CN115850568A - Bio-based hydroxyl polyacrylate emulsion and preparation method and application thereof - Google Patents
Bio-based hydroxyl polyacrylate emulsion and preparation method and application thereof Download PDFInfo
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- CN115850568A CN115850568A CN202211636902.5A CN202211636902A CN115850568A CN 115850568 A CN115850568 A CN 115850568A CN 202211636902 A CN202211636902 A CN 202211636902A CN 115850568 A CN115850568 A CN 115850568A
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Abstract
The invention discloses a bio-based hydroxyl polyacrylate emulsion and a preparation method and application thereof, and the preparation raw materials comprise: a modified bio-based material and a polyacrylate polymer containing hydroxyl groups; the preparation raw material of the modified bio-based material comprises hydrophilic modified epoxy group-containing bio-based oil; the polymerized monomers of the polyacrylate polymer containing hydroxyl groups include hydroxyl acrylate monomers and acrylamide monomers. The paint film of the aqueous two-component polyurethane paint prepared from the emulsion reduces the use of petroleum-based materials, and has the characteristics of high drying speed, high hardness and good chemical resistance.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a bio-based hydroxy polyacrylate emulsion as well as a preparation method and application thereof.
Background
The coating is a substance which is coated on the surface of an object and is used for protecting, decorating and endowing the coated object with certain performance, the existing wood coating is mostly a solvent-based coating and contains more than 50 percent of organic solvent, the solvent can volatilize into the atmosphere in the construction process to pollute the environment and damage the human health, and the organic solvent can bring potential safety hazard. Therefore, the trend of woodware coating is to develop waterborne coatings. The water-based wood coating comprises single-component and double-component water-based 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 water-based wood coating are equivalent to those of a solvent-based wood coating, and the defect of a single-component water-based wood coating is overcome, so that the double-component water-based wood coating becomes the first choice of a high-grade water-based wood coating.
The two-component waterborne polyurethane coating consists of waterborne polymer polyol and waterborne polyisocyanate curing agent, which are packaged separately and 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 water-based polyacrylate polyol has the advantages of excellent color retention, light retention and weather resistance, low price, easy adjustment of molecular weight, glass transition temperature and hydroxyl content and the like, and is the first choice of water-based polymer polyol in the two-component water-based polyurethane coating at present. Two types of polyacrylate polyols, emulsion and dispersion, can be prepared using different polymerization processes. The hydroxyl polyacrylate dispersion has high hydroxyl content, and the prepared coating film has excellent water resistance and chemical resistance, but has the defects of complex production process, product solid content of only 30-40%, slow drying speed of the coating film, high cost and the like. Emulsion type polyacrylate polyol is also called hydroxyl polyacrylate emulsion, and is called hydroxypropyl emulsion for short, but the application is limited due to the defects of low hydroxyl content, poor water resistance and chemical resistance of a paint film and the like. In addition, most of the existing two-component waterborne polyurethane coating is petroleum-based material, and does not meet the requirements of carbon peak reaching and carbon neutralization.
Therefore, there is an urgent need to develop a coating that satisfies the carbon peak demand, and has the advantages of fast drying speed, high hardness, and good chemical resistance.
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 the bio-based hydroxyl polyacrylate emulsion, and a paint film of the bio-based aqueous two-component polyurethane coating prepared by the bio-based hydroxyl polyacrylate emulsion has the characteristics of high drying speed, high hardness and good chemical resistance.
The second aspect of the invention provides a preparation method of the bio-based hydroxyl polyacrylate emulsion.
The third aspect of the invention provides a coating, and the raw materials for preparing the coating comprise the bio-based hydroxyl polyacrylate emulsion.
In a fourth aspect, the present invention provides a use of a coating in the field of decoration.
According to the embodiment of the first aspect of the invention, the preparation raw materials of the bio-based hydroxyl polyacrylate emulsion comprise: modified bio-based materials and polyacrylate polymers containing hydroxyl groups;
the raw materials for preparing the modified bio-based material comprise hydrophilic monomers and the bio-based material
The bio-based material comprises an epoxy-containing bio-based oil;
the hydrophilic monomer includes a sulfonic acid group monomer;
the preparation raw material of the polyacrylate polymer containing hydroxyl comprises a hydroxyl acrylate monomer and an acrylamide monomer.
A bio-based hydroxy polyacrylate emulsion according to embodiments of the first aspect of the present invention has at least the following beneficial effects:
after the hydroxyl polyacrylate polymer is added into the bio-based material, the epoxy group of the bio-based material and the amino group of the acrylamide monomer in the hydroxyl polyacrylate polymer are subjected to polycondensation reaction to regenerate a part of hydroxyl groups, and finally the bio-based hydroxyl polyacrylate emulsion is obtained.
The addition of the bio-based material plays a role in chain extension, the molecular weight of the polymer obtained in the reaction is improved, the polymer can be improved from a linear structure to a net structure, the paint film of the water-based two-component polyurethane paint prepared by the method has the characteristics of high drying speed, high hardness and good chemical resistance, and in addition, the use of petroleum-based materials is reduced by introducing the bio-based material for reaction, and the national requirements on carbon peak reaching and carbon neutralization can also be met.
A bio-based hydroxyl polyacrylate emulsion is prepared from the following raw materials: modified bio-based materials and polyacrylate polymers containing hydroxyl groups;
according to some embodiments of the present invention, the raw material for preparing the hydrophilic modified epoxy-containing bio-based oil comprises a hydrophilic monomer and an epoxy-containing bio-based oil.
According to some embodiments of the invention, the hydrophilic monomer comprises a sulfonic acid group monomer.
According to some embodiments of the invention, the epoxy-containing bio-based oil comprises at least one of epoxidized soybean oil and epoxidized linseed oil.
According to some embodiments of the invention, the epoxidized soybean oil comprises at least one of GreenSoft D specialty epoxidized soybean oil and GreenSoft H specialty epoxidized soybean oil.
According to some embodiments of the invention, the epoxidized linseed oil comprises epoxidized linseed oil ELO
9-5 TM 。
According to some embodiments of the invention, the sulfonic acid group monomer is a monomer containing one secondary amino group and one sulfonic acid group.
In the invention, 1 secondary amino group of the sulfonic acid monomer is used for controlling the reaction of the secondary amino group and an epoxy group of soybean oil, so that one sulfonic acid monomer is ensured to react with only one soybean oil, if 1 primary amino group or a plurality of secondary amino groups are changed, the sulfonic acid monomer can react with two or a plurality of soybean oils, if one sulfonic acid monomer is connected with two or a plurality of soybean oils, on one hand, the hydrophilic modified bio-based material has larger molecular weight, poor hydrophilicity and reduced reactivity, and further the paint film performance is influenced, on the other hand, the hydrophilic modified bio-based material has improved functionality, and the crosslinking reaction is excessive, so that the reaction process of the emulsion and the storage stability are influenced; 1 sulfonic group can also ensure the hydrophilic modification of organisms and materials and simultaneously avoid the water resistance of a paint film from being reduced.
