A bio-based hydroxy polyacrylate emulsion and its preparation method and application

Abstract

The present invention discloses a bio-based hydroxy polyacrylate emulsion and a preparation method and application thereof. The preparation raw materials include: modified bio-based materials and polyacrylate polymers containing hydroxyl groups; the preparation raw materials of the modified bio-based materials include hydrophilically modified bio-based oils containing epoxy groups; the polymerization monomers of the polyacrylate polymers containing hydroxyl groups include hydroxyl acrylate monomers and acrylamide monomers. The paint film of the water-based two-component polyurethane coating prepared by the emulsion of the present invention reduces the use of petroleum-based materials and has the characteristics of fast drying speed, high hardness and good chemical resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of coatings, and in particular relates to a bio-based hydroxy polyacrylate emulsion and a preparation method and application thereof. Background Art

[0002] Paint is a substance applied to the surface of an object for the protection, decoration and certain properties of the coated object. Existing wood coatings are mostly solvent-based coatings, containing more than 50% organic solvents. These solvents will volatilize into the atmosphere during the construction process, polluting the environment and damaging human health. In addition, organic solvents themselves will bring potential safety hazards. Therefore, the water-based nature of wood coatings is the development trend of coatings. Water-based wood coatings include single-component and two-component water-based wood coatings. Among them, the film properties of single-component water-based wood coatings, such as water resistance, chemical resistance and hardness, are quite different from those of oil-based coatings, which seriously limits the promotion and application of water-based wood coatings. The mechanical properties, water resistance and chemical resistance of two-component water-based wood coatings are comparable to those of solvent-based wood coatings, overcoming the shortcomings of single-component water-based wood coatings, and therefore have become the first choice for high-end water-based wood coatings.

[0003] Two-component waterborne polyurethane coatings are composed of waterborne polymer polyols and waterborne polyisocyanate curing agents, which are packaged separately and mixed in proportion when used. Waterborne polymer polyols include waterborne polyacrylate polyols, waterborne polyurethane polyols, waterborne polyester polyols, polyether polyols and mixed polyols. Among them, waterborne polyacrylate polyols have excellent color retention, gloss retention and weather resistance, low price, and easy adjustment of molecular weight, glass transition temperature and hydroxyl content. They are currently the first choice of waterborne polymer polyols in two-component waterborne polyurethane coatings. Two types of polyacrylate polyols, emulsions and dispersions, can be prepared by different polymerization processes. The hydroxyl content in hydroxy polyacrylate dispersions is relatively high, and the prepared coating film has excellent water resistance and chemical resistance, but there are disadvantages such as complex production process, product solid content of only 30%-40%, slow film drying speed and high cost. Emulsion-type polyacrylate polyols are also called hydroxy polyacrylate emulsions, or hydroxypropylene emulsions for short. However, their applications are limited due to their low hydroxyl content and poor water and chemical resistance. In addition, most existing two-component waterborne polyurethane coatings are petroleum-based materials, which do not meet the requirements of carbon peak and carbon neutrality.

[0004] Therefore, there is an urgent need to develop a coating that meets the carbon peak requirements and has a fast drying speed, high hardness and good chemical resistance. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a bio-based hydroxy polyacrylate emulsion, and the paint film of the bio-based water-based two-component polyurethane coating prepared therefrom has the characteristics of fast drying speed, high hardness and good chemical resistance.

[0006] The second aspect of the present invention provides a method for preparing the bio-based hydroxy polyacrylate emulsion.

[0007] The third aspect of the present invention provides a coating, wherein the raw materials for preparing the coating include the bio-based hydroxy polyacrylate emulsion.

[0008] A fourth aspect of the present invention provides an application of a coating in the field of decoration.

[0009] According to a first aspect of the present invention, a bio-based hydroxy polyacrylate emulsion is prepared by raw materials including: modified bio-based materials and polyacrylate polymers containing hydroxyl groups;

[0010] The raw materials for preparing the modified bio-based material include hydrophilic monomers and bio-based materials.

[0011] The bio-based material includes a bio-based oil containing an epoxy group;

[0012] The hydrophilic monomer includes a sulfonic acid monomer;

[0013] The raw materials for preparing the polyacrylate polymer containing hydroxyl groups include hydroxyl acrylate monomers and acrylamide monomers.

[0014] A bio-based hydroxy polyacrylate emulsion according to an embodiment of the first aspect of the present invention has at least the following beneficial effects:

[0015] After the hydroxy polyacrylate polymer is added to the bio-based material, the epoxy group of the bio-based material and the amino group of the acrylamide monomer in the hydroxy polyacrylate polymer undergo a condensation reaction to regenerate a portion of hydroxyl groups, and finally a bio-based hydroxy polyacrylate emulsion is obtained. The hydroxyl groups of the bio-based hydroxy polyacrylate emulsion of the present invention are respectively provided directly by the hydroxy acrylate monomer and generated after the reaction of the bio-based material, thereby ensuring the water resistance and chemical resistance of the paint film.

[0016] The addition of bio-based materials plays a role in chain extension, increasing the molecular weight of the polymer obtained in the reaction, and can improve the polymer from a linear structure to a network structure. The paint film of the water-based two-component polyurethane coating thus produced has the characteristics of fast drying speed, high hardness and good chemical resistance. In addition, by introducing bio-based materials for reaction, the use of petroleum-based materials is reduced, and it can also meet the country's requirements for carbon peak and carbon neutrality.

[0017] A bio-based hydroxy polyacrylate emulsion, the preparation raw materials include: modified bio-based materials and polyacrylate polymers containing hydroxyl groups;

[0018] According to some embodiments of the present invention, the raw materials for preparing the hydrophilic-modified epoxy-containing bio-based oil include a hydrophilic monomer and an epoxy-containing bio-based oil.

[0019] According to some embodiments of the present invention, the hydrophilic monomer includes a sulfonic acid monomer.

[0020] According to some embodiments of the present invention, the epoxy-containing bio-based oil includes at least one of epoxidized soybean oil and epoxidized linseed oil.

[0021] According to some embodiments of the present invention, the epoxidized soybean oil includes at least one of GreenSoft D specialty epoxidized soybean oil and GreenSoft H specialty epoxidized soybean oil.

[0022] According to some embodiments of the present invention, the epoxidized linseed oil comprises epoxidized linseed oil ELO 9-5 TM .

[0023] According to some embodiments of the present invention, the sulfonic acid monomer is a monomer containing one secondary amino group and one sulfonic acid group.

[0024] In the present invention, one secondary amino group of the sulfonic acid monomer is used to control the reaction between the secondary amino group and the epoxy group of soybean oil, ensuring that one sulfonic acid monomer reacts with only one soybean oil. If it is changed to one primary amino group or multiple secondary amino groups, it can react with two or more soybean oils. If one sulfonic acid monomer is connected with two or more soybean oils, on the one hand, the molecular weight of the hydrophilically modified bio-based material will be larger, the hydrophilicity will be worse, and the reaction activity will be reduced, thereby affecting the performance of the paint film. On the other hand, the functionality of the hydrophilically modified bio-based material will be increased, resulting in excessive cross-linking reaction and affecting the reaction process and storage stability of the emulsion. One sulfonic acid group can also ensure the hydrophilic modification of organisms and materials while avoiding the decrease of water resistance of the paint film.

