CN112812212B - Hydroxyl acrylic resin emulsion and preparation method and application thereof - Google Patents
Hydroxyl acrylic resin emulsion and preparation method and application thereof Download PDFInfo
- Publication number
- CN112812212B CN112812212B CN202011613395.4A CN202011613395A CN112812212B CN 112812212 B CN112812212 B CN 112812212B CN 202011613395 A CN202011613395 A CN 202011613395A CN 112812212 B CN112812212 B CN 112812212B
- Authority
- CN
- China
- Prior art keywords
- resin emulsion
- parts
- hydroxyl
- acrylic resin
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a hydroxyl acrylic resin emulsion and a preparation method and application thereof, wherein the preparation raw materials of the hydroxyl acrylic resin emulsion comprise: a combination of trimellitic anhydride, a first hydroxyl-containing acrylic acid, a mixed monomer, an initiator, and a chain transfer agent; the hydroxyl acrylic resin emulsion is prepared by adding trimellitic anhydride into a preparation raw material, and reacting the trimellitic anhydride with hydroxyl-containing acrylic acid to obtain a modified intermediate, wherein the modified intermediate can further react with a mixed monomer, so that the finally obtained hydroxyl acrylic resin has more branched structures and further has lower viscosity, and the solid content of the hydroxyl acrylic resin emulsion is favorably improved; and the preparation method of the hydroxyl acrylic resin emulsion is simple, low in cost and high in economic value.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a hydroxyl acrylic resin emulsion as well as a preparation method and application thereof.
Background
The acrylic resin coating has the excellent performances of light color, light resistance, aging resistance, chemical resistance and the like, and is widely applied to coating and protection in the industrial and civil fields of airplanes, automobiles, instruments, buildings, furniture and the like. At present, the concentration of acrylic resin emulsion is low, the coating workability is poor, a paint film is not full in a net shape, and a large amount of Volatile Organic Compounds (VOC) exist, so that the environmental pollution is caused, and the potential safety hazard is brought. With the increasing awareness of environmental protection and the stricter laws and regulations, high-solid content hydroxy acrylic resin is the target of research.
The traditional hydroxyl acrylic resin is a linear polymer obtained by polymerizing functional ethylene monomers through free radicals, is easy to generate intermolecular entanglement when the concentration is high, has larger movement resistance, and is difficult to obtain low-viscosity emulsion under the condition of ensuring high solid content. At present, the synthesis of hydroxyl acrylic resin with high solid content and low viscosity is realized by changing the monomer ratio, the solvent type, adding different initiators and chain transfer agents and the like. CN101921357A discloses a high-solid low-viscosity hydroxyl acrylic resin and a preparation method thereof. The raw materials comprise the following components in parts by mass: 25-35 parts of solvent, 0.2-2 parts of acrylic acid, 7-16 parts of methyl methacrylate, 15-35 parts of styrene, 3-10.5 parts of butyl methacrylate or butyl acrylate, 12-23 parts of hydroxyl-containing acrylic monomer and 1.5-8 parts of initiator. The preparation method comprises the step of firstly carrying out pressurization reaction to obtain a product. The solid content of the hydroxyl acrylic resin obtained by the method can reach 65-75%, and the viscosity is only 1000-2500 mps. The solvent used in the process is low in price, an expensive high-boiling point solvent is not needed, the preparation process is simple, and the production cost is low. However, the hydroxy acrylic resin prepared by the method still has a linear molecular structure, the winding among molecules is inevitable, the viscosity is overlarge when the solid content is high, and a large amount of organic solvent is required to be added for dilution during construction.
Therefore, it can be seen that it is difficult to obtain a hydroxy acrylic resin emulsion with high solid content and low viscosity by simply changing the monomer ratio, the solvent type and the like. CN101914185A discloses a method for preparing a hydroxy acrylic resin aqueous dispersion, a hydroxy acrylic resin aqueous dispersion prepared by the method and an aqueous coating taking the hydroxy acrylic resin aqueous dispersion as a film forming material, wherein the hydroxy acrylic resin aqueous dispersion is prepared by a step-by-step free radical solution polymerization method, and the obtained water dispersible resin particles have a core-shell structure by adopting a specific type of initiator, assisting with a chain transfer agent and carrying out polymerization reaction at higher temperature. The core has weak hydrophilicity and does not contain carboxyl; the shell has strong hydrophilicity and is rich in carboxyl, so that the shell can be stably stored. The obtained hydroxyl acrylic resin aqueous dispersion has the characteristics of low solvent content, high solid content and low viscosity, and a coating prepared by matching the hydroxyl acrylic resin aqueous dispersion with aqueous amino resin or aqueous polyurethane crosslinking agent has the characteristics of high gloss, good water resistance and excellent weather resistance. Can be used as an excellent base material for preparing high-performance environment-friendly industrial protective paint and is widely applied to finish paint and primer-topcoat paint in various fields. However, the preparation process of the hydroxy acrylic resin involves two steps of operation, and the operation is too complicated, so that the preparation process is not beneficial to industrial mass production.
