CN114573743A - Aqueous secondary dispersion containing copolymer P, method for the production thereof and use thereof - Google Patents

Aqueous secondary dispersion containing copolymer P, method for the production thereof and use thereof Download PDF

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CN114573743A
CN114573743A CN202011386527.4A CN202011386527A CN114573743A CN 114573743 A CN114573743 A CN 114573743A CN 202011386527 A CN202011386527 A CN 202011386527A CN 114573743 A CN114573743 A CN 114573743A
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acrylate
meth
monomer
parts
hydroxyl
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金深波
杨双一
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Nippon Paint China Co Ltd
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Priority to PCT/CN2021/134931 priority patent/WO2022117017A1/en
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    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • 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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • C09D133/08—Homopolymers or copolymers of acrylic acid 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
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

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  • 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)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses an aqueous secondary dispersion containing a copolymer P, which is synthesized by the following components: 1) a hydroxyl group-containing hydrophobic polymer comprising the following components as structural unit monomers: a1 hydroxyl-containing monomer, B1 acrylate monomer and/or vinylic monomer, and 2) hydroxyl-containing hydrophilic polymer comprising the following as structural unit monomers: a2 hydroxyl-containing monomer, B2 homopolymer acrylate monomer and/or ethylene monomer with Tg higher than 80 ℃, C homopolymer acrylate monomer with Tg lower than 80 ℃, and D carboxyl-containing monomer. The dispersion has a high bubble-free film thickness without significant loss of other properties such as hardness and resistance; meanwhile, the weather resistance is good, and the paint can endure low humidity, especially high temperature and low humidity construction environment. The invention also discloses a preparation method and application of the dispersion.

Description

Aqueous secondary dispersion containing copolymer P, method for the production thereof and use thereof
Technical Field
The invention relates to the technical field of coatings. More particularly, it relates to an aqueous secondary dispersion containing copolymer P, a process for its preparation and its use.
Background
In recent years, with the increasing strictness of national environmental protection policies, water-based coatings are becoming research hotspots in the current coating industry due to the advantages of non-toxicity, non-combustibility, environmental friendliness, energy conservation and the like. In these water-based paints, a water-based two-component system in which a hydroxy acrylic acid (ester) dispersion and an isocyanate curing agent are matched is widely used in the application fields of industrial paints for woodware, metal and the like because of having excellent performances such as high gloss, good weather resistance, color and gloss retention and the like. Even can be compared with an oily system in certain application scenes, and has very wide development prospect.
However, in practical applications, when the humidity of the environment is relatively low, especially in a high-temperature and low-humidity construction environment, when the thickness of the paint film reaches a certain level, some bubbles or pinholes often appear on the surface of the paint film, which seriously affects the appearance and performance of the paint film. This is because when a paint film is thickly coated, the gas introduced by stirring and the gas such as carbon dioxide generated by the reaction of isocyanate groups with water, which are mixed in the coating material, do not completely escape. Among them, bubbles are appearance defects left by gas that, while penetrating the surface of a paint film, encounters the paint film curing. In such a situation, we have generally described the coating system as having poor construction application, severely affecting appearance, and being unusable at the customer site. The non-bubble film thickness of the resin and the corresponding coating can be determined by adopting a mode of spraying a sample plate with gradient film thickness, the gas overflow capacity is gradually weakened along with the increase of the thickness of a paint film until pinholes and bubbles appear, and the film thickness in the area is the non-bubble film thickness of the system. On the premise of ensuring other performances, the higher the thickness of the foamless film of the system, the better.
At present, there are some related patents reporting to improve the thickness of the non-foaming film of the resin and further ensure the application property of the corresponding coating. CN 101622309a discloses a method for increasing the thickness of a resin non-bubble film. The patent improves the construction applicability of the coating by introducing a high boiling point nonpolar solvent into the formulation. However, the introduced high-boiling solvent generally cannot be completely evaporated under the conditions of baking, especially low-temperature curing, so that the hardness and the resistance of the paint film are greatly reduced, which seriously restricts the practical applicability of the method.
In view of the above, it is desirable to provide an aqueous dispersion of a hydroxyacrylate having excellent applicability to a construction, which has a high non-bubble film thickness without significant loss of other properties such as hardness and resistance, so as to solve the problems of the prior art.
