangzhou Foucs Carbon Synthetic Material Co ltd
Priority to CN202110687338.9A priority Critical patent/CN113402695B/en
Publication of CN113402695A publication Critical patent/CN113402695A/en
Application granted granted Critical
Publication of CN113402695B publication Critical patent/CN113402695B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12Prepolymer 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203Polyhydroxy compounds
    • C08G18/3206Polyhydroxy compounds aliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4288Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67Unsaturated compounds having active hydrogen
    • C08G18/69Polymers of conjugated dienes
    • C08G18/698Mixtures with compounds of group C08G18/40
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • C08J7/043Improving the adhesiveness of the coatings per se, e.g. forming primers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04Polyurethanes
    • C08J2475/14Polyurethanes having carbon-to-carbon unsaturated bonds

Landscapes

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

Abstract

The invention discloses a waterborne polyurethane resin which comprises the following components in parts by mass: 15-20 parts of isophorone diisocyanate, 5-15 parts of hydroxyl-terminated polybutadiene, 5-18 parts of an organic solvent, 5-12 parts of castor oil modified polyester polyol, 2-8 parts of a hydrophilic chain extender, 2-6 parts of a neutralizer, 0.4-5 parts of a rear chain extender, 0.01-0.25 part of a catalyst and 50-65 parts of deionized water. Has good low temperature resistance and low temperature and high humidity resistance. The hydroxyl-terminated polybutadiene has good high adhesion and low temperature resistance, the castor oil modified polyester polyol has strong crystallinity and excellent high temperature and high humidity resistance, and the castor oil modified polyester polyol and isophorone diisocyanate react to generate interpenetrating network structure resin which has good low temperature and high humidity resistance after film forming, so that the castor oil modified polyester polyol has good adhesion under low temperature and high humidity.

