CN105218778A - A kind of epoxy terminated waterborne polyurethane resin and preparation method thereof - Google Patents
A kind of epoxy terminated waterborne polyurethane resin and preparation method thereof Download PDFInfo
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates 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
- C08G18/753—Polyisocyanates 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
- C08G18/755—Polyisocyanates 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
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- 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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- 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
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- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/2845—Monohydroxy epoxy compounds
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- 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
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- 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
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- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
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- 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
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Abstract
The invention discloses a kind of epoxy terminated waterborne polyurethane resin and preparation method thereof, described resin is obtained by following steps: vegetable oil polyol, small molecule polyol, vulcabond and hydrophilic chain extender are in organic solvent, under catalyst action, addition reaction obtains isocyanate terminated base polyurethane prepolymer for use as; Add the reaction of terminal hydroxy group epoxy compounds, obtain epoxy-terminated polyurethane; Add amine again to neutralize, drip water and carry out phase reversion, insulation, underpressure distillation removing organic solvent, obtains epoxy terminated waterborne polyurethane resin.Described resin is water-borne coatings, does not have volatile organic matter to pollute, environmental friendliness; Be obtained by urethane and epoxy resin chemistry methods combining, described resin not only has the snappiness of urethane, also has the rigidity of epoxy resin, close-burning feature; Adopt vegetable oil polyol to make raw material, do raw material compared to traditional petrochemical complex class glycol products, there is the advantages such as cheap, environmental protection, raw material be renewable.
Description
Technical field
The present invention relates to epoxy resin field, be specifically related to a kind of epoxy terminated waterborne polyurethane resin and preparation method thereof.
Background technology
Epoxy resin has the characteristics such as good cohesiveness, physical strength, electrical insulating property, is thus widely used in each industrial circle of national economy.But traditional epoxy resin contains a large amount of aromatic ring structures, its second-order transition temperature is high, more crisp, and shock resistance is poor, makes it apply and is subject to a definite limitation, is difficult to the requirement meeting many engineering increasingly stringents.Such as the epoxy resin of concrete paint application needs to have good ductility, to ensure its crack tracing ability, realizes concrete available protecting.Therefore how to improve the snappiness of epoxy resin, become an important research direction of Epoxy Resin Technology.
Day by day perfect along with world's environmental regulation, the raising day by day of environmental requirement, traditional solvent based coating is because the discharge of volatile organic matter receives great impact, its market share reduces just rapidly, has the water-borne coatings of environmental protection characteristic, ultraviolet-curing paint, high solid coating and powder coating and then increases rapidly.Wherein, water-borne coatings has environmental protection, coating property close to traditional coating, change little feature to existing application techniques because of it, and thus development rapidly.In the past few years, water-borne coatings has and develops very rapidly in the industries such as woodenware, leather, automobile, industry.Also do not have the aqueous epoxy resins that snappiness is good in the market, the aqueous epoxy resins developing a kind of snappiness good is significant.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of epoxy terminated waterborne polyurethane resin and preparation method thereof.
The technical solution used in the present invention is:
A preparation method for epoxy terminated waterborne polyurethane resin, comprises the following steps:
S1: vegetable oil polyol, small molecule polyol, vulcabond and hydrophilic chain extender in organic solvent, under catalyst action, addition reaction occur, obtains isocyanate terminated base polyurethane prepolymer for use as;
S2: isocyanate terminated base polyurethane prepolymer for use as and the terminal hydroxy group epoxy compounds of getting S1 gained react, and obtain epoxy-terminated polyurethane;
S3: add amine and neutralize in the epoxy-terminated polyurethane of S2 gained, drips water and carries out phase reversion, insulation, and underpressure distillation removing organic solvent, obtains epoxy terminated waterborne polyurethane resin.
Preferably, described vegetable oil polyol is at least one in castor oil polyhydric alcohol, soybean oil polyol, plam oil polyvalent alcohol.
Preferably, described small molecule polyol is at least one in ethylene glycol, propylene glycol, glycol ether, BDO, TriMethylolPropane(TMP).
Preferably, described vulcabond is at least one in tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate.
Preferably, described catalyzer is any one in isopropyl titanate, sad sub-zinc, dibutyl tin laurate.
Preferably, described hydrophilic chain extender is dimethylol propionic acid.
Preferably, described terminal hydroxy group epoxy compounds is 2，3-epoxy-1-propanol.
Preferably, described amine is at least one in trolamine, N, N-dimethylethanolamine.
Further preferably, the mass ratio of described vegetable oil polyol, small molecule polyol, vulcabond, hydrophilic chain extender, catalyzer, terminal hydroxy group epoxy compounds and amine is (300-670): (10-45): (160-250): (20-48): (0.8-2.0): (5-14): (10-35).
Present invention also offers a kind of epoxy terminated waterborne polyurethane resin, adopt above-mentioned preparation method to prepare.
The invention has the beneficial effects as follows: the invention provides a kind of epoxy terminated waterborne polyurethane resin and preparation method thereof, described resin is obtained by following steps: S1: vegetable oil polyol, small molecule polyol, vulcabond and hydrophilic chain extender are in organic solvent, under catalyst action, there is addition reaction, obtain isocyanate terminated base polyurethane prepolymer for use as; S2: isocyanate terminated base polyurethane prepolymer for use as and the terminal hydroxy group epoxy compounds of getting S1 gained react, and obtain epoxy-terminated polyurethane; S3: add amine and neutralize in the epoxy-terminated polyurethane of S2 gained, drips water and carries out phase reversion, insulation, and underpressure distillation removing organic solvent, obtains epoxy terminated waterborne polyurethane resin.Epoxy terminated waterborne polyurethane resin of the present invention is water-borne coatings, and use procedure does not have volatile organic matter and pollutes, environmental friendliness; Be that described resin not only has the snappiness of urethane by urethane and epoxy resin chemistry methods combining, also there is the rigidity of epoxy resin, close-burning feature; Adopt vegetable oil polyol to make raw material, do raw material compared to traditional petrochemical complex class glycol products, there is the advantages such as cheap, environmental protection, raw material be renewable.
Embodiment
embodiment 1:
Step one, by 100 grams of acetone, 398 grams of soybean oil polyol, 40.5 gram 1,4-butyleneglycol, 37.4 grams of dimethylol propionic acids, 222 grams of isophorone diisocyanates are put in reactor, be warmed up to 60 DEG C and make material dissolution, add the dibutyltin dilaurate catalyst of 1.4 grams, be warmed up to 70 DEG C of reactions 3 hours, obtain isocyanate terminated base polyurethane prepolymer for use as.
Step 2, in the isocyanate terminated base polyurethane prepolymer for use as of gained, the 2，3-epoxy-1-propanol adding 11.8 grams enters reactor, within 4 hours, obtains brown color epoxy-terminated polyurethane resin 60 DEG C of reactions;
Step 3, maintain temperature of reaction 60 DEG C, 21 grams of N are dripped in reactor, N-dimethylethanolamine neutralizes, and after having neutralized, point within 2 hours, dripping 990 grams of deionized waters to reactor carries out phase reversion, be incubated after 1 hour, be warmed up to 80 DEG C, underpressure distillation removing acetone, namely obtains the epoxy terminated waterborne polyurethane resin of yellowish colour band blue light.Raw material described in the present embodiment is on market can purchase raw material, and preparing products therefrom solid content is 42.1%, and viscosity is 1500mPaS, and acid number is 23.8mgKOH/g.
embodiment 2:
Step one, 85 grams of acetone, 334 grams of castor oil polyhydric alcohols, 24.1 grams of TriMethylolPropane(TMP)s, 26.5 grams of dimethylol propionic acids, 174 grams of tolylene diisocyanates are put in reactor, be warmed up to 60 DEG C and make material dissolution, add the dibutyltin dilaurate catalyst of 1.1 grams, be warmed up to 70 DEG C of reactions 3 hours, obtain isocyanate terminated base polyurethane prepolymer for use as.
Step 2, in the isocyanate terminated base polyurethane prepolymer for use as of gained, the 2，3-epoxy-1-propanol adding 6.7 grams enters reactor, within 4 hours, obtains brown color epoxy-terminated polyurethane resin 60 DEG C of reactions;
Step 3, maintain temperature of reaction 60 DEG C, 15 grams of N are dripped in reactor, N-dimethylethanolamine neutralizes, and after having neutralized, point within 2 hours, dripping 820 grams of deionized waters to reactor carries out phase reversion, be incubated after 1 hour, be warmed up to 80 DEG C, underpressure distillation removing acetone, namely obtains the epoxy terminated waterborne polyurethane resin of yellowish colour band blue light.Raw material described in the present embodiment is on market can purchase raw material, and preparing products therefrom solid content is 42.4%, and viscosity is 5300mPaS, and acid number is 22.5mgKOH/g.
embodiment 3:
Step one, 90 grams of acetone, 353 grams of plam oil polyvalent alcohols, 13.6 grams of ethylene glycol, 27.9 grams of dimethylol propionic acids, 168 grams of hexamethylene diisocyanates are put in reactor, be warmed up to 60 DEG C and make material dissolution, add the dibutyltin dilaurate catalyst of 1.1 grams, be warmed up to 70 DEG C of reactions 3 hours, obtain isocyanate terminated base polyurethane prepolymer for use as.
Step 2, in the isocyanate terminated base polyurethane prepolymer for use as of gained, the 2，3-epoxy-1-propanol adding 8.7 grams enters reactor, within 4 hours, obtains brown color epoxy-terminated polyurethane resin 60 DEG C of reactions;
Step 3, maintain temperature of reaction 60 DEG C, 16 grams of N are dripped in reactor, N-dimethylethanolamine neutralizes, and after having neutralized, point within 2 hours, dripping 820 grams of deionized waters to reactor carries out phase reversion, be incubated after 1 hour, be warmed up to 80 DEG C, underpressure distillation removing acetone, namely obtains the epoxy terminated waterborne polyurethane resin of yellowish colour band blue light.Raw material described in the present embodiment is on market can purchase raw material, and preparing products therefrom solid content is 42.7%, and viscosity is 1100mPaS, and acid number is 23.2mgKOH/g.
embodiment 4:
Step one, 110 grams of acetone, 561 grams of soybean oil polyol, 36.0 grams of glycol ethers, 42.6 grams of dimethylol propionic acids, 222 grams of isophorone diisocyanates are put in reactor, be warmed up to 60 DEG C and make material dissolution, add the isopropyl titanate catalyzer of 1.7, be warmed up to 70 DEG C of reactions 3 hours, obtain isocyanate terminated base polyurethane prepolymer for use as.
Step 2, in the isocyanate terminated base polyurethane prepolymer for use as of gained, the 2，3-epoxy-1-propanol adding 10.5 grams enters reactor, within 4 hours, obtains brown color epoxy-terminated polyurethane resin 60 DEG C of reactions;
Step 3, maintain temperature of reaction 60 DEG C, 24 grams of N are dripped in reactor, N-dimethylethanolamine neutralizes, and after having neutralized, point within 2 hours, dripping 1200 grams of deionized waters to reactor carries out phase reversion, be incubated after 1 hour, be warmed up to 80 DEG C, underpressure distillation removing acetone, namely obtains the epoxy terminated waterborne polyurethane resin of yellowish colour band blue light.Raw material described in the present embodiment is on market can purchase raw material, and preparing products therefrom solid content is 42.8%, and viscosity is 2200mPaS, and acid number is 21.8mgKOH/g.
embodiment 5:
Step one, by 110 grams of acetone, 461 grams of soybean oil polyol, 28.8 gram 1,4-butyleneglycol, 42.6 grams of dimethylol propionic acids, 244 grams of tetramethylxylylene diisocyanate are put in reactor, be warmed up to 60 DEG C and make material dissolution, add the sad sub-zinc catalyst of 1.7 grams, be warmed up to 70 DEG C of reactions 3 hours, obtain isocyanate terminated base polyurethane prepolymer for use as.
Step 2, in the isocyanate terminated base polyurethane prepolymer for use as of gained, the 2，3-epoxy-1-propanol adding 13.7 grams enters reactor, within 4 hours, obtains brown color epoxy-terminated polyurethane resin 60 DEG C of reactions;
Step 3, maintain temperature of reaction 60 DEG C, 24 grams of N are dripped in reactor, N-dimethylethanolamine neutralizes, and after having neutralized, point within 2 hours, dripping 1240 grams of deionized waters to reactor carries out phase reversion, be incubated after 1 hour, be warmed up to 80 DEG C, underpressure distillation removing acetone, namely obtains the epoxy terminated waterborne polyurethane resin of yellowish colour band blue light.Raw material described in the present embodiment is on market can purchase raw material, and preparing products therefrom solid content is 42.5%, and viscosity is 3500mPaS, and acid number is 22.4mgKOH/g.
embodiment 6:
Step one, by 110 grams of acetone, 461 grams of soybean oil polyol, 28.8 gram 1,4-butyleneglycol, 42.6 grams of dimethylol propionic acids, 244 grams of tetramethylxylylene diisocyanate are put in reactor, be warmed up to 60 DEG C and make material dissolution, add the dibutyltin dilaurate catalyst of 1.7 grams, be warmed up to 70 DEG C of reactions 3 hours, obtain isocyanate terminated base polyurethane prepolymer for use as.
Step 2, in the isocyanate terminated base polyurethane prepolymer for use as of gained, the 2，3-epoxy-1-propanol adding 13.7 grams enters reactor, within 4 hours, obtains brown color epoxy-terminated polyurethane resin 60 DEG C of reactions;
Step 3, maintain temperature of reaction 60 DEG C, 24 grams of N are dripped in reactor, N-dimethylethanolamine neutralizes, and after having neutralized, point within 2 hours, dripping 1240 grams of deionized waters to reactor carries out phase reversion, be incubated after 1 hour, be warmed up to 80 DEG C, underpressure distillation removing acetone, namely obtains the epoxy terminated waterborne polyurethane resin of yellowish colour band blue light.Raw material described in the present embodiment is on market can purchase raw material, and preparing products therefrom solid content is 42.2%, and viscosity is 4200mPaS, and acid number is 22.3mgKOH/g.
embodiment 7:
Step one, by 100 grams of acetone, 312 grams of soybean oil polyol, 93 grams of castor oil polyhydric alcohols, 34.2 gram 1,4-butyleneglycol, 37.4 grams of dimethylol propionic acids, 244 grams of tetramethylxylylene diisocyanate are put in reactor, be warmed up to 60 DEG C and make material dissolution, add the dibutyltin dilaurate catalyst of 1.4 grams, be warmed up to 70 DEG C of reactions 3 hours, obtain isocyanate terminated base polyurethane prepolymer for use as.
Step 2, in the isocyanate terminated base polyurethane prepolymer for use as of gained, the 2，3-epoxy-1-propanol adding 8.2 grams enters reactor, within 4 hours, obtains brown color epoxy-terminated polyurethane resin 60 DEG C of reactions;
Step 3, maintain temperature of reaction 60 DEG C, 21 grams of N are dripped in reactor, N-dimethylethanolamine neutralizes, and after having neutralized, point within 2 hours, dripping 1020 grams of deionized waters to reactor carries out phase reversion, be incubated after 1 hour, be warmed up to 80 DEG C, underpressure distillation removing acetone, namely obtains the epoxy terminated waterborne polyurethane resin of yellowish colour band blue light.Raw material described in the present embodiment is on market can purchase raw material, and preparing products therefrom solid content is 42.4%, and viscosity is 3200mPaS, and acid number is 23.4mgKOH/g.
embodiment 8:
Step one, by 90 grams of acetone, 249 grams of soybean oil polyol, 139 grams of castor oil polyhydric alcohols, 34.2 gram 1,4-butyleneglycol, 31.9 grams of dimethylol propionic acids, 222 grams of isophorone diisocyanates are put in reactor, be warmed up to 60 DEG C and make material dissolution, add the dibutyltin dilaurate catalyst of 1.3 grams, be warmed up to 70 DEG C of reactions 3 hours, obtain isocyanate terminated base polyurethane prepolymer for use as.