[0025] According to some embodiments of the present invention, the sulfonic acid monomer includes at least one of cyclohexylaminoethanesulfonic acid (CHES), cyclohexylaminopropanesulfonic acid (CAPS) and cyclohexylaminobutanesulfonic acid (CABS).

[0026] According to some embodiments of the present invention, the acrylamide monomer is an acrylamide monomer containing one secondary amino group and no hydroxyl group.

[0027] In the present invention, the acrylamide monomer does not contain hydroxyl groups, which can prevent the original hydroxyl groups from forming steric hindrance with the newly generated hydroxyl groups (generated by the reaction of epoxy and secondary amino groups), resulting in the inability of the hydroxyl groups to react completely with NCO, and the residual hydroxyl groups will significantly reduce the water resistance.

[0028] According to some embodiments of the present invention, the mass content of bio-based materials in the bio-based hydroxy polyacrylate emulsion is 5% to 25%.

[0029] According to some embodiments of the present invention, the particle size of the bio-based hydroxy polyacrylate emulsion is 80 nm to 120 nm.

[0030] According to some preferred embodiments of the present invention, the particle size of the bio-based hydroxy polyacrylate emulsion is 90 nm to 110 nm.

[0031] The particle size within the above range can ensure that the emulsion has a slightly transparent appearance.

[0032] According to some embodiments of the present invention, the solid content of the bio-based hydroxy polyacrylate emulsion is 47-52%.

[0033] According to some embodiments of the present invention, the mass content of hydroxyl groups in the bio-based hydroxy polyacrylate emulsion is 2.1% to 4.0%.

[0034] The hydroxyl content and solid content in the present invention are within the above ranges, which can ensure the versatility of the emulsion in subsequent use and the performance of the paint film.

[0035] According to some embodiments of the present invention, the raw materials for preparing the polyacrylate polymer containing hydroxyl groups further include acrylic acid monomers, acrylic acid ester monomers and vinyl monomers.

[0036] According to some embodiments of the present invention, the acrylic monomer includes at least one of an acrylic monomer and a methacrylic monomer.

[0037] According to some preferred embodiments of the present invention, the acrylic acid monomer includes at least one of acrylic acid monomer and methacrylic acid monomer produced by Sanmu Corporation.

[0038] According to some embodiments of the present invention, the acrylamide monomer includes at least one of N-tert-butylacrylamide, N-ethylacrylamide and N-methyl-2-acrylamide.

[0039] According to some preferred embodiments of the present invention, the acrylamide monomer includes at least one of N-tert-butyl acrylamide, N-ethyl acrylamide and N-methyl-2-acrylamide from Aladdin.

[0040] According to some embodiments of the present invention, the acrylate monomer includes at least one of methyl methacrylate, butyl acrylate, isobornyl acrylate, cyclohexyl methacrylate and benzyl methacrylate.

[0041] According to some preferred embodiments of the present invention, the acrylate monomer includes at least one of methyl methacrylate, butyl acrylate, isobornyl acrylate, cyclohexyl methacrylate and benzyl methacrylate produced by Sanmu Corporation.

[0042] According to some embodiments of the invention, the vinyl monomer comprises styrene.

[0043] According to some preferred embodiments of the present invention, the vinyl monomer includes styrene from Miki Corporation.

[0044] According to some embodiments of the present invention, the hydroxyacrylate monomer includes at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.

[0045] According to some preferred embodiments of the present invention, the hydroxyacrylate monomer includes at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate produced by Changxing Company.

[0046] According to an embodiment of the second aspect of the present invention, a method for preparing a bio-based hydroxy polyacrylate emulsion is provided, comprising mixing and reacting the modified bio-based material and the hydroxyl-containing polyacrylate polymer.

[0047] According to some embodiments of the present invention, in the mixing reaction of the modified bio-based material and the hydroxyl-containing polyacrylate polymer, the temperature of the mixing reaction is 70-90°C.

[0048] According to some embodiments of the present invention, in the mixing reaction of the modified bio-based material and the polyacrylate polymer containing hydroxyl groups, the mixing reaction time is 45 to 80 minutes.

[0049] According to some preferred embodiments of the present invention, the method for preparing the bio-based hydroxy polyacrylate emulsion comprises mixing the modified bio-based material and the hydroxyl-containing polyacrylate polymer for 15 to 25 minutes, heating the temperature to 70 to 90° C., reacting for 45 to 80 minutes, stopping the reaction after the epoxy value is less than 0.005 as determined by the hydrochloric acid-acetone method, cooling the temperature to 40° C., and filtering the material to obtain the bio-based hydroxy polyacrylate emulsion.

[0050] According to some embodiments of the present invention, the method for preparing the modified bio-based material includes: mixing and reacting the bio-based material, a hydrophilic monomer and a sulfonic acid neutralizer to obtain a hydrophilic modified bio-based material E for standby use.

[0051] According to some embodiments of the present invention, the modified bio-based material comprises, by weight: 13 to 21 parts of bio-based material, 4 to 5 parts of hydrophilic monomer and 2 to 3 parts of sulfonic acid neutralizer.

[0052] According to some embodiments of the present invention, the sulfonic acid neutralizing agent includes a tertiary amine neutralizing agent that does not contain a hydroxyl group.

[0053] According to some embodiments of the present invention, the sulfonic acid neutralizing agent includes at least one of triethylamine (TEA) and N,N-dimethylcyclohexylamine (DMCHA).

[0054] The sulfonic acid neutralizer of the present invention does not contain hydroxyl groups in order to avoid the reaction between hydroxyl groups and isocyanate, consume curing agent, and affect the final paint film performance; tertiary amines are selected to avoid reaction with epoxy groups, and tertiary amines have the function of catalyzing the reaction between hydroxyl groups and isocyanate, thereby improving the final paint film performance.

[0055] According to some preferred embodiments of the present invention, the preparation method of the modified bio-based material includes: adding 13 to 21 parts of bio-based material, stirring and heating, raising the temperature to 70 to 90°C, adding 4 to 5 parts of sulfonic acid monomer and 2 to 3 parts of sulfonic acid neutralizer, reacting for 50 to 80 minutes, and stopping the reaction after the epoxy value is determined to be 0.195 to 0.331 by the hydrochloric acid-acetone method to obtain a hydrophilic modified bio-based material E for use.

[0056] According to some embodiments of the present invention, the raw materials for preparing the polyacrylate polymer include: polyacrylate polymer, emulsifier, deionizer and neutralizer 1.

[0057] According to some preferred embodiments of the present invention, the method for preparing the polyacrylate polymer comprises:

[0058] S1: Evenly mix acrylic acid monomer, acrylamide monomer, acrylate monomer, vinyl monomer and hydroxy acrylate monomer to form a mixed solution A for later use;

[0059] S2: Mix deionized water, emulsifier and monomer mixed solution A to obtain pre-emulsion solution B for standby use;

[0060] S3: mixing ionized water, initiator and emulsifier to obtain a mixed solution C for standby use;

[0061] S4: Mix deionized water and neutralizer 1 to form a mixed solution D for later use;

[0062] S5: After deionized water, an emulsifier, a buffer and an initiator are mixed, stirred and heated, a part of the pre-emulsion B is added to obtain a seed emulsion, and then the remaining pre-emulsion B and a mixed solution C, a mixed solution D and the hydrophilically modified bio-based material E are added to react to obtain a bio-based hydroxy polyacrylate emulsion.