Description

Waterborne polyurethane resin and low-temperature-resistant waterborne PVC primer
Technical Field
The invention relates to the technical field of PVC (polyvinyl chloride) base coating agents, and particularly relates to a waterborne polyurethane resin and a low-temperature-resistant waterborne PVC base coating agent.
Background
The PVC water-based primer on the market at present is mainly imported from foreign countries, and the existing water-based primer is easy to be anti-adhered after being rolled, has poor peeling force with a bonding layer of a hot melt adhesive at low temperature, and is difficult to deliver in the next procedure. The resistance to migration of the plasticizer is not complete, resulting in the edge strip falling off from the substrate to which it is attached.
Patent CN108003300A discloses a modified polyurethane dispersion for preparing a PVC edge banding treating agent, which is prepared by polymerizing raw materials, wherein the raw materials comprise, by mass: 10-20% of diisophorone diisocyanate, 6-15% of polymeric polyol, 2-10% of a hydrophilic chain extender, 1-4% of a first neutralizer, 0.01-0.1% of a metal catalyst, 2-15% of an organic solvent, 5-15% of a vinyl monomer, 1-4% of a second neutralizer, 0.5-2% of a post chain extender, 0.01-0.5% of an initiator and the balance of water. The PVC edge banding has good adhesive force, can effectively prevent plasticizer migration in PVC, so that the PVC edge banding and a plate are adhered together more tightly, but the PVC edge banding does not have low-temperature and high-humidity resistance, and the application of the PVC edge banding and the plate in low-temperature and cold environments is limited.
Patent CN104927747A discloses an aqueous polyurethane hot melt adhesive, a preparation method and application thereof, and specifically discloses a preparation method of the aqueous polyurethane hot melt adhesive, which comprises the following steps: (1) adding polyether polyol into a reaction kettle, heating to 120-130 ℃, keeping the temperature for dewatering, and cooling to 75-85 ℃; (2) under the condition of stirring, uniformly dropwise adding a catalyst into the reaction kettle in the step (1), then adding the isophorone diisocyanate, heating to 80-88 ℃ after the temperature is stable, and carrying out heat preservation reaction for 2.0-2.5 h to obtain a mixture; (3) dropwise adding a carboxyl monomer solution into the reaction kettle filled with the mixture in the step (2), adjusting the temperature to 80-90 ℃ after dropwise adding, and carrying out heat preservation reaction for 3-4 h to obtain a crude product; wherein the carboxyl monomer solution is obtained by dissolving a carboxyl monomer in an organic solvent; (4) and (3) adding acetone into the crude product obtained in the step (3) to reduce the system viscosity, increasing the rotating speed of a stirrer, cooling to 35-40 ℃, adding a neutralizing agent for neutralization, discharging, adding distilled water, carrying out high-speed shearing emulsification, and carrying out rotary evaporation to obtain the waterborne polyurethane hot melt adhesive. The melting point of the adhesive film is 130-150 ℃, and the adhesive film cannot be used at low temperature.
Disclosure of Invention
The invention provides a waterborne polyurethane resin and a low-temperature-resistant waterborne PVC primer, which have good low-temperature resistance and low-temperature and high-humidity resistance.
The invention adopts the following technical scheme for solving the technical problems:
an aqueous polyurethane resin comprises the following components in parts by mass: 15-20 parts of isophorone diisocyanate, 5-15 parts of hydroxyl-terminated polybutadiene, 5-18 parts of an organic solvent, 5-12 parts of castor oil modified polyester polyol, 2-8 parts of a hydrophilic chain extender, 2-6 parts of a neutralizer, 0.4-5 parts of a rear chain extender, 0.01-0.25 part of a catalyst and 50-65 parts of deionized water.
As a preferable scheme, the aqueous polyurethane resin comprises the following components in parts by mass: 15-20 parts of isophorone diisocyanate, 6-15 parts of hydroxyl-terminated polybutadiene, 5-15 parts of an organic solvent, 5-10 parts of castor oil modified polyester polyol, 3-8 parts of a hydrophilic chain extender, 2-5 parts of a neutralizer, 0.5-5 parts of a post-chain extender, 0.01-0.2 part of a catalyst and 50-60 parts of deionized water.
As a preferable scheme, the hydrophilic chain extender is 1, 4-butanediol, and the post chain extender is 2, 2-dimethylolpropionic acid.
The inventor of the invention finds that hydroxyl-terminated polybutadiene has good high adhesion and low temperature resistance in a large amount of formula researches of aqueous polyurethane resin, castor oil modified polyester polyol has strong crystallinity and excellent high temperature and high humidity resistance, and the castor oil modified polyester polyol and isophorone diisocyanate react to generate interpenetrating network structure resin which has good low temperature and high humidity resistance after film forming so as to have good adhesion under low temperature and high humidity.