CN103319666A discloses a hyperbranched modified hydroxyl acrylic resin aqueous dispersion, a preparation method and application thereof. Mixing a solvent and 5-10% of an initiator by mass, and heating to a reflux temperature; mixing a main monomer, a functional monomer, a hyperbranched modifier, 40-60% by mass of an initiator and a chain transfer agent in a raw material formula to obtain a mixture; firstly, pre-feeding 10-20% of mixture by mass in a container with the temperature being raised to 120-180 ℃ in one step; after half an hour, the rest mixture is dripped; preserving heat, adding the rest initiator, and preserving heat again to obtain acrylic resin; cooling, dropwise adding a neutralizing agent, adding a cosolvent and deionized water, and dispersing to obtain the hyperbranched modified hydroxyl acrylic resin aqueous dispersion; the molecular chain of the dispersion prepared by the invention contains more hyperbranched polymer branched chains, so that the aqueous dispersion of the hydroxyl acrylic resin still keeps very low viscosity at higher solid content, and a coating film with high fullness and uniformity is favorably formed. However, this preparation method requires the use of a hyperbranched modifier oligomer synthesized in advance, which is complicated and expensive to synthesize, and is also disadvantageous for large-scale industrial production.
Therefore, the development of a hydroxy acrylic resin emulsion with low viscosity, high strand content and simple preparation method is an urgent problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a hydroxy acrylic resin emulsion and a preparation method and application thereof; trimellitic anhydride is added into the raw materials for preparing the hydroxyl acrylic resin emulsion, the trimellitic anhydride can react with hydroxyl-containing acrylic ester, the obtained intermediate product can further react with a mixed monomer, and then the hydroxyl acrylic resin emulsion with high branching degree is obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a hydroxy acrylic resin emulsion, wherein the hydroxy acrylic resin emulsion comprises the following raw materials, by weight: 0.3-3 parts of trimellitic anhydride, 0.3-5 parts of first hydroxyl-containing acrylate, 51.5-88 parts of mixed monomer, 0.5-2.5 parts of initiator and 0.5-1.5 parts of chain transfer agent.
The trimellitic anhydride can be 0.6, 0.9, 1.1, 1.3, 1.5, 1.7, 1.9, 2.1, 2.3, 2.5, or 2.9 parts by weight or the like.
The first hydroxyl-containing acrylic acid can be 0.8, 1.5, 1.6, 1.9, 2.5, 2.8, 3.1, 3.4, 3.8, 4.3, or 4.9 parts by weight, and the like.
The mixed monomer may be 53 parts by weight, 56 parts by weight, 59 parts by weight, 63 parts by weight, 66 parts by weight, 69 parts by weight, 73 parts by weight, 76 parts by weight, 79 parts by weight, 83 parts by weight, 86 parts by weight, or the like.
The initiator may be 0.7, 0.9, 1.1, 1.3, 1.5, 1.7, 1.9, 2.1, 2.3, etc. parts by weight.
The chain transfer agent may be 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, or the like.
The preparation raw materials of the hydroxyl acrylic resin emulsion provided by the invention comprise the combination of trimellitic anhydride, first hydroxyl-containing acrylate, a mixed monomer, an initiator and a chain transfer agent; the preparation method comprises the steps of adding a specific part of trimellitic anhydride into a raw material, wherein the trimellitic anhydride can react with first hydroxyl acrylic ester, and the obtained product can further react with a mixed monomer to obtain hydroxyl acrylic resin with higher branching degree and lower viscosity, so that the solid content of the acrylic resin emulsion can be effectively improved.
Preferably, the hydroxyl acrylic resin emulsion has a solids content of greater than 70%, such as 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, or 90%, and specific values therebetween, for brevity and clarity, are not intended to be exhaustive or to limit the invention to the specific values encompassed by the scope disclosed.
Preferably, the viscosity of the hydroxyacrylic resin emulsion is from 2500 to 3500 mPas, such as 2600 mPas, 2700 mPas, 2800 mPas, 2900 mPas, 3000 mPas, 3200 mPas or 3400 mPas, and the specific values therebetween are not exhaustive, and for the sake of brevity.
Preferably, the mixed monomer comprises any one of styrene, alkyl methacrylate, alkyl acrylate, second hydroxyl-containing acrylic acid, acrylic acid or glycidyl versatate or a combination of at least two of the two.
Preferably, the mixed monomers comprise, in parts by weight: 10 to 15 parts by weight (for example, 11 parts by weight, 12 parts by weight, 13 parts by weight or 14 parts by weight, etc.), 15 to 25 parts by weight of an alkyl methacrylate (for example, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight or 24 parts by weight, etc.), 8 to 14 parts by weight of an alkyl acrylate (for example, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight or 13 parts by weight, etc.), 14 to 26 parts by weight of a second hydroxyl-containing acrylic acid (for example, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 22 parts by weight or 24 parts by weight, etc.), 0.5 to 1 part by weight of an acrylic ester (for example, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight or 0.9 parts by weight, etc.), and 4 to 7 parts by weight of a glycidyl ester of a tertiary carbonate (for example, 4.3 parts by weight), 4.6, 4.9, 5.2, 5.5, 5.8, 6.1, 6.4, or 6.7 parts by weight, etc.).
Preferably, the alkyl methacrylate comprises any one of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate, or isobornyl methacrylate, or a combination of at least two thereof.
Preferably, the alkyl acrylate comprises any one of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, or isobornyl acrylate, or a combination of at least two thereof.
Preferably, the first hydroxyl-containing acrylic acid and the second hydroxyl-containing acrylic acid each independently comprise any one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate or hydroxybutyl acrylate or a combination of at least two thereof.
Preferably, the initiator comprises any one of azobisisobutyronitrile, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, tert-butyl peroxyisononanoate or tert-butyl peroxy-2-ethylhexanoate or a combination of at least two of the above.
Preferably, the chain transfer agent comprises mercaptoethanol and/or n-dodecyl mercaptan.
Preferably, the hydroxy acrylic resin emulsion further comprises a catalyst and/or a solvent.
Preferably, the mass ratio of the catalyst to the trimellitic anhydride in the hydroxyl acrylic resin emulsion is 1 (8-12), such as 1:8.3, 1:8.6, 1:8.9, 1:9.3, 1:9.6, 1:9.9, 1:10.3, 1:10.6, 1:10.9, 1:11.3, 1:11.6 or 1: 11.9.
Preferably, the catalyst comprises isopropyl titanate.
Preferably, the content of the solvent in the hydroxyl acrylic resin emulsion is 30 to 35 parts by weight, such as 30.5 parts by weight, 31 parts by weight, 31.5 parts by weight, 32 parts by weight, 32.5 parts by weight, 33 parts by weight, 33.5 parts by weight, 34 parts by weight, 34.5 parts by weight, or the like.
Preferably, the solvent comprises a first solvent and a second solvent; (ii) a The first solvent comprises any one or the combination of at least two of tetrahydrofuran, dimethyl sulfoxide or N, N-dimethylformamide; the second solvent comprises any one or the combination of at least two of xylene, n-butanol, ethyl acetate, acetone or butyl acetate.
As a preferred technical scheme of the invention, the first solvent and the second solvent are selected as mixed solvents, so that the modified intermediate and the mixed monomer can be fully dissolved in a system, and the obtained hydroxy acrylic resin emulsion has low viscosity.
Preferably, the mass ratio of the first solvent to the second solvent is 1 (1.25-4), such as 1:1.5, 1:1.7, 1:1.9, 1:2.1, 1:2.3, 1:2.6, 1:2.9, 1:3.2, 1:3.5 or 1: 3.8.
Preferably, the first solvent comprises any one of tetrahydrofuran, dimethylsulfoxide or N, N-dimethylformamide or a combination of at least two thereof.
Preferably, the second solvent includes any one of xylene, n-butanol, ethyl acetate, acetone, or butyl acetate, or a combination of at least two thereof.
In a second aspect, the present invention provides a method for preparing the hydroxyacrylic resin emulsion according to the first aspect, the method comprising the steps of:
(1) reacting trimellitic anhydride, first hydroxyl-containing acrylate and an optional catalyst in an optional solvent to obtain a modified intermediate;
(2) and (2) reacting the modified intermediate obtained in the step (1), a mixed monomer, a chain transfer agent and an initiator to obtain the hydroxyl acrylic resin emulsion.
Preferably, the reaction in step (1) is carried out under the protection of inert gas, and further preferably under the protection of nitrogen.
Preferably, the reaction of step (1) is carried out under stirring.
Preferably, the stirring speed is 800-1200 rpm, such as 820rpm, 840rpm, 860rpm, 880rpm, 920rpm, 940rpm, 980rpm, 1020rpm, 1050rpm, 1090rpm, 1120rpm, 1150rpm or 1190rpm, and specific values therebetween, which are not intended to be limiting in space and for the sake of brevity, the present invention is not exhaustive.
Preferably, the reaction temperature in step (1) is 80-140 ℃, for example, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃ or 135 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the reaction of step (1) is carried out at elevated temperature.
Preferably, the method for raising the temperature includes: heating the system to 70-90 deg.C (e.g., 72 deg.C, 74 deg.C, 76 deg.C, 78 deg.C, 80 deg.C, 82 deg.C, 84 deg.C, 86 deg.C or 88 deg.C), maintaining the temperature for 0.5-1.5 h (e.g., 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h or 1.4 h), heating to 90-100 deg.C (e.g., 91 deg.C, 92 deg.C, 93 deg.C, 94 deg.C, 95 deg.C, 96 deg.C, 97 deg.C, 98 deg.C or 99 deg.C), maintaining the temperature for 0.5-1.5 h (e.g., 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h or 1.4 h), heating to 120 deg.e.C (e.g., 121 deg.C, 122 deg.C, 123 deg.C, 124 deg.C, 126 deg.C, 128 deg.C or 129 deg.C), maintaining the temperature for 0.5-4 h (e.8 h, 1.3h, 1, 1.C), heating the temperature for 3h, 3h, 3-3 h, etc.), and the like), maintaining the temperature for 0.C, 140 ℃, 142 ℃, 144 ℃, 146 ℃ or 148 ℃ and the like) to carry out the next reaction.
Preferably, the reaction temperature in step (2) is 130-150 ℃, for example, 132 ℃, 134 ℃, 136 ℃, 138 ℃, 140 ℃, 142 ℃, 144 ℃, 146 ℃ or 148 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction time in step (2) is 4.5-5.5 h, such as 4.6h, 4.7h, 4.8h, 4.9h, 5h, 5.1h, 5.2h, 5.3h or 5.4h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be exhaustive.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) under the protection of inert gas and the stirring condition with the rotating speed of 800-1200 rpm, trimellitic anhydride, first hydroxyl-containing acrylate and an optional catalyst are subjected to heating reaction in an optional solvent to obtain a modified intermediate; the method for raising the temperature comprises the following steps: heating the system to 70-90 ℃, preserving heat for 0.5-1.5 h, heating to 90-100 ℃, preserving heat for 0.5-1.5 h, heating to 120-130 ℃, preserving heat for 0.5-4 h, heating to 130-150 ℃, and carrying out the next reaction;
(2) and (2) reacting the modified intermediate obtained in the step (1), the mixed monomer, the chain transfer agent and the initiator at 130-150 ℃ for 4.5-5.5 h to obtain the hydroxyl acrylic resin emulsion.
In a third aspect, the present invention provides a use of the hydroxyacrylic resin emulsion according to the first aspect in a coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the hydroxyl acrylic resin emulsion provided by the invention, trimellitic anhydride is added into a preparation raw material, and reacts with hydroxyl-containing acrylic acid to obtain a modified intermediate, and the modified intermediate further reacts with a mixed monomer, so that the obtained hydroxyl acrylic resin has a plurality of branched structures, the viscosity of the hydroxyl acrylic resin emulsion can be reduced, and the solid content of the hydroxyl acrylic resin emulsion can be improved; and the preparation method of the hydroxyl acrylic resin emulsion is simple, low in cost and high in economic value.
(2) The solid content of the emulsion of the hydroxyl acrylic resin provided by the invention is more than 70%, and exceeds most of acrylic resins with 50-60% solid content in the market, and the VOC emission can be effectively reduced when the emulsion is used; the viscosity of the hydroxyl acrylic resin emulsion at 25 ℃ is 2387-3418 mPa & s, which is lower than that of most acrylic resin emulsions in the market, and the hydroxyl acrylic resin emulsion has good dilutability and leveling property and is easier to process and mold.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A hydroxy acrylic resin emulsion is prepared from the following raw materials: 1.5g of trimellitic anhydride, 0.15g of isopropyl titanate, 1.1g of hydroxyethyl methacrylate, mixed monomers (10 g of methyl methacrylate, 10g of tert-butyl methacrylate, 12.5g of styrene, 5g of methyl acrylate, 5g of butyl acrylate, 5.5g of glycidyl versatate, 0.75g of acrylic acid, 8.4g of hydroxyethyl methacrylate), 1.5g of azobisisobutyronitrile, 1g of mercaptoethanol, 9g of tetrahydrofuran and 24g of xylene.
The preparation method comprises the following steps:
(1) under the protection of nitrogen, dissolving trimellitic anhydride, hydroxyethyl methacrylate and isopropyl titanate in a mixed solution of tetrahydrofuran and xylene, and heating at the rotation speed of 1000rpm (the heating mode is that the system is heated to 80 ℃, kept for 1 hour, heated to 100 ℃, kept for 1 hour, heated to 125 ℃, kept for 3 hours, heated to 140 ℃ for the next reaction), so as to obtain a modified intermediate;
(2) and (2) reacting the modified intermediate obtained in the step (1), the mixed monomer, the azobisisobutyronitrile and the mercaptoethanol at 140 ℃ for 5 hours to obtain the hydroxyl acrylic resin emulsion.
Example 2
A hydroxy acrylic resin emulsion is prepared from the following raw materials: 0.3g of trimellitic anhydride, 0.03g of isopropyl titanate, 0.3g of hydroxyethyl methacrylate, mixed monomers (10 g of ethyl methacrylate, 5g of isooctyl methacrylate, 10g of styrene, 8g of methyl acrylate, 4g of glycidyl versatate, 0.5g of acrylic acid, 13g of hydroxypropyl methacrylate), 0.5g of azobisisobutyronitrile, 0.5g of mercaptoethanol, 15g of tetrahydrofuran and 20g of xylene.
The preparation method is the same as that of example 1.
Example 3
A hydroxy acrylic resin emulsion is prepared from the following raw materials: trimellitic anhydride 3g, isopropyl titanate 0.3g, hydroxyethyl acrylate 1.8g, mixed monomer (methyl methacrylate 18g, isobornyl methacrylate 7g, styrene 15g, ethyl acrylate 14g, hydroxypropyl methacrylate 14g, tertiary carbonic acid glycidyl ester 7g, acrylic acid 1g), benzoyl peroxide 2.5g, mercaptoethanol 1.5g, tetrahydrofuran 6g, butyl acetate 24 g.
The preparation method is the same as that of example 1.
Example 4
A hydroxy acrylic resin emulsion comprises the following raw materials: 0.5g of trimellitic anhydride, 0.05g of isopropyl titanate, 0.35g of hydroxyethyl methacrylate, a mixed monomer (4.5 g of methyl methacrylate, 5.5g of tert-butyl methacrylate, 7.5g of styrene, 1.5g of methyl acrylate, 3.5g of butyl acrylate, 9.2g of hydroxyethyl methacrylate, 2g of glycidyl versatate and 0.5g of acrylic acid), 0.5g of azobisisobutyronitrile, 0.5g of mercaptoethanol, 6g of tetrahydrofuran and 10g of xylene;
the preparation method is the same as that of example 1.
Example 5
A hydroxy acrylic resin emulsion comprises the following raw materials: 0.5g of trimellitic anhydride, 0.05g of isopropyl titanate, 0.3g of hydroxyethyl acrylate, mixed monomers (5 g of ethyl methacrylate, 2.5g of isooctyl methacrylate, 5g of styrene, 5g of methyl acrylate, 8.5g of hydroxyethyl methacrylate, 2.5g of glycidyl versatate, 0.3g of acrylic acid), 0.5g of azobisisobutyronitrile, 0.7g of mercaptoethanol, 6g of tetrahydrofuran and 10g of n-butanol;
the preparation method is the same as that of example 1.
Example 6
A hydroxy acrylic resin emulsion comprises the following raw materials: 1g of trimellitic anhydride, 0.1g of isopropyl titanate, 0.75g of hydroxypropyl methacrylate, a mixed monomer (4.5 g of methyl methacrylate, 3g of isobornyl methacrylate, 5g of styrene, 6.5g of ethyl acrylate, 3g of hydroxyethyl acrylate, 3g of hydroxypropyl methacrylate, 2g of glycidyl versatate, 0.3g of acrylic acid), 0.3g of benzoyl peroxide, 0.5g of mercaptoethanol, 6g of tetrahydrofuran and 11g of butyl acetate;
the preparation method is the same as that of example 1.
Example 7
A hydroxy acrylic resin emulsion comprises the following raw materials: 0.6g of trimellitic anhydride, 0.06g of isopropyl titanate, 0.4g of hydroxyethyl acrylate, a mixed monomer (8 g of methyl methacrylate, 5.5g of styrene, 2.5g of methyl acrylate, 1.5g of ethyl acrylate, 6g of hydroxyethyl acrylate, 5g of hydroxyethyl methacrylate, 2g of glycidyl versatate, 0.5g of acrylic acid), 0.3g of benzoyl peroxide, 0.3g of mercaptoethanol, 6g of tetrahydrofuran and 10g of xylene;
the preparation method is the same as that of example 1.
Example 8
A hydroxy acrylic resin emulsion comprises the following raw materials: 1g of trimellitic anhydride, 0.1g of isopropyl titanate, 0.6g of hydroxyethyl acrylate, a mixed monomer (7.5 g of methyl methacrylate, 5g of styrene, 4g of methyl acrylate, 4g of ethyl acrylate, 7g of hydroxyethyl methacrylate, 2.5g of glycidyl versatate, 0.3g of acrylic acid), 0.3g of benzoyl peroxide, 0.5g of mercaptoethanol, 7g of tetrahydrofuran and 10g of xylene;
the preparation method is the same as that of example 1.
Comparative example 1
A hydroxy acrylic resin emulsion is prepared from the following raw materials: 9.5g of hydroxyethyl methacrylate, 10g of methyl methacrylate, 10g of tert-butyl methacrylate, 12.5g of styrene, 5g of methyl acrylate, 5g of butyl acrylate, 5.5g of glycidyl versatate, 0.75g of acrylic acid, 1.5g of azobisisobutyronitrile, 0.5g of mercaptoethanol, 16g of tetrahydrofuran and 16g of xylene.
The preparation method comprises the following steps:
(1) hydroxyethyl methacrylate, methyl methacrylate, tert-butyl methacrylate, styrene, methyl acrylate, butyl acrylate, tert-glycidyl versatate, acrylic acid, azobisisobutyronitrile, mercaptoethanol, tetrahydrofuran and xylene are reacted for 5 hours at 140 ℃ to obtain the hydroxyacrylic resin emulsion.
Comparative example 2
A hydroxy acrylic resin emulsion is prepared from the following raw materials: 8.5g of hydroxyethyl acrylate, 12g of methyl methacrylate, 9.5g of ethyl methacrylate, 15.5g of styrene, 4.5g of ethyl acrylate, 4g of butyl acrylate, 7.5g of glycidyl methacrylate, 0.75g of acrylic acid, 0.3g of benzoyl peroxide, 1g of mercaptoethanol, 15g of tetrahydrofuran and 25g of xylene.
The preparation method is the same as that of comparative example 1.
Comparative example 3
A hydroxy acrylic resin emulsion is prepared from the following raw materials: 7.5g of hydroxyethyl methacrylate, 9.5g of methyl methacrylate, 9.5g of ethyl acrylate, 15.5g of styrene, 6.5g of methyl acrylate, 4g of butyl methacrylate, 5.5g of glycidyl versatate, 1g of acrylic acid, 0.5g of azobisisobutyronitrile, 1g of mercaptoethanol, 15g of tetrahydrofuran and 20g of xylene.
The preparation method is the same as that of comparative example 1.
And (3) performance testing:
(1) viscosity: the sample viscosity was measured using a Brookfield laminar viscometer model DV-II + CP.
(2) Solid content: the tests were carried out according to GB/T6751-1986 determination of volatile and non-volatile of paints and varnishes.
(3) Pencil hardness: uniformly mixing hydroxyl acrylic resin emulsion and a Bayer HL-BA curing agent in a mass ratio of 5:1 to obtain a coating liquid; the coating liquid was coated on a transparent PET film substrate using a 25 th coating rod (wet film thickness 20 μm, dry film thickness ═ wet film thickness × solid content), baked in an oven at 80 ℃ for 2min, and taken out to obtain a coating layer, and the pencil hardness of the coating layer was measured using a mechanical pencil hardness meter.
The hydroxyl acrylic resin emulsions obtained in examples 1 to 8 and comparative examples 1 to 3 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
| Viscosity (mPa. s) | Solid content (%) | Hardness of pencil | |
| Example 1 | 3021 | 70 | 4H |
| Example 2 | 2387 | 73 | 4H |
| Example 3 | 2765 | 72 | 4H |
| Example 4 | 2461 | 72 | 4H |
| Example 5 | 3418 | 70 | 4H |
| Example 6 | 2884 | 73 | 4H |
| Example 7 | 3021 | 71 | 4H |
| Example 8 | 2685 | 70 | 4H |
| Comparative example 1 | 5686 | 63 | 2H |
| Comparative example 2 | 6315 | 67 | 2H |
| Comparative example 3 | 4976 | 62 | 2H |
As can be seen from the data in table 1: the hydroxyl acrylic resin emulsion provided by the invention has the advantages of high pencil hardness, high solid content and low viscosity, meets the current environmental protection requirement, and has high application value.
Specifically, the hydroxyl acrylic resin emulsion obtained in the embodiments 1 to 8 has the viscosity of 2387 to 3418mPa · s, the solid content of 70 to 73 percent and the pencil hardness of 4H; compared with the hydroxyl acrylic resin emulsion obtained in the comparative examples 1-3, the viscosity is reduced by 46-165%, the solid content is increased by 4-18, and the hardness is lower and is 2H.
The applicant states that the present invention is illustrated by the above examples to describe the preparation method and application of a hydroxy acrylic resin emulsion, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must rely on the above examples to be carried out. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (19)
1. The hydroxyl acrylic resin emulsion is characterized by comprising the following raw materials in parts by weight: 0.3-3 parts by weight of trimellitic anhydride, 0.3-5 parts by weight of first hydroxyl-containing acrylic acid, 51.5-88 parts by weight of mixed monomer, 0.5-2.5 parts by weight of initiator and 0.5-1.5 parts by weight of chain transfer agent;
the mixed monomer comprises the following components in parts by weight: 10-15 parts of styrene, 15-25 parts of alkyl methacrylate, 8-14 parts of alkyl acrylate, 14-26 parts of second hydroxyl-containing acrylic acid, 0.5-1 part of acrylic acid or 4-7 parts of tert-carbonic acid glycidyl ester;
the first hydroxyl-containing acrylic acid and the second hydroxyl-containing acrylic acid respectively and independently comprise any one or a combination of at least two of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate or hydroxybutyl acrylate;
the hydroxy acrylic resin emulsion also comprises a catalyst and a solvent, wherein the catalyst comprises isopropyl titanate, the solvent comprises a first solvent and a second solvent, the first solvent comprises one or a combination of at least two of tetrahydrofuran, dimethyl sulfoxide or N, N-dimethylformamide, and the second solvent comprises one or a combination of at least two of xylene, N-butanol, ethyl acetate, acetone or butyl acetate;
the hydroxy acrylic resin emulsion is prepared by the following method, and the method comprises the following steps:
(1) reacting trimellitic anhydride, first hydroxyl-containing acrylic acid and a catalyst in a solvent to obtain a modified intermediate;
(2) reacting the modified intermediate obtained in the step (1), a mixed monomer, a chain transfer agent and an initiator to obtain the hydroxyl acrylic resin emulsion;
the reaction in the step (1) is carried out under the condition of temperature rise, and the temperature rise method comprises the following steps: and heating the system to 70-90 ℃, preserving heat for 0.5-1.5 h, heating to 90-100 ℃, preserving heat for 0.5-1.5 h, heating to 120-130 ℃, preserving heat for 0.5-4 h, heating to 130-150 ℃, and carrying out the next reaction.
2. The emulsion of claim 1, wherein the acrylic emulsion has a solids content of not less than 70%.
3. The hydroxyacrylic resin emulsion according to claim 1, characterized in that the hydroxyacrylic resin emulsion has a viscosity of 2500 to 3500 mPas.
4. The hydroxyacrylic resin emulsion of claim 1, wherein the alkyl methacrylate comprises any one of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isooctyl methacrylate or isobornyl methacrylate or a combination of at least two thereof.
5. The hydroxyacrylic resin emulsion of claim 1, wherein the alkyl acrylate comprises any one of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, or isobornyl acrylate, or a combination of at least two thereof.
6. The hydroxyacrylic resin emulsion according to claim 1, wherein the initiator comprises any one or a combination of at least two of azobisisobutyronitrile, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, tert-butyl peroxyisononanoate or tert-butyl peroxy-2-ethylhexanoate.
7. The hydroxyacrylic resin emulsion according to claim 1, wherein the chain transfer agent comprises mercaptoethanol and/or n-dodecylmercaptan.
8. The hydroxyl acrylic resin emulsion according to claim 1, wherein the mass ratio of the catalyst to trimellitic anhydride in the hydroxyl acrylic resin emulsion is 1 (8-12).
9. The emulsion of claim 1, wherein the solvent is present in an amount of 30 to 35 parts by weight.
10. The hydroxyacrylic resin emulsion according to claim 1, characterized in that the mass ratio of the first solvent to the second solvent is 1 (1.25-4).
11. A method for preparing the hydroxyacrylic resin emulsion as claimed in any one of claims 1 to 10, characterized in that the method comprises the following steps:
(1) reacting trimellitic anhydride, first hydroxyl-containing acrylic acid and a catalyst in a solvent to obtain a modified intermediate;
(2) reacting the modified intermediate obtained in the step (1), a mixed monomer, a chain transfer agent and an initiator to obtain the hydroxyl acrylic resin emulsion;
the reaction in the step (1) is carried out under the condition of temperature rise, and the temperature rise method comprises the following steps: and heating the system to 70-90 ℃, preserving heat for 0.5-1.5 h, heating to 90-100 ℃, preserving heat for 0.5-1.5 h, heating to 120-130 ℃, preserving heat for 0.5-4 h, heating to 130-150 ℃, and carrying out the next reaction.
12. The method according to claim 11, wherein the reaction in step (1) is carried out under an inert gas atmosphere.
13. The method according to claim 12, wherein the reaction of step (1) is carried out under nitrogen protection.
14. The method according to claim 11, wherein the reaction in step (1) is carried out under stirring.
15. The method according to claim 14, wherein the stirring is performed at a rotation speed of 800 to 1200 rpm.
16. The method according to claim 11, wherein the temperature of the reaction in the step (2) is 130 to 150 ℃.
17. The preparation method according to claim 11, wherein the reaction time in the step (2) is 4.5-5.5 h.
18. The method according to any one of claims 11 to 17, comprising the steps of:
(1) under the protection of inert gas and the stirring condition with the rotating speed of 1000rpm, trimellitic anhydride, first hydroxyl-containing acrylic acid and a catalyst are heated and reacted in a solvent to obtain a modified intermediate; the method for raising the temperature comprises the following steps: heating the system to 70-90 ℃, preserving heat for 0.5-1.5 h, heating to 90-100 ℃, preserving heat for 0.5-1.5 h, heating to 120-130 ℃, preserving heat for 0.5-4 h, heating to 130-150 ℃, and carrying out the next reaction;
(2) and (2) reacting the modified intermediate obtained in the step (1), the mixed monomer, the chain transfer agent and the initiator at 130-150 ℃ for 4.5-5.5 h to obtain the hydroxyl acrylic resin emulsion.
19. Use of the hydroxyacrylic resin emulsion according to any one of claims 1 to 10 in a coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011613395.4A CN112812212B (en) | 2020-12-30 | 2020-12-30 | Hydroxyl acrylic resin emulsion and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011613395.4A CN112812212B (en) | 2020-12-30 | 2020-12-30 | Hydroxyl acrylic resin emulsion and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112812212A CN112812212A (en) | 2021-05-18 |
| CN112812212B true CN112812212B (en) | 2022-08-09 |
Family
ID=75854899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011613395.4A Active CN112812212B (en) | 2020-12-30 | 2020-12-30 | Hydroxyl acrylic resin emulsion and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112812212B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114525073B (en) * | 2021-12-25 | 2022-08-23 | 山西中涂交通科技股份有限公司 | Two-component polyurethane marking paint and preparation method thereof |
| CN117946350B (en) * | 2024-03-27 | 2024-06-14 | 安徽三旺化学有限公司 | Normal-temperature-cured aqueous acrylic resin emulsion |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919893A (en) * | 2005-08-26 | 2007-02-28 | 中国科学院成都有机化学有限公司 | Hyperbranched great macromonomer, acrylate resin containing hyperbranched structure and preparation method |
| CN101381457A (en) * | 2007-09-05 | 2009-03-11 | 中国科学院成都有机化学有限公司 | Preparation method of aqueous hyperbranched intermediate and water soluble hyperbranched propenoic acid resin |
| CN106009454A (en) * | 2016-05-25 | 2016-10-12 | 华南理工大学 | High-solid low-viscosity hydroxy acrylic resin as well as preparation method and application thereof |
| CN110790870A (en) * | 2018-08-01 | 2020-02-14 | 恒昌涂料（惠阳）有限公司 | Modified hydroxyl acrylic resin, preparation method and modified hydroxyl acrylic ester coating |
| CN111548457A (en) * | 2020-05-29 | 2020-08-18 | 怡成屏障（张家港）科技有限公司 | Preparation method of high-solid low-viscosity polyester modified water-soluble acrylic resin |
-
2020
- 2020-12-30 CN CN202011613395.4A patent/CN112812212B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1919893A (en) * | 2005-08-26 | 2007-02-28 | 中国科学院成都有机化学有限公司 | Hyperbranched great macromonomer, acrylate resin containing hyperbranched structure and preparation method |
| CN101381457A (en) * | 2007-09-05 | 2009-03-11 | 中国科学院成都有机化学有限公司 | Preparation method of aqueous hyperbranched intermediate and water soluble hyperbranched propenoic acid resin |
| CN106009454A (en) * | 2016-05-25 | 2016-10-12 | 华南理工大学 | High-solid low-viscosity hydroxy acrylic resin as well as preparation method and application thereof |
| CN110790870A (en) * | 2018-08-01 | 2020-02-14 | 恒昌涂料（惠阳）有限公司 | Modified hydroxyl acrylic resin, preparation method and modified hydroxyl acrylic ester coating |
| CN111548457A (en) * | 2020-05-29 | 2020-08-18 | 怡成屏障（张家港）科技有限公司 | Preparation method of high-solid low-viscosity polyester modified water-soluble acrylic resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112812212A (en) | 2021-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109608575B (en) | Hydroxyl-containing polyacrylate secondary aqueous dispersion and preparation method thereof | |
| EP0506703B1 (en) | Soluble cross-linkable copolymers based on vinyl ester, vinyl aromat and acrylate monomers, process for their production and their use in coatings | |
| CN112812212B (en) | Hydroxyl acrylic resin emulsion and preparation method and application thereof | |
| CA2694758C (en) | Water-based dispersions of highly-branched polymers | |
| CN110511388B (en) | Modified hydroxyl acrylic emulsion for water-based metal decorating paint and preparation method thereof | |
| GB2068384A (en) | Coatings of acrylic-fatty acid drying oil resins | |
| CN106188563B (en) | Hydrazide-terminated dendritic polyurethane dispersion and preparation method and application thereof | |
| CN111793160A (en) | Water-based acrylic resin for industrial baking varnish and preparation method thereof | |
| CN114316854B (en) | Acrylic acid adhesive with high solid content and low viscosity and preparation method thereof | |
| CN110951006A (en) | Preparation method of room-temperature self-crosslinking water-based alkyd resin | |
| DE60121870T2 (en) | Pigment dispersing resins | |
| CN112341566B (en) | Sulfonic acid type hydroxyl acrylic resin aqueous dispersion and preparation method thereof | |
| CA1298010C (en) | Two component polyurethane coating | |
| JPS6137282B2 (en) | ||
| CN115073651B (en) | Water-based acrylic resin for glass bottle and preparation method thereof | |
| AU2006302124B2 (en) | High temperature polymerization process for making branched acrylic polymers, caprolactone-modified branched acrylic polymers, and uses thereof | |
| CN112759720B (en) | Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof | |
| JP5524786B2 (en) | Modified vinyl resin having carbonyl group, dispersion thereof, and water-based coating composition containing the dispersion | |
| CN114230717A (en) | Preparation process of water-based acrylic resin | |
| EP4196506A1 (en) | Waterborne coating composition | |
| CN114316160A (en) | Acrylic emulsion polymer and preparation method of water-based paint based on polymer | |
| CN111548457A (en) | Preparation method of high-solid low-viscosity polyester modified water-soluble acrylic resin | |
| CN111492019A (en) | Powder coating material and article having coating film of the same | |
| CN116622032A (en) | High-solid low-viscosity hydroxyl acrylic resin and preparation method thereof | |
| Yu et al. | Synthesis and properties of hydroxy acrylic resin with high solid content |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |