CN107474179B - Hydroxyl acrylic resin aqueous dispersion capable of constructing dual-mode network and preparation method thereof - Google Patents
Hydroxyl acrylic resin aqueous dispersion capable of constructing dual-mode network and preparation method thereof Download PDFInfo
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- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/022—Emulsions, e.g. oil in water
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention provides a hydroxyl acrylic resin aqueous dispersion capable of constructing a dual-mode network and a preparation method thereof, and relates to the field of fine chemical engineering. In the preparation process of the hydroxyl acrylic resin aqueous dispersion, two or more functional monomers with long and short molecular chains of reactive groups are adopted as comonomers; the prepared hydroxyl acrylic resin aqueous dispersion can form a topological dual-mode cross-linked network with long and short molecular chains with active components such as amino resin, isocyanate and the like, and can endow a coating film with excellent hardness, good toughness and excellent gloss.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a hydroxyl acrylic resin aqueous dispersion capable of constructing a dual-mode network and a preparation method thereof.
Background
The water-based resins currently selected for metal and glass coatings are: alkyd resins, polyester resins, epoxy resins, acrylic resins, and the like. The alkyd resin film forming material has excellent flexibility and low price, but has relatively poor weather resistance, water resistance and alcohol resistance; the polyester resin paint film has good hardness and toughness, but the paint film has large shrinkage and poor chemical medium resistance and water resistance; the epoxy resin has good film-forming material mechanical property and excellent adhesive force, but has poor impact resistance, toughness and weather resistance, is easy to yellow and is inconvenient to construct by adopting a double-component process; the hydroxyl acrylic resin film forming material has good mechanical property, hardness and weather resistance, moderate resin price and easily adjustable performance, and when the hydroxyl acrylic resin film forming material is matched with amino curing resin or isocyanate for use, a film can obtain excellent water resistance and alcohol resistance, good fullness and the like, so the hydroxyl acrylic resin becomes the first choice base resin of water-based paint for metal and glass in terms of product performance, cost and convenience of application and construction.
According to the preparation process, the water-based hydroxy acrylic resin is divided into a water-soluble type, a water-emulsion type and a water-dispersible type, and the preparation process comprises the following steps:
1) because of the use of more hydrophilic groups and surfactants in water-soluble type and water-emulsion type (CN1557892A, CN1583917A, CN1162964 and CN1230971), the water resistance and the alcohol resistance of the water-soluble type and the water-emulsion type are difficult to meet the requirements;
2) the water dispersion type hydroxyl acrylic resin water dispersion prepared by adopting the secondary dispersion process completely eliminates the use of a surfactant in a common emulsion polymerization method, has fewer hydrophilic monomers, has better water resistance, alcohol resistance and acid and alkali corrosion resistance, just overcomes the defect that water-soluble type and water-emulsion type water resistance and alcohol resistance are difficult to meet the requirements, for example, CN101457005A adopts the secondary dispersion process to prepare the hydroxyl acrylic resin water dispersion, but can not completely meet the application requirements in the aspects of film distinctness of image, salt fog resistance, hardness, flexibility and the like.
Disclosure of Invention
The invention provides a hydroxyl acrylic resin aqueous dispersion capable of constructing a dual-mode network and a preparation method thereof, which aim to solve the technical problem that the hydroxyl acrylic resin is difficult to have good water resistance, alcohol resistance, film distinctness of image, salt spray resistance, hardness and flexibility.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
an aqueous hydroxy acrylic resin dispersion capable of constructing a bimodal network, wherein hydroxy functional monomers adopted in the preparation of the aqueous hydroxy acrylic resin dispersion comprise at least one long-chain hydroxy functional monomer and at least one short-chain hydroxy functional monomer, and the aqueous hydroxy acrylic resin dispersion has functional groups which react with amino resin and isocyanate active ingredients.
Preferably, the raw materials in the preparation process comprise the following components in percentage by mass:
a: 20-30% of acrylate monomer and/or methacrylate monomer
B: 2 to 8 percent of long-chain hydroxyl functional monomer
C: 2-8% of short-chain hydroxyl functional monomer
D: 0 to 10 percent of vinyl monomer
E: acrylic acid or methacrylic acid 1-4%
F: 0.1 to 2 percent of initiator
G: 0.1-2% of molecular weight regulator
H: 3 to 8 percent of solvent
I: 1 to 4 percent of amine neutralizer
J: 40-50% of water.
Preferably, the long-chain hydroxyl functional monomer is one or more of polyethylene glycol methacrylate, polyethylene glycol acrylate and poly 1, 2-propylene glycol monomethacrylate.
Preferably, the short-chain hydroxyl functional monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, glycerol- (2-versatic acid-3-acrylic acid) ester, glycerol- (2-versatic acid-3-methacrylic acid) ester, hydroxybutyl acrylate and hydroxybutyl methacrylate.
Preferably, the acrylate monomer is one or more of methyl acrylate, ethyl acrylate, butyl acrylate, isobornyl acrylate, isooctyl acrylate and glycidyl acrylate, and the methacrylate monomer is one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobornyl methacrylate, isooctyl methacrylate and glycidyl methacrylate.
Preferably, the vinyl monomer is one or more of styrene, vinyl versatate and acrylonitrile.
Preferably, the solvent is one or more of 100# solvent oil, 200# solvent oil, ethanol, isopropanol, n-butanol, isobutanol, methyl isobutyl ketone, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, dipropylene glycol methyl ether, and dipropylene glycol butyl ether.
Preferably, the initiator is one or more of azo type and organic peroxy type thermal initiators, and more preferably, one or more of azobisisobutyronitrile, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyacetate, ditert-amyl peroxide, tert-butyl peroxy-3, 5, 5-trimethyl hexanoate.
Preferably, the amine neutralizer is one or more of ammonia, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, diisopropanolamine, and trimethylolmethylamine.
A preparation method of a hydroxyl acrylic resin aqueous dispersion capable of constructing a bimodal network comprises the following preparation steps:
(1) adding solvent and 10-40% of initiator mass in a reactor in advance, and heating to 70-125 ℃; then, dropwise adding the mixed monomer, the initiator and the molecular weight regulator, adding a small amount of the initiator after dropwise adding within 2-4 hours, and reacting for 1-4 hours under heat preservation;
(2) cooling the resin to 60-75 ℃, adding an amine neutralizer, and stirring and dispersing for 0.5-2 hours;
(3) and (3) dropwise adding deionized water under the stirring condition, and obtaining the hydroxyl acrylic resin aqueous dispersion through the self-emulsifying effect of the polymer.
The molecular weight regulator of the invention is one or more of aliphatic mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, octadecyl mercaptan, styrene dimer, isopropanol, mercaptoethanol, mercaptopropanol, thioglycolic acid, mercaptopropionic acid, isooctyl mercaptopropionate and dithioester.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the beneficial effects that:
in the preparation process of the hydroxyl acrylic resin aqueous dispersion, two or more functional monomers with long and short molecular chains of reactive groups are adopted as comonomers; the prepared hydroxyl acrylic resin aqueous dispersion can form a topological dual-mode cross-linked network with long and short molecular chains with active components such as amino resin, isocyanate and the like, and can endow a coating film with excellent hardness, good toughness and excellent gloss.
Detailed Description
All features disclosed in this specification may be combined in any combination, except features and/or steps that are mutually exclusive.
Example 1
The synthetic formulation of the aqueous dispersion of hydroxyacrylic resins is given in table 1.
TABLE 1
The preparation method comprises the following steps: ethylene glycol butyl ether is added into a reactor in advance, tert-butyl peroxybenzoate accounting for 10% of the total amount of the initiator is added, the temperature is raised to 120 ℃ of the set reaction temperature, then the mixed monomer, the initiator accounting for 85% of the total amount and the molecular weight regulator are added dropwise, the dropwise addition is completed within 3 hours, then the rest 5% of the initiator is added, and the temperature is kept for 3 hours. And cooling the resin to 60 ℃, adding an amine neutralizer N, N-dimethylethanolamine, and stirring and dispersing for 2 hours.
And dropwise adding deionized water under the stirring condition, and obtaining the hydroxyl acrylic resin aqueous dispersion through the self-emulsifying effect of the polymer.
The coating is prepared by mixing the hydroxyl acrylic resin aqueous dispersion and cymel-325 amino resin according to the proportion of 6:1, the adhesive force of a coating film in a cross-cut method on a metal substrate is 0 grade, the hardness of the coating film is 2H, the impact strength is 50kg cm, and the coating film does not crack or fall off when the curvature radius is 1mm when the coating film is measured in flexibility.
Example 2
The synthetic formulation of the aqueous hydroxyacrylic resin dispersion is shown in Table 2.
TABLE 2
The preparation method comprises the following steps: propylene glycol methyl ether is added into a reactor in advance, Benzoyl Peroxide (BPO) accounting for 10% of an initiator is added, the temperature is raised to a set reaction temperature of 80 ℃, then a mixed monomer, 85% of the initiator and a molecular weight regulator dodecanethiol are dropwise added, the dropwise addition is completed within 3 hours, then the rest 5% of the initiator is added, and the temperature is kept for 3 hours. And cooling the resin to 60 ℃, adding an amine neutralizer N, N-dimethylethanolamine, and stirring and dispersing for 2 hours.
And dropwise adding deionized water under the stirring condition, and obtaining the hydroxyl acrylic resin aqueous dispersion through the self-emulsifying effect of the polymer.
The hydroxyl acrylic resin aqueous dispersion and American screw-25 amino resin are prepared into a coating according to a ratio of 6:1, on a metal substrate, the adhesion force of a coating cross-cut method is 0 grade, the hardness of the coating is 1H, the impact strength is 50kg cm, and the coating does not crack or fall off when the curvature radius is 1mm when the coating is measured by flexibility.
Example 3
The synthetic formulation of the aqueous hydroxyacrylic resin dispersion is shown in Table 3.
TABLE 3
The preparation method comprises the following steps: ethylene glycol butyl ether is added into a reactor in advance, tert-butyl peroxybenzoate accounting for 10% of the total amount of the initiator is added, the temperature is raised to 120 ℃ of the set reaction temperature, then the mixed monomer, the initiator accounting for 85% of the total amount and the molecular weight regulator are added dropwise, the dropwise addition is completed within 3 hours, then the rest 5% of the initiator is added, and the temperature is kept for 3 hours. And cooling the resin to 60 ℃, adding an amine neutralizer N, N-dimethylethanolamine, and stirring and dispersing for 2 hours.
And dropwise adding deionized water under the stirring condition, and obtaining the hydroxyl acrylic resin aqueous dispersion through the self-emulsifying effect of the polymer.
The coating is prepared by the hydroxy acrylic resin aqueous dispersion and cymel-325 amino resin according to the proportion of 4:1, the adhesion force on a glass substrate is 1 grade, the hardness of the coating film is 2H, and the 20-degree angle gloss is 96 Gu.
Claims (4)
1. The hydroxyl acrylic resin aqueous dispersion capable of constructing a dual-mode network is characterized in that hydroxyl functional monomers adopted during preparation of the hydroxyl acrylic resin aqueous dispersion comprise at least one long-chain hydroxyl functional monomer and at least one short-chain hydroxyl functional monomer, and the hydroxyl acrylic resin aqueous dispersion has functional groups which react with amino resin and isocyanate active ingredients;
the preparation method comprises the following steps of:
a: 20-30% of acrylate monomer and/or methacrylate monomer
B: 2 to 8 percent of long-chain hydroxyl functional monomer
C: 2-8% of short-chain hydroxyl functional monomer
D: 0 to 10 percent of vinyl monomer
E: acrylic acid or methacrylic acid 1-4%
F: 0.1 to 2 percent of initiator
G: 0.1-2% of molecular weight regulator
H: 3 to 8 percent of solvent
I: 1 to 4 percent of amine neutralizer
J: 40-50% of water;
the amine neutralizer is one or more of ammonia water, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, diisopropanolamine and trimethylolmethylamine;
the long-chain hydroxyl functional monomer is one or more of polyethylene glycol methacrylate, polyethylene glycol acrylate and poly (1, 2-propylene glycol) monomethacrylate;
the short-chain hydroxyl functional monomer is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate;
the acrylate monomer is one or more of methyl acrylate, ethyl acrylate, butyl acrylate and isobornyl acrylate, and the methacrylate monomer is one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobornyl methacrylate, isooctyl methacrylate and glycidyl methacrylate;
the vinyl monomer is styrene.
2. The aqueous dispersion of hydroxyacrylic resin capable of forming bimodal network as claimed in claim 1, wherein said solvent is one or more of 100# solvent oil, 200# solvent oil, ethanol, isopropanol, n-butanol, isobutanol, methyl isobutyl ketone, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, dipropylene glycol methyl ether and dipropylene glycol butyl ether.
3. An aqueous dispersion of hydroxyacrylic resins capable of building bimodal networks according to claim 1, characterized in that said initiator is one or more of azo type, organic peroxy type thermal initiators.
4. A process for the preparation of an aqueous dispersion of a hydroxyacrylic resin capable of building bimodal networks according to any one of claims 1 to 3, comprising the following preparation steps:
(1) adding solvent and 10-40% of initiator mass in a reactor in advance, and heating to 70-125 ℃; then, dropwise adding the mixed monomer, the initiator and the molecular weight regulator, adding a small amount of the initiator after dropwise adding within 2-4 hours, and reacting for 1-4 hours under heat preservation;
(2) cooling the resin to 60-75 ℃, adding an amine neutralizer, and stirring and dispersing for 0.5-2 hours;
(3) and (3) dropwise adding deionized water under the stirring condition, and obtaining the hydroxyl acrylic resin aqueous dispersion through the self-emulsifying effect of the polymer.
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| CN110845656B (en) * | 2019-11-21 | 2023-01-13 | 万华化学集团股份有限公司 | Hydroxyl acrylic emulsion and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1130633A (en) * | 1994-12-01 | 1996-09-11 | 赫彻斯特股份公司 | Functional copolymers of low molar mass processes for their preparation, and their use |
| JP2003238883A (en) * | 2002-02-20 | 2003-08-27 | Hitachi Maxell Ltd | Aqueous dispersion and its preparation process |
| CN1771301A (en) * | 2003-04-30 | 2006-05-10 | 日立麦克赛尔株式会社 | Aqueous dispersion and process for production thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1130633A (en) * | 1994-12-01 | 1996-09-11 | 赫彻斯特股份公司 | Functional copolymers of low molar mass processes for their preparation, and their use |
| JP2003238883A (en) * | 2002-02-20 | 2003-08-27 | Hitachi Maxell Ltd | Aqueous dispersion and its preparation process |
| CN1771301A (en) * | 2003-04-30 | 2006-05-10 | 日立麦克赛尔株式会社 | Aqueous dispersion and process for production thereof |
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