The inventor further discovers in a great deal of research that under the formula system of the invention, the addition reaction of the hydrophilic chain extender (1, 4-butanediol) and the post chain extender (2, 2-dimethylolpropionic acid) generates a cured product with a three-dimensional network structure, further improves the low-temperature and high-humidity resistance, and ensures that the cured product has good adhesion at low temperature and high humidity.
Meanwhile, the inventors have found that the low-temperature and high-humidity resistance is significantly reduced by replacing the castor oil-modified polyester polyol and the hydroxyl-terminated polybutadiene with another polyester polyol. That is, only by combining hydroxyl-terminated polybutadiene, castor oil modified polyester polyol, isophorone diisocyanate, a hydrophilic chain extender (1, 4-butanediol) and a rear chain extender (2, 2-dimethylolpropionic acid), good adhesion can be achieved at low temperature and high humidity.
In the present invention, the hydroxyl-terminated polybutadiene is purchased from Nippon Caoda corporation under the designations JP-100, JP-200, GI-2000 and GI-3000.
In the present invention, the castor oil modified polyester polyol is purchased from Vanderues, U.S. designations D1000, D2000, D3000.
As a preferable scheme, the organic solvent is acetone, the neutralizing agent is dimethylethanolamine, and the catalyst is organic bismuth.
The invention also provides a preparation method of the waterborne polyurethane resin, which comprises the following steps:
adding hydroxyl-terminated polybutadiene, castor oil modified polyester polyol and a hydrophilic chain extender into a reaction kettle, heating to 100-140 ℃, performing vacuum dehydration, cooling to 40-60 ℃ under the protection of inert gas, adding isophorone diisocyanate and a catalyst, heating to 80-90 ℃, performing heat preservation for 2.5-4 h, adding a rear chain extender, heating to 90-100 ℃, and performing heat preservation reaction for 1-5 h; and cooling to 35-45 ℃, adding part of the neutralizer, uniformly stirring, adding the organic solvent, uniformly dispersing, adding deionized water and the neutralizer, uniformly stirring, and removing the organic solvent to obtain the waterborne polyurethane resin.
The invention also provides a low-temperature-resistant water-based PVC primer which comprises the following components in parts by mass: 80-90 parts of water-based polyurethane resin, 0.1-0.3 part of flatting agent, 0.1-0.3 part of defoaming agent, 0.1-0.3 part of thickening agent and 12-18 parts of deionized water.
In the invention, the leveling agent is Hydropalat WE 3120; the defoamer is Fomaster NO 2306, the thickener is Rheovis PU1331, and the thickener is purchased from Basff.
As a preferable scheme, the aqueous polyurethane resin comprises the following components in parts by mass: 15-20 parts of isophorone diisocyanate, 5-15 parts of hydroxyl-terminated polybutadiene, 5-18 parts of an organic solvent, 5-12 parts of castor oil modified polyester polyol, 2-8 parts of a hydrophilic chain extender, 2-5 parts of a neutralizer, 0.4-5 parts of a rear chain extender, 0.01-0.25 part of a catalyst and 50-65 parts of deionized water.
As a preferable scheme, the hydrophilic chain extender is 1, 4-butanediol, and the post chain extender is 2, 2-dimethylolpropionic acid; the organic solvent is acetone, the neutralizer is dimethylethanolamine, and the catalyst is organic bismuth.
As a preferable scheme, the preparation method of the aqueous polyurethane resin comprises the following steps: adding a hydrophilic chain extender into a reaction kettle, heating to 100-140 ℃, performing vacuum dehydration, cooling to 40-60 ℃ under the protection of inert gas, adding isophorone diisocyanate and a catalyst, heating to 80-90 ℃, preserving heat for 2.5-4 h, adding a rear chain extender, heating to 90-100 ℃, and preserving heat for 1-5 h; and cooling to 35-45 ℃, adding part of the neutralizer, uniformly stirring, adding the organic solvent, uniformly dispersing, adding deionized water and the neutralizer, uniformly stirring, and removing the organic solvent to obtain the waterborne polyurethane resin.
The invention also provides a preparation method of the low-temperature-resistant water-based PVC primer, which comprises the following steps: adding the waterborne polyurethane resin, the flatting agent, the defoaming agent, the thickening agent and the deionized water into a reaction kettle, and uniformly stirring to obtain the low-temperature-resistant waterborne PVC primer.
The invention has the beneficial effects that: the low-temperature-resistant water-based PVC primer prepared from the water-based polyurethane resin has good low-temperature-resistant and high-humidity-resistant performances, is scientific and simple in formula, has good adhesion force under low-temperature and high-humidity conditions after being optimized, and has good low-temperature-resistant and high-humidity-resistant performances after being formed into a film by using hydroxyl-terminated polybutadiene and castor oil modified polyester polyol to react with isophorone diisocyanate to generate interpenetrating network-structure resin.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the present invention, unless otherwise specified, the parts are all parts by mass.