[0063] According to some more preferred embodiments of the present invention, the method for preparing the polyacrylate polymer comprises:

[0064] S1: Evenly mix acrylic acid monomer, acrylamide monomer, acrylate monomer, vinyl monomer and hydroxy acrylate monomer to form a mixed solution A for later use;

[0065] S2: After deionized water and emulsifier are mixed, monomer mixed solution A is added and then dispersed to obtain pre-emulsion solution B for later use;

[0066] S3: mixing ionized water, initiator and emulsifier to obtain a mixed solution C for standby use;

[0067] S4: Mix deionized water and neutralizer 1 to form a mixed solution D for later use;

[0068] S5: After deionized water, an emulsifier, a buffer and an initiator are mixed, stirred and heated, a part of the pre-emulsion B is added to obtain a seed emulsion, and then the remaining pre-emulsion B and a mixed solution C, a mixed solution D and the hydrophilically modified bio-based material E are added to react to obtain a bio-based hydroxy polyacrylate emulsion.

[0069] According to some embodiments of the present invention, the mixed solution A in step S1 includes, by weight, 0.9 to 1.1 parts of acrylic acid monomer, 3.5 to 8.5 parts of acrylamide monomer, 15 to 31 parts of acrylate monomer, 5 to 9 parts of vinyl monomer and 5 to 15 parts of hydroxy acrylate monomer.

[0070] According to some embodiments of the present invention, the pre-emulsion B in step S2 includes, by weight, 28 to 33 parts of deionized water, 0.45 to 2.1 parts of emulsifier, and 42.1 to 48.3 parts of monomer mixed solution A.

[0071] According to some preferred embodiments of the present invention, step S2 includes dissolving 0.45 to 2.1 parts of emulsifier in 28 to 33 parts of deionized water, stirring evenly, adjusting the disperser to 700 rpm, dripping 42.1 to 48.3 parts of monomer mixed solution A, dripping for 15 to 25 minutes, and continuing to disperse for 10 to 20 minutes after dripping to obtain pre-emulsion B for standby use.

[0072] According to some embodiments of the present invention, the mixed solution C in step S3 includes, by weight, 5 to 7 parts of deionized water, 0.2 to 0.6 parts of initiator, and 0 to 1 parts of emulsifier.

[0073] According to some embodiments of the present invention, the mixed solution D in step S4 includes 5 to 8.5 parts of deionized water and 0.5 to 0.7 parts of neutralizer 1 by weight.

[0074] According to some embodiments of the present invention, the bio-based hydroxy polyacrylate emulsion in step S5 includes, by weight, 30 to 38 parts of deionized water, 0.3 to 0.8 parts of emulsifier, 0.1 to 0.25 parts of buffer, 0.1 to 0.2 parts of initiator, 71 to 84.5 parts of pre-emulsion B, 6.5 to 8.5 parts of mixed solution C, 5.5 to 9.5 parts of mixed solution D, and 19 to 28 parts of hydrophilic modified bio-based material E.

[0075] According to some embodiments of the invention, the initiator comprises a persulfate.

[0076] According to some embodiments of the present invention, the emulsifier includes at least one of a non-reactive emulsifier and a reactive emulsifier.

[0077] According to some embodiments of the present invention, the non-reactive emulsifier includes at least one of sodium dodecyl sulfate (SDS), Dow's isomeric alcohol polyoxyethylene ether (EH-9), DOWFAX-2A1 and fatty alcohol polyoxyethylene ether ammonium sulfate (KL-525).

[0078] According to some embodiments of the present invention, the reactive emulsifier includes at least one of sodium 3-allyloxy-1-hydroxypropane sulfonate (COPS-1), sodium 2-acrylamido-2-methylpropane sulfonate (COPS-2), SR-10 and ER-30.

[0079] According to some embodiments of the present invention, the neutralizer 1 includes a neutralizer containing a tertiary amine.

[0080] According to some embodiments of the present invention, the neutralizing agent 1 includes at least one of triethylamine (TEA), N,N-dimethylethanolamine (DMEA) and N,N-dimethylcyclohexylamine (DMCHA).

[0081] According to some embodiments of the present invention, the buffer comprises sodium bicarbonate (NaHCO 3 ) and sodium carbonate (Na 2 CO 3 ) at least one of.

[0082] According to some embodiments of the present invention, the initiator includes at least one of potassium persulfate (KPS) and ammonium persulfate (APS).

[0083] According to an embodiment of the third aspect of the present invention, a coating is provided, wherein the raw materials for preparing the coating include the bio-based hydroxy polyacrylate emulsion.

[0084] According to some embodiments of the present invention, the coating preparation method includes mixing agent A and agent B at an NCO / OH molar ratio of 1.0-1.8:1 during construction;

[0085] In parts by weight, the agent A comprises: 60-65 parts of bio-based hydroxy polyacrylate emulsion, 30-36 parts of water, 2-4 parts of film-forming aid, 0.05-0.2 parts of defoaming agent, 0.5-0.8 parts of thickener, 0.05-0.2 parts of wetting agent and 0.2-0.5 parts of neutralizer 2;

[0086] In parts by weight, the agent B comprises: 15-30 parts of water-based polyisocyanate curing agent.

[0087] In the present invention, the NCO / OH molar ratio is 1.0-1.8:1. Under this ratio, the low hardness and poor resistance of the paint film caused by a too low ratio and the appearance of "prickly heat" and other defects on the paint film surface caused by a too high ratio are avoided.

[0088] According to some embodiments of the present invention, the film-forming aid includes at least one of propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether and dipropylene glycol butyl ether.

[0089] According to some embodiments of the present invention, the defoaming agent includes at least one of a polyether siloxane copolymer defoaming agent and a modified polysiloxane copolymer solution.

[0090] According to some embodiments of the present invention, the polyether siloxane copolymer defoamer includes at least one of TEGO-800, TEGO-805, TEGO-815 and TEGO-825.

[0091] According to some embodiments of the present invention, the modified polysiloxane copolymer solution includes at least one of BYK-019 and BYK-020.

[0092] According to some embodiments of the present invention, the thickener includes at least one of a nonionic polyurethane associative thickener, a hydrophobically modified alkali-swellable associative thickener, an alkali-swellable non-associative thickener, and a nonionic associative thickener.

[0093] According to some embodiments of the present invention, the nonionic polyurethane associative thickener includes RM-8W.

[0094] According to some embodiments of the present invention, the hydrophobically modified alkali-swellable associative thickener is TT-935.

[0095] According to some embodiments of the present invention, the alkali-swellable non-associative thickener includes ASE-60.

[0096] According to some embodiments of the present invention, the nonionic associative thickener includes at least one of TEGO ViscoPlus 3000, TEGO ViscoPlus 3030, and TEGO ViscoPlus 3060.

[0097] According to some embodiments of the present invention, the wetting agent includes at least one of a polyether siloxane copolymer, a nonionic organic surfactant, and a polyether-modified polysiloxane solution.

[0098] According to some embodiments of the present invention, the polyether siloxane copolymer includes TEGO-245.

[0099] According to some embodiments of the present invention, the nonionic organic surfactant includes TEGO-500.

[0100] According to some embodiments of the present invention, the polyether-modified polysiloxane solution includes BYK-346.

[0101] According to some embodiments of the present invention, the neutralizer 2 includes at least one of triethylamine and dimethylethanolamine.

[0102] According to some embodiments of the present invention, the polyisocyanate curing agent includes at least one of sulfonates, carboxylates, and alkoxy hydrophilically modified hexamethylene diisocyanate (HDI).