Disclosure of Invention
It is a first object of the present invention to provide an aqueous secondary dispersion comprising a copolymer P, which has a high bubble-free film thickness without any significant loss in properties such as hardness and resistance; meanwhile, the weather resistance is good, and the paint can endure low humidity, especially high temperature and low humidity construction environment.
A second object of the present invention is to provide a process for the preparation of aqueous secondary dispersions containing copolymers P.
The third purpose of the invention is to provide a water-based paint.
In order to achieve the purpose, the invention adopts the following technical scheme:
an aqueous secondary dispersion containing a copolymer P, characterized in that said copolymer P is synthesized from:
1) a hydroxyl-containing hydrophobic polymer comprising as structural unit monomers:
a1 is a hydroxyl-containing monomer,
b1 acrylate monomer and/or vinyl monomer, and
2) a hydroxyl group-containing hydrophilic polymer comprising the following components as structural unit monomers:
A2A is a hydroxyl-containing monomer,
the Tg of the B2 homopolymer is more than 80 ℃ of acrylate monomer and/or vinyl monomer,
the Tg of the C homopolymer is below 80 ℃,
d carboxyl-containing monomer.
Further, in the copolymer P, the content of the hydroxyl group-containing hydrophobic polymer and the hydroxyl group-containing hydrophilic polymer is:
50-90 wt% of hydroxyl-containing hydrophobic polymer;
10-50 wt% of hydroxyl-containing hydrophilic polymer.
Further, the copolymer P is synthesized from the following components:
1) a hydroxyl group-containing hydrophobic polymer comprising the following components as structural unit monomers:
a1 hydroxyl-containing monomer 10-30 wt%,
b1 acrylate monomer and/or vinyl monomer 70-90 wt%, and
2) a hydroxyl group-containing hydrophilic polymer comprising the following components as structural unit monomers:
Figure BDA0002811145040000021
further, the solids content of the aqueous secondary dispersion is 30% to 70%, preferably 40% to 60%.
Further, the molecular weight of the copolymer P is 4000-.
Further, the monomer of the structural unit of the hydroxyl-containing hydrophobic polymer and/or the hydroxyl-containing hydrophilic polymer also contains a monomer Y;
wherein the monomer Y is an acrylate monomer prepared by ring opening of a carboxyl-containing monomer and tertiary carboxylic acid glycidyl ester, and the content of the monomer Y accounts for 2-10 wt% of the total content of all the components of the copolymer P.
Further, the structural formula of the monomer Y is shown as the following formula I:
Figure BDA0002811145040000022
wherein R is1And R2Each independently selected from alkyl, and R1And R2The total number of carbon atoms of (2) is 7.
Further, each of the hydroxyl group-containing monomers a1 and a2 is independently at least one selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
Further, the D carboxyl-containing monomer is selected from at least one of acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid.
Further, the B1 acrylate monomer is selected from methyl (meth) acrylate, sec-butyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, coco oleate, octadecyl (meth) acrylate, at least one of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
Further, the B1 vinyl monomer is at least one selected from the group consisting of vinyl acetate, dichloroethylene, styrene, acrylonitrile, (meth) acrylamide, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, and divinylbenzene.
Further, the B2 acrylate monomer and/or vinyl monomer is selected from one or more of methyl methacrylate, styrene, methacrylic acid cyclic ester and isobornyl methacrylate.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a process for the preparation of an aqueous secondary dispersion containing a copolymer P, comprising the steps of:
adding a structural unit monomer for forming a hydroxyl-containing hydrophobic polymer and an initiator into a solvent at a reaction temperature under a nitrogen atmosphere, and carrying out primary heat preservation;
adding a structural unit monomer for forming a hydroxyl-containing hydrophilic polymer and an initiator, and carrying out second heat preservation;
cooling, adding a neutralizing agent, and carrying out third heat preservation;
adding deionized water for emulsification, and keeping the temperature for the fourth time;
filtering to obtain the aqueous secondary dispersion containing the copolymer P.
In order to achieve the third object, the present invention also provides an aqueous coating material comprising the aqueous secondary dispersion containing the copolymer P as described above in the first object.
Further, the water-based paint also comprises a cross-linking agent.
Further, the cross-linking agent is selected from one or more of hydrophilic polyisocyanate and hydrophobic polyisocyanate.
The invention has the following beneficial effects:
according to the water-based secondary dispersion provided by the invention, as the hydroxyl-containing hydrophilic polymer (dispersion shell polymer) is specially designed, the constituent monomers of the water-based secondary dispersion comprise the acrylate monomer and/or the ethylene monomer with high Tg, when the water-based secondary dispersion is used for preparing a water-based coating, the chain segment motion is weakened and the reaction speed is reduced when the water-based secondary dispersion is crosslinked with a curing agent in the early stage, so that the viscosity of a coating in the solvent volatilization process is reduced, a condition is created for releasing bubbles, the bubble-free film thickness of the resin is obviously improved, and the resin construction applicability is obviously improved. And as the solidification progresses, the hydrophilic polymer chain segment gradually unfreezes under baking to start moving and participate in the solidification. The hardness and the resistances of the paint film are not lost. Further, in the aqueous secondary dispersion provided by the present invention, the monomer Y is preferably added so as to increase the distance between the polymer segments, which also helps to reduce the viscosity of the polymer and improve the thickness of the bubble-free film.
In the water-based paint provided by the invention, a water-based paint coating film obtained by matching the water-based secondary dispersion and the water-based diisocyanate curing agent has the characteristics of excellent construction applicability, high gloss, high hardness and excellent weather resistance.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
According to one embodiment of the present invention, an aqueous secondary dispersion containing a copolymer P is provided in order to improve the thickness of a bubble-free film of an aqueous coating while maintaining good workability, high gloss, hardness and good weather resistance.
The invention finds that the prepared dispersion is very suitable for preparing paint films with high bubble-free film thickness and obviously improved construction application performance by uniquely designing the polymer chain segment in the copolymer of the aqueous secondary dispersion. In the invention, the aqueous secondary dispersion is an acrylic dispersion, wherein the copolymer P is synthesized from the following components:
1) a hydroxyl group-containing hydrophobic polymer (P1) comprising the following components as structural unit monomers:
A1A is a hydroxyl-containing monomer,
b1 acrylate monomer and/or vinyl monomer, and
2) a hydroxyl group-containing hydrophilic polymer (P2) comprising the following components as structural unit monomers:
A2A is a hydroxyl-containing monomer,
the Tg of the B2 homopolymer is more than 80 ℃ of acrylate monomer and/or vinyl monomer,
the Tg of the C homopolymer is below 80 ℃,
d carboxyl-containing monomer.
In a preferred example, the copolymer P is synthesized from:
1) a hydroxyl group-containing hydrophobic polymer comprising, as structural unit monomers, the following components in terms of the total mass of the structural unit monomers forming the hydroxyl group-containing hydrophobic polymer:
a1 hydroxyl-containing monomer 10-30 wt%,
b1 acrylate monomer and/or vinyl monomer 70-90 wt%, and
2) a hydroxyl group-containing hydrophilic polymer comprising, as structural unit monomers, the following components, based on the total mass of the structural unit monomers forming the hydroxyl group-containing hydrophilic polymer:
Figure BDA0002811145040000041
in general, acrylic dispersions have at least two polymer stages, one hydrophilic and one hydrophobic, which, after neutralization and emulsification, act as an emulsifier to entrap and disperse the hydrophobic polymer in the water. Conventional designs have chosen a way to design polymers that are hard inside and soft outside. Few studies have been conducted on the glass transition temperature of hydrophilic polymers, i.e., polymers of the shell of the dispersion. We have surprisingly found that when the above specific amounts of the acrylate monomer and/or the vinyl monomer having a homopolymer Tg of greater than 80 ℃ are contained in the constituent monomers of the hydroxyl group-containing hydrophilic polymer, the resin is remarkably improved in the thickness of the non-foamed film and is also excellent in hardness and weather resistance (particularly in environments of low humidity, high temperature and low humidity).
In a preferred example, the Tg of the homopolymer of the B2 acrylate monomer and/or vinylic monomer is > 80 ℃. Under these conditions, the resin is improved in the thickness of the non-foamed film and is improved in the hardness and weather resistance.
Illustratively, the B2 acrylate monomer and/or vinyl monomer is selected from one or more of methyl methacrylate, styrene, cyclic methacrylate and isobornyl methacrylate.
Suitable hydroxyl-containing monomers for a1 and a2 may include, but are not limited to, at least one selected from the group consisting of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate. The hydroxyl-containing monomers in A1 and A2 may be the same or different.