Example 1
An aqueous polyurethane resin comprises the following components in parts by mass: 20 parts of isophorone diisocyanate, 15 parts of hydroxyl-terminated polybutadiene, 15 parts of acetone, 10 parts of castor oil modified polyester polyol, 8 parts of 1, 4-butanediol, 4 parts of dimethylethanolamine, 5 parts of 2, 2-dimethylolpropionic acid, 0.05 part of organic bismuth and 60 parts of deionized water.
In this example, the hydroxyl-terminated polybutadiene was purchased from Nippon Caoda corporation under the designation JP-200.
In this example, the castor oil-modified polyester polyol is purchased from Vanderues, U.S. under the designation D2000.
The preparation method of the waterborne polyurethane resin comprises the following steps:
adding hydroxyl-terminated polybutadiene, castor oil modified polyester polyol and 1, 4-butanediol into a reaction kettle, heating to 130 ℃, carrying out vacuum dehydration for 2h, cooling to 50 ℃ under the protection of inert gas, adding isophorone diisocyanate and organic bismuth, heating to 85 ℃, carrying out heat preservation for 3.5h, adding 2, 2-dimethylolpropionic acid, heating to 95 ℃, and carrying out heat preservation reaction for 4 h; cooling to 40 ℃, adding 50% of dimethylethanolamine by mass, uniformly stirring, adding acetone, uniformly dispersing, adding deionized water and the rest dimethylethanolamine, uniformly stirring, and removing the acetone to obtain the waterborne polyurethane resin.
Preparing a low-temperature-resistant water-based PVC primer: 85 parts by mass of the prepared waterborne polyurethane resin, 0.2 parts by mass of Hydropagat WE3120, 0.2 parts by mass of Fomaster NO 2306, 0.2 parts by mass of Rheovis PU1331 and 15 parts by mass of deionized water are added into a reaction kettle and stirred uniformly at 2000rpm to obtain the low temperature resistant waterborne PVC primer.
In the embodiment, hydroxyl-terminated polybutadiene has good high adhesion and low temperature resistance, the castor oil modified polyester polyol has strong crystallinity and excellent high temperature and high humidity resistance, the two are reacted with isophorone diisocyanate to generate interpenetrating network resin, the interpenetrating network resin has good low temperature and high humidity resistance after film formation, so that the castor oil modified polyester polyol has good adhesion at low temperature and high humidity, and the hydrophilic chain extender (1, 4-butanediol) and the post chain extender (2, 2-dimethylolpropionic acid) are added and reacted to generate a cured product with a three-dimensional network structure, so that the low temperature and high humidity resistance is further improved, and the castor oil modified polyester polyol has good adhesion at low temperature and high humidity.
Example 2
An aqueous polyurethane resin comprises the following components in parts by mass: 15 parts of isophorone diisocyanate, 6 parts of hydroxyl-terminated polybutadiene, 5 parts of acetone, 5 parts of castor oil modified polyester polyol, 3 parts of 1, 4-butanediol, 2 parts of dimethylethanolamine, 0.5 part of 2, 2-dimethylolpropionic acid, 0.05 part of organic bismuth and 50 parts of deionized water.
In this example, the hydroxyl-terminated polybutadiene was purchased from Nippon Caoda corporation under the designation JP-100.
In this example, the castor oil-modified polyester polyol is purchased from Vanderues, U.S. under the designation D1000.
The preparation method of the waterborne polyurethane resin comprises the following steps:
adding hydroxyl-terminated polybutadiene, castor oil modified polyester polyol and 1, 4-butanediol into a reaction kettle, heating to 130 ℃, carrying out vacuum dehydration for 2h, cooling to 50 ℃ under the protection of inert gas, adding isophorone diisocyanate and organic bismuth, heating to 85 ℃, carrying out heat preservation for 3.5h, adding 2, 2-dimethylolpropionic acid, heating to 95 ℃, and carrying out heat preservation reaction for 4 h; cooling to 40 ℃, adding 50% of dimethylethanolamine by mass, uniformly stirring, adding acetone, uniformly dispersing, adding deionized water and the rest dimethylethanolamine, uniformly stirring, and removing the acetone to obtain the waterborne polyurethane resin.
Preparing a low-temperature-resistant water-based PVC primer: 85 parts by mass of the prepared waterborne polyurethane resin, 0.2 parts by mass of Hydropagat WE3120, 0.2 parts by mass of Fomaster NO 2306, 0.2 parts by mass of Rheovis PU1331 and 15 parts by mass of deionized water are added into a reaction kettle and stirred uniformly at 2000rpm to obtain the low temperature resistant waterborne PVC primer.
Example 3
An aqueous polyurethane resin comprises the following components in parts by mass: 18 parts of isophorone diisocyanate, 12 parts of hydroxyl-terminated polybutadiene, 10 parts of acetone, 8 parts of castor oil modified polyester polyol, 5 parts of 1, 4-butanediol, 2.5 parts of dimethylethanolamine, 3 parts of 2, 2-dimethylolpropionic acid, 0.05 part of organic bismuth and 55 parts of deionized water.
In this example, the hydroxyl-terminated polybutadiene is purchased from Nippon Caoda corporation under the designation GI-2000.
In this example, the castor oil-modified polyester polyol is purchased from Vanderues, U.S. under the designation D1000.
The preparation method of the waterborne polyurethane resin comprises the following steps:
adding hydroxyl-terminated polybutadiene, castor oil modified polyester polyol and 1, 4-butanediol into a reaction kettle, heating to 130 ℃, carrying out vacuum dehydration for 2h, cooling to 50 ℃ under the protection of inert gas, adding isophorone diisocyanate and organic bismuth, heating to 85 ℃, carrying out heat preservation for 3.5h, adding 2, 2-dimethylolpropionic acid, heating to 95 ℃, and carrying out heat preservation reaction for 4 h; cooling to 40 ℃, adding 40% of dimethylethanolamine by mass, uniformly stirring, adding acetone, uniformly dispersing, adding deionized water and the rest dimethylethanolamine, uniformly stirring, and removing the acetone to obtain the waterborne polyurethane resin.
Preparing a low-temperature-resistant water-based PVC primer: 85 parts by mass of the prepared waterborne polyurethane resin, 0.2 parts by mass of Hydropagat WE3120, 0.2 parts by mass of Fomaster NO 2306, 0.2 parts by mass of Rheovis PU1331 and 15 parts by mass of deionized water are added into a reaction kettle and stirred uniformly at 2000rpm to obtain the low temperature resistant waterborne PVC primer.
Example 4
Example 4 differs from example 1 in that example 4 uses the same amount of ethylene glycol instead of 1, 4-butanediol and the same amount of ethylene diamine instead of 2, 2-dimethylolpropionic acid, all else being the same, i.e. in this example the hydrophilic chain extender and the post-chain extender are replaced by ethylene glycol, ethylene diamine.
Comparative example 1
Comparative example 1 differs from example 1 in that comparative example 1 uses the same amount of polycaprolactone diol (molecular weight 1000) in place of the castor oil-modified polyester polyol of example 1, all else being identical.
Comparative example 2
Comparative example 2 differs from example 1 in that comparative example 2 uses an equal amount of polybutadiene instead of the hydroxyl-terminated polybutadiene described in example 1, all else being equal.
Comparative example 3
Comparative example 3 is different from example 1 in that in comparative example 3, the modified polyurethane dispersant prepared in example 1 of CN108003300A is used to replace the aqueous polyurethane resin described in example 1, and the rest is the same.
To further demonstrate the effect of the present invention, the following test methods were provided:
the primer described in each example and comparative example is respectively coated on a PVC edge banding (3 test examples are selected for each example and comparative example, the test is carried out on the primer, the PVC edge banding coated with the primer and a high-density plate are heat-sealed and attached by using a hot melt adhesive, construction is respectively carried out at different environmental temperatures, after one week of gluing, the low-temperature resistance is detected at-10 ℃ after one week of gluing, the low-temperature and high-humidity resistance is detected at 0 ℃ and the humidity of 80%, and the test results are shown in table 1 after one week of gluing.
TABLE 1 test results
Figure 990734DEST_PATH_IMAGE001
As can be seen from Table 1, the low-temperature-resistant PVC primer prepared from the waterborne polyurethane resin has good low-temperature resistance and low-temperature and high-humidity resistance.
As can be seen from comparative examples 1 to 3, the PVC primer prepared from the waterborne polyurethane resin with the optimized formula has good low-temperature resistance and low-temperature and high-humidity resistance.
Comparing example 1 with example 4, it can be seen that, under the formula system of the present invention, the selection of different hydrophilic chain extenders and post chain extenders can also affect the low temperature resistance and the low temperature and high humidity resistance to a certain extent, wherein the 1, 4-butanediol and 2, 2-dimethylolpropionic acid according to the present invention have better applicability, and have better low temperature resistance and low temperature and high humidity resistance.
As can be seen from comparison of example 1 with comparative examples 1 and 2, if the castor oil-modified polyester polyol of the present invention is replaced with another substance or the hydroxyl-terminated polybutadiene is replaced with another substance, the low temperature resistance and the low temperature and high humidity resistance are both significantly reduced.
It can be seen that good adhesion can be achieved at low temperature and high humidity only by combining hydroxyl-terminated polybutadiene, castor oil modified polyester polyol, isophorone diisocyanate, a hydrophilic chain extender (1, 4-butanediol), and a post chain extender (2, 2-dimethylolpropionic acid).
In light of the foregoing description of preferred embodiments according to the invention, it is clear that many changes and modifications can be made by the person skilled in the art without departing from the scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined according to the scope of the claims.