[0103] According to some embodiments of the present invention, the polyisocyanate curing agent includes at least one of Bayhydur XP2487 / 1 and Bayhydur XP 2655.

[0104] According to some embodiments of the present invention, the method for preparing the bio-based waterborne two-component polyurethane coating comprises the following steps:

[0105] Premix water and film-forming aids and add them to hydroxy polyacrylate emulsion, then add defoamer, thickener, wetting agent and neutralizer 2 in sequence, disperse for 10-30 minutes, and filter to obtain agent A;

[0106] During construction, the water-based polyisocyanate curing agent is added to the A agent according to the NCO / OH molar ratio of 1.0-1.8, and stirred for 5-8 minutes to obtain a bio-based water-based two-component polyurethane coating.

[0107] The present invention uses the bio-based two-component polyurethane coating agent A and agent B prepared by the above method in combination, and the obtained bio-based water-based two-component polyurethane coating film has the advantages of high gloss, high transparency, excellent water resistance and chemical resistance, high cross-linking density, high hardness, scratch resistance, wear resistance and fast drying speed, and can be applied to high-end wood coatings, automotive coatings, metal anti-corrosion coatings and other industrial protective coatings.

[0108] According to an embodiment of the fourth aspect of the present invention, a coating is used in the field of decoration.

[0109] According to some embodiments of the present invention, the coating decoration field includes wood products.

[0110] According to some embodiments of the present invention, the coating decoration field includes metal.

[0111] According to some embodiments of the present invention, the paint decoration field includes automobiles.

[0112] According to some embodiments of the present invention, the coating decoration field includes metal corrosion protection. DETAILED DESCRIPTION

[0113] The following will be combined with the embodiments to clearly and completely describe the concept of the present invention and the technical effects produced, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.

[0114] The (meth)acrylic acid monomer is acrylic acid or methacrylic acid from Miki Corporation;

[0115] The acrylamide monomers are N-tert-butyl acrylamide, N-ethyl acrylamide, and N-methyl-2-acrylamide from Aladdin;

[0116] The (meth)acrylate monomers are methyl methacrylate, butyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, and benzyl methacrylate from Sanmu Company;

[0117] The vinyl monomer was styrene from Miki Corporation;

[0118] The hydroxy acrylate monomer is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate of Changxing Company;

[0119] The non-reactive emulsifiers are sodium dodecyl sulfate (SDS) from BASF, isomeric alcohol polyoxyethylene ether (EH-9) and DOWFAX-2A1 from Dow, and fatty alcohol polyoxyethylene ether ammonium sulfate (KL-525) from Guangzhou Hangqin.

[0120] The reactive emulsifiers were 3-allyloxy-1-hydroxypropane sulfonate (COPS-1) and 2-acrylamido-2-methylpropane sulfonate (COPS-2) from Solvay, and SR-10 and ER-30 from Japan Aidico;

[0121] The buffers are sodium bicarbonate (NaHCO3) and sodium carbonate (Na2CO3) from Xilong Chemical;

[0122] The initiators are potassium persulfate (KPS) and ammonium persulfate (APS) from Xilong Chemical;

[0123] The bio-based materials are GreenSoft D special epoxy soybean oil, GreenSoft H special epoxy soybean oil, and epoxy linseed oil ELO from Xingbang Polymer Materials Co., Ltd. 9-5 TM ;

[0124] The sulfonic acid monomers are cyclohexylaminoethanesulfonic acid (CHES), cyclohexylaminopropanesulfonic acid (CAPS), and cyclohexylaminobutanesulfonic acid (CABS);

[0125] The sulfonic acid neutralizers are triethylamine (TEA) and N,N-dimethylcyclohexylamine (DMCHA) from Dow; the neutralizers are triethylamine (TEA), N,N-dimethylethanolamine (DMEA), and N,N-dimethylcyclohexylamine (DMCHA) from Dow;

[0126] The defoamers are TEGO's polyether siloxane copolymer defoamers TEGO-800, TEGO-805, TEGO-815, TEGO-825, BYK's modified polysiloxane copolymer solutions BYK-019 and BYK-020;

[0127] The thickeners are DOW's nonionic polyurethane associative thickener RM-8W, hydrophobically modified alkali-swellable associative thickener TT-935, alkali-swellable non-associative thickener ASE-60, TEGO's nonionic associative thickeners TEGOViscoPlus 3000, TEGO ViscoPlus 3030, TEGO ViscoPlus 3060; the wetting agents are TEGO's polyether siloxane copolymer TEGO-245, nonionic organic surfactant TEGO-500, BYK's polyether-modified polysiloxane solution BYK-346;

[0128] The neutralizing agents were triethylamine and dimethylethanolamine from Dow;

[0129] Polyisocyanate curing agents include sulfonates, carboxylates, and alkoxy hydrophilically modified hexamethylene diisocyanate (HDI);

[0130] The polyisocyanate curing agents were Bayhydur XP 2487 / 1 and Bayhydur XP 2655 from Covestro;

[0131] Example 1

[0132] A bio-based hydroxy polyacrylate emulsion 1 is prepared by the following steps:

[0133] S1. In parts by mass, 0.9 parts of acrylic acid, 8.5 parts of N-tert-butyl acrylamide, 5.5 parts of cyclohexyl methacrylate, 5.2 parts of methyl methacrylate, 5 parts of butyl acrylate, 7 parts of styrene, and 10 parts of hydroxyethyl methacrylate were mixed to form a mixed solution A1 for standby use;

[0134] S2. Add 33 parts of deionized water to the dispersion tank, dissolve 0.5 parts of SDS and 1 part of EH-9, stir well and adjust the disperser to 700 rpm, add 42.1 parts of the mixed solution A1, drip it for 25 minutes, and continue to disperse it for 10 minutes after dripping to obtain a pre-emulsion B1 for standby;

[0135] S3. Dissolve 0.45 parts of APS and 1 part of COPS-1 in 7 parts of deionized water to form a mixed solution C1 for standby use;

[0136] S4. By mass, 8.5 parts of deionized water and 0.6 parts of DMEA were mixed to form a mixed solution D1 for standby use;

[0137] S5. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 20.7 parts of epoxidized soybean oil GreenSoft D were added, stirred and heated to 70°C, 4.6 parts of cyclohexylaminoethanesulfonic acid and 2.3 parts of TEA were added, and the reaction was stopped after the epoxy value was determined to be 0.241 by the hydrochloric acid-acetone method to obtain the hydrophilic modified bio-based material E1 for standby use;

[0138] S6. Add 36.3 parts of deionized water, 0.25 parts of SDS, 0.5 parts of EH-9, 0.2 parts of NaHCO into a four-necked flask equipped with a thermometer, condenser, stirring paddle and constant pressure dropping funnel. 3 and 0.15 parts of APS, stir and heat. When the temperature reaches 77°C, add 7.7 parts of pre-emulsion B1 in 15 minutes, stabilize for 10 minutes after the addition to obtain the seed emulsion. Raise the temperature to 80°C, and simultaneously add 68.9 parts of pre-emulsion B1 and 8.45 parts of mixed solution C1, and add them in 3.5 hours. After the addition, raise the temperature to 85°C, keep warm for 2 hours, cool to 55°C, add 9.1 parts of mixed solution D1, stir for 10 minutes, then add 27.6 parts of hydrophilic modified bio-based material E1, stir for 15 minutes, then raise the temperature to 80°C, react for 60 minutes, and stop the reaction when the epoxy value is less than 0.005 as determined by the hydrochloric acid-acetone method;

[0139] S7. Cool down to 40° C., filter the material to obtain the bio-based hydroxy polyacrylate emulsion 1.

[0140] Example 2

[0141] Example A bio-based water-based two-component polyurethane coating 1 was prepared. The bio-based hydroxy polyacrylate emulsion was prepared in Example 1. The specific steps were as follows:

[0142] During construction, mix A1 and B1 agents at a NCO / OH molar ratio of 1.8:1;

[0143] Wherein, agent A1 is composed of the following components in parts by weight:

[0144]

[0145] Agent B1 is a water-based polyisocyanate curing agent, the water-based polyisocyanate curing agent is Bayhydur XP2487 / 1, and the mass fraction of Bayhydur XP 2487 / 1 is 21.4 parts;

[0146] The preparation method of agent A1 is as follows: add bio-based hydroxy polyacrylate emulsion 1 into a stirring tank at a rotation speed of 700 rpm, premix water, dipropylene glycol butyl ether and dipropylene glycol methyl ether and add them into the stirring tank, add TEGO-800, RM-8W, TEGO-245 and TEA in sequence, disperse for 20 minutes, and filter the material.

[0147] During construction, agent B1 was added to agent A1 and stirred for 6 minutes to obtain a bio-based waterborne two-component polyurethane coating 1, whose bio-based content was 11.4%.

[0148] The paint film prepared from the bio-based waterborne two-component polyurethane coating 1 was cured and dried at room temperature for 7 days, and its properties are shown in Table 1.

[0149] Example 3

[0150] A bio-based hydroxy polyacrylate emulsion 2 is prepared by the following steps:

[0151] S1. In parts by mass, 1 part of methacrylic acid, 3.8 parts of N-ethylacrylamide, 9.5 parts of isobornyl acrylate, 11 parts of methyl methacrylate, 10.45 parts of butyl acrylate, 5.5 parts of styrene, 5.5 parts of hydroxyethyl acrylate were mixed to form a mixed solution A2 for standby use;

[0152] S2. Add 28 parts of deionized water to the dispersion tank, dissolve 0.45 parts of KL-525, stir well and adjust the disperser to 700 rpm, add 46.75 parts of the mixture A2, drip for 20 minutes, continue to disperse for 8 minutes after dripping, and obtain the pre-emulsion B2 for standby;

[0153] S3. In parts by mass, 0.2 parts of KPS and 0.75 parts of COPS-2 were dissolved in 5 parts of deionized water to form a mixed solution C2 for standby use;

[0154] S4. In parts by mass, 5.5 parts of deionized water and 0.5 parts of TEA were mixed to form a mixed solution D2 for standby use;

[0155] S5. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 13 parts of epoxidized soybean oil GreenSoft H were added, stirred and heated to 80°C, 4.3 parts of cyclohexylaminopropanesulfonic acid and 2.4 parts of DMCHA were added, and the reaction was stopped after the epoxy value was determined to be 0.195 by the hydrochloric acid-acetone method to obtain the hydrophilic modified bio-based material E2 for standby use;

[0156] S6. Add 30.7 parts of deionized water, 0.3 parts of KL-525, 0.15 parts of NaHCO into a four-necked flask equipped with a thermometer, condenser, stirring paddle and constant pressure dropping funnel. 3 and 0.1 parts of KPS, mix, stir and heat. When the temperature reaches 80°C, add 6 parts of pre-emulsion B2 in 20 minutes, stabilize for 15 minutes after the addition, and obtain the seed emulsion. The temperature is maintained at 80°C, and 69.2 parts of pre-emulsion B2 and 5.95 parts of mixed solution C2 are added at the same time. The mixture is added in 4 hours. After the addition, the temperature is raised to 90°C, kept warm for 1 hour, cooled to 50°C, 6 parts of mixed solution D2 are added, stirred for 8 minutes, and 19.7 parts of hydrophilic modified bio-based material E2 are added. Stir for 20 minutes, heat to 70°C, react for 80 minutes, and stop the reaction when the epoxy value is less than 0.005 as determined by the hydrochloric acid-acetone method;

[0157] S7. Cool down to 40° C. and filter the material to obtain the bio-based hydroxy polyacrylate emulsion 2.

[0158] Example 4

[0159] This example also prepares a bio-based water-based two-component polyurethane coating 2, and the bio-based hydroxy polyacrylate emulsion is prepared in Example 3, and the specific steps are as follows:

[0160] During construction, mix A2 and B2 agents at a NCO / OH molar ratio of 1.8:1;

[0161] Wherein, agent A2 is composed of the following components in parts by weight:

[0162]

[0163] Agent B2 is a water-based polyisocyanate curing agent, the water-based polyisocyanate curing agent is Bayhydur XP 2655, and the mass fraction of Bayhydur XP 2655 is 14.7 parts;

[0164] The preparation method of the A2 agent of the above-mentioned bio-based water-based two-component polyurethane coating 2 is as follows: add the bio-based hydroxy polyacrylate emulsion 2 into a stirring tank at a rotation speed of 700 rpm, premix water, dipropylene glycol butyl ether and dipropylene glycol methyl ether and add them into the stirring tank, add TEGO-805, TT-935, BYK-346 and DMEA in sequence, disperse for 10 minutes, and filter the material.

[0165] During construction, agent B2 was added to agent A2 and stirred for 5 minutes to obtain a bio-based waterborne two-component polyurethane coating 2, whose bio-based content was 12%.

[0166] The paint film prepared from the bio-based waterborne two-component polyurethane coating 2 was cured and dried at room temperature for 7 days, and its properties are shown in Table 1.

[0167] Example 5

[0168] A bio-based hydroxy polyacrylate emulsion 3 is prepared by the following steps:

[0169] S1. In parts by mass, 1.1 parts of acrylic acid, 6.3 parts of N-methyl-2-acrylamide, 5 parts of Bian methacrylate, 5 parts of methyl methacrylate, 7 parts of butyl acrylate, 8.9 parts of styrene, and 15 parts of hydroxypropyl methacrylate were mixed to form a mixed solution A3 for standby use;

[0170] S2. Add 30 parts of deionized water to the dispersion tank, dissolve 0.6 parts of DOWFAX-2A1, 0.5 parts of SR-10, and 1 part of ER-30, stir well, adjust the disperser to 700 rpm, add 48.3 parts of the mixture A3, drip it for 30 minutes, continue to disperse it for 12 minutes after dripping, and obtain the pre-emulsion B3 for standby;

[0171] S3. In parts by mass, 0.6 parts of APS were dissolved in 6 parts of deionized water to form a mixed solution C3 for standby use;

[0172] S4. In parts by mass, 7 parts of deionized water and 0.7 parts of DMCHA were mixed to form a mixed solution D3 for standby use;

[0173] S5. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 15.6 parts of epoxy linseed oil ELO were added. 9-5, stirring and heating, raising the temperature to 90°C, adding 4.4 parts of cyclohexylaminobutanesulfonic acid and 2.3 parts of DMCHA, reacting for 50 minutes, and stopping the reaction after the epoxy value is determined to be 0.331 by the hydrochloric acid-acetone method to obtain the hydrophilic modified bio-based material E3 for standby use;