According to some embodiments of the invention, the sulfonic acid monomer comprises at least one of cyclohexylaminoethanesulfonic acid (CHES), cyclohexylaminopropanesulfonic Acid (CAPS), and cyclohexylaminobutanesulfonic acid (cab).
According to some embodiments of the invention, the acrylamide monomer is an acrylamide monomer containing one secondary amino group and no hydroxyl group.
In the invention, the acrylamide monomer does not contain hydroxyl, so that the phenomenon that the original hydroxyl and a newly generated hydroxyl (generated by the reaction of epoxy and a secondary amino) form steric hindrance, the hydroxyl cannot completely react with NCO, and the water resistance is obviously reduced by the residual hydroxyl can be avoided.
According to some embodiments of the invention, the bio-based hydroxy polyacrylate emulsion has a bio-based mass content of 5% to 25%.
According to some embodiments of the invention, the bio-based hydroxy polyacrylate emulsion has a particle size of 80nm to 120nm.
According to some preferred embodiments of the present invention, the bio-based hydroxy polyacrylate emulsion has a particle size of 90nm to 110nm.
The particle diameter in the above range can ensure the appearance of the emulsion to take a micro-penetration state.
According to some embodiments of the invention, the bio-based hydroxy polyacrylate emulsion has a solids content of 47-52%.
According to some embodiments of the invention, the bio-based hydroxyl polyacrylate emulsion has a hydroxyl content of 2.1% to 4.0% by mass.
The hydroxyl content and the solid content in the invention are in the ranges, so that the universality of the emulsion in subsequent use and the paint film performance can be ensured.
According to some embodiments of the present invention, the raw material for preparing the hydroxyl group-containing polyacrylate polymer further includes an acrylic monomer, an acrylate monomer, and a vinyl monomer.
According to some embodiments of the invention, the acrylic monomer comprises at least one of an acrylic monomer and a methacrylic monomer.
According to some preferred embodiments of the present invention, the acrylic monomer comprises at least one of acrylic and methacrylic monomers of sambucus.
According to some embodiments of the invention, the acrylamide monomer comprises at least one of N-tert-butyl acrylamide, N-ethyl acrylamide, and N-methyl-2-acrylamide.
According to some preferred embodiments of the present invention, the acrylamide monomer comprises at least one of N-t-butylacrylamide, N-ethylacrylamide, and N-methyl-2-acrylamide, available from Allantin.
According to some embodiments of the present invention, the acrylate monomer comprises at least one of methyl methacrylate, butyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, and benzyl methacrylate.
According to some preferred embodiments of the present invention, the acrylate monomer comprises at least one of methyl methacrylate, butyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, and benzyl methacrylate from Sanko.
According to some embodiments of the invention, the vinyl monomer comprises styrene.
According to some preferred embodiments of the present invention, the vinyl monomer comprises styrene from sambucus.
According to some embodiments of the invention, the hydroxy acrylate monomer comprises at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
According to some preferred embodiments of the present invention, the hydroxy acrylate monomer comprises at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate of chang corporation.
Embodiments according to the second aspect of the present invention provide a method for preparing a bio-based hydroxy polyacrylate emulsion, which comprises mixing and reacting the modified bio-based material and the polyacrylate polymer containing hydroxyl.
According to some embodiments of the invention, the modified bio-based material and the polyacrylate polymer containing hydroxyl groups are mixed at a temperature of 70 to 90 ℃.
According to some embodiments of the invention, in the mixing reaction of the modified bio-based material and the polyacrylate polymer containing hydroxyl, the mixing reaction time is 45 to 80 minutes.
According to some preferred embodiments of the present invention, the preparation method of the bio-based hydroxyl polyacrylate emulsion comprises mixing and stirring the modified bio-based material and the polyacrylate polymer containing hydroxyl groups for 15 to 25 minutes, heating to 70 to 90 ℃, reacting for 45 to 80 minutes, stopping the reaction after the epoxy value is less than 0.005 determined by a hydrochloric acid-acetone method, cooling to 40 ℃, and filtering to obtain the bio-based hydroxyl polyacrylate emulsion.
According to some embodiments of the invention, the method of preparing the modified bio-based material comprises: and mixing the bio-based material, the hydrophilic monomer and a sulfonic acid neutralizer for reaction to obtain a hydrophilic modified bio-based material E for later use.
According to some embodiments of the invention, the modified bio-based material comprises, in parts 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.
According to some embodiments of the invention, the sulfonic acid neutralizing agent comprises a tertiary amine neutralizing agent that does not contain a hydroxyl group.
According to some embodiments of the invention, the sulfonic acid neutralizing agent comprises at least one of Triethylamine (TEA) and N, N-Dimethylcyclohexylamine (DMCHA).
The sulfonic acid neutralizer does not contain hydroxyl so as to avoid the reaction of the hydroxyl and isocyanate, consume a curing agent and influence the performance of a final paint film; the tertiary amine is selected to avoid the reaction with the epoxy group, and simultaneously has the function of catalyzing the reaction of hydroxyl and isocyanate, so that the performance of the final paint film can be improved.
According to some preferred embodiments of the present invention, the method of preparing the modified bio-based material comprises: adding 13-21 parts of bio-based material, stirring and heating, heating to 70-90 ℃, adding 4-5 parts of sulfonic monomer and 2-3 parts of sulfonic acid neutralizer, reacting for 50-80 minutes, determining that the epoxy value is 0.195-0.331 by a hydrochloric acid-acetone method, and stopping the reaction to obtain the hydrophilic modified bio-based material E for later use.
According to some embodiments of the invention, the polyacrylate polymer is prepared from raw materials comprising: polyacrylate polymer, emulsifier, deionization and neutralizer 1.
According to some preferred embodiments of the present invention, the method of preparing the polyacrylate polymer comprises:
s1: uniformly mixing an acrylic monomer, an acrylamide monomer, an acrylate monomer, a vinyl monomer and a hydroxyl acrylate monomer to form a mixed solution A for later use;
s2: mixing deionized water, an emulsifier and a monomer mixed solution A to obtain a pre-emulsion B for later use;
s3: mixing the ionized water, the initiator and the emulsifier to obtain a mixed solution C for later use;
s4: mixing deionized water and the neutralizing agent 1 to form a mixed solution D for later use;
s5: and mixing and stirring deionized water, an emulsifier, a buffering agent and an initiator, heating, adding part of the pre-emulsion B to obtain a seed emulsion, adding the rest of the pre-emulsion B, the mixed solution C, the mixed solution D and the hydrophilic modified bio-based material E, and reacting to obtain the bio-based hydroxyl polyacrylate emulsion.