In the present invention, hydroxyethyl (meth) acrylate means hydroxyethyl methacrylate or hydroxyethyl acrylate. Other materials in this writing are also similar in meaning and will not be described herein.
Illustratively, the B1 acrylate monomer is selected from the group consisting of methyl (meth) acrylate, sec-butyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, coco oleate, octadecyl (meth) acrylate, at least one of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
Illustratively, the B1 vinylic monomer is selected from at least one of vinyl acetate, dichloroethylene, styrene, acrylonitrile, (meth) acrylamide, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, divinylbenzene.
In a preferred example, the D carboxyl group-containing monomer is at least one selected from acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid.
In a preferred example, the B2 acrylate monomer and/or vinyl monomer is selected from one or more of methyl methacrylate, styrene, cyclic methacrylate (e.g., cyclohexyl methacrylate), and isobornyl methacrylate.
Illustratively, the C acrylate monomer is selected from the group consisting of methyl acrylate, sec-butyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, coco (meth) acrylate, octadecyl (meth) acrylate, at least one of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
In a preferred example, in the present embodiment, the monomer of the structural unit of the hydroxyl group-containing hydrophobic polymer and/or the hydroxyl group-containing hydrophilic polymer further contains a monomer Y; wherein the monomer Y is an acrylate monomer prepared by ring opening of a carboxyl-containing monomer and tert-carbonic acid glycidyl ester. In the present invention, it has been found that the incorporation of monomer Y makes it possible to reduce the viscosity of the polymer and also to contribute to an improvement in the bubble-free film thickness of a coating comprising the aqueous secondary dispersion. While the applicability of the resin in construction is significantly improved (improvement of the thickness of the non-foamed film), the basic properties of the paint film (in particular hardness and resistance) remain good.
Suitable monomers Y are acrylate monomers prepared by ring opening of a carboxyl group-containing monomer, preferably methacrylic acid and acrylic acid, and of glycidyl versatate. Preferably, the ring-opening reaction is carried out with the addition of a polymerization inhibitor between 100 ℃ and 150 ℃.
Further, the preparation method of the monomer Y comprises the following steps:
200-300 parts of tertiary carbonic acid glycidyl ester, 60-80 parts of acrylic acid and 0-1 part of p-hydroxyanisole are mixed and then added into a reaction kettle, the reaction kettle is heated to 100-160 ℃, the acid value is tested until the acid value is less than 1mgKOH/g, and the mixture is cooled to room temperature for discharging.
The formula of monomer Y is preferably as shown in formula I below:
Figure BDA0002811145040000061
wherein R is1And R2Each independently selected from alkyl, and R1And R2The total number of carbon atoms of (2) is 7. Under such preferable conditions, the coating material containing the aqueous secondary dispersion obtained has a higher non-foaming film thickness and more remarkable effects of improving hardness, weather resistance and the like.
The content of monomer Y is preferably from 2 to 10% by weight, based on the total content of the components of the copolymer P. Illustratively, the amount of monomer Y includes, but is not limited to, from 2 to 8 weight percent, from 4 to 10 weight percent, from 4 to 8 weight percent, and the like, based on the total amount of components of copolymer P.
In a preferred example, the content of the hydroxyl group-containing hydrophobic polymer and the hydroxyl group-containing hydrophilic polymer in the copolymer P is:
50-90 wt% of hydroxyl-containing hydrophobic polymer;
10-50 wt% of hydroxyl-containing hydrophilic polymer.
In the present embodiment, suitable copolymers P have a molecular weight of 4000-10000g/mol, preferably of 5000-8000 g/mol.
In this embodiment, the solids content of the aqueous secondary dispersion is suitably from 30 to 70%, preferably from 40 to 60%.
A further embodiment of the present invention provides a process for the preparation of an aqueous secondary dispersion containing copolymer P as described above, comprising the steps of:
adding a monomer (namely, components A1 and B1) which forms a structural unit of the hydroxyl-containing hydrophobic polymer and an initiator into a solvent at a reaction temperature under a nitrogen atmosphere, and carrying out primary heat preservation at a polymerization temperature;
adding a monomer (namely components A2, B2, C and D) forming a structural unit of the hydroxyl-containing hydrophilic polymer and an initiator, and carrying out second heat preservation at the polymerization temperature;
cooling, adding a neutralizing agent, and carrying out third heat preservation within the range of the neutralizing temperature;
adding deionized water for emulsification, and keeping the temperature for the fourth time at about 50 ℃;
filtering to obtain the aqueous secondary dispersion containing the copolymer P.
Illustratively, each incubation time is independently from 0.5 to 2 hours.
Furthermore, the above reaction temperature is determined by the chosen initiation system. The temperature after temperature reduction is preferably 80-120 ℃.
In this embodiment, the method of polymerizing the unsaturated monomer is well known to those skilled in the art, and typically, the polymerization is carried out by placing the reaction solvent in a reaction vessel and dropping the monomer and the initiator.
Preferably, the initiator is at least one selected from the group consisting of azobisisobutyronitrile, dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, t-amyl peroxyacetate, t-butyl peroxybenzoate, t-amyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxyvalerate, di-t-butyl peroxide and di-t-amyl peroxide. The amount of initiator used is determined according to the desired molecular weight.
Preferably, the solvent is selected from at least one of butyl acetate, diethylene glycol dimethyl ether, No. 100 solvent oil, No. 200 solvent oil, toluene, xylene, ethanol, isopropanol, n-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, diacetone alcohol, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol methyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, and dipropylene glycol dimethyl ether. The solvent or mixture of solvents is selected on the basis that the boiling point of the solvent is slightly above the reaction temperature. The solvent content is determined by the solids content at the end of the polymerization of the copolymer P being between 50% and 90%, particularly preferably between 70% and 85%.
In the present embodiment, the neutralizing agent is preferably an organic amine neutralizing agent. The carboxyl groups on the P segment of the copolymer are neutralized with an organic amine to provide the resin with sufficient water-curing ability. Preferably, the organic amine is selected from at least one of ammonia, triethylamine, triethanolamine, dimethylethanolamine, 2-methyl-2-aminopropanol, dimethylisopropanolamine, methyldiethanolamine, ethyldiisopropylamine and diethylethanolamine; the degree of neutralization is 50 to 110%, preferably 75 to 100%.
Emulsifying with deionized water to obtain final hydroxyl acrylate aqueous dispersion to reach the solid content required by the final dispersion.
A further embodiment of the present invention provides an aqueous coating comprising an aqueous secondary dispersion containing a copolymer P as described above.
Specifically, the aqueous dispersion resin is contacted with a crosslinking agent and mixed to prepare the aqueous coating. Preferably, the crosslinking agent is selected from one or more of hydrophilic polyisocyanate and hydrophobic polyisocyanate.
The technical solution of the present invention is described below with reference to some specific examples:
preparation of monomer Y
The preparation method of the monomer Y comprises the following steps:
200-300 parts of tertiary carbonic acid glycidyl ester, 60-80 parts of acrylic acid and 0-1 part of p-hydroxyanisole are mixed and then added into a reaction kettle, the reaction kettle is heated to 100-160 ℃, the acid value is tested until the acid value is less than 1mgKOH/g, and the mixture is cooled to room temperature for discharging. Obtaining a monomer Y, wherein the structural formula of the monomer Y is shown as the following formula I:
Figure BDA0002811145040000071
in the following examples, unless otherwise specified, the monomer Y was prepared by the above-mentioned preparation method.
Example 1 (styrene as hard monomer, 50 wt% in P2)
Adding 200 parts of propylene glycol butyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 100 parts of n-butyl acrylate, 100 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate, 120 parts of n-butyl methacrylate and 80 parts of monomer Y)) and 5 parts of di-tert-amyl peroxide, preserving heat for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 60 parts of hydroxyethyl methacrylate, 120 parts of styrene and 20 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, preserving heat for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, preserving heat for 0.5 hour, finally dropwise adding 1000 parts of deionized water, preserving heat for 1 hour, filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion with excellent foamless film thickness.
Example 2 (hard monomer is cyclohexyl methacrylate, content 50% by weight in P2)
Adding 200 parts of dipropylene glycol methyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 100 parts of n-butyl acrylate, 100 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate, 120 parts of butyl methacrylate and 80 parts of monomer Y)) and 5 parts of di-tert-amyl peroxide, preserving heat for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 60 parts of hydroxyethyl methacrylate, 120 parts of cyclohexyl methacrylate and 20 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, preserving heat for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, preserving heat for 0.5 hour, finally dropwise adding 1000 parts of deionized water, preserving heat for 1 hour, filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion with excellent non-bubble film thickness.
Example 3
Adding 200 parts of propylene glycol butyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 100 parts of n-butyl acrylate, 100 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate, 120 parts of butyl methacrylate and 80 parts of monomer Y)) and 5 parts of di-tert-amyl peroxide, preserving heat for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 60 parts of hydroxyethyl methacrylate, 120 parts of cyclohexyl methacrylate and 20 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, preserving heat for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, preserving heat for 0.5 hour, finally dropwise adding 1000 parts of deionized water, preserving heat for 1 hour, filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion with excellent non-bubble film thickness.
Example 4
Adding 200 parts of propylene glycol butyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 140 parts of n-butyl acrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate, 220 parts of butyl methacrylate and 40 parts of monomer Y)) and 5 parts of di-tert-amyl peroxide, keeping the temperature for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 40 parts of hydroxyethyl methacrylate, 120 parts of styrene, 20 parts of acrylic acid and 40 parts of monomer Y) and 2 parts of di-tert-amyl peroxide, keeping the temperature for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, keeping the temperature for 0.5 hour, finally dropwise adding 1000 parts of deionized water, keeping the temperature for 1 hour, and filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion with excellent foamless film thickness.
Example 5
Adding 200 parts of propylene glycol butyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 140 parts of n-butyl acrylate, 220 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate and 40 parts of self-made monomer Y)) and 5 parts of di-tert-amyl peroxide, preserving heat for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 40 parts of hydroxyethyl methacrylate, 120 parts of isobornyl methacrylate, 20 parts of acrylic acid and 40 parts of self-made monomer Y) and 1.5 parts of di-tert-amyl peroxide, preserving heat for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, preserving heat for 0.5 hour, finally dropwise adding 1000 parts of deionized water, preserving heat for 1 hour, filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion with excellent foamless film thickness.
Example 6
Adding 200 parts of dipropylene glycol methyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 100 parts of n-butyl acrylate, 100 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate, 120 parts of butyl methacrylate and 80 parts of self-made monomer Y)) and 5 parts of di-tert-amyl peroxide, preserving heat for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 60 parts of hydroxyethyl methacrylate, 120 parts of methyl methacrylate and 20 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, preserving heat for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, preserving heat for 0.5 hour, finally dropwise adding 1000 parts of deionized water, preserving heat for 1 hour, filtering and discharging to obtain the hydroxyacrylate aqueous secondary dispersion with excellent non-foaming film thickness.
Example 7
Adding 200 parts of propylene glycol butyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 140 parts of n-butyl acrylate, 220 parts of methyl methacrylate, 140 parts of isooctyl acrylate, 140 parts of styrene and 160 parts of hydroxyethyl methacrylate) and 5 parts of di-tert-amyl peroxide, keeping the temperature for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 40 parts of hydroxyethyl methacrylate, 120 parts of isobornyl methacrylate, 20 parts of acrylic acid and 40 parts of self-made monomer Y) and 1.5 parts of di-tert-amyl peroxide, keeping the temperature for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, keeping the temperature for 0.5 hour, finally dropwise adding 1000 parts of deionized water, keeping the temperature for 1 hour, and filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion with excellent foamless film thickness.
Comparative example 1
Adding 200 parts of propylene glycol butyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 100 parts of n-butyl acrylate, 100 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate and 200 parts of butyl methacrylate) and 5 parts of di-tert-amyl peroxide, preserving heat for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 60 parts of hydroxyethyl methacrylate, 70 parts of butyl methacrylate, 50 parts of butyl acrylate and 20 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, preserving heat for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, preserving heat for 0.5 hour, finally dropwise adding 1000 parts of deionized water, preserving heat for 1 hour, and filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion.
Comparative example 2
Adding 200 parts of propylene glycol butyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 100 parts of n-butyl acrylate, 100 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate and 200 parts of butyl methacrylate) and 5 parts of di-tert-amyl peroxide, keeping the temperature for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 60 parts of hydroxyethyl methacrylate, 50 parts of styrene, 70 parts of butyl acrylate and 20 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, keeping the temperature for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, keeping the temperature for 0.5 hour, finally dropwise adding 1000 parts of deionized water, keeping the temperature for 1 hour, and filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion.
Comparative example 3
Adding 200 parts of propylene glycol butyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 100 parts of n-butyl acrylate, 100 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate and 200 parts of isobornyl methacrylate) and 5 parts of di-tert-amyl peroxide, preserving heat for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 60 parts of hydroxyethyl methacrylate, 50 parts of styrene, 70 parts of butyl acrylate and 20 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, preserving heat for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, preserving heat for 0.5 hour, finally dropwise adding 1000 parts of deionized water, preserving heat for 1 hour, filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion.
Comparative example 4
Adding 200 parts of propylene glycol butyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 100 parts of n-butyl acrylate, 100 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate, 120 parts of n-butyl methacrylate and 80 parts of monomer Y)) and 5 parts of di-tert-amyl peroxide, preserving heat for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 60 parts of hydroxyethyl methacrylate, 70 parts of styrene, 50 parts of n-butyl acrylate and 20 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, keeping the temperature for 1 hour, and then cooling to a certain temperature, adding 25 parts of triethylamine, preserving the heat for 0.5 hour, finally dropwise adding 1000 parts of deionized water, preserving the heat for 1 hour, filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion with excellent bubble-free film thickness.
Comparative example 5
Adding 200 parts of propylene glycol butyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 100 parts of n-butyl acrylate, 100 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate, 120 parts of n-butyl methacrylate and 80 parts of monomer Y)) and 5 parts of di-tert-amyl peroxide, preserving heat for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 50 parts of hydroxyethyl methacrylate, 145 parts of styrene and 5 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, preserving heat for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, preserving heat for 0.5 hour, finally dropwise adding 1000 parts of deionized water, preserving heat for 1 hour, filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion with excellent foamless film thickness.
Comparative example 6
Adding 200 parts of dipropylene glycol methyl ether, heating to 150 ℃ under the protection of nitrogen, dropwise adding a first part of monomer mixture (comprising 100 parts of n-butyl acrylate, 100 parts of methyl methacrylate, 100 parts of isooctyl acrylate, 140 parts of styrene, 160 parts of hydroxyethyl methacrylate, 120 parts of butyl methacrylate and 80 parts of monomer Y)) and 5 parts of di-tert-amyl peroxide, preserving heat for 1 hour, continuously dropwise adding a second part of monomer mixture (comprising 60 parts of hydroxyethyl methacrylate, 120 parts of lauryl acrylate and 20 parts of acrylic acid) and 2 parts of di-tert-amyl peroxide, preserving heat for 1 hour, then cooling to a certain temperature, adding 25 parts of triethylamine, preserving heat for 0.5 hour, finally dropwise adding 1000 parts of deionized water, preserving heat for 1 hour, filtering and discharging to obtain the hydroxyl acrylate aqueous secondary dispersion with excellent non-bubble film thickness.
The results of the performance test of each example and comparative example are shown in table 1 below:
TABLE 1
Figure BDA0002811145040000101
Figure BDA0002811145040000111
Note:
the thickness of the foamless film is tested under the conditions of 35 ℃ and 40% RH, the foamless film is matched with a Kostewa 3900 curing agent for use, the gradient film thickness is sprayed on a tin plate by means of automatic spraying equipment, the baking condition is 60 ℃ for 1h, and then the foaming limit is observed and tested.
In the monomer composition and formulation of comparative example 1, the hydrophobic polymer does not contain a hard monomer, so the foamless film thickness is low, and the application property is affected. In contrast, comparative example 2, which contains a small amount of the hard monomer (styrene) in the hydrophobic polymer segment, is not very significant in the improvement of the thickness of the non-foamed film. While comparative example 6 increased the bubble-free film thickness of the resin by introducing a long carbon chain acrylate structure into the resin structure, the introduction of the monomer greatly reduced the glass transition temperature, resulting in a softer film, which affected the final properties.
The hydroxyl acrylate aqueous dispersion prepared by the invention has simple and operable synthesis process, high resin foamless film thickness and hardness tolerance meeting the application requirements, and can be used as a hydroxyl resin component of a two-component polyurethane coating to prepare a high-performance aqueous polyurethane coating with aqueous and oily diisocyanate components.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. An aqueous secondary dispersion containing a copolymer P, characterized in that said copolymer P is synthesized from:
1) a hydroxyl group-containing hydrophobic polymer comprising the following components as structural unit monomers:
A1A is a hydroxyl-containing monomer,
b1 acrylate monomer and/or vinyl monomer, and
2) a hydroxyl group-containing hydrophilic polymer comprising the following components as structural unit monomers:
A2A is a hydroxyl-containing monomer,
the Tg of the B2 homopolymer is more than 80 ℃ of acrylate monomer and/or vinyl monomer,
the Tg of the C homopolymer is below 80 ℃,
d, carboxyl-containing monomer.
2. Aqueous secondary dispersion containing a copolymer P according to claim 1, characterized in that the copolymer P is synthesized from:
1) a hydroxyl-containing hydrophobic polymer comprising as structural unit monomers:
a1 hydroxyl-containing monomer 10-30 wt%,
b1 acrylate monomer and/or vinyl monomer 70-90 wt%, and
2) a hydroxyl group-containing hydrophilic polymer comprising the following components as structural unit monomers:
a2 hydroxyl-containing monomer 15-35 wt%,
40-70 wt% of acrylate monomer and/or vinyl monomer with Tg higher than 80 deg.C of B2 homopolymer,
0 to 10 weight percent of acrylate monomer with the Tg of C homopolymer below 80 ℃,
d, 10-15 wt% of carboxyl-containing monomer.
3. The aqueous secondary dispersion according to claim 1, wherein the copolymer P contains a hydrophobic hydroxyl group-containing polymer and a hydrophilic hydroxyl group-containing polymer in the following amounts:
50-90 wt% of hydroxyl-containing hydrophobic polymer;
10-50 wt% of hydroxyl-containing hydrophilic polymer.
4. Aqueous secondary dispersion containing copolymer P according to claim 1, characterized in that the solids content of the aqueous secondary dispersion is 30% to 70%, preferably 40% to 60%.
5. The aqueous secondary dispersion comprising copolymer P according to claim 1, characterized in that the molecular weight of copolymer P is 4000-10000g/mol, preferably 5000-8000 g/mol.
6. The aqueous secondary dispersion containing copolymer P according to any of claims 1 to 5, characterized in that the monomers of the structural units of the hydroxyl-containing hydrophobic polymer and/or the hydroxyl-containing hydrophilic polymer also contain monomers Y;
wherein the monomer Y is an acrylate monomer prepared by ring opening of a carboxyl-containing monomer and tertiary carboxylic acid glycidyl ester, and the content of the monomer Y accounts for 2-10 wt% of the total content of all the components of the copolymer P.
7. The aqueous secondary dispersion containing copolymer P according to claim 6, wherein the monomer Y has the formula I:
Figure FDA0002811145030000021
wherein R is1And R2Each independently selected from alkyl, and R1And R2The total number of carbon atoms of (2) is 7.
8. The aqueous secondary dispersion containing copolymer P according to claim 1, wherein the hydroxyl group-containing monomers a1 and a2 are each independently selected from at least one of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate;
preferably, the D carboxyl-containing monomer is at least one selected from acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid;
preferably, the B1 acrylate monomer is selected from the group consisting of methyl (meth) acrylate, sec-butyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, cocoate (meth) acrylate, octadecyl (meth) acrylate, at least one of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate;
preferably, the B1 ethylene monomer is at least one selected from vinyl acetate, dichloroethylene, styrene, acrylonitrile, (meth) acrylamide, N-dimethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide and divinylbenzene;
preferably, the B2 acrylate monomer and/or vinyl monomer is selected from one or more of methyl methacrylate, styrene, methacrylic acid cyclic ester and isobornyl methacrylate;
preferably, the C acrylate monomer is selected from the group consisting of methyl acrylate, sec-butyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, isooctyl (meth) acrylate, dodecyl (meth) acrylate, coco (meth) acrylate, octadecyl (meth) acrylate, at least one of dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.
9. Process for the preparation of an aqueous secondary dispersion containing a copolymer P according to any of claims 1 to 8, characterized in that it comprises the following steps:
adding a structural unit monomer for forming a hydroxyl-containing hydrophobic polymer and an initiator into a solvent at a reaction temperature under a nitrogen atmosphere, and carrying out primary heat preservation;
adding a structural unit monomer for forming a hydroxyl-containing hydrophilic polymer and an initiator, and carrying out second heat preservation;
cooling, adding a neutralizing agent, and carrying out third heat preservation;
adding deionized water for emulsification, and keeping the temperature for the fourth time;
filtering to obtain the aqueous secondary dispersion containing the copolymer P.
10. Aqueous coating material comprising an aqueous secondary dispersion containing a copolymer P as claimed in any of claims 1 to 8.
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