[0174] S6. Add 34.3 parts of deionized water, 0.5 parts of DOWFAX-2A1, 0.2 parts of SR-10, 0.25 parts of NaHCO into a four-necked flask equipped with a thermometer, a condenser, a stirring paddle and a constant pressure dropping funnel. 3 and 0.1 parts of KPS, mix, stir and heat. When the temperature reaches 83°C, drip 9.5 parts of pre-emulsion B3 in 25 minutes, stabilize for 20 minutes after dripping to obtain seed emulsion. Raise the temperature to 85°C, and drip 70.9 parts of pre-emulsion B3 and 6.6 parts of mixed solution C3 at the same time, drip them in 5 hours, maintain 85°C after dripping, keep warm for 1.5 hours, cool to 60°C, add 7.5 parts of mixed solution D3, stir for 12 minutes, then add 22.3 parts of hydrophilic modified bio-based material E3, stir for 25 minutes, heat to 90°C, react for 45 minutes, and stop the reaction when the epoxy value is less than 0.005 measured by hydrochloric acid-acetone method;

[0175] S7. Cool down to 40° C., filter out the material and obtain the bio-based hydroxy polyacrylate emulsion 3.

[0176] Example 6

[0177] Example A bio-based water-based two-component polyurethane coating 3 was prepared. The bio-based hydroxy polyacrylate emulsion was prepared in Example 5. The specific steps were:

[0178] During construction, mix A3 and B3 agents at a NCO / OH molar ratio of 1.8:1;

[0179] Wherein, the A3 agent comprises the following components in parts by weight:

[0180]

[0181] Agent B3 is a water-based polyisocyanate curing agent, the water-based polyisocyanate curing agent is Bayhydur XP2487 / 1, and the mass fraction of Bayhydur XP 2487 / 1 is 26.0 parts;

[0182] The preparation method of the A3 agent of the above-mentioned bio-based water-based two-component polyurethane coating 3 is as follows: add the bio-based hydroxy polyacrylate emulsion 3 into a stirring tank at a rotation speed of 700 rpm, premix water, dipropylene glycol butyl ether and dipropylene glycol methyl ether and add them into the stirring tank, add TEGO-805, TT-935, BYK-346 and DMEA in sequence, disperse for 30 minutes, and filter the material.

[0183] During construction, agent B3 was added to agent A3 and stirred for 8 minutes to obtain a bio-based waterborne two-component polyurethane coating 3, whose bio-based content was 10.35%.

[0184] The paint film prepared from the bio-based waterborne two-component polyurethane coating 3 was cured and dried at room temperature for 7 days, and its properties are shown in Table 1.

[0185] Comparative Example 1

[0186] The difference between this comparative example and Example 1 is that no hydroxy polyacrylate emulsion synthesized from bio-based materials is added, and the specific steps are as follows:

[0187] S1. In parts by mass, 0.9 parts of acrylic acid, 8.5 parts of N-tert-butyl acrylamide, 5.5 parts of cyclohexyl methacrylate, 5.2 parts of methyl methacrylate, 5 parts of butyl acrylate, 7 parts of styrene, and 10 parts of hydroxyethyl methacrylate were mixed to form a mixed solution A4 for standby use;

[0188] S2. Add 33 parts of deionized water to the dispersion tank, dissolve 0.5 parts of SDS and 1 part of EH-9, stir well and adjust the disperser to 700 rpm, add 42.1 parts of the mixture A4, drip it for 25 minutes, continue to disperse for 10 minutes after dripping, and obtain the pre-emulsion B4 standby;

[0189] S3. In parts by mass, 0.45 parts of APS and 1 part of COPS-1 were dissolved in 7 parts of deionized water to form a mixed solution C4 for standby use;

[0190] S4. By mass, 8.5 parts of deionized water and 0.6 parts of DMEA were mixed to form a mixed solution D4 for standby use;

[0191] S5. Add 26.3 parts of deionized water, 0.25 parts of SDS, 0.5 parts of EH-9, 0.2 parts of NaHCO into a four-necked flask equipped with a thermometer, condenser, stirring paddle and constant pressure dropping funnel. 3 and 0.15 parts of APS, stir and heat. When the temperature reaches 77°C, add 7.7 parts of pre-emulsion B4 in 15 minutes, stabilize for 10 minutes after the addition to obtain seed emulsion. Raise the temperature to 80°C, and simultaneously add 68.9 parts of pre-emulsion B4 and 8.45 parts of mixed solution C4, and add them in 3.5 hours. After the addition, raise the temperature to 85°C, keep warm for 2 hours, cool to 55°C, add 9.1 parts of mixed solution D4, stir for 10 minutes, disperse at high speed for 15 minutes, then raise the temperature to 80°C, react for 60 minutes, and stop the reaction when the epoxy value is less than 0.005 as determined by the hydrochloric acid-acetone method;

[0192] S6. Cool down to 40°C, filter the material to obtain hydroxy polyacrylate emulsion 4.

[0193] Comparative Example 2

[0194] A water-based two-component polyurethane coating 4 was prepared in the comparative example. The emulsion was prepared in the comparative example 1. The specific steps were as follows:

[0195] During construction, mix A4 and B4 agents at a NCO / OH molar ratio of 1.8:1;

[0196] Wherein, the A4 agent comprises the following components in parts by weight:

[0197]

[0198] Agent B4 is a water-based polyisocyanate curing agent, the water-based polyisocyanate curing agent is Bayhydur XP2487 / 1, and the mass fraction of Bayhydur XP 2487 / 1 is 28.4 parts;

[0199] The preparation method of the A4 agent of the above-mentioned water-based two-component polyurethane coating 4 is as follows: add the hydroxy polyacrylate emulsion 4 into a stirring tank at a rotation speed of 700 rpm, premix water, dipropylene glycol butyl ether and dipropylene glycol methyl ether and add them into the stirring tank, add TEGO-800, RM-8W, TEGO-245 and TEA in sequence, disperse for 20 minutes, and filter the material.

[0200] During construction, agent B4 was added to agent A4 and stirred for 6 minutes to obtain a water-based two-component polyurethane coating 4, whose biobased content was 0%.

[0201] The paint film prepared by the water-based two-component polyurethane coating 4 was cured and dried at room temperature for 7 days, and its properties are shown in Table 1.

[0202] Comparative Example 3

[0203] This comparative example is a bio-based hydroxy polyacrylate emulsion synthesized from bio-based materials without hydrophilic modification. The specific steps are:

[0204] S1. In parts by mass, 0.9 parts of acrylic acid, 8.5 parts of N-tert-butyl acrylamide, 5.5 parts of cyclohexyl methacrylate, 5.2 parts of methyl methacrylate, 5 parts of butyl acrylate, 7 parts of styrene, 6.3 parts of hydroxyethyl methacrylate were mixed to form a mixed solution A5 for standby use;

[0205] S2. Add 33 parts of deionized water to the dispersion tank, dissolve 0.5 parts of SDS and 1 part of EH-9, stir well and adjust the disperser to 700 rpm, add 38.4 parts of the mixture A5, drip it for 25 minutes, continue to disperse for 10 minutes after dripping, and obtain the pre-emulsion B5 standby;

[0206] S3. In parts by mass, 0.45 parts of APS and 1 part of COPS-1 were dissolved in 7 parts of deionized water to form a mixed solution C5 for standby use;

[0207] S4. By mass, 8.5 parts of deionized water and 0.6 parts of DMEA were mixed to form a mixed solution D5 for standby use;

[0208] S5. Add 36.3 parts of deionized water, 0.25 parts of SDS, 0.5 parts of EH-9, 0.2 parts of NaHCO into a four-necked flask equipped with a thermometer, condenser, stirring paddle and constant pressure dropping funnel. 3 and 0.15 parts of APS, stir and heat. When the temperature reaches 77°C, add 7.3 parts of pre-emulsion B1 in 15 minutes, stabilize for 10 minutes after the addition, and obtain seed emulsion. Raise the temperature to 80°C, and simultaneously add 65.6 parts of pre-emulsion B1 and 8.45 parts of mixed solution C1, and add them in 3.5 hours. After the addition, raise the temperature to 85°C, keep warm for 2 hours, cool to 55°C, add 9.1 parts of mixed solution D1, stir for 10 minutes, add 15.6 parts of epoxidized soybean oil GreenSoft D, stir for 15 minutes, raise the temperature to 80°C, react for 60 minutes, and stop the reaction when the epoxy value is less than 0.005 as determined by the hydrochloric acid-acetone method;

[0209] S7. Cool down to 40° C. and filter the material to obtain the bio-based hydroxy polyacrylate emulsion 5.

[0210] Comparative Example 4

[0211] The comparative example prepared a water-based two-component polyurethane coating 5, and the emulsion was prepared in the comparative example 3, and the specific steps were:

[0212] During construction, mix A5 and B5 agents at a NCO / OH molar ratio of 1.8:1;

[0213] Wherein, the A5 agent comprises the following components in parts by weight:

[0214]

[0215] Agent B5 is a water-based polyisocyanate curing agent, the water-based polyisocyanate curing agent is Bayhydur XP2487 / 1, and the mass fraction of Bayhydur XP 2487 / 1 is 21.4 parts;

[0216] The preparation method of the A5 agent of the above-mentioned bio-based water-based two-component polyurethane coating 5 is as follows: add the bio-based hydroxy polyacrylate emulsion 5 into a stirring tank at a rotation speed of 700 rpm, premix water, dipropylene glycol butyl ether and dipropylene glycol methyl ether and add them into the stirring tank, add TEGO-800, RM-8W, TEGO-245 and TEA in sequence, disperse for 20 minutes, and filter the material.

[0217] During construction, agent B5 was added to agent A5 and stirred for 6 minutes to obtain a bio-based waterborne two-component polyurethane coating 5, whose bio-based content was 14.4%.

[0218] The paint film prepared from the bio-based waterborne two-component polyurethane coating 5 was cured and dried at room temperature for 7 days, and its properties are shown in Table 1.

[0219] Comparative Example 5

[0220] This comparative example is different from Example 1 in that no hydroxy acrylate monomer is added, and the specific steps are:

[0221] S1. In parts by mass, 0.9 parts of acrylic acid, 18.3 parts of N-tert-butyl acrylamide, 5.5 parts of cyclohexyl methacrylate, 5.2 parts of methyl methacrylate, 5 parts of butyl acrylate, and 7 parts of styrene were mixed to form a mixed solution A6 for standby use;

[0222] S2. Add 33 parts of deionized water to the dispersion tank, dissolve 0.5 parts of SDS and 1 part of EH-9, stir well and adjust the disperser to 700 rpm, add 41.9 parts of the mixture A6, drip for 25 minutes, continue to disperse for 10 minutes after dripping, and obtain the pre-emulsion B6 standby;

[0223] S3. In parts by mass, 0.45 parts of APS and 1 part of COPS-1 were dissolved in 7 parts of deionized water to form a mixed solution C6 for standby use;

[0224] S4. By mass, 8.5 parts of deionized water and 0.6 parts of DMEA were mixed to form a mixed solution D6 for standby use;

[0225] S5. In a four-necked flask equipped with a thermometer, a condenser and a stirring paddle, 44.8 parts of GreenSoft D were added, stirred and heated to 70°C, 9.9 parts of cyclohexylaminoethanesulfonic acid and 4.8 parts of TEA were added, and the reaction was stopped after the epoxy value was determined to be 0.241 by the hydrochloric acid-acetone method to obtain the hydrophilic modified bio-based material E1 for standby use;

[0226] S6. Add 65.05 parts of deionized water, 0.25 parts of SDS, 0.5 parts of EH-9, 0.2 parts of NaHCO into a four-necked flask equipped with a thermometer, condenser, stirring paddle and constant pressure dropping funnel. 3 and 0.15 parts of APS, stir and heat. When the temperature reaches 77°C, add 7.6 parts of pre-emulsion B1 in 15 minutes, stabilize for 10 minutes after the addition to obtain seed emulsion. Raise the temperature to 80°C, and simultaneously add 68.8 parts of pre-emulsion B1 and 8.45 parts of mixed solution C1, and add them in 3.5 hours. After the addition, raise the temperature to 85°C, keep warm for 2 hours, cool to 55°C, add 9.1 parts of mixed solution D1, stir for 10 minutes, then add 59.5 parts of hydrophilic modified bio-based material E1, stir for 15 minutes, then raise the temperature to 80°C, react for 60 minutes, and stop the reaction when the epoxy value is less than 0.005 as determined by the hydrochloric acid-acetone method;

[0227] S7. Cool down to 40° C. and filter the material to obtain the bio-based hydroxy polyacrylate emulsion 6.

[0228] Comparative Example 6

[0229] The comparative example prepared a water-based two-component polyurethane coating 6, and the emulsion was prepared in the comparative example 5, and the specific steps were:

[0230] During construction, mix A5 and B5 agents at a NCO / OH molar ratio of 1.8:1;

[0231] Wherein, the A6 agent comprises the following components in parts by weight:

[0232]

[0233]

[0234] Agent B6 is a water-based polyisocyanate curing agent, the water-based polyisocyanate curing agent is Bayhydur XP2487 / 1, and the mass fraction of Bayhydur XP 2487 / 1 is 14.6 parts;

[0235] The preparation method of the A6 agent of the above-mentioned bio-based water-based two-component polyurethane coating 6 is as follows: add the bio-based hydroxy polyacrylate emulsion 6 into a stirring tank at a rotation speed of 700 rpm, premix water, dipropylene glycol butyl ether and dipropylene glycol methyl ether and add them into the stirring tank, add TEGO-800, RM-8W, TEGO-245 and TEA in sequence, disperse for 20 minutes, and filter the material.

[0236] During construction, agent B6 was added to agent A6 and stirred for 6 minutes to obtain a bio-based waterborne two-component polyurethane coating 6, whose bio-based content was 26.1%.

[0237] The paint film prepared from the bio-based waterborne two-component polyurethane coating 6 was cured and dried at room temperature for 7 days, and its properties are shown in Table 1.

[0238] Test Example 1

[0239] The water-based two-component polyurethane coatings prepared in the examples and comparative examples were cured and dried at room temperature for 7 days, and their properties are shown in Table 1.

[0240] The test standards are:

[0241] Coating appearance: visual inspection;

[0242] Surface drying time: GB / T1728-2020;

[0243] Drying time: GB / T1728-2020;

[0244] Pencil hardness: GB / T6739-2006;

[0245] Coating gloss / (60°,%): GB / T9754-2007;

[0246] Water resistance (25℃, 24h): GB / T4893.1-2020;

[0247] Dry heat resistance (70±2℃, 15h): GB / T4893.3-2020;

[0248] Ethanol resistance (50%, 1h): GB / T4893.1-2020;

[0249] The detection method is as follows:

[0250] Basic performance tests include: Bio-based hydroxy polyacrylate emulsions are tested in accordance with GB / T11175-2002 "Test Methods for Synthetic Resin Emulsions", and the appearance, pH, solid content, viscosity, and gel fraction (coarse particles) of the emulsions are tested. Paint film performance is tested in accordance with GB / T23999-2009 "Water-based Wood Coatings for Interior Decoration and Renovation", and the gloss, hardness, water resistance, dry heat resistance, and alcohol resistance are tested. The average particle size of the emulsion is measured using a nanoparticle size analyzer (ZS Nano S).

[0251] Table 1 Comprehensive properties of bio-based waterborne two-component polyurethane coating 1

[0252]

[0253] It can be seen from the above table that the water-based two-component polyurethane coating 4 of Comparative Example 2 has a longer surface drying time compared with the bio-based water-based two-component polyurethane coating 1 of Example 2, which is not conducive to improving the construction efficiency, and is far inferior to the embodiment in terms of the pencil hardness, water resistance, dry heat resistance and ethanol resistance of the paint film; compared with the bio-based water-based two-component polyurethane coating 1 of Example 2, the bio-based water-based two-component polyurethane coating 5 of Comparative Example 4 first has an unacceptable paint film defect - oil pits, and in addition, the surface drying time is slightly longer, which is not conducive to improving the construction efficiency, and is also inferior to the embodiment in terms of the pencil hardness, water resistance, dry heat resistance and ethanol resistance of the paint film; compared with the bio-based water-based two-component polyurethane coating 1 of Example 2, the bio-based water-based two-component polyurethane coating 6 of Comparative Example 6 has a longer surface drying time, which is not conducive to improving the construction efficiency, and is also inferior to the embodiment in terms of the pencil hardness, water resistance, dry heat resistance and ethanol resistance of the paint film. It can be seen from Examples 2, 4, and 6 that the present invention discloses a method for preparing a bio-based hydroxy polyacrylate emulsion. The bio-based hydroxy polyacrylate emulsion prepared by the preparation method has a high hydroxyl content, good appearance and good stability; the paint film made of the prepared bio-based water-based two-component polyurethane coating has the advantages of high hardness, high gloss, high transparency, excellent water and chemical resistance, high crosslinking density, scratch resistance, wear resistance and fast drying speed, and can be applied to high-end wood coatings, automotive coatings, metal anti-corrosion coatings and other industrial protective coatings.

[0254] Test Example 2

[0255] This test example tested the performance of the emulsions in Examples 1, 3, 5 and Comparative Examples 1, 3, 5. The data results are shown in Table 2.

[0256] Table 2: Emulsion performance comparison table

[0257]

[0258]

[0259] The difference between Comparative Example 1 and Example 1 is that the hydroxy polyacrylate emulsion synthesized without adding bio-based materials. Compared with Example 1, the bio-based content of Comparative Example 1 is 0%, the solid content is slightly lower, part of the hydroxyl groups are replaced by secondary amino groups, and the total content of hydroxyl groups and secondary amino groups is relatively high. The reason for the above changes is that no epoxy soybean oil is added to react with the secondary amino groups of the hydroxy polyacrylate polymer. Comparative Example 2 is a bio-based hydroxy polyacrylate emulsion synthesized by adding unhydrophilically modified bio-based materials. The hydroxyl content and solid content of this comparative example are consistent with those of Example 1, and the bio-based content is slightly higher. However, the particle size of Comparative Example 2 is slightly larger and the appearance is slightly worse. The main reason for the above problems is that the unhydrophilically modified bio-based material is hydrophobic and cannot be fully miscible with the emulsion under stirring conditions. Comparative Example 3 does not add hydroxyl acrylate monomers, and its hydroxyl groups are only generated by the reaction of hydrophilically modified epoxy soybean oil with secondary amino groups. Compared with Example 1, its solid content is slightly lower, the bio-based content is higher, and the content is 42.2%, but the hydroxyl content is lower, the thermal storage stability is poor, and the higher gel rate indicates that the polymerization stability is poor. The reasons for the above problems are that the amount of epoxidized soybean oil added is too high and the cross-linking density of the polymer is too high.

[0260] The above is a detailed description of the embodiments of the present invention, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the relevant technical field without departing from the purpose of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

Claims

1. A bio-based hydroxy polyacrylate emulsion, characterized in that: The preparation raw materials include: modified bio-based materials and polyacrylate polymers containing hydroxyl groups; The raw materials for preparing the modified bio-based material include hydrophilic monomers and bio-based materials; The bio-based material includes a bio-based oil containing an epoxy group; The hydrophilic monomer includes a sulfonic acid monomer; The raw materials for preparing the polyacrylate polymer containing hydroxyl groups include hydroxyl acrylate monomers and acrylamide monomers, acrylic acid monomers, acrylate monomers and vinyl monomers; The acrylic acid ester monomer comprises at least one of methyl methacrylate, butyl acrylate, isobornyl acrylate, cyclohexyl methacrylate and benzyl methacrylate; The sulfonic acid monomer is a monomer containing a secondary amino group and a sulfonic acid group; The acrylamide monomer is an acrylamide monomer containing one secondary amino group and no hydroxyl group; The hydroxy acrylate monomer includes at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate; The method for preparing the bio-based hydroxy polyacrylate emulsion comprises mixing and reacting the modified bio-based material and the polyacrylate polymer containing hydroxyl groups; S1: Evenly mix acrylic acid monomer, acrylamide monomer, acrylate monomer, vinyl monomer and hydroxy acrylate monomer to form a mixed solution A for later use; S2: Mix deionized water, emulsifier and monomer mixed solution A to obtain pre-emulsion solution B for standby use; S3: mixing ionized water, initiator and emulsifier to obtain a mixed solution C for standby use; S4: Mix deionized water and neutralizer 1 to form a mixed solution D for later use; S5: After deionized water, an emulsifier, a buffer and an initiator are mixed, stirred and heated, a part of the pre-emulsion B is added to obtain a seed emulsion, and then the remaining pre-emulsion B and mixed solution C, mixed solution D and the modified bio-based material are added to react to obtain a bio-based hydroxy polyacrylate emulsion.

2. The bio-based hydroxy polyacrylate emulsion according to claim 1, characterized in that The mass content of bio-based materials in the bio-based hydroxy polyacrylate emulsion is 5% to 25%.

3. The bio-based hydroxy polyacrylate emulsion according to claim 1, characterized in that The particle size of the bio-based hydroxy polyacrylate emulsion is 80nm~120nm.

4. The bio-based hydroxy polyacrylate emulsion according to claim 1, characterized in that The solid content of the bio-based hydroxy polyacrylate emulsion is 47-52%.

5. The bio-based hydroxy polyacrylate emulsion according to claim 1, characterized in that The mass content of hydroxyl groups in the bio-based hydroxy polyacrylate emulsion is 2.1% to 4.0%.

6. The bio-based hydroxy polyacrylate emulsion according to claim 1, characterized in that The temperature of the mixed reaction is 70-90°C.

7. A coating, characterized in that: The raw materials for preparing the coating include the bio-based hydroxy polyacrylate emulsion according to any one of claims 1 to 6.

8. Use of the coating according to claim 7 in the field of decoration.

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