CN115215983B - Cationic aqueous polyurethane emulsion with high solid content and preparation method thereof - Google Patents
Cationic aqueous polyurethane emulsion with high solid content and preparation method thereof Download PDFInfo
- Publication number
- CN115215983B CN115215983B CN202210968149.3A CN202210968149A CN115215983B CN 115215983 B CN115215983 B CN 115215983B CN 202210968149 A CN202210968149 A CN 202210968149A CN 115215983 B CN115215983 B CN 115215983B
- Authority
- CN
- China
- Prior art keywords
- parts
- reaction
- prepolymer
- chain extender
- aqueous polyurethane
- 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.)
- Active
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
- C08G18/08—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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
-
- 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
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
-
- 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
- C08G18/3271—Hydroxyamines
-
- 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
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty 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
- C08G18/42—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of waterborne polyurethane. The invention provides a high-solid-content cationic aqueous polyurethane emulsion, which comprises the following raw materials in percentage by mass: 215-275: 2 to 7 of a prepolymer A, a prepolymer B and a neutralizing agent; the prepolymer A is prepared from polyalcohol, castor oil, isocyanate, a small molecule chain extender, a silane coupling agent, a solvent and water; the prepolymer B is prepared from polyalcohol, castor oil, isocyanate, a small molecule chain extender, a hydrophilic chain extender, a silane coupling agent, a solvent and water. The invention also provides a preparation method of the high-solid-content cationic aqueous polyurethane emulsion. The hydrophilic chain extender is less in dosage, the viscosity of emulsion is reduced, and the cost of raw materials is reduced; the solid content of the aqueous polyurethane is high, so that the moisture volatilization load is effectively reduced, and the film forming and drying time is shortened; the tensile strength and the elongation at break of emulsion film forming are obviously improved, and the viscosity is obviously reduced; the storage stability is good.
Description
Technical Field
The invention relates to the technical field of waterborne polyurethane, in particular to a high-solid-content cationic waterborne polyurethane emulsion and a preparation method thereof.
Background
The aqueous polyurethane takes water as a dispersion medium, has the characteristics of no solvent, no odor, no pollution, incombustibility, easy mixing with other emulsions, favorable modification and the like, and has been widely applied to products such as adhesives, coatings, paper coatings, leather finishing agents, fibers or fabric treatment agents and the like.
The aqueous polyurethane can be classified into anionic, cationic, nonionic and amphoteric types according to the difference in the chargeability of the introduced groups. The waterborne polyurethane has a plurality of defects in practical application, such as small binding force, low mechanical property, poor water resistance and the like, and cannot meet the requirements of practical application. Therefore, the production of the high-solid-content aqueous polyurethane product is one of the development directions of the aqueous polyurethane emulsion. In the reaction process of the common polyether-type waterborne polyurethane, the system viscosity is continuously improved along with the progress of the reaction, the reaction is difficult due to the high viscosity, the molecular weight difference of the generated polymer is large, the hydrophilic groups are unevenly distributed, the solid content of the polyether-type waterborne polyurethane is low, and the application of the polyether-type waterborne polyurethane is limited.
The cationic water-based polyurethane has the advantages that the framework of the cationic water-based polyurethane is provided with cations, so that the cationic water-based polyurethane has unique properties, and has better application in the fields of leather, paint, textile, papermaking and the like. However, the cationic aqueous polyurethane emulsion in the prior art is difficult to realize high solid content, high mechanical property, faster film forming speed and low viscosity simultaneously.
Disclosure of Invention
The invention aims to provide a high-solid-content cationic aqueous polyurethane emulsion and a preparation method thereof, aiming at the defects of the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-solid-content cationic aqueous polyurethane emulsion, which comprises the following raw materials in percentage by mass: 217 to 275:2 to 7 of a prepolymer A, a prepolymer B and a neutralizing agent;
the prepolymer A is prepared from the following raw materials in parts by mass: 35-45 parts of polyalcohol, 5-8 parts of castor oil, 20-30 parts of isocyanate, 3-5 parts of small molecule chain extender, 0.1-0.5 part of silane coupling agent, 40-50 parts of solvent and 100-120 parts of water;
the prepolymer B is prepared from the following raw materials in parts by mass: 30-40 parts of polyalcohol, 5-8 parts of castor oil, 25-35 parts of isocyanate, 3-5 parts of small molecule chain extender, 3-7 parts of hydrophilic chain extender, 0.1-0.3 part of silane coupling agent, 40-50 parts of solvent and 110-130 parts of water.