According to some more preferred embodiments of the present invention, the method of preparing the polyacrylate polymer comprises:
s1: uniformly mixing an acrylic monomer, an acrylamide monomer, an acrylate monomer, a vinyl monomer and a hydroxyl acrylate monomer to form a mixed solution A for later use;
s2: mixing deionized water and an emulsifier, adding the monomer mixed solution A, and continuously dispersing to obtain a pre-emulsion B for later use;
s3: mixing the ionized water, the initiator and the emulsifier to obtain a mixed solution C for later use;
s4: mixing deionized water and the neutralizing agent 1 to form a mixed solution D for later use;
s5: and mixing and stirring deionized water, an emulsifier, a buffering agent and an initiator, heating, adding part of the pre-emulsion B to obtain a seed emulsion, adding the rest of the pre-emulsion B, the mixed solution C, the mixed solution D and the hydrophilic modified bio-based material E, and reacting to obtain the bio-based hydroxyl polyacrylate emulsion.
According to some embodiments of the present invention, the mixed solution a of step S1 includes, by weight, 0.9 to 1.1 parts of an acrylic monomer, 3.5 to 8.5 parts of an acrylamide monomer, 15 to 31 parts of an acrylate monomer, 5 to 9 parts of a vinyl monomer, and 5 to 15 parts of a hydroxy acrylate monomer.
According to some embodiments of the present invention, the pre-emulsion B of step S2 comprises, by weight, 28 to 33 parts of deionized water, 0.45 to 2.1 parts of an emulsifier, and 42.1 to 48.3 parts of the monomer mixture a.
According to some preferred embodiments of the present invention, step S2 includes dissolving 0.45-2.1 parts of emulsifier in 28-33 parts of deionized water, stirring uniformly, adjusting the dispersing machine to 700 rpm, dropping 42.1-48.3 parts of monomer mixed solution a, dropping for 15-25 minutes, and continuing to disperse for 10-20 minutes to obtain pre-emulsion B for use.
According to some embodiments of the present invention, the mixed solution C of step S3 comprises 5 to 7 parts by weight of deionized water, 0.2 to 0.6 part by weight of an initiator, and 0 to 1 part by weight of an emulsifier.
According to some embodiments of the present invention, the mixed solution D of step S4 comprises 5 to 8.5 parts by weight of deionized water and 0.5 to 0.7 part by weight of neutralizing agent 1.
According to some embodiments of the present invention, the bio-based hydroxy polyacrylate emulsion in step S5 comprises, by weight, 30 to 38 parts of deionized water, 0.3 to 0.8 part of an emulsifier, 0.1 to 0.25 part of a buffer, 0.1 to 0.2 part of an initiator, 71 to 84.5 parts of a pre-emulsion B, 6.5 to 8.5 parts of a mixed solution C, 5.5 to 9.5 parts of a mixed solution D, and 19 to 28 parts of a hydrophilic modified bio-based material E.
According to some embodiments of the invention, the initiator comprises a persulfate.
According to some embodiments of the invention, the emulsifier comprises at least one of a non-reactive emulsifier and a reactive emulsifier.
According to some embodiments of the present invention, the non-reactive emulsifier comprises at least one of Sodium Dodecyl Sulfate (SDS), isomeric alcohol ethoxylates (EH-9) from Dow corporation, DOWFAX-2A1, and ammonium fatty alcohol polyoxyethylene ether sulfate (KL-525).
According to some embodiments of the invention, the reactive emulsifier comprises at least one of sodium 3-allyloxy-1-hydroxypropanesulfonate (COPS-1), sodium 2-acrylamido-2-methylpropanesulfonate (COPS-2), SR-10, and ER-30.
According to some embodiments of the invention, the neutralizing agent 1 comprises a neutralizing agent comprising a tertiary amine.
According to some embodiments of the invention, the neutralizing agent 1 comprises at least one of Triethylamine (TEA), N-Dimethylethanolamine (DMEA) and N, N-Dimethylcyclohexylamine (DMCHA).
According to some embodiments of the invention, the buffer comprises sodium bicarbonate (NaHCO) 3 ) And sodium carbonate (Na) 2 CO 3 ) At least one of (1).
According to some embodiments of the invention, the initiator comprises at least one of potassium persulfate (KPS) and Ammonium Persulfate (APS).
The embodiment of the third aspect of the invention provides a coating, and the raw material for preparing the coating comprises the bio-based hydroxyl polyacrylate emulsion.
According to some embodiments of the invention, the coating is prepared by a method comprising mixing an agent A and an agent B at the NCO/OH molar ratio of 1.0-1.8 during construction;
the agent A comprises the following components in parts by weight: 60-65 parts of bio-based hydroxy polyacrylate emulsion, 30-36 parts of water, 2-4 parts of film-forming additive, 0.05-0.2 part of defoaming agent, 0.5-0.8 part of thickening agent, 0.05-0.2 part of wetting agent and 2.2-0.5 part of neutralizing agent;
the agent B comprises the following components in parts by weight: 15-30 parts of a water-based polyisocyanate curing agent.
According to the invention, the NCO/OH molar ratio is 1.0-1.8, and by adopting the ratio, the defects of low hardness and poor resistance of a paint film caused by too low ratio and miliaria on the surface of the paint film caused by too high ratio are avoided.
According to some embodiments of the invention, the coalescent comprises at least one of propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, and dipropylene glycol butyl ether.
According to some embodiments of the invention, the defoamer comprises at least one of a polyether siloxane copolymer defoamer and a modified polysiloxane interpolymer solution.
According to some embodiments of the invention, the polyether siloxane copolymer defoamer comprises at least one of TEGO-800, TEGO-805, TEGO-815 and TEGO-825.
According to some embodiments of the invention, the modified polysiloxane interpolymer solution comprises at least one of BYK-019 and BYK-020.
According to some embodiments of the invention, the thickener comprises 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.
According to some embodiments of the invention, the nonionic polyurethane associative thickener comprises RM-8W.
According to some embodiments of the invention, the hydrophobically modified alkali-swellable associative thickener TT-935.
According to some embodiments of the invention, the alkali swelling non-associative thickener comprises ASE-60.
According to some embodiments of the invention, the nonionic associative thickener comprises at least one of TEGO ViscoPlus3000, TEGO ViscoPlus 3030, TEGO ViscoPlus 3060.
According to some embodiments of the invention, the wetting agent comprises at least one of a polyether siloxane copolymer, a nonionic organic surfactant, and a polyether modified polysiloxane solution.
According to some embodiments of the invention, the polyether siloxane copolymer comprises TEGO-245.
According to some embodiments of the invention, the non-ionic organic surfactant comprises TEGO-500.
According to some embodiments of the invention, the polyether modified polysiloxane solution comprises BYK-346.
According to some embodiments of the invention, the neutralizing agent 2 comprises at least one of triethylamine, dimethylethanolamine.
According to some embodiments of the invention, the polyisocyanate curing agent comprises at least one of a sulfonate, a carboxylate, and an alkoxy hydrophilically modified Hexamethylene Diisocyanate (HDI).
According to some embodiments of the present invention, the polyisocyanate curing agent comprises at least one of Bayhydur XP2487/1 and Bayhydur XP 2655.
According to some embodiments of the present invention, the method for preparing the bio-based aqueous two-component polyurethane coating comprises the following steps:
premixing water and a film-forming additive, adding a hydroxyl polyacrylate emulsion, sequentially adding a defoaming agent, a thickening agent, a wetting agent and a neutralizing agent 2, dispersing for 10-30 minutes, and filtering to obtain an agent A;
during construction, the waterborne polyisocyanate curing agent is added into the agent A according to the NCO/OH molar ratio of 1.0-1.8, and stirred for 5-8 minutes to obtain the bio-based waterborne two-component polyurethane coating.
According to the invention, the agent A and the agent B of the bio-based two-component polyurethane coating prepared by the method are matched for use, and the paint film of the bio-based water-based two-component polyurethane coating has the advantages of high gloss, high transparency, excellent water resistance and chemical resistance, high crosslinking density, high hardness, scratch resistance, wear resistance, high drying speed and the like, and can be applied to high-grade wood coatings, automobile coatings, metal anticorrosive coatings and other industrial protective coatings.
Embodiments according to a fourth aspect of the present invention provide for the use of a coating in the field of decoration.
According to some embodiments of the invention, the field of paint decoration comprises woodware.
According to some embodiments of the invention, the paint finishing field comprises metal.
According to some embodiments of the invention, the paint finishing field comprises automobiles.
According to some embodiments of the invention, the paint decoration field comprises metal corrosion protection.
Detailed Description
The idea of the invention and the resulting technical effects will be clearly and completely described below in connection with the embodiments, so that the objects, features and effects of the invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
The (meth) acrylic acid monomer is acrylic acid or methacrylic acid from Sanmu corporation;
the acrylamide monomer is N-tert-butyl acrylamide, N-ethyl acrylamide and N-methyl-2-acrylamide of the Aladdin company;
the (methyl) acrylate monomer is methyl methacrylate, butyl acrylate, isobornyl acrylate, cyclohexyl methacrylate and benzyl methacrylate from Sanwood company;
the vinyl monomer is styrene from Sanko;
the hydroxyl acrylate monomer is hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate of Changxing company;
the non-reactive emulsifier is Sodium Dodecyl Sulfate (SDS) of Pasteur, isomeric alcohol polyoxyethylene ether (EH-9) of Dow, DOWFAX-2A1, and ammonium fatty alcohol polyoxyethylene ether sulfate (KL-525) of Guangzhou airline;
the reactive emulsifier is sodium 3-allyloxy-1-hydroxypropanesulfonate (COPS-1), sodium 2-acrylamido-2-methylpropanesulfonate (COPS-2), SR-10 and ER-30 from Ediko, japan;
the buffering agent is sodium bicarbonate (NaHCO 3) and sodium carbonate (Na 2CO 3) in West Longdu chemistry;
the initiator is potassium persulfate (KPS) and Ammonium Persulfate (APS) in Szelong chemical;
the bio-based material 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 ；
The sulfonic monomer is cyclohexylaminoethanesulfonic acid (CHES), cyclohexylaminopropanesulfonic Acid (CAPS) and Cyclohexylaminobutanesulfonic Acid (CABS);
the sulfonic acid neutralizer is Triethylamine (TEA) and N, N-Dimethylcyclohexylamine (DMCHA) from the Dow company; the neutralizer is Triethylamine (TEA), N-Dimethylethanolamine (DMEA) and N, N-Dimethylcyclohexylamine (DMCHA) from the Dow company;
the defoaming agent is TEGO-800, TEGO-805, TEGO-815, TEGO-825, BYK-019 or BYK-020 solution of modified polysiloxane copolymer of TEGO, inc.;
the thickener is nonionic polyurethane associative thickener RM-8W of DOW company, hydrophobic modified alkali swelling associative thickener TT-935, alkali swelling nonionic thickener ASE-60, nonionic associative thickener TEGO Visco plus3000, TEGO Visco plus 3030 and TEGO Visco plus 3060 of TEGO company; the wetting agent is polyether siloxane copolymer TEGO-245 of TEGO company, a nonionic organic surfactant TEGO-500 and polyether modified polysiloxane solution BYK-346 of BYK company;
the neutralizer is triethylamine and dimethylethanolamine from Dow company;
the polyisocyanate curing agent comprises sulfonate, carboxylate and alkoxy hydrophilic modified Hexamethylene Diisocyanate (HDI);
the polyisocyanate curing agent is Bayhydur XP2487/1 and Bayhydur XP 2655 of Corseus corporation;
example 1
A bio-based hydroxyl polyacrylate emulsion 1 is prepared by the following steps:
s1, uniformly mixing 0.9 part 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 in parts by mass to form a mixed solution A1 for later use;
s2, adding 33 parts of deionized water into a dispersion cylinder, dissolving 0.5 part of SDS and 1 part of EH-9, uniformly stirring, adjusting a dispersion machine to 700 revolutions per minute, dropwise adding 42.1 parts of mixed solution A1, completing dropwise adding in 25 minutes, and continuing to disperse for 10 minutes after completing dropwise adding to obtain pre-emulsion B1 for later use;
s3, dissolving 0.45 part of APS and 1 part of COPS-1 by 7 parts of deionized water in parts by mass to form a mixed solution C1 for later use;
s4, uniformly mixing 8.5 parts of deionized water and 0.6 part of DMEA in parts by mass to form a mixed solution D1 for later use;
s5, adding 20.7 parts of epoxidized soybean oil GreenSoft D into a four-neck flask provided with a thermometer, a condenser pipe and a stirring paddle in parts by mass, stirring and heating, heating to 70 ℃, adding 4.6 parts of cyclohexylaminoethanesulfonic acid and 2.3 parts of TEA, reacting for 80 minutes, determining that the epoxy value is 0.241 by using a hydrochloric acid-acetone method, and stopping the reaction to obtain a hydrophilic modified bio-based material E1 for later use;
s6, a thermometer, a condenser pipe and a stirrer are arranged36.3 parts of deionized water, 0.25 part of SDS, 0.5 part of EH-9,0.2 part of NaHCO were placed in a four-necked flask with a paddle and a constant pressure dropping funnel 3 And 0.15 part of APS, stirring and heating, and after the temperature reaches 77 ℃, dropwise adding 7.7 parts of pre-emulsion B1 for 15 minutes, and stabilizing for 10 minutes after dropwise adding to obtain the seed emulsion. Heating to 80 ℃, simultaneously dropwise adding 68.9 parts of pre-emulsion B1 and 8.45 parts of mixed solution C1, finishing dripping after 3.5 hours, heating to 85 ℃ after finishing dripping, keeping the temperature for 2 hours, cooling to 55 ℃, adding 9.1 parts of mixed solution D1, stirring for 10 minutes, adding 27.6 parts of hydrophilic modified bio-based material E1, stirring for 15 minutes, heating to 80 ℃, reacting for 60 minutes, determining that the epoxy value is less than 0.005 by using a hydrochloric acid-acetone method, and stopping the reaction;
s7, cooling to 40 ℃, and filtering to obtain the bio-based hydroxyl polyacrylate emulsion 1.
Example 2
The embodiment prepares a bio-based aqueous two-component polyurethane coating 1, and the bio-based hydroxyl polyacrylate emulsion is prepared in the embodiment 1, and the concrete steps are as follows:
in construction, according to the NCO/OH molar ratio of 1.8:1 agent A1 and agent B1 mixed;
wherein the A1 agent consists of the following components in parts by weight:
the B1 agent is a waterborne polyisocyanate curing agent, the waterborne polyisocyanate curing agent is Bayhydur XP2487/1, and 21.4 parts of Bayhydur XP2487/1 by mass;
the preparation method of the A1 agent comprises the following steps: adding the bio-based hydroxyl polyacrylate emulsion 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, dispersing for 20 minutes, filtering and discharging.
During construction, the B1 agent is added into the A1 agent and stirred for 6 minutes to obtain the bio-based aqueous two-component polyurethane coating 1, wherein the bio-based content of the coating is 11.4 percent.
A paint film prepared from the bio-based water-based two-component polyurethane paint 1 is cured and dried for 7 days at normal temperature, and the performances of the paint film are shown in Table 1.
Example 3
A bio-based hydroxyl polyacrylate emulsion 2 is prepared by the following steps:
s1, uniformly mixing 1 part of methacrylic acid, 3.8 parts of N-ethyl acrylamide, 9.5 parts of isobornyl acrylate, 11 parts of methyl methacrylate, 10.45 parts of butyl acrylate, 5.5 parts of styrene and 5.5 parts of hydroxyethyl acrylate in parts by mass to form a mixed solution A2 for later use;
s2, adding 28 parts of deionized water into a dispersion cylinder, dissolving 0.45 part of KL-525, uniformly stirring, adjusting a dispersion machine to 700 revolutions per minute, dropwise adding 46.75 parts of mixed solution A2, finishing dropping in 20 minutes, and continuously dispersing for 8 minutes after finishing dropping to obtain pre-emulsion B2 for later use;
s3, dissolving 0.2 part of KPS and 0.75 part of COPS-2 by using 5 parts of deionized water in parts by mass to form a mixed solution C2 for later use;
s4, uniformly mixing 5.5 parts of deionized water and 0.5 part of TEA in parts by mass to form a mixed solution D2 for later use;
s5, adding 13 parts of epoxidized soybean oil GreenSoft H into a four-neck flask provided with a thermometer, a condenser and a stirring paddle in parts by mass, stirring and heating, heating to 80 ℃, adding 4.3 parts of cyclohexylaminopropanesulfonic acid and 2.4 parts of DMCHA, reacting for 65 minutes, determining that the epoxy value is 0.195 by using a hydrochloric acid-acetone method, and stopping the reaction to obtain a hydrophilic modified bio-based material E2 for later use;
s6, adding 30.7 parts of deionized water, 0.3 part of KL-525 and 0.15 part of NaHCO into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant-pressure dropping funnel 3 And 0.1 part of KPS, mixing, stirring and heating, dripping 6 parts of pre-emulsion B2 after the temperature reaches 80 ℃, and stabilizing for 15 minutes after dripping to obtain the seed emulsion. Maintaining the temperature at 80 ℃, simultaneously dripping 69.2 parts of pre-emulsion B2 and 5.95 parts of mixed solution C2, finishing dripping within 4 hours, heating to 90 ℃ after finishing dripping, preserving heat for 1 hour, cooling to 50 ℃, adding 6 parts of mixed solution D2, stirring for 8 minutes, adding 19.7 parts of hydrophilic modified bio-based material E2, stirring for 20 minutes, heating to 70 ℃, and reversely stirringThe reaction is stopped after 80 minutes, and the epoxy value is less than 0.005 by using a hydrochloric acid-acetone method;
s7, cooling to 40 ℃, and filtering to obtain the bio-based hydroxyl polyacrylate emulsion 2.
Example 4
In this embodiment, a bio-based aqueous two-component polyurethane coating 2 is further prepared, and the bio-based hydroxyl polyacrylate emulsion is prepared in embodiment 3, and the specific steps are as follows:
in construction, according to the NCO/OH molar ratio of 1.8:1 mixed agent A2 and agent B2;
wherein the A2 agent consists of the following components in parts by weight:
the B2 agent is a waterborne polyisocyanate curing agent, the waterborne polyisocyanate curing agent is Bayhydur XP 2655, and the Bayhydur XP 2655 accounts for 14.7 parts by mass;
the preparation method of the A2 agent of the bio-based water-based two-component polyurethane coating 2 comprises the following steps: adding the bio-based hydroxyl polyacrylate emulsion 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 10 minutes, filtering and discharging.
During construction, the B2 agent is added into the A2 agent, and stirring is carried out for 5 minutes to obtain the bio-based water-based two-component polyurethane coating 2, wherein the bio-based content is 12%.
A paint film prepared from the bio-based water-based two-component polyurethane paint 2 is cured and dried for 7 days at normal temperature, and the performances are shown in Table 1.
Example 5
A bio-based hydroxyl polyacrylate emulsion 3 is prepared by the following steps:
s1, uniformly mixing 1.1 parts of acrylic acid, 6.3 parts of N-methyl-2-acrylamide, 5 parts of benzyl methacrylate, 5 parts of methyl methacrylate, 7 parts of butyl acrylate, 8.9 parts of styrene and 15 parts of hydroxypropyl methacrylate in parts by mass to form a mixed solution A3 for later use;
s2, adding 30 parts of deionized water into a dispersion cylinder, dissolving 0.6 part of DOWFAX-2A1, 0.5 part of SR-10 and 1 part of ER-30, uniformly stirring, adjusting a dispersion machine to 700 revolutions per minute, dropwise adding 48.3 parts of mixed solution A3, finishing dropping in 30 minutes, and continuously dispersing for 12 minutes after finishing dropping to obtain pre-emulsion B3 for later use;
s3, dissolving 0.6 part of APS by 6 parts of deionized water to form a mixed solution C3 for later use;
s4, uniformly mixing 7 parts of deionized water and 0.7 part of DMCHA by mass to form a mixed solution D3 for later use;
s5, adding 15.6 parts of epoxy linseed oil ELO (Eleox) into a four-neck flask with a thermometer, a condenser pipe and a stirring paddle in parts by mass
9-5, stirring and heating, heating to 90 ℃, adding 4.4 parts of cyclohexylaminobutanesulfonic acid and 2.3 parts of DMCHA, reacting for 50 minutes, determining that the epoxy value is 0.331 by a hydrochloric acid-acetone method, and stopping the reaction to obtain a hydrophilic modified bio-based material E3 for later use;
s6, adding 34.3 parts of deionized water, 0.5 part of DOWFAX-2A1, 0.2 part of SR-10 and 0.25 part of NaHCO into a four-neck flask provided with a thermometer, a condenser tube, a stirring paddle and a constant-pressure dropping funnel 3 And 0.1 part of KPS, stirring and heating, and dripping 9.5 parts of pre-emulsion B3 after the temperature reaches 83 ℃ for 25 minutes, and stabilizing for 20 minutes after dripping to obtain the seed emulsion. Heating to 85 ℃, simultaneously dropwise adding 70.9 parts of pre-emulsion B3 and 6.6 parts of mixed solution C3, dropwise adding after 5 hours, maintaining at 85 ℃ after dropwise adding, keeping the temperature for 1.5 hours, cooling to 60 ℃, adding 7.5 parts of mixed solution D3, stirring for 12 minutes, adding 22.3 parts of hydrophilic modified bio-based material E3, stirring for 25 minutes, heating to 90 ℃, reacting for 45 minutes, and stopping the reaction after the epoxy value is less than 0.005 measured by a hydrochloric acid-acetone method;
s7, cooling to 40 ℃, and filtering to obtain the bio-based hydroxyl polyacrylate emulsion 3.
Example 6
The embodiment prepares a bio-based aqueous two-component polyurethane coating 3, and the bio-based hydroxyl polyacrylate emulsion is prepared in the embodiment 5, and the concrete steps are as follows:
in construction, according to the NCO/OH molar ratio of 1.8:1 mixed agent A3 and agent B3;
wherein, the A3 agent comprises the following components in parts by weight:
the B3 agent is a waterborne polyisocyanate curing agent, the waterborne polyisocyanate curing agent is Bayhydur XP2487/1, and the Bayhydur XP2487/1 accounts for 26.0 parts by mass;
the preparation method of the A3 agent of the bio-based water-based two-component polyurethane coating 3 comprises the following steps: adding the bio-based hydroxyl polyacrylate emulsion 3 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 30 minutes, filtering and discharging.
During construction, the B3 agent is added into the A3 agent, and stirring is carried out for 8 minutes to obtain the bio-based water-based two-component polyurethane coating 3, wherein the bio-based content is 10.35%.
A paint film prepared from the bio-based water-based two-component polyurethane paint 3 is cured and dried for 7 days at normal temperature, and the performances are shown in Table 1.
Comparative example 1
The difference between the comparative example and the example 1 is that hydroxyl polyacrylate emulsion synthesized by adding no bio-based material comprises the following specific steps:
s1, uniformly mixing 0.9 part 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 in parts by mass to form a mixed solution A4 for later use;
s2, adding 33 parts of deionized water into a dispersion tank, dissolving 0.5 part of SDS and 1 part of EH-9, uniformly stirring, adjusting a dispersion machine to 700 revolutions per minute, dropwise adding 42.1 parts of mixed solution A4, finishing dripping after 25 minutes, and continuously dispersing for 10 minutes after finishing dripping to obtain a pre-emulsion B4 for later use;
s3, dissolving 0.45 part of APS and 1 part of COPS-1 by using 7 parts of deionized water in parts by mass to form a mixed solution C4 for later use;
s4, uniformly mixing 8.5 parts of deionized water and 0.6 part of DMEA in parts by mass to form a mixed solution D4 for later use;
s5, adding 26.3 parts of deionized water, 0.25 part of SDS, 0.5 part of EH-9 and 0.2 part of NaHCO into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant-pressure dropping funnel 3 And 0.15 part of APS, stirring and heating, and after the temperature reaches 77 ℃, dropwise adding 7.7 parts of pre-emulsion B4 for 15 minutes, and stabilizing for 10 minutes after dropwise adding to obtain the seed emulsion. Heating to 80 ℃, simultaneously dropwise adding 68.9 parts of pre-emulsion B4 and 8.45 parts of mixed solution C4, finishing dripping within 3.5 hours, heating to 85 ℃ after finishing dripping, keeping the temperature for 2 hours, cooling to 55 ℃, adding 9.1 parts of mixed solution D4, stirring for 10 minutes, then dispersing at a high speed for 15 minutes, heating to 80 ℃, reacting for 60 minutes, and stopping the reaction after determining that the epoxy value is less than 0.005 by using a hydrochloric acid-acetone method;
s6, cooling to 40 ℃, and filtering to obtain the hydroxyl polyacrylate emulsion 4.
Comparative example 2
Comparative example a water-borne two-component polyurethane coating 4 was prepared, the emulsion was prepared as in comparative example 1, the specific steps being:
in construction, according to the NCO/OH molar ratio of 1.8:1 mixed agent A4 and agent B4;
wherein, the A4 agent comprises the following components in parts by weight:
the B4 agent is a waterborne polyisocyanate curing agent, the waterborne polyisocyanate curing agent is Bayhydur XP2487/1, and the Bayhydur XP2487/1 accounts for 28.4 parts by mass;
the preparation method of the A4 agent of the water-based two-component polyurethane coating 4 comprises the following steps: adding the hydroxyl polyacrylate emulsion 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, dispersing for 20 minutes, filtering and discharging.
During construction, the B4 agent is added into the A4 agent and stirred for 6 minutes to obtain the water-based two-component polyurethane coating 4 with the bio-based content of 0%.
A paint film prepared from the water-based two-component polyurethane paint 4 is cured and dried for 7 days at normal temperature, and the performances are shown in Table 1.