Step 2, in the isocyanate terminated base polyurethane prepolymer for use as of gained, the 2，3-epoxy-1-propanol adding 11.8 grams enters reactor, within 4 hours, obtains brown color epoxy-terminated polyurethane resin 60 DEG C of reactions;
Step 3, maintain temperature of reaction 60 DEG C, 18 grams of N are dripped in reactor, N-dimethylethanolamine neutralizes, and after having neutralized, point within 2 hours, dripping 950 grams of deionized waters to reactor carries out phase reversion, be incubated after 1 hour, be warmed up to 80 DEG C, underpressure distillation removing acetone, namely obtains the epoxy terminated waterborne polyurethane resin of yellowish colour band blue light.Raw material described in the present embodiment is on market can purchase raw material, and preparing products therefrom solid content is 42.8%, and viscosity is 3600mPaS, and acid number is 22.1mgKOH/g.
embodiment 9:
Step one, by 90 grams of acetone, 208 grams of soybean oil polyol, 185 grams of plam oil polyvalent alcohols, 28.8 gram 1,4-butyleneglycol, 31.9 grams of dimethylol propionic acids, 222 grams of isophorone diisocyanates are put in reactor, be warmed up to 60 DEG C and make material dissolution, add the dibutyltin dilaurate catalyst of 1.3 grams, be warmed up to 70 DEG C of reactions 3 hours, obtain isocyanate terminated base polyurethane prepolymer for use as.
Step 2, in the isocyanate terminated base polyurethane prepolymer for use as of gained, the 2，3-epoxy-1-propanol adding 10.6 grams enters reactor, within 4 hours, obtains brown color epoxy-terminated polyurethane resin 60 DEG C of reactions;
Step 3, maintain temperature of reaction 60 DEG C, in reactor, drip 31 grams of trolamines neutralize, after having neutralized, point within 2 hours, dripping 950 grams of deionized waters to reactor carries out phase reversion, is incubated after 1 hour, is warmed up to 80 DEG C, underpressure distillation removing acetone, namely obtains the epoxy terminated waterborne polyurethane resin of yellowish colour band blue light.Raw material described in the present embodiment is on market can purchase raw material, and preparing products therefrom solid content is 42.6%, and viscosity is 4200mPaS, and acid number is 22.4mgKOH/g.
Claims (10)
1. a preparation method for epoxy terminated waterborne polyurethane resin, is characterized in that, comprises the following steps:
S1: vegetable oil polyol, small molecule polyol, vulcabond and hydrophilic chain extender in organic solvent, under catalyst action, addition reaction occur, obtains isocyanate terminated base polyurethane prepolymer for use as;
S2: isocyanate terminated base polyurethane prepolymer for use as and the terminal hydroxy group epoxy compounds of getting S1 gained react, and obtain epoxy-terminated polyurethane;
S3: add amine and neutralize in the epoxy-terminated polyurethane of S2 gained, drips water and carries out phase reversion, insulation, and underpressure distillation removing organic solvent, obtains epoxy terminated waterborne polyurethane resin.
2. preparation method according to claim 1, is characterized in that, described vegetable oil polyol is at least one in castor oil polyhydric alcohol, soybean oil polyol, plam oil polyvalent alcohol.
3. preparation method according to claim 1, is characterized in that, described small molecule polyol is at least one in ethylene glycol, propylene glycol, glycol ether, BDO, TriMethylolPropane(TMP).
4. preparation method according to claim 1, is characterized in that, described vulcabond is at least one in tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate.
5. preparation method according to claim 1, is characterized in that, described catalyzer is any one in isopropyl titanate, sad sub-zinc, dibutyl tin laurate.
6. preparation method according to claim 1, is characterized in that, described hydrophilic chain extender is dimethylol propionic acid.
7. preparation method according to claim 1, is characterized in that, described terminal hydroxy group epoxy compounds is 2，3-epoxy-1-propanol.
8. preparation method according to claim 1, is characterized in that, described amine is at least one in trolamine, N, N-dimethylethanolamine.
9. the preparation method according to any one of claim 1-8, it is characterized in that, the mass ratio of described vegetable oil polyol, small molecule polyol, vulcabond, hydrophilic chain extender, catalyzer, terminal hydroxy group epoxy compounds and amine is (300-670): (10-45): (160-250): (20-48): (0.8-2.0): (5-14): (10-35).
10. an epoxy terminated waterborne polyurethane resin, is characterized in that, adopts the preparation method described in any one of claim 1-9 to prepare.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535376A (en) * | 2018-12-03 | 2019-03-29 | 山东天庆科技发展有限公司 | A kind of preparation method of high-peeling strength waterborne epoxy-polyurethane |
| CN109651588A (en) * | 2018-11-21 | 2019-04-19 | 万华化学集团股份有限公司 | Castor oil modified cation self-crosslinkable polyurethane polyurea water dispersion and preparation method and application |
| CN109851753A (en) * | 2018-11-21 | 2019-06-07 | 上海华峰新材料研发科技有限公司 | The polyurethane and its preparation method and application of epoxy-modified polymer modification |
| CN110814273A (en) * | 2019-11-14 | 2020-02-21 | 安徽索立德铸业有限公司 | Modified molding sand with furan resin loaded with nano ceramic |
| CN110951382A (en) * | 2019-12-20 | 2020-04-03 | 刘艳蕊 | Environment-friendly three-proofing paint and preparation method thereof |
| CN111635499A (en) * | 2020-06-05 | 2020-09-08 | 西安增材制造国家研究院有限公司 | Epoxy modified polyurethane resin, system, preparation method and application thereof |
| CN113651939A (en) * | 2021-08-04 | 2021-11-16 | 合肥科天水性科技有限责任公司 | Preparation method of medical micro-nano waterborne polyurethane fiber |
| CN114907543A (en) * | 2022-06-21 | 2022-08-16 | 武汉弘毅共聚新材料科技有限公司 | Waterborne polyurethane resin for medicine packaging and preparation method and application thereof |
| CN115612372A (en) * | 2022-10-09 | 2023-01-17 | 中昊北方涂料工业研究设计院有限公司 | RB epoxy resin condensate and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651588A (en) * | 2018-11-21 | 2019-04-19 | 万华化学集团股份有限公司 | Castor oil modified cation self-crosslinkable polyurethane polyurea water dispersion and preparation method and application |
| CN109851753A (en) * | 2018-11-21 | 2019-06-07 | 上海华峰新材料研发科技有限公司 | The polyurethane and its preparation method and application of epoxy-modified polymer modification |
| CN109651588B (en) * | 2018-11-21 | 2021-09-07 | 万华化学集团股份有限公司 | Castor oil modified cationic self-crosslinking polyurethane polyurea aqueous dispersion, preparation method and application |
| CN109535376A (en) * | 2018-12-03 | 2019-03-29 | 山东天庆科技发展有限公司 | A kind of preparation method of high-peeling strength waterborne epoxy-polyurethane |
| CN110814273A (en) * | 2019-11-14 | 2020-02-21 | 安徽索立德铸业有限公司 | Modified molding sand with furan resin loaded with nano ceramic |
| CN110951382A (en) * | 2019-12-20 | 2020-04-03 | 刘艳蕊 | Environment-friendly three-proofing paint and preparation method thereof |
| CN111635499A (en) * | 2020-06-05 | 2020-09-08 | 西安增材制造国家研究院有限公司 | Epoxy modified polyurethane resin, system, preparation method and application thereof |
| CN113651939A (en) * | 2021-08-04 | 2021-11-16 | 合肥科天水性科技有限责任公司 | Preparation method of medical micro-nano waterborne polyurethane fiber |
| CN114907543A (en) * | 2022-06-21 | 2022-08-16 | 武汉弘毅共聚新材料科技有限公司 | Waterborne polyurethane resin for medicine packaging and preparation method and application thereof |
| CN115612372A (en) * | 2022-10-09 | 2023-01-17 | 中昊北方涂料工业研究设计院有限公司 | RB epoxy resin condensate and preparation method thereof |
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