CN115838451A - Bio-based hydroxyl polyacrylate dispersion and preparation method and application thereof - Google Patents
Bio-based hydroxyl polyacrylate dispersion and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of coatings, and discloses a bio-based hydroxyl polyacrylate dispersoid and a preparation method and application thereof. The raw material components used by the preparation method comprise acrylic monomers, acrylate monomers, vinyl-containing monomers and bio-based chain extenders; the bio-based chain extender is vegetable oil containing more than three epoxy groups, and the bio-based chain extender participates in the reaction at the temperature of more than 140 ℃ to prepare the bio-based hydroxyl polyacrylate dispersoid. The bio-based hydroxyl polyacrylate dispersoid has a solid content of more than 45 percent according to mass fraction. The bio-based hydroxyl polyacrylate dispersoid is applied to a two-component polyurethane coating, so that the physical properties of a paint film formed by the coating, such as chemical resistance and water resistance, are improved. Vegetable oil containing more than three epoxy groups is used as a bio-based chain extender to participate in the reaction, so that a product with a high molecular weight and a branched structure can be obtained, the generation of a product with a net structure can be promoted, and the drying speed of a paint film is improved.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a bio-based hydroxyl polyacrylate dispersoid and a preparation method and application thereof.
Background
The coating is coated on the surface of an object, and can play a role in protecting, decorating or other functions for the object. Most of the existing wood coatings are solvent-based coatings (also called oil-based coatings), which contain more than 50% of organic solvents, the solvents can volatilize into the atmosphere during the construction process to pollute the environment and damage the human health, and the organic solvents can bring about potential safety hazards. Therefore, the water-based woodware coating is a trend of international coating development. The water-borne wood coatings comprise single-component and double-component water-borne wood coatings. Wherein, the difference between the paint film performances of the single-component waterborne wood coating, such as water resistance, chemical resistance, hardness and the like, and the oily coating is large, thereby seriously limiting the popularization and the application of the waterborne wood coating. The mechanical property, water resistance and chemical resistance of the double-component aqueous woodenware coating are equivalent to those of an oily coating, and the defects of a single-component aqueous woodenware coating are overcome.
The two-component waterborne polyurethane coating has excellent coating performance and is widely researched and applied, and the two-component waterborne polyurethane coating consists of waterborne polymer polyol and waterborne polyisocyanate curing agent, is packaged separately and is mixed in proportion when in use. The aqueous polymer polyols include aqueous polyacrylate polyols, aqueous polyurethane polyols, aqueous polyester polyols and polyether polyols and mixed polyols. The waterborne polyacrylate polyol has the advantages of excellent color retention, gloss retention and weather resistance, low price, easiness in adjustment of molecular weight, glass transition temperature and hydroxyl content and the like, and is the first choice for waterborne polymer polyol in the existing two-component waterborne polyurethane coating. Two types of polyacrylate polyols, emulsion and dispersion, can be prepared using different polymerization processes. The emulsion type polyacrylate polyol has simple production process and low cost, but has the problems of low hydroxyl content, poor transparency, poor leveling property, poor chemical resistance, low hardness and the like of a paint film prepared by mixing the emulsion type polyacrylate polyol with a water-based polyisocyanate curing agent. In contrast, the hydroxyl content of the dispersion type polyacrylate polyol is higher, and a paint film prepared by mixing the dispersion type polyacrylate polyol with the water-based polyisocyanate curing agent is high in transparency and good in leveling property, and has excellent water resistance and chemical resistance, so that the dispersion type polyacrylate polyol has a larger development space in the future.
The dispersion type polyacrylate polyol is also called hydroxyl polyacrylate dispersion, and is called hydroxypropyl dispersion for short. The existing hydroxyl polyacrylate dispersoid still has the problems of low solid content, poor storage stability, poor appearance of milky appearance, poor water resistance, poor chemical resistance and the like, and a paint film prepared by mixing the hydroxyl polyacrylate dispersoid with a water-based polyisocyanate curing agent has the problems of slow drying speed, low hardness and the like, so the main reasons for causing the problems are that the polymer macromolecules of the hydroxyl polyacrylate dispersoid are in a linear structure and have small molecular weight. When the molecular weight of the polymer is increased by adjusting the addition amount of an initiator or a chain transfer agent and the like by adopting a conventional synthesis process, the viscosity of the hydroxyl polyacrylate dispersion prepolymer can be obviously increased, the dispersion by adding water is not facilitated, and the prepolymer gel appears in serious cases.
In addition, petroleum-based hydroxyl polyacrylate dispersoids are mostly used in the market to prepare the double-component waterborne polyurethane coating, which is not favorable for environmental protection.
Accordingly, there is a need to provide a new hydroxy polyacrylate dispersion.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a bio-based hydroxyl polyacrylate dispersion and a preparation method and application thereof, the bio-based hydroxyl polyacrylate dispersion is applied to a two-component polyurethane coating, and a formed paint film has good water resistance, chemical resistance, high hardness and high drying speed.
The invention conception of the invention is as follows: the raw material components for preparing the bio-based hydroxyl polyacrylate dispersion comprise an acrylic monomer, an acrylate monomer, a vinyl-containing monomer and a bio-based chain extender, wherein the bio-based chain extender is vegetable oil containing more than three epoxy groups. The bio-based chain extender is added before the prepolymer is dispersed, so that the viscosity of the hydroxyl polyacrylate prepolymer can be reduced, and the dispersing effect of the bio-based hydroxyl polyacrylate prepolymer is improved. The bio-based chain extender participates in the reaction at the high temperature of more than 140 ℃, the epoxy group in the bio-based chain extender and the carboxyl group of the hydroxyl polyacrylate prepolymer generate a ring opening reaction, the prepolymer realizes chain extension in latex particles to generate hydroxyl, the storage stability of the dispersion is improved, and the bio-based hydroxyl polyacrylate dispersion is applied to the two-component polyurethane coating to improve the physical properties of a paint film, such as chemical resistance and water resistance. Moreover, vegetable oil containing more than three epoxy groups is used as a bio-based chain extender to participate in the reaction, so that a product with a high molecular weight and a branched structure can be obtained, namely, the generation of a product with a net structure can be promoted, and the drying speed of a paint film is improved.