Claims (10)

1. The waterborne polyurethane resin is characterized by comprising the following components in parts by mass: 15-20 parts of isophorone diisocyanate, 5-15 parts of hydroxyl-terminated polybutadiene, 5-18 parts of an organic solvent, 5-12 parts of castor oil modified polyester polyol, 2-8 parts of a hydrophilic chain extender, 2-6 parts of a neutralizer, 0.4-5 parts of a rear chain extender, 0.01-0.25 part of a catalyst and 50-65 parts of deionized water.
2. The aqueous polyurethane resin according to claim 1, wherein the aqueous polyurethane resin comprises, in parts by mass: 15-20 parts of isophorone diisocyanate, 6-15 parts of hydroxyl-terminated polybutadiene, 5-15 parts of an organic solvent, 5-10 parts of castor oil modified polyester polyol, 3-8 parts of a hydrophilic chain extender, 2-5 parts of a neutralizer, 0.5-5 parts of a post-chain extender, 0.01-0.2 part of a catalyst and 50-60 parts of deionized water.
3. The aqueous polyurethane resin according to claim 1, wherein the hydrophilic chain extender is 1, 4-butanediol and the post-chain extender is 2, 2-dimethylolpropionic acid.
4. The aqueous polyurethane resin according to claim 1, wherein the organic solvent is acetone, the neutralizer is dimethylethanolamine, and the catalyst is organic bismuth.
5. The method for producing an aqueous polyurethane resin according to any one of claims 1 to 4, characterized by comprising the steps of:
adding hydroxyl-terminated polybutadiene, castor oil modified polyester polyol and a hydrophilic chain extender into a reaction kettle, heating to 100-140 ℃, performing vacuum dehydration, cooling to 40-60 ℃ under the protection of inert gas, adding isophorone diisocyanate and a catalyst, heating to 80-90 ℃, performing heat preservation for 2.5-4 h, adding a rear chain extender, heating to 90-100 ℃, and performing heat preservation reaction for 1-5 h; and cooling to 35-45 ℃, adding part of the neutralizer, uniformly stirring, adding the organic solvent, uniformly dispersing, adding deionized water and the neutralizer, uniformly stirring, and removing the organic solvent to obtain the waterborne polyurethane resin.
6. The low-temperature-resistant water-based PVC primer is characterized by comprising the following components in parts by mass: 80-90 parts of water-based polyurethane resin, 0.1-0.3 part of flatting agent, 0.1-0.3 part of defoaming agent, 0.1-0.3 part of thickening agent and 12-18 parts of deionized water.
7. The PVC primer according to claim 6, wherein the aqueous polyurethane resin comprises, in parts by mass: 15-20 parts of isophorone diisocyanate, 5-15 parts of hydroxyl-terminated polybutadiene, 5-18 parts of an organic solvent, 5-12 parts of castor oil modified polyester polyol, 2-8 parts of a hydrophilic chain extender, 2-5 parts of a neutralizer, 0.4-5 parts of a rear chain extender, 0.01-0.25 part of a catalyst and 50-65 parts of deionized water.
8. The PVC primer coating according to claim 6, wherein the hydrophilic chain extender is 1, 4-butanediol and the post-chain extender is 2, 2-dimethylolpropionic acid; the organic solvent is acetone, the neutralizer is dimethylethanolamine, and the catalyst is organic bismuth.
9. The PVC primer coating according to claim 7, wherein the preparation method of the aqueous polyurethane resin comprises the following steps: adding a hydrophilic chain extender into a reaction kettle, heating to 100-140 ℃, performing vacuum dehydration, cooling to 40-60 ℃ under the protection of inert gas, adding isophorone diisocyanate and a catalyst, heating to 80-90 ℃, preserving heat for 2.5-4 h, adding a rear chain extender, heating to 90-100 ℃, and preserving heat for 1-5 h; and cooling to 35-45 ℃, adding part of the neutralizer, uniformly stirring, adding the organic solvent, uniformly dispersing, adding deionized water and the neutralizer, uniformly stirring, and removing the organic solvent to obtain the waterborne polyurethane resin.
10. The preparation method of the low-temperature-resistant water-based PVC primer according to any one of claims 6 to 9, characterized by comprising the following steps: adding the waterborne polyurethane resin, the flatting agent, the defoaming agent, the thickening agent and the deionized water into a reaction kettle, and uniformly stirring to obtain the low-temperature-resistant waterborne PVC primer.
CN202110687338.9A 2021-06-21 2021-06-21 Waterborne polyurethane resin and low-temperature-resistant waterborne PVC primer Active CN113402695B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110687338.9A CN113402695B (en) 2021-06-21 2021-06-21 Waterborne polyurethane resin and low-temperature-resistant waterborne PVC primer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110687338.9A CN113402695B (en) 2021-06-21 2021-06-21 Waterborne polyurethane resin and low-temperature-resistant waterborne PVC primer

Publications (2)

Publication Number Publication Date
CN113402695A true CN113402695A (en) 2021-09-17
CN113402695B CN113402695B (en) 2022-12-13

Family

ID=77682179

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110687338.9A Active CN113402695B (en) 2021-06-21 2021-06-21 Waterborne polyurethane resin and low-temperature-resistant waterborne PVC primer

Country Status (1)

Country Link
CN (1) CN113402695B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117264596A (en) * 2023-10-10 2023-12-22 佛山市极威新材料有限公司 Honeycomb glue with good water resistance and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5288796A (en) * 1990-05-30 1994-02-22 Henkel Kommanditgesellschaft Auf Aktien Friable sealing compound for sealing joint boxes
CN101818021A (en) * 2010-01-29 2010-09-01 北京高盟新材料股份有限公司 Preparation method of waterborne primer for polyvinylidene chloride
CN102585154A (en) * 2012-03-13 2012-07-18 上海材料研究所 Method for preparing waterborne polyurethane
CN102863607A (en) * 2012-08-28 2013-01-09 东莞市万钧化工新材料科技有限公司 Emulsion of water-based primer for EVA materials
CN106243316A (en) * 2016-07-29 2016-12-21 肇庆浩城树脂科技有限公司 A kind of aqueous pu dispersions and application thereof
CN108003300A (en) * 2017-12-18 2018-05-08 广州聚碳合成材料有限公司 Modified polyurethane dispersion and preparation method thereof and water-based PVC edge bands inorganic agent
CN110862506A (en) * 2019-10-29 2020-03-06 中国科学院山西煤炭化学研究所 Synthetic method of waterborne polyurethane primer

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5288796A (en) * 1990-05-30 1994-02-22 Henkel Kommanditgesellschaft Auf Aktien Friable sealing compound for sealing joint boxes
CN101818021A (en) * 2010-01-29 2010-09-01 北京高盟新材料股份有限公司 Preparation method of waterborne primer for polyvinylidene chloride
CN102585154A (en) * 2012-03-13 2012-07-18 上海材料研究所 Method for preparing waterborne polyurethane
CN102863607A (en) * 2012-08-28 2013-01-09 东莞市万钧化工新材料科技有限公司 Emulsion of water-based primer for EVA materials
CN106243316A (en) * 2016-07-29 2016-12-21 肇庆浩城树脂科技有限公司 A kind of aqueous pu dispersions and application thereof
CN108003300A (en) * 2017-12-18 2018-05-08 广州聚碳合成材料有限公司 Modified polyurethane dispersion and preparation method thereof and water-based PVC edge bands inorganic agent
CN110862506A (en) * 2019-10-29 2020-03-06 中国科学院山西煤炭化学研究所 Synthetic method of waterborne polyurethane primer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
钟达飞等: "端羟基聚丁二烯橡胶对水性聚氨酯性能的影响", 《中国涂料》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117264596A (en) * 2023-10-10 2023-12-22 佛山市极威新材料有限公司 Honeycomb glue with good water resistance and preparation method thereof
CN117264596B (en) * 2023-10-10 2024-05-10 佛山市极威新材料有限公司 Honeycomb glue with good water resistance and preparation method thereof

Also Published As

Publication number Publication date
CN113402695B (en) 2022-12-13

Similar Documents

Publication Publication Date Title
EP1754737B1 (en) Polyester resin and thermosetting aqueous coating composition
CN101824299B (en) Method for preparing single-component high-solid content water-based polyurethane adhesive
CN109880494B (en) 50:50 polyester resin for indoor high-hardness and high-gloss powder and preparation method thereof
EP0541607B1 (en) Process for producing aqueous polyurethane dispersions
CN102093530A (en) Preparation method of organosilicon-modified aqueous polyurethane
EP0841382B1 (en) Organosol polyester paints and process for their preparation
EP3536730B1 (en) Aqueous polyhydroxyurethane resin dispersion, method for producing said aqueous dispersion, gas-barrier resin film produced using said aqueous dispersion, aqueous polyhydroxyurethane resin dispersion composition containing clay mineral, gas-barrier coating agent comprising said composition, and gas-barrier resin film
JPWO2008133073A1 (en) Conductive paste, printed circuit using the same, and planar heating element
CN113402695B (en) Waterborne polyurethane resin and low-temperature-resistant waterborne PVC primer
CN108350139A (en) Include the water-borne base coating of cross-linked polyurethane base-material and specific solvent composition
US9534154B2 (en) Semiconductor device using composition for anisotropic conductive adhesive film or anisotropic conductive adhesive film
CN101565494B (en) Waterborne cation polyurethane hot melt adhesive preformed polymer and production method of emulsion thereof
CN113249080A (en) Water-dispersible hot melt adhesive and preparation method thereof
CN109135607A (en) A kind of lamination fabrication Film laminated substrate and the manufacturing process of durability
CN109180901A (en) From delustring aqueous polyurethane and preparation method thereof
CN111925607B (en) Polyvinyl chloride elastomer and preparation method and application thereof
WO2020262645A1 (en) Adhesive for laminate
CN109627907B (en) Static-conducting heat-dissipating coating and preparation method thereof
US20150191626A1 (en) Process for multi-layer coating
KR101874301B1 (en) Polyurethane resin for hot melt adhesive and two-component polyurethane hot melt adhesive comprising the same, and method for forming polyurethane resin for hot melt adhesive
CN112898533A (en) Multi-curing polyurethane latent curing agent and preparation method thereof
WO2023074667A1 (en) Adhesive for laminates
CN105754536A (en) Transparent antistatic pressure-sensitive adhesive
JP7457464B2 (en) adhesive for lamination
CN115322348B (en) Low-temperature-cured semi-crystalline polyester resin and preparation method and application thereof

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
TA01 Transfer of patent application right

Effective date of registration: 20221104

Address after: No. 812, building G1, South China new material innovation park, No. 31 Kefeng Road, Guangzhou high tech Industrial Development Zone, Guangdong 510000

Applicant after: Guangzhou Haoyi New Material Technology Co.,Ltd.

Address before: 510000 room 410, building G5, South China new material innovation park, No. 31, Kefeng Road, Science City, high tech Industrial Development Zone, Guangzhou, Guangdong

Applicant before: GUANGZHOU FOUCS CARBON SYNTHETIC MATERIAL CO.,LTD.

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant