CN111087549A - Waterborne polyurethane resin, coating and preparation method thereof - Google Patents
Waterborne polyurethane resin, coating and preparation method thereof Download PDFInfo
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- CN111087549A CN111087549A CN201911416256.XA CN201911416256A CN111087549A CN 111087549 A CN111087549 A CN 111087549A CN 201911416256 A CN201911416256 A CN 201911416256A CN 111087549 A CN111087549 A CN 111087549A
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- polyurethane resin
- chain extender
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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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
- C08G18/40—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
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/6755—Unsaturated carboxylic acids
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
Abstract
The invention discloses a waterborne polyurethane resin, a coating and a preparation method thereof, wherein saturated polyester polyol, (methyl) acrylate and the like are mixed with polyisocyanate and a solvent for reaction, then a chain extender, a cosolvent, a modified chain extender, a free radical initiator and vinyl polysiloxane are added for reaction, neutralization and cooling are carried out, water is added for dispersion and emulsification, and then chain extension reaction is carried out, so as to obtain the waterborne polyurethane resin. The waterborne polyurethane resin disclosed by the invention combines the high hardness and high resilience flexibility of polyurethane with the temperature resistance, high light transmittance, wear resistance and the like of vinyl polysiloxane, the resin grafting rate is high, the emulsion stability is good, and a paint film has excellent glossiness, hardness and heat resistance.
Description
Technical Field
The invention relates to an aqueous polyurethane resin which is prepared into an aqueous polyurethane coating and has good glossiness and heat resistance.
Technical Field
The waterborne polyurethane is a high molecular material taking water as a dispersion medium instead of an organic solvent, has the advantages of good film forming property, high bonding strength, high glossiness, strong corrosion resistance, excellent mechanical property, environmental protection and the like, and is a necessary trend for replacing solvent type polyurethane.
However, the existing waterborne polyurethane transparent varnish for wood protection generally has the problems of low heat resistance and high activation temperature. Due to the characteristic of carbamate in a molecular structure, the heat-resistant temperature of the single aqueous polyurethane material is usually below 80 ℃, and the dry heat-resistant requirement of varnish for furniture wood and tea table wood can not be met. The heat-resistant temperature of the high heat-resistant product can be adjusted by adjusting the proportion of the soft segment and the soft segment, but the activation temperature of the high heat-resistant product obtained by the method is also high, so that a curing agent is required to be added when the high heat-resistant product is used to improve the crosslinking density of resin, but the rebound flexibility of a paint film is reduced, a glass cup or a disposable paper cup filled with boiled water is placed on a paint film coating of the high heat-resistant product, the glass cup or the disposable paper cup is removed after the boiled water is cooled, unrecoverable dents are also left on the coating. Therefore, research on synthesizing waterborne polyurethane high-performance furniture water paint with high hardness, high flexibility, high resilience and high heat resistance has become a research hotspot of many researchers.
Patent CN201110028348.8 discloses a method for preparing a single-component high heat-resistant waterborne polyurethane adhesive, which uses nano-silica to modify waterborne polyurethane to prepare an adhesive with a single-component heat-resistant temperature of above 160 ℃, but the nano-silica is difficult to dissolve and disperse uniformly in the preparation process, and the permeability of a paint film is affected in the curing and film-forming process, so that the application has limitations.
Patent CN101633828A discloses a preparation method of a high heat-resistant aqueous polyurethane adhesive, which is to obtain the high heat-resistant aqueous polyurethane adhesive by introducing a silane coupling agent for secondary chain extension and compounding functional polyvinyl alcohol, but the polyvinyl alcohol is soft and is not suitable for wood lacquer with high requirements on hardness, scratch resistance and other properties.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the waterborne polyurethane resin, the coating and the preparation method thereof, the high hardness and high resilience flexibility of polyurethane and the temperature resistance, high light transmittance, wear resistance and the like of vinyl polysiloxane are combined, the prepared waterborne polyurethane resin has high grafting rate and good emulsion stability, the phenomena of floating oil, gel, phase separation and the like do not occur after the waterborne polyurethane resin is placed for 6 months, the hardness of a paint film is improved quickly, the phenomenon of 'oil pit' does not occur, and the waterborne polyurethane resin has excellent glossiness, hardness, flexibility and heat resistance.
The technical scheme of the invention is as follows:
the preparation method of the waterborne polyurethane resin comprises the following steps:
mixing unsaturated polyester polyol, saturated polyester polyol, (meth) acrylate, polyisocyanate and a solvent, reacting, adding a chain extender, a cosolvent, a modified chain extender and a free radical initiator, heating, adding vinyl polysiloxane for reaction, neutralizing, cooling after the reaction is finished, adding water for dispersion and emulsification, adding a chain extender 2 for secondary reaction, and removing the solvent after the reaction is finished to obtain the waterborne polyurethane resin; the modified chain extender is obtained by reacting an alkenyl compound containing an epoxy group with hydroxycarboxylic acid.
The unsaturated polyester polyol is prepared from unsaturated polybasic acid and polyhydric alcohol through esterification and polycondensation reaction, or is prepared from unsaturated polybasic acid and unsaturated polyhydric alcohol through esterification and polycondensation reaction, or is prepared from saturated polybasic acid and unsaturated polyhydric alcohol through esterification and polycondensation reaction, and comprises unsaturated aliphatic polyester polyol, and the preparation method thereof is the prior art.
Preferably, the unsaturated polyester polyol is prepared by esterification and polycondensation of unsaturated polybasic acid and polyhydric alcohol, and the molar ratio of the unsaturated polybasic acid to the polyhydric alcohol is 1: (1.2-1.5), wherein the unsaturated polybasic acid is itaconic acid, fumaric acid, glutaconic acid or maleic anhydride; the polyhydric alcohol is preferably one or more of neopentyl glycol, 1, 4-butanediol, diethylene glycol, ethylene glycol and trimethylolpropane, and the preparation method can be referred to the literature: wang Xingxing, Xuwen Qin, Yangming, etc., synthesis of poly (butylene itaconate) [ J ], school newspaper of petrochemical industry, etc., Vol.30, 2 nd (7-11) in 2017.
Specifically, the unsaturated polyester polyol is prepared by mixing unsaturated polybasic acid, polyhydric alcohol, catalyst and polymerization inhibitor, heating for esterification, heating under vacuum condition for polycondensation to obtain unsaturated polyester polyol; the catalyst comprises stannous chloride, and the polymerization inhibitor is preferably hydroquinone; the temperature of the esterification reaction is 140-160 ℃, and the time is 1-5 hours; the temperature of the polycondensation reaction is 170-180 ℃, and the reaction time is 2-3 hours.
Preferably, the number average molecular weight of the unsaturated polyester polyol is 2000-3000, the hydroxyl value is 40-80mgKOH/g, and the hydroxyl value is tested according to GB/T7193-2003.
The saturated polyester polyol is obtained by condensation esterification (or ester exchange) reaction of organic dicarboxylic acid or dicarboxylic anhydride and polyhydric alcohol, or polymerization of lactone and polyhydric alcohol, the saturated polyester polyol comprises saturated aliphatic polyester polyol, aromatic polyester polyol and the like, and the organic dicarboxylic acid or dicarboxylic anhydride is preferably adipic acid, phthalic acid or phthalic anhydride; the polyhydric alcohol is preferably one or more of neopentyl glycol, 1, 4-butanediol, diethylene glycol, ethylene glycol and trimethylolpropane.
Preferably, the number average molecular weight of the saturated polyester polyol is 1000-2500, and the hydroxyl value is 45-90 mgKOH/g. In order to reduce the occurrence of side reactions, it is necessary to subject raw materials such as unsaturated polyester polyols and saturated polyester polyols to water removal treatment, which is a common practice in the art.
The (meth) acrylate is a compound having one or more (meth) acrylate groups in a molecular structure, preferably a compound having two or more (meth) acrylate groups in a molecular structure, and is specifically one or more selected from the group consisting of polyethylene glycol diacrylate, ethylene glycol diacrylate, 1, 6-hexanediol diacrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tripropylene glycol di (meth) acrylate. Further preferably, the number average molecular weight of the polyethylene glycol diacrylate is 200-1000. the meaning of the (meth) acrylate in the present invention is methacrylate and/or acrylate, which is generally described in the art.
Preferably, the mass ratio of the (methyl) acrylate to the polyisocyanate is (3-7): (12-25).
The polyisocyanate is a compound having two or more isocyanate groups in a molecule, and specifically may be selected from Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate, isophorone diisocyanate or polyphenyl polymethylene polyisocyanate (PAPI). The NCO content is determined by reference to GB/T29493.6-2013.
Preferably, the unsaturated polyester polyol: saturated polyester polyol: the mass ratio of the polyisocyanate is (5-10): (8-15): (12-25).
Preferably, the unsaturated polyester polyol, the saturated polyester polyol, the (meth) acrylate, the polyisocyanate and the solvent are mixed and then reacted until the NCO content is 2.0g to 4.0g/100g, and the reaction temperature is 65 ℃ to 75 ℃.
The solvent comprises acetone, and preferably, the weight ratio of the polyisocyanate to the solvent is (3-4): (0.5 to 1.5).
In the preparation method of the aqueous polyurethane resin, the cosolvent is not particularly limited, and can be N, N-dimethylformamide, N-methylpyrrolidone, acetone or butanone. Preferably, the cosolvent is N, N-dimethylformamide or N-methylpyrrolidone, and the mass of the cosolvent is 1.5-2.5 times that of the chain extender.
The chain extender is not particularly limited, and is preferably one or more of dimethylolpropionic acid, dimethylolbutyric acid, ethylene diamino ethyl sodium sulfonate and N-methyl diethanolamine.
The modified chain extender is prepared from an epoxy group-containing alkenyl compound and hydroxycarboxylic acid through a ring-opening reaction, wherein the alkenyl group is a group capable of performing a radical polymerization reaction and comprises vinyl and allyl, and preferably, the epoxy group-containing alkenyl compound is one or more of 2-vinyl oxirane, 1, 2-epoxy-9-decene, 1, 2-epoxy-5-hexene, allyl glycidyl ether, 4-vinylbenzyl glycidyl ether, methacrylic acid glycidyl ether and acrylic acid glycidyl ether; preferably, the hydroxycarboxylic acid is at least one of hydroxymethylformic acid, hydroxymethylacetic acid, hydroxymethylpropionic acid, dimethylolformic acid, dimethylolacetic acid, dimethylolpropionic acid and dimethylolbutyric acid.
Preferably, the ratio of the amount of the chain extender to the modified chain extender is (0.60-2.2): 1.
Preferably, the mass ratio of the modified chain extender to the polyisocyanate is (0.05-0.15): 1.
Preferably, the preparation method of the modified chain extender comprises the following steps: mixing 35-45 parts by weight of an epoxy group-containing alkenyl compound with a catalyst and a polymerization inhibitor, heating to 110-120 ℃, adding 25-30 parts by weight of hydroxycarboxylic acid and a cosolvent, reacting at 110-120 ℃ for 8-12 hours after dropwise addition is completed, and removing small molecules and the cosolvent through reduced pressure distillation to obtain the modified chain extender.
In the preparation method of the modified chain extender, the catalyst is not particularly limited, preferably, the catalyst is tetrabutylammonium bromide, triphenylphosphine or triethylamine, and the weight ratio of the catalyst to the hydroxycarboxylic acid is (4-6): 25 to 30.
In the preparation method of the modified chain extender, the polymerization inhibitor is not particularly limited, and preferably, the polymerization inhibitor is one or more of p-methoxyphenol, hydroquinone, 2, 5-dimethylhydroquinone and 2, 6-di-tert-butyl-p-cresol; more preferably, the mass ratio of the polymerization inhibitor to the hydroxycarboxylic acid is (0.02-0.05): (25-30).
In the preparation method of the modified chain extender, preferably, the cosolvent is N, N-dimethylformamide or N-methylpyrrolidone, and the mass of the cosolvent is 1.0-1.5 times that of the hydroxycarboxylic acid. The reduced pressure distillation is to remove a catalyst, a cosolvent, an unreacted epoxy group-containing alkenyl compound, a hydroxycarboxylic acid, and the like, and the temperature of the reduced pressure distillation is preferably 150 to 160 ℃.
The vinyl polysiloxane is a linear organopolysiloxane containing a silicon-bonded vinyl group at one or both ends of the molecule, and may or may not contain a vinyl group bonded to a silicon atom at a side position. Preferably, the vinyl polysiloxane is one or more of dimethyl vinyl siloxy-terminated polymethylvinyl siloxane, a copolymer of dimethyl vinyl siloxy-terminated methyl vinyl siloxane and dimethyl siloxane, dimethyl vinyl siloxy-terminated polydimethylsiloxane, methylphenyl vinyl siloxy-terminated polymethylphenyl siloxane and dimethyl vinyl siloxy-terminated polymethylphenyl siloxane. More preferably, the vinyl polysiloxane has the vinyl mass percent of 1.2-3.5% and the dynamic viscosity at 25 ℃ of 100-1000 mm2And s. The phenyl group content of the vinyl polysiloxane is preferably 2-5% by mass, and the phenyl-containing vinyl polysiloxane can remarkably improve the transparency and heat resistance of the modified resin after film formation. Preferably, the ratio of the amount of vinyl species to the amount of chain extender species in the vinyl polysiloxane is(0.1-0.3):1。
Preferably, the vinyl polysiloxane is added for reaction after the temperature is raised, the vinyl polysiloxane is added after the temperature is raised to 78-85 ℃, and then the reaction is carried out for 1-5 hours at 78-85 ℃.
The radical initiator is not particularly limited, and may be one or more of azobisisobutyronitrile, azobisisoheptonitrile, azobisisobutyronitrile formamide, benzoyl peroxide t-butyl peroxide, benzoyl peroxide t-amyl peroxide, and t-butyl peroxymaleate. Preferably, the mass ratio of the free radical initiator to the (methyl) acrylate is (0.2-0.4): (6-12).
The neutralization is not particularly limited, and common alkalescent substances including triethylamine, ammonia water and the like are adopted for neutralization, and the specific dosage is not particularly limited.
Preferably, the stirring speed of the water for dispersion and emulsification is 1500-2000 r/min, self-emulsification dispersion is realized through high-speed shearing stirring, and the stability of the emulsion is improved.
In the operation of adding the chain extender 2 for secondary reaction, the chain extender 2 is preferably selected from ethylenediamine, diethylenetriamine and triethylenetetramine, and the mass of the chain extender 2 is 3-8% of that of the polyisocyanate. Removal of the solvent after completion of the reaction, including removal of the solvent added in the preparation process by distillation, is a routine operation in the art.
The solid content of the waterborne polyurethane resin prepared by the invention is 42-72%, and the viscosity at 25 ℃ is 80-2000 mpa.s.
The waterborne polyurethane coating comprises the following components in parts by weight: 70-85 parts of waterborne polyurethane resin, 0.1-0.3 part of defoaming agent, 3-5 parts of film-forming additive, 0.1-0.3 part of wetting agent, 0.2-0.5 part of thickening agent and 8-12 parts of water.
The specific kinds of the defoaming agent, the film-forming aid, the wetting agent and the thickener are not particularly limited. When in use, the components are uniformly mixed and then coated.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the vinyl polysiloxane is adopted to modify the waterborne polyurethane, so that the product has excellent temperature resistance, heat resistance, high light transmittance, wear resistance and the like.
2. According to the invention, the modified chain extender with the side group containing carbon-carbon double bond is combined with the unsaturated polyester polyol, so that the polymerization grafting rate of the vinyl polysiloxane is effectively improved;
3. the prepared waterborne polyurethane resin emulsion has good stability, no phenomena of floating oil, gel, phase separation and the like after being placed for 6 months, and the prepared coating does not contain toxic solvent, is environment-friendly, does not self-ignite, is convenient and fast to construct and has excellent comprehensive performance.
Detailed Description
Example 1
The preparation method of the modified chain extender comprises the following steps:
accurately weighing 400g of glycidyl methacrylate, 4.5g of tetrabutylammonium bromide and 0.03g of hydroquinone in a four-neck flask with a reflux device, heating to 120 ℃ while stirring, dropwise adding 270g of dimethylolpropionic acid and 300g of a mixed solution of N, N-dimethylformamide, continuing to keep the temperature of 120 ℃ for reaction for 9 hours after 1 hour of dropwise adding is completed, heating to 160 ℃, removing N, N-dimethylformamide, a catalyst tetrabutylammonium bromide and residual low-molecular monomers by reduced pressure distillation, cooling to room temperature, and filtering to obtain the modified chain extender.
The unsaturated polyester polyol was prepared as follows:
adding 1mol of itaconic acid and 1.2mol of 1, 4-butanediol into a four-neck flask, adding 1.5g of stannous chloride and 0.5g of hydroquinone, heating to 160 ℃ for esterification reaction for 3 hours, heating to 180 ℃ under a vacuum condition for polycondensation reaction for 3 hours to obtain unsaturated polyester polyol, and testing the number average molecular weight of the unsaturated polyester polyol to be 2680 and the hydroxyl value to be 58mgKOH/g according to GB/T7193 plus 2003.
Example 2
The preparation method of the waterborne polyurethane resin comprises the following steps:
75g of the unsaturated polyester polyol prepared in example 1, 100g of polyester polyol (adipic acid, ethylene glycol, diethylene glycol-based polyester polyol, type PE-1280S, hydroxyl number 79-86, molecular weight 1200, Zhejiang Huafeng New Material Strand)Parts of Co., Ltd.), 40g of polyethylene glycol diacrylate (molecular weight 200, from Engguan city, Eng diligent industries Co., Ltd.) were dehydrated by vacuum pumping, 150g of TDI and 60g of acetone were added and reacted at 65 ℃ for 2 hours, the NCO content was measured by sampling and was 2.82g/100g (the NCO content was measured according to GB/T29493.6-2013), a mixture of 15g of dimethylolpropionic acid and 30g of N, N-dimethylformamide and 20g of the modified chain extender prepared in example 1 were added dropwise and the reaction was completed within 0.5 hour, and the reaction was carried out for 1.5 hours, 2.5g of AIBN was added and the temperature was raised to 80 ℃, and 25g of vinyl silicone oil (vinyl content 3.1% and kinematic viscosity 100 mm) was slowly added dropwise2And/s, from Anhui Aizhita silicone oil Co., Ltd.), finishing the dripping within 0.5 hour, carrying out heat preservation reaction for 2 hours, adding 13g of triethylamine, carrying out neutralization reaction for 30 minutes, then cooling to room temperature, raising the stirring speed to 1500r/min, dripping 500g of deionized water, continuing adding 8g of ethylenediamine after finishing the dripping, carrying out stirring reaction for 0.5 hour, heating to 65 ℃, carrying out reduced pressure distillation to remove acetone, cooling, and filtering to obtain the waterborne polyurethane resin.
Example 3
The preparation method of the waterborne polyurethane resin comprises the following steps:
60g of the unsaturated polyester polyol prepared in example 1, 120g of the saturated polyester polyol (polyester polyol based on adipic acid, diethylene glycol and 1, 4-butanediol, PE-2348, hydroxyl value of 45-50, molecular weight of 2350, New Material Ltd. Zhejiang Huafeng), 60g of polyethylene glycol (400) diacrylate (from diligent, Utility Co., Ltd. of Dongguan) were dehydrated under vacuum at 110 ℃ for 2 hours, cooled to room temperature, 180g of diphenylmethane diisocyanate (MDI) and 120g of acetone were added, the temperature was raised to 68 ℃ to react for 1.5 hours, the NCO content was measured by sampling and was 3.1g/100g (GB/T29493.6-2013 for NCO content determination), 17g of a mixture of dimethylolpropionic acid and 35g of N, N-dimethylformamide and 25g of the modified chain extender prepared in example 1 were added dropwise, dripping within 0.5 h, reacting for 1.5 h while maintaining the temperature, adding 3g AIBN, heating to 80 deg.C, slowly dripping 35g phenyl vinyl silicone oil (IOTA252, phenyl content 2.3%, vinyl content 1.6%, kinematic viscosity 1000 mm)2S from Anhui Aiyuta Silicone oil Co., Ltd.) within 0.5 hr, reacting for 2 hr under heat preservation, adding 15g triethylamine, and neutralizingAnd reacting for 35 minutes, cooling to room temperature, raising the stirring speed to 1800r/min, simultaneously dripping 540g of deionized water, continuously adding 8g of ethylenediamine after the dripping is finished, stirring and reacting for 0.5 hour, heating to 65 ℃, distilling under reduced pressure to remove acetone, cooling, and filtering to obtain the waterborne polyurethane resin.
Example 4
The preparation method of the waterborne polyurethane resin comprises the following steps:
95g of the unsaturated polyester polyol prepared in example 1, 120g of saturated polyester polyol (polyester polyol based on adipic acid, 1, 4-butanediol and ethylene glycol, PE-1320, hydroxyl value of 53-59, molecular weight of 2180 and available from New Material Ltd. of Zhejiang Huafeng), 35g of 1, 6-hexanediol diacrylate were mixed, vacuum dewatered for 2 hours, 220g of phenyl polymethylene polyisocyanate (PAPI) and 50g of acetone were added, the temperature was raised to 72 ℃ and the reaction was carried out for 1.5 hours, the NCO content was 3.5g/100g (for NCO content measurement, GB/T29493.6-2013) was sampled and detected, a mixture of 24g of dimethylolpropionic acid and 40g N, N-dimethylpyrrolidone and 25g of the modified chain extender prepared in example 1 were added dropwise thereto, the dropping was completed within 0.5 hours, the reaction was carried out with heat preservation for 1.5 hours, adding 3g AIBN, heating to 80 deg.C, slowly dropping 55g phenyl vinyl silicone oil (IOTA252, phenyl content 2.1%, vinyl content 1.5%, kinematic viscosity 1000 mm)2And/s, Anhui Eyota silicone oil Co., Ltd.) within 0.5 hour, carrying out heat preservation reaction for 2 hours, adding 21g of triethylamine, carrying out neutralization reaction for 35 minutes, cooling to room temperature, raising the stirring speed to 1800r/min, slowly adding 320g of deionized water dropwise, continuing adding 12g of ethylenediamine after dropwise addition is finished, carrying out stirring reaction for 1 hour, heating to 65 ℃, carrying out reduced pressure distillation to remove acetone, cooling, and filtering to obtain the waterborne polyurethane resin.
Example 5
The preparation method of the modified chain extender comprises the following steps:
accurately weighing 400g of allyl glycidyl ether, 45g of tetrabutylammonium bromide and 0.3g of hydroquinone in a four-neck flask with a reflux device, heating to 120 ℃ while stirring, starting to dropwise add 270g of dimethylolpropionic acid and 300g N, N-dimethylformamide mixed solution, continuing to perform heat preservation reaction for 9 hours after 1 hour of dropwise addition is completed, heating to 160 ℃, removing N, N-dimethylformamide, catalyst tetrabutylammonium bromide and residual low molecular monomers by reduced pressure distillation, cooling to room temperature, and filtering to obtain the modified chain extender.
The preparation method of the waterborne polyurethane resin comprises the following steps:
75g of the unsaturated polyester polyol prepared in example 1, 100g of polyester polyol (polyester polyol based on adipic acid, ethylene glycol and diethylene glycol, model PE-1280S, hydroxyl value of 79-86, molecular weight of 1200, Zhejiang Huafeng New Material Co., Ltd.), 40g of polyethylene glycol diacrylate (molecular weight of 200, from diligent practical Co., Ltd. of Dongguan), vacuum dehydration, addition of 150g of TDI and 60g of acetone, heating to 65 ℃ for reaction for 2 hours, sampling to detect the NCO content of 2.82g/100g (the NCO content is measured according to GB/T29493.6-2013), dropwise addition of a mixed solution of 15g of dimethylolpropionic acid and 30g N and N-dimethylformamide and 20g of the modified chain extender prepared in the example, dropwise addition within 0.5 hours, heat preservation for reaction for 1.5 hours, addition of 2.5g of AIBN, heating to 80 ℃, slowly dropwise adding 25g of phenyl vinyl silicone oil (IOTA252, phenyl content is 4.4%, vinyl content is 3.1%, kinematic viscosity is 100 mm)2And/s, from Anhui Aizhita silicone oil Co., Ltd.), finishing the dripping within 0.5 hour, carrying out heat preservation reaction for 2 hours, adding 13g of triethylamine, carrying out neutralization reaction for 30 minutes, then cooling to room temperature, raising the stirring speed to 1500r/min, dripping 500g of deionized water, continuing adding 8g of ethylenediamine after finishing the dripping, carrying out stirring reaction for 0.5 hour, heating to 65 ℃, carrying out reduced pressure distillation to remove acetone, cooling, and filtering to obtain the waterborne polyurethane resin.
Application examples
1-4# aqueous polyurethane coating is prepared from the aqueous polyurethane resin (resin for short) prepared in examples 2-5, and the dosage of each component is as follows: 80g of resin, 0.2g of defoaming agent, 4g of film forming additive, 0.3g of wetting agent, 0.3g of thickening agent and 15.2g of deionized water, wherein the defoaming agent is TEGO-810, the film forming additive is dipropylene glycol butyl ether (DPNB), the wetting agent is TEGO-245 and the thickening agent is PUR40, and the waterborne polyurethane coating is obtained by uniformly mixing the components.
Test examples
The aqueous polyurethane resins prepared in examples 2 to 5 were subjected to a performance test comprising:
1. solid content and viscosity: the solid content is tested according to GB/T8077-.
2. Storage stability: 150g of waterborne polyurethane resin is filled into a closed conical flask, the flask is transferred into a baking oven with the temperature of 50 +/-2 ℃, and the flask is taken out after 30 days to observe the appearance state.
The performance test is carried out on the 1-4# waterborne polyurethane coating, and the specific steps are as follows:
uniformly spraying 50g of waterborne polyurethane coating on a blank woodware test board with the specification of 40 × 20cm, drying for 8 hours at room temperature, then polishing with 600-plus 800-mesh abrasive paper until the surface of a paint film is smooth and flat, continuously spraying the waterborne polyurethane coating with the same mass for the second time, drying for 7 days at room temperature to obtain a sample plate with the paint film coating, and carrying out performance test, wherein the test method comprises the following steps:
heat resistance: and (3) flatly placing a 250ml glass cup on the paint film coating of the sample plate, filling the glass cup with boiling water, removing the glass cup after the boiling water is cooled to room temperature, observing the damage condition of the paint film coating, and testing to pass if no dent is formed on the paint film coating, or else, testing to fail.
Hardness: reference is made to ISO 15184.
Gloss: reference is made to GB/T4893.6-2013.
Wear resistance: reference is made to GB/T1768-.
The test results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the waterborne polyurethane resin disclosed by the invention has good storage stability, and a coating obtained from the waterborne polyurethane coating prepared from the waterborne polyurethane resin has good heat resistance, environmental friendliness, a simple preparation method and a good application prospect.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (9)
1. An aqueous polyurethane resin, characterized by being prepared by a method comprising the steps of:
mixing unsaturated polyester polyol, saturated polyester polyol, (meth) acrylate, polyisocyanate and a solvent, reacting, adding a chain extender, a cosolvent, a modified chain extender and a free radical initiator, heating, adding vinyl polysiloxane for reaction, neutralizing, cooling after the reaction is finished, adding water for dispersion and emulsification, adding a chain extender 2 for secondary reaction, and removing the solvent after the reaction is finished to obtain the waterborne polyurethane resin; the modified chain extender is obtained by reacting an alkenyl compound containing an epoxy group with hydroxycarboxylic acid.
2. The aqueous polyurethane resin according to claim 1, wherein the unsaturated polyester polyol is prepared by reacting an unsaturated polybasic acid with a polyhydric alcohol, wherein the unsaturated polybasic acid is itaconic acid, fumaric acid, glutaconic acid or maleic anhydride; the polyhydric alcohol is preferably one or more of neopentyl glycol, 1, 4-butanediol, diethylene glycol, ethylene glycol and trimethylolpropane, and the molar ratio of the unsaturated polybasic acid to the polyhydric alcohol is 1: (1.2-1.5).
3. The aqueous polyurethane resin according to claim 1, wherein the unsaturated polyester polyol: saturated polyester polyol: the mass ratio of the polyisocyanate is (5-10): (8-15): (12-25).
4. The aqueous polyurethane resin according to claim 3, wherein the mass ratio of the (meth) acrylate to the polyisocyanate is (3 to 7): (12-25).
5. The aqueous polyurethane resin according to claim 4, wherein the unsaturated polyester polyol, the saturated polyester polyol, the (meth) acrylic ester, the polyisocyanate and the solvent are mixed and reacted until the NCO content is 2.0g to 4.0g/100 g.
6. The aqueous polyurethane resin according to any one of claims 1 to 5, wherein the modified chain extender is prepared by a ring-opening reaction of an epoxy group-containing alkenyl compound and a hydroxycarboxylic acid, the alkenyl group is a group capable of undergoing a radical polymerization reaction, and the ratio of the amounts of the substances of the chain extender and the modified chain extender is (0.60-2.2): 1.
7. The aqueous polyurethane resin according to claim 6, wherein the ratio of the amount of the substance of the modified chain extender to the amount of the substance of the polyisocyanate is (0.05-0.15): 1.
8. The aqueous polyurethane resin according to any one of claims 1 to 5, wherein the vinyl polysiloxane is a linear organopolysiloxane containing a silicon-bonded vinyl group at one or both ends of the molecule, and the ratio of the amount of the vinyl group substance of the vinyl polysiloxane to the amount of the chain extender substance is (0.1-0.30): 1.
9. The waterborne polyurethane coating comprises the following components in parts by weight: 70-85 parts of the aqueous polyurethane resin according to any one of claims 1-5, 0.1-0.3 part of a defoaming agent, 3-5 parts of a film-forming aid, 0.1-0.3 part of a wetting agent, 0.2-0.5 part of a thickener and 8-12 parts of water.
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