The preparation method of the bio-based hydroxyl polyacrylate dispersoid relates to a pre-polymer of the bio-based hydroxyl polyacrylate dispersoid in a reaction process, the pre-polymer is dispersed under low viscosity, each latex particle becomes a micro-reactor, and the chain extension reaction carried out by the bio-based chain extender is carried out in the latex particle, so that the stability of the dispersion process is ensured, the storage stability of the bio-based hydroxyl polyacrylate dispersoid is also ensured, and the obtained bio-based hydroxyl polyacrylate dispersoid has high solid content and good appearance.
The invention also provides a two-component polyurethane coating, a paint film prepared by mixing the bio-based hydroxyl polyacrylate dispersoid and the water-based polyisocyanate curing agent is quick to dry and high in hardness, and the obtained water-based two-component polyurethane paint film has the advantages of high gloss, high transparency, excellent water resistance and chemical resistance, high crosslinking density, high hardness, scratch resistance, wear resistance and the like, and can be applied to high-grade wood coatings, automobile coatings, metal anticorrosive coatings and other industrial protective coatings.
The first aspect of the invention provides a preparation method of a bio-based hydroxy polyacrylate dispersion.
Specifically, the raw material components used in the preparation method comprise acrylic monomers, acrylate monomers, monomers containing vinyl and bio-based chain extenders;
the bio-based chain extender is vegetable oil containing more than three epoxy groups, and the bio-based chain extender participates in the reaction at the temperature of more than 140 ℃ to prepare the bio-based hydroxyl polyacrylate dispersoid.
Preferably, the raw material components used in the preparation method further comprise an initiator, a reactive diluent, a neutralizing agent and water.
Preferably, the preparation method comprises the following steps:
mixing the acrylic monomer, the acrylate monomer, the monomer containing vinyl and the initiator to form a mixed solution;
heating the active diluent to 135-155 ℃, then dripping the mixed solution, stirring, preserving heat, then cooling to 70-85 ℃, adding the bio-based chain extender, the neutralizer and the water, dispersing, and then reacting at the temperature of more than 160 ℃ for 40-80 minutes to prepare the bio-based hydroxyl polyacrylate dispersoid.
Preferably, the bio-based chain extender is added and then reacted for 45 to 75 minutes at 160 to 175 ℃.
Preferably, the acrylic monomer is selected from at least one of acrylic acid or methacrylic acid.
Preferably, the acrylate monomer comprises a hydroxyl acrylate monomer and at least one of methyl methacrylate, butyl acrylate, isobornyl acrylate, cyclohexyl methacrylate or benzyl methacrylate.
Preferably, the hydroxy acrylate monomer is selected from at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
Preferably, the vinyl-containing monomer comprises styrene.
Preferably, the initiator is selected from at least one of di-tert-amyl hydroperoxide or di-tert-butyl hydroperoxide.
Preferably, the reactive diluent is a material containing one epoxy group and no double bond. The double-bond-free reactive diluent is added into a reaction container by a primer solution, and the double bond-free reactive diluent ensures that the reactive diluent does not react at the temperature of about 150 ℃ and does not have free radical polymerization reaction with an acrylate monomer. The prior free radical polymerization takes a solvent as a base solution to enable substances in a reaction container to be normally stirred and react, the epoxy-containing reactive diluent is taken as the base solution and can gradually react with carboxyl on a main chain of a hydroxyl polyacrylate polymer to finally realize solvent-free polymerization, and the reactive diluent only contains one epoxy group, so that the prepolymer is ensured not to form a cross-linked structure in a prepolymerization stage, and the dispersion of the prepolymer is facilitated.
Preferably, the reactive diluent is selected from at least one of glycidyl versatate, glycidyl 4-tert-butylbenzoate or glycidyl p-toluenesulfonate.
Preferably, the bio-based chain extender is selected from at least one of epoxidized soybean oil or epoxidized linseed oil.
More preferably, the bio-based chain extender is GreenSoft D special epoxidized soybean oil, greenSoft H special epoxidized soybean oil and epoxidized linseed oil ELO of Xingbang high polymer materials Co
9-5 TM.
Preferably, the neutralizing agent is a tertiary amine substance; further preferably, the neutralizing agent is at least one selected from triethylamine, N-dimethylethanolamine or N, N-dimethylcyclohexylamine.
Preferably, the preparation method comprises the following steps:
uniformly mixing 10-28 parts of acrylic monomers, 30-58 parts of acrylate monomers, 12-25 parts of vinyl-containing monomers and 1-3.5 parts of initiators by mass to form a mixed solution;
heating 20-40 parts of active diluent to 135-155 ℃, dripping the mixed solution at a constant pressure within 2-5 hours, stirring and keeping the temperature for 20-40 minutes after dripping, cooling to 70-85 ℃, adding 8-25 parts of bio-based chain extender and 3.0-5.3 parts of neutralizer, adding 135-150 parts of water for dispersing for 3-5 minutes after stirring for 3-5 minutes, transferring to a reaction kettle, pressurizing to 2-2.5MPa, heating to 160-185 ℃, reacting for 40-85 minutes, stopping the reaction after the epoxy value of the product is less than 0.005 determined by a hydrochloric acid-acetone method, cooling to below 40 ℃, decompressing, filtering and discharging to obtain the bio-based hydroxyl polyacrylate dispersion.
Further preferably, the preparation method comprises the following steps:
uniformly mixing 15-22 parts of acrylic monomers, 34-53 parts of acrylate monomers, 15-20 parts of vinyl-containing monomers and 1.5-2.5 parts of initiators by mass to form a mixed solution;
heating 25-31 parts by mass of reactive diluent to 140-150 ℃, dripping the mixed solution at a constant pressure within 4-5 hours, stirring and preserving heat for 20-30 minutes after dripping, cooling to 75-80 ℃, adding 10-20 parts by mass of bio-based chain extender and 3.2-4.3 parts by mass of neutralizer, stirring for 3-5 minutes, adding 135-150 parts by mass of water for dispersing for 3-5 minutes, transferring to a high-pressure reaction kettle, pressurizing to 2-2.5MPa, heating to 160-175 ℃, reacting for 45-75 minutes, stopping the reaction after the epoxy value is less than 0.005 determined by a hydrochloric acid-acetone method, cooling to below 40 ℃, relieving pressure, filtering and discharging to obtain the bio-based hydroxyl polyacrylate dispersion.
Preferably, the 34-53 parts of acrylate monomers comprise 9-20 parts of hydroxyl acrylate monomers.
A bio-based hydroxy polyacrylate dispersion prepolymer is produced in the system prior to the addition of the bio-based chain extender. According to the invention, the bio-based chain extender is added before the hydroxyl polyacrylate dispersoid prepolymer is dispersed, and the bio-based chain extender can play a role of viscosity reduction so that the hydroxyl polyacrylate dispersoid prepolymer is dispersed at low viscosity, thereby avoiding the problem that the prepolymer is high in viscosity and difficult to disperse when the molecular weight of the polymer is too large. Meanwhile, each dispersed latex particle becomes a micro-reactor, and the post-chain extension reaction is carried out in the latex particle, so that the stability of the dispersing process is ensured, the storage stability of the bio-based hydroxyl polyacrylate dispersion is also ensured, and the problems of low solid content, poor milky appearance and poor appearance of the hydroxyl polyacrylate dispersion, slow drying speed, low hardness and the like of a paint film prepared by mixing the hydroxyl polyacrylate dispersion with a water-based polyisocyanate curing agent are solved.
In a second aspect of the invention, a bio-based hydroxy polyacrylate dispersion is provided.
In particular to a bio-based hydroxyl polyacrylate dispersoid which is prepared by the preparation method.
Preferably, the bio-based content of the bio-based hydroxyl polyacrylate dispersion is more than or equal to 5 percent;
preferably, the pH of the bio-based hydroxy polyacrylate dispersion is 7.5-8, and the alkalescence is favorable for improving the storage stability of the dispersion.
Preferably, the particle size of the bio-based hydroxy polyacrylate dispersion is < 110nm. The appearance of the dispersion can be made semi-permeable.
Preferably, the bio-based hydroxy polyacrylate dispersion has a solid content of more than 45%, preferably 45-48%, in terms of mass fraction. Higher than 40% of the solid content of the mainstream products in the market.
Preferably, the hydroxyl content of the bio-based hydroxyl polyacrylate dispersion is 3.6-4.5% by mass. Belongs to a product with high hydroxyl content, and is beneficial to improving the water resistance, medium resistance and the like of a bio-based bi-component waterborne polyurethane paint film.
In a third aspect of the invention, a two-component polyurethane coating is provided.
Specifically, the two-component polyurethane coating comprises an agent A and an agent B;
the agent A comprises the bio-based hydroxyl polyacrylate dispersion;
the agent B comprises a water-based polyisocyanate curing agent;
the molar ratio of NCO in the agent B to OH in the agent A is 1.0-2.0.
Preferably, the molar ratio of NCO in the agent B to OH in the agent A is 1.0-1.8.
Preferably, the two-component polyurethane coating comprises an agent A and an agent B;
the agent A comprises the following components in parts by weight:
the agent B comprises 20-30 parts of a water-based polyisocyanate curing agent.
Preferably, the two-component polyurethane coating comprises an agent A and an agent B;
the agent A comprises the following components in parts by weight:
the agent B comprises 20-30 parts of a water-based polyisocyanate curing agent.
Preferably, the film-forming assistant is at least one of propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether or dipropylene glycol butyl ether.
Preferably, the defoaming agent is at least one of TEGO-800, TEGO-805, TEGO-815, TEGO-825 or BYK-020 modified polysiloxane copolymer solution.
Preferably, the thickener is at least one of nonionic polyurethane associative thickener RM-8W of DOW company, hydrophobically modified alkali swelling associative thickener TT-935, alkali swelling non-associative thickener ASE-60 and nonionic associative thickener TEGO Visco plus 3000, TEGO Visco plus 3030 and TEGO Visco plus 3060 of TEGO company.
Preferably, the wetting agent is at least one of a polyether siloxane copolymer TEGO-245 from TEGO, a nonionic organic surfactant TEGO-500 or a polyether modified polysiloxane solution BYK-346 from BYK.
Preferably, the neutralizing agent is at least one of triethylamine, dimethylethanolamine and triethanolamine.
Preferably, the aqueous polyisocyanate curing agent includes at least one of sulfonate, carboxylate and alkoxy hydrophilic modified Hexamethylene Diisocyanate (HDI).
More preferably, the aqueous polyisocyanate curing agent is at least one of Bayhydur XP 2487/1 and Bayhydur XP 2655 of Corseus.
A preparation method of a two-component polyurethane coating comprises the following steps:
premixing water and a film-forming auxiliary agent, adding the bio-based hydroxyl polyacrylate dispersoid, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent, dispersing for 10-30 minutes, and filtering to obtain an agent A;
the agent B comprises a water-based polyisocyanate curing agent;
the two-component polyurethane coating is prepared.
When the two-component polyurethane coating is constructed, the agent B is added into the agent A, and the mixture is stirred for 5 to 8 minutes, so that the construction can be carried out.
The two-component polyurethane coating is applied to the field of wood ware, automobiles or metal corrosion prevention.
Compared with the prior art, the invention has the following beneficial effects:
(1) The raw material components for preparing the bio-based hydroxyl polyacrylate dispersion comprise an acrylic monomer, an acrylate monomer, a vinyl-containing monomer and a bio-based chain extender, wherein the bio-based chain extender is vegetable oil containing more than three epoxy groups. The bio-based chain extender is added before the prepolymer is dispersed, so that the viscosity of the hydroxyl polyacrylate prepolymer can be reduced, and the dispersing effect of the bio-based hydroxyl polyacrylate prepolymer is further improved. The bio-based chain extender participates in the reaction at the high temperature of more than 140 ℃, the epoxy group in the bio-based chain extender and the carboxyl group of the hydroxyl polyacrylate prepolymer generate a ring opening reaction, the prepolymer realizes chain extension in latex particles to generate hydroxyl, the storage stability of the dispersion is improved, and the bio-based hydroxyl polyacrylate dispersion is applied to the two-component polyurethane coating to improve the physical properties of a paint film, such as chemical resistance and water resistance. Moreover, vegetable oil containing more than three epoxy groups is used as a bio-based chain extender to participate in the reaction, so that a product with a high molecular weight and a branched structure can be obtained, namely, the generation of a product with a net structure can be promoted, and the drying speed of a paint film is improved.
(2) The bio-based hydroxyl polyacrylate dispersoid has the characteristics of large molecular weight, branched structure, good storage stability, good appearance and high solid content; the preparation method of the bio-based hydroxyl polyacrylate dispersoid has the advantages of simplicity in operation, easiness in control and low cost, and can be used for preparing the bio-based hydroxyl polyacrylate dispersoid in batches.
Detailed Description
In order to make the technical solutions of the present invention more clearly apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
The bio-based chain extenders used in the following examples are GreenSoft D Special epoxidized soybean oil, greenSoft H Special epoxidized soybean oil, epoxidized linseed oil ELO from Xingbang high molecular materials Co
9-5 TM.
The defoaming agent is TEGO-800, TEGO-805, TEGO-815, TEGO-825 or BYK-020 modified polysiloxane copolymer solution.
The thickener is nonionic polyurethane associative thickener RM-8W of DOW company, hydrophobic modified alkali swelling associative thickener TT-935, alkali swelling associative thickener ASE-60, nonionic associative thickener TEGO Visco plus 3000, TEGO Visco plus 3030 and TEGO Visco plus 3060 of TEGO company.
The wetting agent is a polyether siloxane copolymer TEGO-245 from TEGO company, a nonionic organic surfactant TEGO-500 or a polyether modified polysiloxane solution BYK-346 from BYK company.
The water-based polyisocyanate curing agent is Bayhydur XP 2487/1 or Bayhydur XP 2655 of Corseus.
The basic performance tests include: the bio-based hydroxyl polyacrylate dispersoid is tested according to GB/T11175-2002 synthetic resin emulsion test method, and the appearance, pH, solid content and viscosity of the bio-based hydroxyl polyacrylate dispersoid are tested. The average particle size of the biobased hydroxy polyacrylate dispersion was determined using a nanometer particle size analyzer (ZS Nano S).
The performance of a paint film formed by the double-component polyurethane paint is tested according to GB/T23999-2009 waterborne wood paint for indoor decoration, and the gloss, hardness, water resistance, dry heat resistance and alcohol resistance of the paint film are tested.
Example 1: preparation of bio-based hydroxyl polyacrylate dispersoid and two-component polyurethane coating
A preparation method of bio-based hydroxyl polyacrylate dispersion 1 comprises the following steps:
(1) Uniformly mixing 16.3 parts of acrylic acid, 12.7 parts of methyl methacrylate, 20 parts of styrene, 8.7 parts of butyl acrylate, 10.7 parts of hydroxyethyl methacrylate, 10.6 parts of isobornyl acrylate and 1.5 parts of di-tert-amyl peroxide in parts by mass to form a mixed solution;
(2) Adding 30 parts of tertiary carboxylic acid glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant-pressure dropping funnel, mixing, stirring and heating, starting to dropwise add the mixed solution prepared in the step (1) when the temperature reaches 145 ℃, completing dropwise addition for 4 hours, stirring and preserving heat for 30 minutes after completing dropwise addition, cooling to 80 ℃, adding 15 parts of GreenSoft D special epoxy soybean oil and 4.3 parts of N, N-dimethylcyclohexylamine, stirring for 5 minutes, adding 150 parts of deionized water, dispersing at high speed for 3 minutes (the rotating speed of high-speed dispersion is 1000 revolutions per minute), transferring to a high-pressure reaction kettle, pressurizing to 2MPa, heating to 160 ℃, reacting for 60 minutes, stopping reaction after the epoxy value of a product is determined to be less than 0.005 by a hydrochloric acid-acetone method, cooling to below 40 ℃, decompressing, filtering and discharging to obtain the bio-based hydroxyl polyacrylate dispersoid 1.
The bio-based hydroxy polyacrylate dispersion 1 prepared in this example had a bio-based content of 11.6%, a semi-permeable appearance, a pH of 8, a hydroxy content of 3.6%, a solid content of 46.5%, a viscosity of 1350cp at 25 ℃, an average particle size of 98nm, and no change upon heat storage at 50 ℃ for 1 month.
A two-component polyurethane coating 1 comprises an agent A and an agent B;
the agent A comprises the following components in parts by weight:
the agent B comprises 22.5 parts of waterborne polyisocyanate curing agent (Bayhydur XP 2487/1).
The molar ratio of NCO in the agent B to OH in the agent A in the two-component polyurethane coating 1 is 1.8:1.
the preparation method of the A agent of the two-component polyurethane coating comprises the following steps: adding the bio-based hydroxyl polyacrylate dispersoid 1 into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing water, dipropylene glycol butyl ether and dipropylene glycol methyl ether, adding into the stirring kettle, sequentially adding TEGO-800, RM-8W, TEGO-245 and TEA (triethanolamine), dispersing for 20 minutes, filtering and discharging.
During construction, the agent B is added into the agent A, and stirring is carried out for 6 minutes, so that the two-component polyurethane coating 1 with the bio-based content of 6.1 percent is obtained.
A paint film prepared by using the two-component polyurethane coating 1 is cured and dried for 7 days at normal temperature, and the performances of the paint film are shown in Table 1:
table 1: combination of Properties of two-component polyurethane coating 1
Example 2: preparation of bio-based hydroxyl polyacrylate dispersoid and two-component polyurethane coating
A bio-based hydroxy polyacrylate dispersion 2 is prepared by the following steps:
(1) According to the mass parts, 21.7 parts of methacrylic acid, 10.7 parts of methyl methacrylate, 15.1 parts of styrene, 6 parts of butyl acrylate, 9.6 parts of hydroxyethyl acrylate, 9 parts of cyclohexyl methacrylate and 2 parts of di-tert-butyl peroxide are uniformly mixed to form a mixed solution for later use;
(2) Adding 31 parts of 4-tert-butyl benzoic acid glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant pressure dropping funnel, mixing, stirring and heating, starting to dropwise add the mixed solution prepared in the step (1) when the temperature reaches 140 ℃, completing dropwise addition within 4.5 hours, stirring and preserving heat for 30 minutes after completing dropwise addition, cooling to 75 ℃, adding 20 parts of GreenSoft H special epoxy soybean oil and 3.2 parts of triethylamine, stirring for 3 minutes, adding 139 parts of deionized water for high-speed dispersion for 5 minutes, transferring to a high-pressure reaction kettle, pressurizing to 2.2MPa, heating to 165 ℃, reacting for 75 minutes, determining that the epoxy value is less than 0.005 by using a hydrochloric acid-acetone method, and stopping the reaction; cooling to 40 ℃, filtering and discharging to obtain the bio-based hydroxyl polyacrylate dispersoid 2.
The bio-based hydroxy polyacrylate dispersoid 2 prepared in the example has the bio-based content of 15.6 percent, semi-permeable appearance, pH of 7.5, the hydroxy content of 4.0 percent, solid content of 48 percent, viscosity of 1550cp at 25 ℃, average particle size of 105nm and no change after being stored for 1 month at 50 ℃.
A two-component polyurethane coating 2 comprises an agent A and an agent B;
the agent A comprises the following components in parts by weight:
the agent B is 25 parts of water-based polyisocyanate curing agent (Bayhydur XP 2655);
the molar ratio of NCO in the agent B to OH in the agent A in the two-component polyurethane coating 2 is 1.8:1.
the preparation method of the agent A of the two-component polyurethane coating 2 comprises the following steps: adding the bio-based hydroxyl polyacrylate dispersoid 2 into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing water, dipropylene glycol butyl ether and dipropylene glycol methyl ether, adding into the stirring kettle, sequentially adding TEGO-805, TT-935, BYK-346 and DMEA, dispersing for 15 minutes, filtering and discharging.
During construction, the agent B is added into the agent A, and stirring is carried out for 7 minutes, so that the two-component polyurethane coating 2 with the bio-based content of 7.8 percent is obtained.
The paint film prepared from the two-component polyurethane paint 2 was cured and dried for 7 days at normal temperature, and the properties thereof are shown in table 2.
Table 2: combination of properties of two-component polyurethane coating 2
| Detecting items | Performance of | Detection method |
| Surface drying time/min | 32 | GB/T1728-2020 |
| Actual drying time/d | 3 | GB/T1728-2020 |
| Hardness of pencil | H | GB/T6739-2006 |
| Coating film gloss/(60 °,%) | 91 | GB/T9754-2007 |
| Water resistance (25 ℃,24 h) | 1, no change | GB/T4893.1-2020 |
| Resistant dry heat (70 +/-2 ℃,15 h) | 1, no change | GB/T4893.3-2020 |
| Resistance to ethanol (50%, 1 h) | 1, no change | GB/T4893.1-2020 |
Example 3: preparation of bio-based hydroxyl polyacrylate dispersoid and two-component polyurethane coating
A bio-based hydroxy polyacrylate dispersion 3 is prepared by the following steps:
(1) Uniformly mixing 15.8 parts of acrylic acid, 15 parts of methyl methacrylate, 15 parts of styrene, 5 parts of butyl acrylate, 20 parts of hydroxypropyl acrylate, 9.5 parts of benzyl methacrylate and 2.5 parts of di-tert-amyl peroxide by mass part to form a mixed solution for later use;
(2) Adding 25 parts of p-toluenesulfonic acid glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant-pressure dropping funnel, mixing, stirring and heating, starting to dropwise add the mixed solution prepared in the step (1) when the temperature reaches 150 ℃, completing dropwise addition within 5 hours, stirring and preserving heat for 20 minutes after completing dropwise addition, cooling to 75 ℃, adding 10 parts of epoxy linseed oil and 4.2 parts of N, N-dimethylethanolamine, stirring for 5 minutes, adding 150 parts of deionized water for high-speed dispersion for 5 minutes, transferring to a high-pressure reaction kettle, pressurizing to 2.5MPa, heating to 175 ℃, reacting for 45 minutes, determining that the epoxy value is less than 0.005 by using a hydrochloric acid-acetone method, and stopping the reaction; cooling to 40 ℃, filtering and discharging to obtain the bio-based hydroxyl polyacrylate dispersoid 3.
The bio-based hydroxyl polyacrylate dispersion 3 prepared in the example has a bio-based content of 8.2%, a semi-permeable appearance, a pH of 8, a hydroxyl content of 4.5%, a solid content of 45%, a viscosity of 1300cp at 25 ℃, an average particle size of 100nm, and no change after being stored for 1 month at 50 ℃.
A two-component polyurethane coating 3 which comprises,
comprises an agent A and an agent B;
the agent A comprises the following components in parts by weight:
the agent B is 28.5 parts of waterborne polyisocyanate curing agent (Bayhydur XP 2487/1);
the molar ratio of NCO in the agent B to OH in the agent A in the two-component polyurethane coating 3 is 1.8:1.
the preparation method of the agent A of the two-component polyurethane coating 3 comprises the following steps: adding the hydroxyl polyacrylate dispersion 3 into a stirring kettle at the rotation speed of 700 revolutions per minute, premixing water, propylene glycol methyl ether and dipropylene glycol butyl ether, adding into the stirring kettle, sequentially adding TEGO-815, TEGO ViscoPlus 3000, TEGO-500 and TEA, dispersing for 30 minutes, filtering and discharging.
During construction, the agent B is added into the agent A, and stirring is carried out for 8 minutes, so that the double-component polyurethane coating 3 with the bio-based content of 3.9 percent is obtained.
A paint film prepared from the bi-component polyurethane paint 3 is cured and dried for 7 days at normal temperature, and the performances are shown in Table 3.
Table 3: combination of properties of two-component polyurethane coating 3
Comparative example 1
A process for preparing a hydroxy polyacrylate dispersion 4 comprising the steps of:
(1) Uniformly mixing 16.3 parts of acrylic acid, 12.7 parts of methyl methacrylate, 20 parts of styrene, 8.7 parts of butyl acrylate, 10.7 parts of hydroxyethyl methacrylate, 10.6 parts of isobornyl acrylate and 1.5 parts of di-tert-amyl peroxide in parts by mass to form a mixed solution;
(2) And (2) adding 30 parts of tertiary carbonic acid glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant-pressure dropping funnel, mixing, stirring and heating, starting to dropwise add the mixed solution prepared in the step (1) when the temperature reaches 145 ℃, completing dropwise addition after 4 hours, stirring and keeping the temperature for 30 minutes after completing dropwise addition, cooling to 80 ℃, adding 4.3 parts of N, N-dimethylcyclohexylamine, stirring for 5 minutes, adding 150 parts of deionized water, dispersing at a high speed for 3 minutes, transferring to a high-pressure reaction kettle, pressurizing to 2MPa, heating to 160 ℃, reacting for 60 minutes, stopping the reaction after the epoxy value of a product is less than 0.005 determined by a hydrochloric acid-acetone method, cooling to below 40 ℃, relieving pressure, filtering and discharging to obtain the hydroxyl polyacrylate dispersoid 4.
The hydroxyl polyacrylate dispersion 4 prepared in this comparative example had a biobased content of 0%, a semi-permeable appearance, a pH of 5, a hydroxyl content of 3.2%, a solid content of 43.3%, a viscosity of 1650cp at 25 ℃, an average particle size of 85nm, and gelation upon heat storage at 50 ℃ for 1 month.
This comparative example differs from example 1 in that it does not have GreenSoft D special epoxidized soybean oil added. In comparison with example 1, the hydroxyl polyacrylate dispersion 4 prepared in comparative example 1 had a biobased content of 0%, a pH of acidity, a low hydroxyl content, a low solid content, and a poor thermal storage stability, and the above problems were caused because epoxidized soybean oil was not added to react with the carboxyl groups of the hydroxyl polyacrylate polymer, and the residual carboxyl group content of the polymer was too high.
A two-component polyurethane coating 4 comprises an agent A and an agent B;
the agent A comprises the following components in parts by weight:
the B agent comprises 18.6 parts of waterborne polyisocyanate curing agent (Bayhydur XP 2487/1).
The molar ratio of NCO in the agent B to OH in the agent A in the two-component polyurethane coating 4 is 1.8:1.
the preparation method of the agent A of the two-component polyurethane coating 4 comprises the following steps: adding the hydroxyl polyacrylate dispersoid 4 into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing water, dipropylene glycol butyl ether and dipropylene glycol methyl ether, adding into the stirring kettle, sequentially adding TEGO-800, RM-8W, TEGO-245 and TEA (triethanolamine), dispersing for 20 minutes, filtering and discharging.
During construction, the agent B is added into the agent A, and stirring is carried out for 6 minutes, so as to obtain the double-component polyurethane coating 4 with the bio-based content of 0%.
A paint film prepared by using the two-component polyurethane coating 4 is cured and dried for 7 days at normal temperature, and the performances of the paint film are shown in Table 4:
table 4: combination of properties of two-component polyurethane coating 4
| Detecting items | Performance of | Detection method |
| Surface drying time/min | 75 | GB/T1728-2020 |
| Actual drying time/d | 4 | GB/T1728-2020 |
| Hardness of pencil | 3B | GB/T6739-2006 |
| Coating film gloss/(60 °,%) | 95 | GB/T9754-2007 |
| Water resistance (25 ℃,24 h) | 4, severe marking | GB/T4893.1-2020 |
| Resistant dry heat (70 +/-2 ℃,15 h) | 4, severe marking | GB/T4893.3-2020 |
| Resistance to ethanol (50%, 1 h) | 4, severe marking | GB/T4893.1-2020 |
As can be seen from the above table, the two-component polyurethane coating 4 of this comparative example has longer tack-free and tack-free times than the bio-based two-component polyurethane coating 1 of example 1, is not good for improving the construction efficiency, and is far inferior to example 1 in pencil hardness, water resistance, dry heat resistance, and ethanol resistance of the paint film.
Comparative example 2
A method for preparing a hydroxy polyacrylate dispersant 5, comprising the steps of:
(1) Uniformly mixing 11.7 parts of acrylic acid, 15.7 parts of methyl methacrylate, 20 parts of styrene, 17 parts of butyl acrylate, 19 parts of hydroxyethyl methacrylate, 10.6 parts of isobornyl acrylate and 1.5 parts of di-tert-amyl peroxide in parts by mass to form a mixed solution;
(2) Adding 30 parts of tertiary carbonic acid glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant pressure dropping funnel, mixing, stirring and heating, starting to dropwise add the mixed solution prepared in the step (1) when the temperature reaches 145 ℃, completing dropwise addition within 4 hours, stirring and preserving heat for 30 minutes after completing dropwise addition, cooling to 80 ℃, adding 4.3 parts of N, N-dimethylcyclohexylamine, stirring for 5 minutes, adding 150 parts of deionized water for high-speed dispersion for 3 minutes, transferring to a high-pressure reaction kettle, pressurizing to 2MPa, heating to 160 ℃, reacting for 60 minutes, stopping the reaction after the epoxy value of a product is determined to be less than 0.005 by a hydrochloric acid-acetone method, cooling to below 40 ℃, decompressing, filtering and discharging to obtain the hydroxyl polyacrylate dispersoid 5.
The hydroxyl polyacrylate dispersoid 5 prepared by the comparative example has the advantages of 0 percent of bio-based content, semi-transparent appearance, 8 pH, 3.6 percent of hydroxyl content, 46.5 percent of solid content, 1550cp of viscosity at 25 ℃, 108nm of average particle size and no change after being stored for 1 month at 50 ℃.
This comparative example is a hydroxy polyacrylate dispersion synthesized according to the conventional process without the addition of bio-based materials, with hydroxy content and solids content parameters consistent with example 1. In contrast to example 1, comparative example 2 had no chain extender added.
A two-component polyurethane coating 5 comprises an agent A and an agent B;
the agent A comprises the following components in parts by weight:
the agent B comprises 22.5 parts of waterborne polyisocyanate curing agent (Bayhydur XP 2487/1).
The molar ratio of NCO in the agent B to OH in the agent A in the two-component polyurethane coating 5 is 1.8:1.
the preparation method of the A agent of the two-component polyurethane coating 5 comprises the following steps: adding the hydroxyl polyacrylate dispersoid 5 into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing water, dipropylene glycol butyl ether and dipropylene glycol methyl ether, adding into the stirring kettle, sequentially adding TEGO-800, RM-8W, TEGO-245 and TEA (triethanolamine), dispersing for 20 minutes, filtering and discharging.
During construction, the agent B is added into the agent A, and stirring is carried out for 6 minutes, so as to obtain the two-component polyurethane coating 5, wherein the bio-based content of the two-component polyurethane coating is 0%.
A paint film prepared by using the two-component polyurethane paint 5 is cured and dried for 7 days at normal temperature, and the performances of the paint film are shown in Table 5:
table 5: combination of properties of two-component polyurethane coating 5
| Detecting items | Performance of | Detection method |
| Surface drying time/min | 90 | GB/T1728-2020 |
| Actual drying time/d | 5 | GB/T1728-2020 |
| Hardness of pencil | 2B | GB/T6739-2006 |
| Coating film gloss/(60 °,%) | 97 | GB/T9754-2007 |
| Water resistance (25 ℃,24 h) | 4, severe marking | GB/T4893.1-2020 |
| Resistant dry heat (70 +/-2 ℃,15 h) | 4, severe marking | GB/T4893.3-2020 |
| Resistance to ethanol (50%, 1 h) | 4, severe marking | GB/T4893.1-2020 |
As can be seen from the above table, the two-component polyurethane coating 5 of the present comparative example has longer tack-free and tack-free times than the bio-based two-component polyurethane coating 1 of example 1, is not good for improving the construction efficiency, and is far inferior to example 1 in pencil hardness, water resistance, dry heat resistance, and ethanol resistance of the paint film.
Comparative example 3
A preparation method of bio-based hydroxyl polyacrylate dispersoid 6 comprises the following steps:
(1) Uniformly mixing 22.2 parts of acrylic acid, 9.2 parts of methyl methacrylate, 14.5 parts of styrene, 6.3 parts of butyl acrylate, 7.6 parts of isobornyl acrylate and 1.5 parts of di-tert-amyl peroxide in parts by mass to form a mixed solution;
(2) Adding 30 parts of tertiary carboxylic acid glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant-pressure dropping funnel, mixing, stirring and heating, starting to dropwise add the mixed solution prepared in the step (1) when the temperature reaches 145 ℃, completing dropwise addition for 4 hours, stirring and preserving heat for 30 minutes after completing dropwise addition, cooling to 80 ℃, adding 34.2 parts of GreenSoft D epoxy soybean oil and 4.3 parts of N, N-dimethylcyclohexylamine, stirring for 5 minutes, adding 150 parts of deionized water for high-speed dispersion for 3 minutes, transferring to a high-pressure reaction kettle, pressurizing to 2MPa, heating to 160 ℃, reacting for 60 minutes, determining that the epoxy value of a product is less than 0.005 by a hydrochloric acid-acetone method, stopping reaction, cooling to below 40 ℃, relieving pressure, filtering and discharging to obtain the bio-based hydroxyl polyacrylate dispersion 6.
The bio-based hydroxy polyacrylate dispersoid 6 prepared by the comparative example has the bio-based content of 26.3 percent, semi-permeable appearance, 8 pH, 3.6 percent of hydroxyl content, 46.5 percent of solid content, 1250cp of viscosity at 25 ℃, 103nm of average grain diameter and delamination after being stored for 1 month at 50 ℃.
The hydroxyl content and solid content parameters of the bio-based hydroxy polyacrylate dispersant 6 of the comparative example are the same as those of example 1, but hydroxyethyl methacrylate is not added, and the hydroxyl group is generated only after the epoxidized soybean oil reacts with the carboxyl group. Comparative example 3 has a higher biobased content of 26.3% compared to example 1, but has poor thermal storage stability. The reason for the above problems is that the addition amount of epoxidized soybean oil is too high and the crosslinking density of the polymer is too high.
A two-component polyurethane coating 6 comprises an agent A and an agent B;
the agent A comprises the following components in parts by weight:
the agent B comprises 22.5 parts of waterborne polyisocyanate curing agent (Bayhydur XP 2487/1).
The molar ratio of NCO in the agent B to OH in the agent A in the two-component polyurethane coating 6 is 1.8:1.
the preparation method of the A agent of the two-component polyurethane coating 6 comprises the following steps: adding the bio-based hydroxyl polyacrylate dispersoid 6 into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing water, dipropylene glycol butyl ether and dipropylene glycol methyl ether, adding into the stirring kettle, sequentially adding TEGO-800, RM-8W, TEGO-245 and TEA (triethanolamine), dispersing for 20 minutes, filtering and discharging.
During construction, the agent B is added into the agent A, and stirring is carried out for 6 minutes, so as to obtain the two-component polyurethane coating 6, wherein the bio-based content of the two-component polyurethane coating is 13.9%.
A paint film prepared by using the two-component polyurethane coating 6 is cured and dried for 7 days at normal temperature, and the performances of the paint film are shown in Table 6:
table 6: combination of properties of two-component polyurethane coating 6
| Detecting items | Performance of | Detection method |
| Surface drying time/min | 100 | GB/T1728-2020 |
| Actual drying time/d | 5 | GB/T1728-2020 |
| Hardness of pencil | 5B | GB/T6739-2006 |
| Coating film gloss/(60 °,%) | 91 | GB/T9754-2007 |
| Water resistance (25 ℃,24 h) | 4, severe marking | GB/T4893.1-2020 |
| Resistant dry heat (70 +/-2 ℃,15 h) | 4, severe marking | GB/T4893.3-2020 |
| Resistance to ethanol (50%, 1 h) | 4, severe marking | GB/T4893.1-2020 |
As can be seen from the above table, the bio-based two-component polyurethane coating 6 of the present comparative example has longer surface drying and solid drying time than the bio-based two-component polyurethane coating 1 of example 1, is not good for improving the construction efficiency, and is far inferior to example 1 in pencil hardness, water resistance, dry heat resistance and ethanol resistance of the paint film.
Comparative example 4
A preparation method of a bio-based hydroxy polyacrylate dispersoid 7 comprises the following steps:
(1) Uniformly mixing 16.3 parts of acrylic acid, 12.7 parts of methyl methacrylate, 20 parts of styrene, 8.7 parts of butyl acrylate, 10.7 parts of hydroxyethyl methacrylate, 10.6 parts of isobornyl acrylate and 1.5 parts of di-tert-amyl peroxide in parts by mass to form a mixed solution;
(2) Adding 30 parts of tertiary carbonic acid glycidyl ester monomer into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant pressure dropping funnel, mixing, stirring and heating, starting to dropwise add the mixed solution prepared in the step (1) when the temperature reaches 145 ℃, completing dropwise addition within 4 hours, stirring and preserving heat for 30 minutes after completing dropwise addition, cooling to 80 ℃, adding 15 parts of GreenSoft D special epoxy soybean oil and 4.3 parts of N, N-dimethylcyclohexylamine, stirring for 5 minutes, adding 150 parts of deionized water for high-speed dispersion for 3 minutes, transferring to a high-pressure reaction kettle, pressurizing to 2MPa, heating to 80 ℃, reacting for 60 minutes, determining the epoxy value of the product to be 0.023 by using a hydrochloric acid-acetone method, enabling the epoxy soybean oil not to have polycondensation reaction with a hydroxyl acrylate polymer, cooling to below 40 ℃, decompressing, filtering and discharging to obtain the bio-based hydroxyl polyacrylate dispersoid 7.
The bio-based hydroxy polyacrylate dispersion 7 prepared in this example had a bio-based content of 11.6%, a semi-permeable appearance, a pH of 5, a hydroxy content of 2.8%, a solid content of 46.5%, a viscosity of 1750cp, an average particle size of 118nm, and delamination upon thermal storage at 50 ℃ for 1 month.
This comparative example is a hydroxy polyacrylate dispersion synthesized by the high temperature reaction of example 1, modified to the 80 ℃ reaction. The bio-based content, solid content and appearance were the same as those of example 1, but the pH was acidic and the hydroxyl content was low. The reason for the above problem is that the epoxy group of epoxidized soybean oil does not react with the carboxyl group of the hydroxypolyacrylate polymer at 80 ℃.
A two-component polyurethane coating 7 comprises an agent A and an agent B;
the agent A comprises the following components in parts by weight:
the agent B comprises 17.5 parts of waterborne polyisocyanate curing agent (Bayhydur XP 2487/1).
The molar ratio of NCO in the agent B to OH in the agent A in the two-component polyurethane coating 1 is 1.8:1.
the preparation method of the A agent of the two-component polyurethane coating comprises the following steps: adding the bio-based hydroxyl polyacrylate dispersoid 7 into a stirring kettle at the rotating speed of 700 revolutions per minute, premixing water, dipropylene glycol butyl ether and dipropylene glycol methyl ether, adding into the stirring kettle, sequentially adding TEGO-800, RM-8W, TEGO-245 and TEA (triethanolamine), dispersing for 20 minutes, filtering and discharging.
During construction, the agent B is added into the agent A, and stirring is carried out for 6 minutes, so as to obtain the two-component polyurethane coating 7, wherein the bio-based content of the two-component polyurethane coating is 6.1%.
A paint film prepared by using the two-component polyurethane coating 7 is cured and dried for 7 days at normal temperature, and the performances of the paint film are shown in Table 7:
table 7: combination of properties of the two-component polyurethane coating 7
As can be seen from the above table, the bio-based two-component polyurethane coating 7 of the present comparative example has longer surface drying and solid drying time than the bio-based two-component polyurethane coating 1 of example 1, which is not good for improving the construction efficiency, and is far inferior to example 1 in pencil hardness of paint film, coating film gloss, water resistance, dry heat resistance, and ethanol resistance.
From the examples 1 to 3, the invention discloses a preparation method of a bio-based hydroxy polyacrylate dispersoid, and the bio-based hydroxy polyacrylate dispersoid prepared by the preparation method has high solid content, good appearance and good stability; a paint film prepared from the prepared bio-based water-based bi-component polyurethane paint has the advantages of high hardness, high gloss, high transparency, excellent water and chemical resistance, high crosslinking density, scratch resistance, wear resistance, high drying speed and the like, and can be applied to high-grade wood paints, automobile paints, metal anticorrosive paints and other industrial protective paints.
Finally, it should be noted that: the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the bio-based hydroxyl polyacrylate dispersion is characterized in that raw material components used by the preparation method comprise acrylic monomers, acrylate monomers, monomers containing vinyl and bio-based chain extenders;
the bio-based chain extender is vegetable oil containing more than three epoxy groups, and the bio-based chain extender participates in the reaction at the temperature of more than 140 ℃ to prepare the bio-based hydroxyl polyacrylate dispersoid.
2. The preparation method of claim 1, wherein the raw material components used in the preparation method further comprise an initiator, a reactive diluent, a neutralizer and water.
3. The method of claim 2, comprising the steps of:
mixing the acrylic monomer, the acrylate monomer, the monomer containing vinyl and the initiator to form a mixed solution;
heating the active diluent to 135-155 ℃, then dripping the mixed solution, stirring, preserving heat, then cooling to 70-85 ℃, adding the bio-based chain extender, the neutralizer and the water, dispersing, and then reacting at the temperature of more than 160 ℃ for 40-80 minutes to prepare the bio-based hydroxyl polyacrylate dispersoid.
4. The production method according to claim 1, wherein the acrylic monomer is selected from at least one of acrylic acid or methacrylic acid; the acrylic ester monomer comprises a hydroxyl acrylic ester monomer and at least one of methyl methacrylate, butyl acrylate, isobornyl acrylate, cyclohexyl methacrylate or benzyl methacrylate; the hydroxy acrylate monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
5. The method of claim 1, wherein the vinyl group-containing monomer comprises styrene; the reactive diluent is a substance containing an epoxy group and no double bond; the bio-based chain extender is selected from at least one of epoxidized soybean oil or epoxidized linseed oil.
6. The method of claim 2, comprising the steps of:
mixing 10-28 parts of acrylic monomers, 30-58 parts of acrylate monomers, 12-25 parts of vinyl-containing monomers and 1-3.5 parts of initiators by mass to form a mixed solution;
heating 20-40 parts of active diluent to 135-155 ℃, dripping the mixed solution at a constant pressure within 2-5 hours, stirring and keeping the temperature for 20-40 minutes after dripping, cooling to 70-85 ℃, adding 8-25 parts of bio-based chain extender and 3.0-5.3 parts of neutralizer, adding 135-150 parts of water for dispersing for 3-5 minutes after stirring for 3-5 minutes, transferring to a reaction kettle, pressurizing to 2-2.5MPa, heating to 160-185 ℃, reacting for 40-85 minutes, stopping the reaction after the epoxy value of the product is less than 0.005 determined by a hydrochloric acid-acetone method, cooling to below 40 ℃, decompressing, filtering and discharging to obtain the bio-based hydroxyl polyacrylate dispersion.
7. A biobased hydroxy polyacrylate dispersion produced by the production method according to any one of claims 1 to 6, wherein the biobased hydroxy polyacrylate dispersion has a solid content of more than 45% by mass fraction.
8. A two-component polyurethane coating is characterized by comprising an agent A and an agent B;
the agent A comprises the biobased hydroxy polyacrylate dispersion of claim 7;
the agent B comprises a water-based polyisocyanate curing agent;
the molar ratio of NCO in the agent B to OH in the agent A is 1.0-2.0.
9. The two-component polyurethane coating according to claim 8,
the agent A comprises the following components in parts by weight:
the agent B comprises 20-30 parts of a water-based polyisocyanate curing agent.
10. Use of the two-component polyurethane coating according to claim 8 or 9 in the field of wood, automotive or metal corrosion protection.
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