Comparative example 3
The comparative example is a bio-based hydroxyl polyacrylate emulsion synthesized from bio-based materials which are not modified by hydrophile. The method comprises the following specific steps:
s1, uniformly mixing 0.9 part 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 6.3 parts of hydroxyethyl methacrylate in parts by mass to form a mixed solution A5 for later use;
s2, adding 33 parts of deionized water into a dispersion cylinder, dissolving 0.5 part of SDS and 1 part of EH-9, uniformly stirring, adjusting a dispersion machine to 700 revolutions per minute, dropwise adding 38.4 parts of mixed solution A5, completing dropwise adding in 25 minutes, and continuing to disperse for 10 minutes after completing dropwise adding to obtain pre-emulsion B5 for later use;
s3, dissolving 0.45 part of APS and 1 part of COPS-1 by 7 parts of deionized water in parts by mass to form a mixed solution C5 for later use;
s4, uniformly mixing 8.5 parts of deionized water and 0.6 part of DMEA in parts by mass to form a mixed solution D5 for later use;
s5, adding 36.3 parts of deionized water, 0.25 part of SDS, 0.5 part of EH-9,0.2 part of NaHCO into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant pressure dropping funnel 3 And 0.15 part of APS, stirring and heating, and after the temperature reaches 77 ℃, dropwise adding 7.3 parts of pre-emulsion B1 for 15 minutes, and stabilizing for 10 minutes after dropwise adding to obtain the seed emulsion. Heating to 80 ℃, simultaneously dripping 65.6 parts of pre-emulsion B1 and 8.45 parts of mixed solution C1, finishing dripping within 3.5 hours, heating to 85 ℃ after finishing dripping, preserving heat for 2 hours, cooling to 55 ℃, adding 9.1 parts of mixed solution D1, stirring for 10 minutes, adding 15.6 parts of epoxidized soybean oil GreenSoft D, stirring for 15 minutes, heating to 80 ℃ after stirring for 60 minutes, reacting with hydrochloric acid-acetoneStopping the reaction after the epoxy value is less than 0.005;
s7, cooling to 40 ℃, and filtering to obtain the bio-based hydroxyl polyacrylate emulsion 5.
Comparative example 4
The comparative example prepares the aqueous two-component polyurethane coating 5, the emulsion is prepared in the comparative example 3, and the concrete steps are as follows:
in construction, according to the NCO/OH molar ratio of 1.8:1 mixed agent A5 and agent B5;
wherein, the A5 agent comprises the following components in parts by weight:
the B5 agent is a waterborne polyisocyanate curing agent, the waterborne polyisocyanate curing agent is Bayhydur XP2487/1, and 21.4 parts of Bayhydur XP2487/1 by mass;
the preparation method of the A5 agent of the bio-based water-based two-component polyurethane coating 5 comprises the following steps: adding the bio-based hydroxyl polyacrylate emulsion 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, dispersing for 20 minutes, filtering and discharging.
During construction, the B5 agent is added into the A5 agent and stirred for 6 minutes to obtain the bio-based aqueous two-component polyurethane coating 5, wherein the bio-based content of the coating is 14.4 percent.
A paint film prepared from the bio-based water-based two-component polyurethane paint 5 is cured and dried for 7 days at normal temperature, and the performances are shown in Table 1.
Comparative example 5
The comparative example is example 1, except that no hydroxy acrylate monomer is added, and the specific steps are as follows:
s1, uniformly mixing 0.9 part 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 in parts by mass to form a mixed solution A6 for later use;
s2, adding 33 parts of deionized water into a dispersion cylinder, dissolving 0.5 part of SDS and 1 part of EH-9, uniformly stirring, adjusting a dispersion machine to 700 revolutions per minute, dropwise adding 41.9 parts of mixed solution A6, completing dropwise adding in 25 minutes, and continuing to disperse for 10 minutes after completing dropwise adding to obtain pre-emulsion B6 for later use;
s3, dissolving 0.45 part of APS and 1 part of COPS-1 by 7 parts of deionized water in parts by mass to form a mixed solution C6 for later use;
s4, uniformly mixing 8.5 parts of deionized water and 0.6 part of DMEA in parts by mass to form a mixed solution D6 for later use;
s5, adding 44.8 parts of GreenSoft D into a four-neck flask provided with a thermometer, a condenser and a stirring paddle in parts by mass, stirring and heating, heating to 70 ℃, adding 9.9 parts of cyclohexylaminoethanesulfonic acid and 4.8 parts of TEA, reacting for 80 minutes, determining the epoxy value to be 0.241 by using a hydrochloric acid-acetone method, and stopping the reaction to obtain a hydrophilic modified bio-based material E1 for later use;
s6, adding 65.05 parts of deionized water, 0.25 part of SDS, 0.5 part of EH-9,0.2 part of NaHCO into a four-neck flask provided with a thermometer, a condenser pipe, a stirring paddle and a constant-pressure dropping funnel 3 And 0.15 part of APS, stirring and heating, and after the temperature reaches 77 ℃, 7.6 parts of pre-emulsion B1 is dropwise added for 15 minutes, and after the dropwise addition is finished, the mixture is stabilized for 10 minutes to obtain a seed emulsion. Heating to 80 ℃, simultaneously dropwise adding 68.8 parts of pre-emulsion B1 and 8.45 parts of mixed solution C1, finishing dripping within 3.5 hours, heating to 85 ℃ after finishing dripping, keeping the temperature for 2 hours, cooling to 55 ℃, adding 9.1 parts of mixed solution D1, stirring for 10 minutes, adding 59.5 parts of hydrophilic modified bio-based material E1, stirring for 15 minutes, heating to 80 ℃, reacting for 60 minutes, determining that the epoxy value is less than 0.005 by using a hydrochloric acid-acetone method, and stopping the reaction;
s7, cooling to 40 ℃, and filtering to obtain the bio-based hydroxyl polyacrylate emulsion 6.
Comparative example 6
The comparative example prepares the aqueous two-component polyurethane coating 6, the emulsion is prepared in the comparative example 5, and the concrete steps are as follows:
when in construction, according to the NCO/OH molar ratio of 1.8:1 mixed agent A5 and agent B5;
the A6 agent comprises the following components in parts by weight:
the B6 agent is a waterborne polyisocyanate curing agent, the waterborne polyisocyanate curing agent is Bayhydur XP2487/1, and the Bayhydur XP2487/1 accounts for 14.6 parts by mass;
the preparation method of the A6 agent of the bio-based water-based two-component polyurethane coating 6 comprises the following steps: adding the bio-based hydroxyl polyacrylate emulsion 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, dispersing for 20 minutes, filtering and discharging.
During construction, the B6 agent is added into the A6 agent and stirred for 6 minutes to obtain the bio-based aqueous two-component polyurethane coating 6, wherein the bio-based content of the coating is 26.1 percent.
A paint film prepared from the bio-based water-based two-component polyurethane paint 6 is cured and dried for 7 days at normal temperature, and the performances are shown in Table 1.
Test example 1
The aqueous two-component polyurethane coatings prepared in examples and comparative examples were cured and dried at room temperature for 7 days, and the properties thereof are shown in table 1.
The test criteria were:
appearance of the coating film: visual inspection;
surface drying time: GB/T1728-2020;
the actual drying time is as follows: GB/T1728-2020;
pencil hardness: GB/T6739-2006;
film gloss/(60 °,%): GB/T9754-2007;
water resistance (25 ℃,24 h): GB/T4893.1-2020;
resistance to dry heat (70. + -. 2 ℃,15 h): GB/T4893.3-2020;
ethanol resistance (50%, 1 h): GB/T4893.1-2020;
the detection method comprises the following steps:
the basic performance tests include: the bio-based hydroxyl polyacrylate emulsion is tested according to GB/T11175-2002 synthetic resin emulsion test method, and the appearance, pH, solid content, viscosity and gel fraction (coarse particles) of the emulsion are tested. The paint film performance is tested according to GB/T23999-2009 waterborne wood coating for interior decoration, and the gloss, hardness, water resistance, dry heat resistance and alcohol resistance are tested. The average particle size of the emulsion was measured using a nanometer particle size analyzer (ZS Nano S).
TABLE 1 comprehensive Properties of Bio-based waterborne two-component polyurethane coating 1
As can be seen from the above table, the aqueous two-component polyurethane coating 4 of the comparative example 2 has a longer surface drying time than the bio-based aqueous two-component polyurethane coating 1 of the example 2, which is not favorable for improving the construction efficiency, and is far inferior to the examples in terms of pencil hardness, water resistance, dry heat resistance and ethanol resistance of a paint film; compared with the bio-based water-based two-component polyurethane coating 1 of the embodiment 2, the bio-based water-based two-component polyurethane coating 5 of the comparative example 4 firstly has an unacceptable defect of paint film, namely oil pits, and in addition, the surface drying time is slightly long, which is not beneficial to improving the construction efficiency, and the pencil hardness, the water resistance, the dry heat resistance and the ethanol resistance of the paint film are inferior to those of the embodiment; the bio-based aqueous two-component polyurethane coating 6 of comparative example 6 has a longer surface drying time than the bio-based aqueous two-component polyurethane coating 1 of example 2, is not favorable for improving the construction efficiency, and is inferior to the examples in the aspects of pencil hardness, water resistance, dry heat resistance and ethanol resistance of the paint film. From the examples 2,4 and 6, the invention discloses a preparation method of bio-based hydroxy polyacrylate emulsion, and the bio-based hydroxy polyacrylate emulsion prepared by the preparation method has high hydroxy content, good appearance and good stability; a paint film prepared from the prepared bio-based aqueous two-component polyurethane paint has the advantages of high hardness, high gloss, high transparency, excellent water resistance and chemical resistance, high crosslinking density, scratch resistance, wear resistance, high drying speed and the like, and can be applied to high-grade wood coatings, automobile coatings, metal anticorrosive coatings and other industrial protective coatings.
Test example 2
The emulsions of examples 1,3,5 and comparative examples 1,3,5 were tested for their performance and the data results are shown in Table 2.
Table 2: comparison table of emulsion properties
Comparative example 1 differs from example 1 in that no biobased synthetic hydroxy polyacrylate emulsion is added. In comparison with example 1, comparative example 1 has a bio-based content of 0%, a slightly lower solid content, a part of hydroxyl groups are replaced by secondary amino groups, and the total content of hydroxyl groups and secondary amino groups is higher, which is caused by the fact that epoxidized soybean oil is not added to react with the secondary amino group of the hydroxy polyacrylate polymer. Comparative example 2 is the synthesis of bio-based hydroxy polyacrylate emulsion by adding bio-based material without hydrophilic modification. The hydroxyl content and solids content of this comparative example are the same as in example 1, with a slightly higher biobased content. However, the comparative example 2 has a slightly larger particle size and a slightly poor appearance, and the main reason for the above problems is that the bio-based material which is not modified by hydrophilicity is hydrophobic and cannot be fully dissolved with the emulsion under stirring. Comparative example 3 no hydroxy acrylate monomer was added and the hydroxyl group was only generated after reaction of the hydrophilically modified epoxidized soybean oil with the secondary amino group. It was slightly lower in solid content and higher in biobased content of 42.2% as compared with example 1, but lower in hydroxyl group content and poor in heat storage stability, and in addition, higher in gel fraction indicates poor in polymerization 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.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The bio-based hydroxyl polyacrylate emulsion is characterized by comprising the following preparation raw materials: modified bio-based materials and polyacrylate polymers containing hydroxyl groups;
the preparation raw material of the modified bio-based material comprises a hydrophilic monomer and a bio-based material, wherein the bio-based material comprises epoxy-containing bio-based oil;
the hydrophilic monomer includes a sulfonic acid group monomer;
the preparation raw material of the polyacrylate polymer containing hydroxyl comprises a hydroxyl acrylate monomer and an acrylamide monomer.
2. The bio-based hydroxy polyacrylate emulsion according to claim 1, wherein the sulfonic acid group monomer is a monomer containing one secondary amino group and one sulfonic acid group.
3. The bio-based hydroxy polyacrylate emulsion of claim 1, wherein the acrylamide monomer is a secondary amino group-containing and hydroxyl group-free acrylamide monomer.
4. The bio-based hydroxy polyacrylate emulsion according to claim 1, wherein the bio-based weight content of the bio-based hydroxy polyacrylate emulsion is 5% to 25%.
5. The bio-based hydroxy polyacrylate emulsion according to claim 1, wherein the particle size of the bio-based hydroxy polyacrylate emulsion is 80nm to 120nm; preferably, the solid content of the bio-based hydroxyl polyacrylate emulsion is 47-52%; preferably, the hydroxyl content of the bio-based hydroxyl polyacrylate emulsion is 2.1-4.0% by mass.
6. The bio-based hydroxy polyacrylate emulsion according to claim 1, wherein the raw material for preparing the hydroxy group-containing polyacrylate polymer further comprises acrylic acid monomer, acrylate monomer and vinyl monomer.
7. A method for preparing a bio-based hydroxy polyacrylate emulsion according to any one of claims 1 to 6, comprising mixing and reacting said modified bio-based material and said hydroxy group containing polyacrylate polymer.
8. The method according to claim 7, wherein the temperature of the mixing reaction is 70 to 90 ℃.
9. A coating, characterized in that the raw materials for preparing the coating comprise the bio-based hydroxyl polyacrylate emulsion as claimed in any one of claims 1 to 6.
10. Use of the coating according to claim 9 in the field of decoration.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117343563A (en) * | 2023-09-01 | 2024-01-05 | 江门瓦铂新材料有限公司 | Bio-based polyacrylate dispersion and preparation method and application thereof |
| CN117343563B (en) * | 2023-09-01 | 2024-07-02 | 江门瓦铂新材料有限公司 | Bio-based polyacrylate dispersion and preparation method and application thereof |
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