Preferably, the polyol comprises one or more of polyethylene adipate, polybutylene adipate, polycaprolactone polyol, polypropylene glycol, and polycarbonate diol.
Preferably, the isocyanate comprises one or more of xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate, 2, 4-trimethylhexane diisocyanate and naphthalene-1, 5-diisocyanate.
Preferably, the hydrophilic chain extender comprises one or more of N-methyldiethanolamine, sodium ethylenediamine-based ethanesulfonate, tertiary butyl diethanolamine and 3-dimethylamino-1, 2-propanediol.
Preferably, the small molecule chain extender in the prepolymer A is diethylene glycol, trimethylolpropane, 3-methylpentanediol or 2-methyl-2-ethylpropanediol;
the micromolecular chain extender in the prepolymer B is pentanediamine, cyclohexanediamine, hydrazine hydrate or N-aminoethylethanolamine.
Preferably, the solvent is N-methyl pyrrolidone, acetone or dimethyl sulfoxide; the silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane or gamma-glycidyl ether oxypropyl triethoxy silane; the neutralizing agent comprises phosphoric acid, phytic acid, glycolic acid or methyl sulfate.
The invention also provides a preparation method of the high-solid-content cationic aqueous polyurethane emulsion, which comprises the following steps:
1) Under the protective atmosphere, the polyalcohol, castor oil, isocyanate, small molecular chain extender and silane coupling agent in the raw materials of the prepolymer A are reacted, a solvent is added in the reaction process to reduce the viscosity, and the reaction product and water are subjected to emulsification reaction to obtain the prepolymer A;
2) Under the protective atmosphere, carrying out a first reaction on polyalcohol, castor oil, isocyanate, 50-70% of small molecular chain extender, hydrophilic chain extender and silane coupling agent in the raw materials of the prepolymer B, adding a solvent in the reaction process to reduce the viscosity, carrying out a second reaction on a first reaction product and the rest small molecular chain extender, and carrying out an emulsification reaction on the second reaction product and water to obtain the prepolymer B;
3) And (3) dropwise adding the prepolymer B into the prepolymer A, adding a neutralizing agent for reaction, and then performing reduced pressure distillation to obtain the high-solid-content cationic aqueous polyurethane emulsion.
Preferably, the temperature of the reaction in the step 1) is 75-85 ℃, the reaction time is 2-5 h, the stirring rate of the emulsification reaction is 500-800 r/min, the temperature of the emulsification reaction is 15-35 ℃, and the time of the emulsification reaction is 20-30 min.
Preferably, the temperature of the first reaction in the step 2) is 75-85 ℃, the time is 1-4 h, the stirring speed is 1500-2000 r/min, and the time of the second reaction is 0.5-1.5 h; the stirring speed of the emulsification reaction is 1500-2000 r/min, the temperature is 15-35 ℃ and the time is 25-35 min.
Preferably, the pH value of the reaction liquid after the neutralizing agent is added in the step 3) is 6.5-7.5.
The beneficial effects of the invention include the following points:
1) The hydrophilic chain extender is less in dosage, the viscosity of emulsion is reduced, and the cost of raw materials is reduced; the solid content of the aqueous polyurethane is high, so that the moisture volatilization load is effectively reduced, and the film forming and drying time is shortened; the tensile strength and elongation at break of the emulsion film forming are obviously improved, and the viscosity is obviously reduced.
2) The reaction condition for preparing the high-solid-content aqueous polyurethane is mild and easy to control, and the aqueous polyurethane has good storage stability.
Detailed Description
The invention provides a high-solid-content cationic aqueous polyurethane emulsion, which comprises the following raw materials in percentage by mass: 217 to 275:2 to 7 of a prepolymer A, a prepolymer B and a neutralizing agent;
the prepolymer A is prepared from the following raw materials in parts by mass: 35-45 parts of polyalcohol, 5-8 parts of castor oil, 20-30 parts of isocyanate, 3-5 parts of small molecule chain extender, 0.1-0.5 part of silane coupling agent, 40-50 parts of solvent and 100-120 parts of water;
the prepolymer B is prepared from the following raw materials in parts by mass: 30-40 parts of polyalcohol, 5-8 parts of castor oil, 25-35 parts of isocyanate, 3-5 parts of small molecule chain extender, 3-7 parts of hydrophilic chain extender, 0.1-0.3 part of silane coupling agent, 40-50 parts of solvent and 110-130 parts of water.
In the preparation raw materials of the high-solid-content cationic aqueous polyurethane emulsion, the mass ratio of the prepolymer A to the prepolymer B to the neutralizer is preferably 210-240: 220-265: 3 to 6, more preferably 220 to 230:230 to 250:4 to 5.
The prepolymer A of the invention is preferably prepared from the following raw materials in parts by mass: 37-42 parts of polyol, 6-7 parts of castor oil, 22-28 parts of isocyanate, 3.5-4.5 parts of small molecule chain extender, 0.2-0.4 part of silane coupling agent, 42-48 parts of solvent and 105-115 parts of water, and is further preferably prepared from the following raw materials in parts by mass: 39-41 parts of polyol, 6.5 parts of castor oil, 24-26 parts of isocyanate, 4 parts of small molecule chain extender, 0.3 part of silane coupling agent, 44-46 parts of solvent and 108-112 parts of water.
The prepolymer B of the invention is preferably prepared from the following raw materials in parts by mass: 32-38 parts of polyalcohol, 6-7 parts of castor oil, 28-32 parts of isocyanate, 3.5-4.5 parts of small molecule chain extender, 4-6 parts of hydrophilic chain extender, 0.15-0.25 part of silane coupling agent, 42-48 parts of solvent and 115-125 parts of water, and is further preferably prepared from the following raw materials in parts by mass: 34-36 parts of polyol, 6.5 parts of castor oil, 29-30 parts of isocyanate, 4 parts of small molecule chain extender, 5 parts of hydrophilic chain extender, 0.2 part of silane coupling agent, 44-46 parts of solvent and 118-122 parts of water.
In the present invention, the polyol preferably contains one or more of polyethylene adipate, polybutylene adipate, polycaprolactone polyol, polypropylene glycol, and polycarbonate diol.
The polyol and castor oil of the invention can improve the mechanical property, the wear resistance, the water resistance and the solvent resistance of the aqueous polyurethane adhesive film.
In the present invention, the isocyanate preferably contains one or more of xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate, 2, 4-trimethylhexane diisocyanate, and naphthalene-1, 5-diisocyanate.
In the invention, the hydrophilic chain extender preferably comprises one or more of N-methyldiethanolamine, sodium ethylenediamine-based ethanesulfonate, tertiary butyl diethanolamine and 3-dimethylamino-1, 2-propanediol.
In the invention, the small molecular chain extender in the prepolymer A is preferably diethylene glycol, trimethylolpropane, 3-methylpentanediol or 2-methyl-2-ethylpropanediol;
the small molecule chain extender in the prepolymer B is preferably pentanediamine, cyclohexanediamine, hydrazine hydrate or N-aminoethylethanolamine.
The small molecular chain extender ensures the mildness and controllability of the whole chain extension reaction and the grafting efficiency of the chain extender, and improves the stability of the aqueous polyurethane emulsion.
In the present invention, the solvent is preferably N-methylpyrrolidone, acetone or dimethyl sulfoxide; the neutralizing agent comprises phosphoric acid, phytic acid, glycolic acid or methyl sulfate; the purity of phosphoric acid is preferably more than or equal to 90%, and the purity of phytic acid is preferably more than or equal to 60%.
The morphology of the aqueous polyurethane emulsion particles obtained by the neutralizer is spherical, and the particle size distribution is uniform.
In the invention, the silane coupling agent is preferably gamma-glycidoxypropyl trimethoxysilane or gamma-glycidoxypropyl triethoxysilane; the gamma-glycidoxypropyl trimethoxy silane and the gamma-glycidoxypropyl triethoxy silane are silanes containing three siloxane bonds and epoxy functional groups, and a cross-linked network structure is formed in a polyurethane system due to hydrolysis of the siloxane bonds, so that the mechanical strength of a coating film can be remarkably improved, the water resistance of the material can be further improved due to enrichment of siloxane on the surface of the material, and meanwhile, the adhesive property of the material can be remarkably improved due to the existence of the epoxy functional groups.
The invention also provides a preparation method of the high-solid-content cationic aqueous polyurethane emulsion, which comprises the following steps:
1) Under the protective atmosphere, the polyalcohol, castor oil, isocyanate, small molecular chain extender and silane coupling agent in the raw materials of the prepolymer A are reacted, a solvent is added in the reaction process to reduce the viscosity, and the reaction product and water are subjected to emulsification reaction to obtain the prepolymer A;
2) Under the protective atmosphere, carrying out a first reaction on polyalcohol, castor oil, isocyanate, 50-70% of small molecular chain extender, hydrophilic chain extender and silane coupling agent in the raw materials of the prepolymer B, adding a solvent in the reaction process to reduce the viscosity, carrying out a second reaction on a first reaction product and the rest small molecular chain extender, and carrying out an emulsification reaction on the second reaction product and water to obtain the prepolymer B;
3) And (3) dropwise adding the prepolymer B into the prepolymer A, adding a neutralizing agent for reaction, and then performing reduced pressure distillation to obtain the high-solid-content cationic aqueous polyurethane emulsion.
In the present invention, the temperature of the reaction in step 1) is preferably 75 to 85 ℃, more preferably 77 to 82 ℃, and even more preferably 79 to 81 ℃; the reaction time is preferably 2 to 5 hours, more preferably 3 to 4 hours; the stirring rate of the emulsification reaction is preferably 500-800 r/min, and more preferably 600-700 r/min; the temperature of the emulsification reaction is preferably 15 to 35 ℃, more preferably 20 to 30 ℃, and even more preferably 24 to 26 ℃; the time for the emulsification reaction is preferably 20 to 30 minutes, more preferably 22 to 28 minutes, and still more preferably 24 to 26 minutes.
In the present invention, the temperature of the first reaction in step 2) is preferably 75 to 85 ℃, more preferably 77 to 82 ℃, and even more preferably 79 to 81 ℃; the time of the first reaction is preferably 1 to 4 hours, more preferably 2 to 3 hours; the stirring rate of the first reaction is preferably 1500 to 2000r/min, more preferably 1600 to 1900r/min, still more preferably 1700 to 1800r/min; the time of the second reaction is preferably 0.5 to 1.5 hours, more preferably 1 hour; the stirring rate of the emulsification reaction is preferably 1500-2000 r/min, more preferably 1600-1900 r/min, and even more preferably 1700-1800 r/min; the temperature of the emulsification reaction is preferably 15 to 35 ℃, more preferably 20 to 30 ℃, and even more preferably 24 to 26 ℃; the time for the emulsification reaction is preferably 25 to 35 minutes, more preferably 28 to 32 minutes, and still more preferably 30 minutes.
In the step 2), part of the small molecular chain extender is added after the emulsion is formed, and the post-chain extension reaction is carried out, so that the mechanical property of the aqueous polyurethane emulsion can be further improved compared with the case that all the small molecular chain extender is added during the chain extension reaction.
The protective atmosphere in step 1) and step 2) of the invention is preferably nitrogen or argon.
In the present invention, the pH of the reaction solution after the addition of the neutralizing agent in step 3) is preferably 6.5 to 7.5, more preferably 7, and the reaction time is preferably 0.5 to 1.5 hours, more preferably 1 hour.
According to the invention, the particle size of the prepolymer A is large, the particle size of the prepolymer B is small, the prepolymer B is dropwise added into the prepolymer A, small particles are dispersed in gaps of large particles, the space utilization rate of emulsion particles is improved, and the aqueous polyurethane emulsion with wide particle size distribution, low viscosity, stability and high solid content is obtained.
In the present invention, the polyol in the prepolymer A and the prepolymer B is preferably dried before the reaction, and the drying temperature is preferably 85 to 95℃independently, more preferably 88 to 92℃more preferably 90℃independently, and the drying time is preferably 2 to 3 hours independently, more preferably 2.5 hours.
According to the invention, the small molecular chain extender and the hydrophilic chain extender are added, no catalyst is added, the reaction rate is low, the hydrophilic groups can be uniformly connected into the molecular chains, the prepolymer with uniform molecular chains is formed, and the preparation of the high-content aqueous polyurethane emulsion is facilitated.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Under nitrogen atmosphere, 36 parts of polyethylene glycol adipate (dried at 87 ℃ for 3 hours), 5 parts of castor oil, 20 parts of xylylene diisocyanate, 3 parts of diethylene glycol and 0.15 part of gamma-glycidoxypropyl trimethoxy silane are reacted for 5 hours at the rotating speed of 77 ℃ and 550r/min, 42 parts of N-methylpyrrolidone is added for three times in average in the reaction process to reduce the viscosity of the system, and the reaction product and 105 parts of deionized water are subjected to emulsification reaction at the rotating speed of 15 ℃ and 550r/min for 30 minutes to obtain the prepolymer A.
Under nitrogen atmosphere, 32 parts of polyethylene glycol adipate (dried at 87 ℃ for 3 hours), 5 parts of castor oil, 25 parts of xylylene diisocyanate, 2 parts of pentanediamine, 3 parts of N-methyldiethanolamine and 0.15 part of gamma-glycidyl ether oxypropyl trimethoxysilane are reacted for 4 hours at the temperature of 77 ℃ and the rotating speed of 1500r/min, 42 parts of N-methylpyrrolidone are added for reducing the viscosity of the system in the reaction process, the reaction product and 1 part of pentanediamine react for 0.5 hour, then 115 parts of deionized water are added for emulsion reaction at the rotating speed of 15 ℃ and the rotating speed of 1500r/min, and the time of the emulsion reaction is 35 minutes, so that a prepolymer B is obtained.
The prepolymer B is dripped into the prepolymer A at the rate of 3mL/min, 3 parts of phosphoric acid (the purity is 92%) is added, the pH value of the reaction solution is 7.5, and the reaction solution is distilled under reduced pressure after 0.5h of reaction, so that the high-solid-content cationic aqueous polyurethane emulsion is obtained.
The high solids cationic aqueous polyurethane emulsion of example 1 has a solids content of 60%, a particle size of 110nm, a low viscosity, and good storage stability without precipitation or delamination when centrifuged at 3500rpm for 15 min. The emulsion was film-formed and dried, and then subjected to a tensile test, with a tensile strength of 62MPa and an elongation at break of 750%.
Example 2
Under nitrogen atmosphere, 42 parts of polybutylene adipate (dried at 93 ℃ for 2 hours), 8 parts of castor oil, 28 parts of diphenylmethane diisocyanate, 5 parts of trimethylolpropane and 0.45 part of gamma-glycidyl ether oxypropyl triethoxysilane are reacted for 3 hours at the rotation speed of 83 ℃ and 750r/min, 48 parts of acetone is added for three times in average in the reaction process to reduce the viscosity of the system, and the reaction product and 115 parts of deionized water are subjected to emulsification reaction at the rotation speed of 32 ℃ and 750r/min for 20 minutes to obtain the prepolymer A.
Under nitrogen atmosphere, 38 parts of polybutylene adipate (dried at 93 ℃ for 2 hours), 8 parts of castor oil, 32 parts of diphenylmethane diisocyanate, 2.5 parts of cyclohexanediamine, 6 parts of tertiary butyl diethanolamine and 0.25 part of gamma-glycidyl ether oxypropyl triethoxysilane are reacted for 1.5 hours at the rotating speed of 1900r/min at 83 ℃, 48 parts of acetone is added for reducing the system viscosity in an average three times in the reaction process, the reaction product and 2.5 parts of cyclohexanediamine react for 1.5 hours, then 125 parts of deionized water are added for emulsification reaction at the rotating speed of 32 ℃ and 1900r/min, and the time of the emulsification reaction is 25 minutes, so that a prepolymer B is obtained.
The prepolymer B is dripped into the prepolymer A at the rate of 3.5mL/min, 6 parts of phytic acid (the purity is 60%) is added, the pH value of the reaction solution is 6.5, and the reaction is carried out for 1.5h and then reduced pressure distillation is carried out, so that the high-solid-content cationic aqueous polyurethane emulsion is obtained.
The high solids cationic aqueous polyurethane emulsion of example 2 has a solids content of 63%, a particle size of 95nm, a low viscosity, and good storage stability without precipitation or delamination when centrifuged at 3500rpm for 15 min. The emulsion is subjected to tensile test after film forming and drying, the tensile strength is 65MPa, and the elongation at break is 780%.
Example 3
Under the nitrogen atmosphere, 40 parts of polycarbonate dihydric alcohol (dried at 90 ℃ for 2 hours), 6 parts of castor oil, 25 parts of naphthalene-1, 5-diisocyanate, 4 parts of 3-methylpentanediol and 0.3 part of gamma-glycidyl ether oxypropyl trimethoxysilane are reacted for 3 hours at the rotating speed of 80 ℃ and 700r/min, 45 parts of dimethyl sulfoxide is added for reducing the viscosity of the system in the reaction process in three equal parts, and the reaction product and 110 parts of deionized water are subjected to emulsification reaction at the rotating speed of 25 ℃ and 700r/min for 25 minutes to obtain the prepolymer A.
Under nitrogen atmosphere, 35 parts of polycarbonate dihydric alcohol (dried at 90 ℃ for 2 hours), 6 parts of castor oil, 30 parts of naphthalene-1, 5-diisocyanate, 2.4 parts of N-aminoethylethanolamine, 5 parts of 3-dimethylamino-1, 2-propanediol and 0.2 part of gamma-glycidoxypropyl trimethoxysilane are reacted for 3 hours at the rotating speed of 80 ℃ and 1700r/min, 45 parts of dimethyl sulfoxide is added for three times in average in the reaction process to reduce the viscosity of the system, the reaction product and 1.6 parts of N-aminoethylethanolamine are reacted for 1 hour, then 120 parts of deionized water is added for emulsification reaction at the rotating speed of 25 ℃ and 1700r/min, and the time of the emulsification reaction is 30 minutes, so that a prepolymer B is obtained.
The prepolymer B is dripped into the prepolymer A at the rate of 2.5mL/min, 5 parts of phytic acid (with the purity of 65%) is added, the pH value of the reaction solution is 7, and the reaction solution is distilled under reduced pressure after 1h of reaction, so that the high-solid-content cationic aqueous polyurethane emulsion is obtained.
The high solids cationic aqueous polyurethane emulsion of example 3 has a solids content of 65%, a particle size of 100nm, a low viscosity, and good storage stability without precipitation or delamination when centrifuged at 3500rpm for 15 min. The emulsion was film-formed and dried and then subjected to a tensile test, with a tensile strength of 69MPa and an elongation at break of 830%.
Comparative example 1
N-aminoethylethanolamine in the preparation of the prepolymer B in example 3 was changed to be added simultaneously, and gamma-glycidoxypropyl trimethoxysilane in the preparation of the prepolymer A and the prepolymer B was omitted, and the other conditions were the same as in example 3.
The high solids cationic aqueous polyurethane emulsion of comparative example 1 had a solids content of 53% and was centrifuged at 3500rpm for 15min with partial precipitation or delamination. The emulsion was film-formed and dried and then subjected to a tensile test, with a tensile strength of 50MPa and an elongation at break of 560%.
Comparative example 2
The castor oil in the prepolymer A and the prepolymer B of example 3 was omitted, the phytic acid in example 3 was changed to acetic acid, the rotation speed in the preparation process of the prepolymer A was changed to 1700r/min, and other conditions were the same as in example 3.
The high solids cationic aqueous polyurethane emulsion of comparative example 2 had a solids content of 51% and was centrifuged at 3500rpm for 15min with little settling or delamination. The emulsion is subjected to tensile test after film forming and drying, the tensile strength is 45MPa, and the elongation at break is 580%.
The examples and the comparative examples show that the high-solid-content cationic aqueous polyurethane emulsion has high solid content, good mechanical property and good storage stability, the performance of the high-solid-content cationic aqueous polyurethane emulsion is closely related to the raw materials and the technological parameters, and the change of the raw materials or the technological parameters can lead to the reduction of the solid content and the mechanical property of the aqueous polyurethane emulsion.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. The high-solid-content cationic aqueous polyurethane emulsion is characterized in that the preparation raw materials comprise 205-258 by mass: 217-275: 2-7 of a prepolymer A, a prepolymer B and a neutralizer;
the prepolymer A is prepared from the following raw materials in parts by mass: 35-45 parts of polyalcohol, 5-8 parts of castor oil, 20-30 parts of isocyanate, 3-5 parts of small molecule chain extender, 0.1-0.5 part of silane coupling agent, 40-50 parts of solvent and 100-120 parts of water;
the prepolymer B is prepared from the following raw materials in parts by mass: 30-40 parts of polyalcohol, 5-8 parts of castor oil, 25-35 parts of isocyanate, 3-5 parts of small molecule chain extender, 3-7 parts of hydrophilic chain extender, 0.1-0.3 part of silane coupling agent, 40-50 parts of solvent and 110-130 parts of water;
the hydrophilic chain extender comprises one or more of N-methyldiethanolamine, tert-butyldiethanolamine and 3-dimethylamino-1, 2-propanediol;
the small molecular chain extender in the prepolymer A is diethylene glycol, trimethylolpropane, 3-methylpentanediol or 2-methyl-2-ethylpropanediol;
the small molecular chain extender in the prepolymer B is pentanediamine, cyclohexanediamine, hydrazine hydrate or N-aminoethylethanolamine;
in the preparation process of the prepolymer B, part of small molecular chain extender is added after emulsion is formed, and post-chain extension reaction is carried out.
2. The high solids cationic aqueous polyurethane emulsion of claim 1, wherein the polyol comprises one or more of polyethylene adipate, polybutylene adipate, polycaprolactone polyol, polypropylene glycol, and polycarbonate diol.
3. The high-solid cationic aqueous polyurethane emulsion according to claim 1 or 2, wherein the isocyanate comprises one or more of xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate, 2, 4-trimethylhexane diisocyanate and naphthalene-1, 5-diisocyanate.
4. The high solids cationic aqueous polyurethane emulsion of claim 3, wherein the solvent is N-methylpyrrolidone, acetone, or dimethyl sulfoxide; the silane coupling agent is gamma-glycidyl ether oxypropyl trimethoxy silane or gamma-glycidyl ether oxypropyl triethoxy silane; the neutralizing agent comprises phosphoric acid, phytic acid, glycolic acid or methyl sulfate.
5. The method for preparing the high-solid-content cationic aqueous polyurethane emulsion according to any one of claims 1 to 4, which is characterized by comprising the following steps:
1) Under the protective atmosphere, the polyalcohol, castor oil, isocyanate, small molecular chain extender and silane coupling agent in the raw materials of the prepolymer A are reacted, a solvent is added in the reaction process to reduce the viscosity, and the reaction product and water are subjected to emulsification reaction to obtain the prepolymer A;
2) Under a protective atmosphere, carrying out a first reaction on polyalcohol, castor oil, isocyanate, 50-70% of small molecular chain extender, hydrophilic chain extender and silane coupling agent in the raw materials of the prepolymer B, adding a solvent in the reaction process to reduce the viscosity, carrying out a second reaction on a first reaction product and the rest small molecular chain extender, and carrying out an emulsification reaction on the second reaction product and water to obtain the prepolymer B;
3) And (3) dropwise adding the prepolymer B into the prepolymer A, adding a neutralizing agent for reaction, and then performing reduced pressure distillation to obtain the high-solid-content cationic aqueous polyurethane emulsion.
6. The preparation method according to claim 5, wherein the reaction temperature in step 1) is 75-85 ℃, the reaction time is 2-5 h, the stirring rate of the emulsification reaction is 500-800 r/min, the temperature of the emulsification reaction is 15-35 ℃, and the time of the emulsification reaction is 20-30 min.
7. The preparation method according to claim 5 or 6, wherein in the step 2), the temperature of the first reaction is 75-85 ℃, the time is 1-4 hours, the stirring speed is 1500-2000 r/min, and the time of the second reaction is 0.5-1.5 hours; the stirring speed of the emulsification reaction is 1500-2000 r/min, the temperature is 15-35 ℃ and the time is 25-35 min.
8. The preparation method according to claim 7, wherein the pH value of the reaction solution after the addition of the neutralizing agent in the step 3) is 6.5 to 7.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210968149.3A CN115215983B (en) | 2022-08-12 | 2022-08-12 | Cationic aqueous polyurethane emulsion with high solid content and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210968149.3A CN115215983B (en) | 2022-08-12 | 2022-08-12 | Cationic aqueous polyurethane emulsion with high solid content and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115215983A CN115215983A (en) | 2022-10-21 |
| CN115215983B true CN115215983B (en) | 2023-05-02 |
Family
ID=83616259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210968149.3A Active CN115215983B (en) | 2022-08-12 | 2022-08-12 | Cationic aqueous polyurethane emulsion with high solid content and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115215983B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087291B (en) * | 2013-02-01 | 2015-05-20 | 陕西科技大学 | Preparation method of high solid content waterborne polyurethane |
| CN103146181B (en) * | 2013-03-01 | 2014-08-20 | 四川大学 | Preparation method of high-solid content wide-temperature range damping polyurethane aqueous dispersion containing nanofiller |
| EP3481884B1 (en) * | 2016-07-11 | 2021-03-03 | Dow Global Technologies LLC | High-solids content solvent-based adhesive compositions and methods of making same |
| CN107057027B (en) * | 2017-01-16 | 2019-08-20 | 北京理工大学 | A kind of preparation method of high-solid-content and low-viscosity aqueous polyurethane |
| CN108864400A (en) * | 2018-07-10 | 2018-11-23 | 合肥科天水性科技有限责任公司 | A kind of high-performance cationic water polyurethane resin and preparation method thereof |
| CN109354671B (en) * | 2018-11-08 | 2021-07-30 | 中北大学 | Preparation method of high-solid-content low-viscosity aqueous polyurethane emulsion |
| CN109970948B (en) * | 2019-04-10 | 2021-02-23 | 武汉纺织大学 | High-solid-content anion water-based polyurethane emulsion and preparation method thereof |
-
2022
- 2022-08-12 CN CN202210968149.3A patent/CN115215983B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115215983A (en) | 2022-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101845217B (en) | Preparation method of water-based polyurethane/nano-silicon dioxide composite emulsion | |
| JP7481341B2 (en) | Automotive glitter paint | |
| CN111171285B (en) | Epoxy resin curing agent microcapsule taking polyurethane as shell material and preparation method thereof | |
| CN109988538B (en) | Preparation method of solvent-free polyurethane adhesive | |
| CN106519169B (en) | Waterborne organic silicon dispersions of polyurethanes and its preparation and application | |
| CN104231209A (en) | Preparation method for high-hardness waterborne polyurethane dispersion | |
| CN1951968A (en) | Fluorin-silicon modified core-shell structure polyurethane-acrylate emulsion preparation method | |
| CN103450438A (en) | Waterborne polyurethane resin with high solid content and synthesis method thereof | |
| CN111087568A (en) | Solvent-resistant self-extinction waterborne polyurethane resin and preparation method thereof | |
| CN111533880B (en) | Preparation method of nano-silica modified waterborne polyurethane | |
| CN109135530A (en) | DAPBI modified aqueous polyurethane coating and preparation method thereof | |
| CN112679993A (en) | In-situ nano composite coated aluminum paste | |
| CN115215983B (en) | Cationic aqueous polyurethane emulsion with high solid content and preparation method thereof | |
| CN114853970A (en) | Closed cationic waterborne polyurethane curing agent and preparation method and application thereof | |
| CN108485506B (en) | Nano CaCO3Nano SiO2Dual-modified waterborne polyurethane coating and preparation method thereof | |
| CN114805734B (en) | Water-based polyurethane dispersoid and preparation method thereof, and self-crosslinking water-based polyurethane waterproof coating | |
| CN108086045A (en) | A kind of preparation method of wear-resisting and waterproof waterborne polyurethane resin coating coating paper | |
| CN114933690A (en) | Method for preparing stain-resistant ultraviolet curing resin by utilizing core-shell structure | |
| CN114921168A (en) | Carbon-silicon nano material modified waterborne polyurethane emulsion, and synthesis method and application thereof | |
| CN111484594A (en) | Method for preparing high-elongation-at-break waterborne polyurethane by adopting polyester polyol | |
| CN113174194B (en) | Wear-resistant super-hydrophobic self-cleaning composite coating and preparation method thereof | |
| CN114605685B (en) | WPU-RCNs-PEDOT nano composite film with high tensile strength and high conductivity | |
| CN111961329B (en) | Water-based PU waterproof moisture-permeable film and preparation method thereof | |
| CN114369406B (en) | Graphene zinc powder anticorrosion primer for high-flash-point steel structure and preparation method thereof | |
| CN116640505B (en) | Functional photo-curable leather finishing agent system 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |