CN110894265A - Single-component quick self-drying epoxy ester/acrylate composite emulsion and preparation method thereof - Google Patents
Single-component quick self-drying epoxy ester/acrylate composite emulsion and preparation method thereof Download PDFInfo
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1472—Fatty acids
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a preparation method of a single-component quick self-drying epoxy ester/acrylic ester composite emulsion, which comprises the steps of reacting epoxy resin with hydroxy acid and organic monobasic fatty acid in sequence at 160-260 ℃ under the action of catalyst organic lithium until the acid value of a system is less than 15mgKOH/g, cooling and adding a solvent to obtain the epoxy ester. Then dropping an acrylic ester monomer dissolved with an initiator into the obtained epoxy ester, controlling the reaction temperature at 110-130 ℃, cooling to 60-65 ℃ after the reaction is finished, adding triethylamine for neutralization, and adding water for dispersion to obtain the normal-temperature single-component self-drying epoxy ester/acrylic ester composite emulsion. The surface drying and actual drying time of the composite emulsion prepared by the invention is greatly shortened at normal temperature, the VOC content of the epoxy ester is greatly reduced, the use of organic solvents harmful to human bodies is avoided, the environment-friendly requirement is met, the surface drying can be realized after the composite emulsion is placed for 10-15min at normal temperature, the adhesive force is developed within 1h, and the construction requirement under outdoor rainy conditions can be met.
Description
Technical Field
The invention belongs to the technical field of acrylate modified epoxy ester emulsion, and particularly relates to normal-temperature single-component self-drying epoxy ester/acrylate composite emulsion capable of being quickly dried and attached to metal and a preparation method thereof.
Background
With the increasing awareness of environmental protection and stricter laws and regulations on environmental protection, water-based coatings are receiving more attention due to their safety and environmental protection. The epoxy ester has the advantages of excellent adhesive force, good water resistance, excellent corrosion resistance and the like, and is widely applied. However, the conventional epoxy ester contains a large amount of organic solvents, and a large amount of Volatile Organic Compounds (VOCs) and harmful substances are released in the film forming process, so that environmental pollution and health hazard are caused, and thus the application of the epoxy ester is more and more limited. People can add water for dispersion or dilution by modifying the epoxy ester and introducing hydrophilic groups, thereby greatly reducing the discharge of VOC and meeting the requirement of environmental protection. At present, the commercially available waterborne epoxy ester has the defects of slow surface drying, more organic solvent content, poor water resistance and the like, so that the invention of the epoxy ester/acrylic ester composite emulsion is necessary to solve the problems.
Disclosure of Invention
The invention aims to provide a normal-temperature single-component self-drying epoxy ester/acrylic ester composite emulsion which can be quickly dried and quickly attached to metal and a preparation method thereof, and aims to overcome the defects of low surface drying and actual drying speed of epoxy ester, reduce the VOC content of the epoxy ester and improve the outdoor durability of the epoxy ester.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a single-component quick self-drying epoxy ester/acrylic ester composite emulsion comprises the following steps:
(1) synthesis of epoxy ester: firstly, adding epoxy resin and hydroxy acid into a reactor, heating to form a homogeneous phase, then adding a catalyst organic lithium, reacting at 160-190 ℃, adding organic monobasic fatty acid and xylene which accounts for 3-6% of the total mass fraction of homogeneous phase reactants when the acid value of a reaction solution is measured to be less than 5mgKOH/g, then heating to 230-260 ℃ for reaction, cooling to 80-100 ℃, adding a solvent for dilution until the solid content is 60-80% to obtain epoxy ester;
(2) synthesizing acrylic ester monomer modified epoxy ester: adding the epoxy ester obtained in the step (1) into a reactor, heating to 110-130 ℃, then dropwise adding an acrylate monomer dissolved with three-fourths of initiator into the epoxy ester for 2.5-3 h, then preserving heat for 0.5h, then dividing the rest of initiator into two equal parts, supplementing one initiator every 0.5h, and preserving heat for 2-3 h after supplementing is finished, thus obtaining the acrylate monomer modified epoxy ester;
(3) and (3) cooling the acrylate monomer modified epoxy ester obtained in the step (2) to 60-65 ℃, adding triethylamine for neutralization for 20-30 min, adding water for dispersion for 1.5-2 h when the neutralization degree is 90-120%, and adjusting the solid content to 41% to obtain the normal-temperature single-component self-drying epoxy ester/acrylate composite emulsion.
Preferably, the epoxy resin in the step (1) is one or more of E-51, E-44, E-20 or E-12; the hydroxy acid is one or more of salicylic acid and derivatives thereof, 2-hydroxypropionic acid or ricinoleic acid and derivatives thereof.
Preferably, the organic lithium in step (1) is one or more of lithium laurate or lithium neodecanoate.
Preferably, the organic monobasic fatty acid in the step (1) is one or more of eleostearic acid, linoleic acid, oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid or abietic acid and derivatives thereof.
Preferably, the molar ratio of the epoxy resin to the hydroxy acid in step (1) is 1: 0.5-2.5, wherein the molar ratio of the epoxy resin to the organic monobasic fatty acid is 1: 1-4, and the dosage of the catalyst organic lithium is 0.5-2 wt% of the total weight of the homogeneous reactants.
Preferably, the solvent in step (1) is any one or more of ethylene glycol monobutyl ether, propylene glycol methyl ether or propylene glycol methyl ether acetate.
Preferably, the initiator in step (2) is any one or more of dibenzoyl peroxide (BPO) or benzoyl tert-butyl peroxide (TBPB).
Preferably, the acrylate monomer in step (2) is a mixture of methyl methacrylate, styrene, butyl acrylate, butyl methacrylate, isooctyl acrylate, methacrylic acid and hydroxypropyl acrylate; the mass fractions of the various acrylate monomers in the mixture are respectively as follows: 15-30% of methyl methacrylate, 15-40% of styrene, 15-25% of butyl acrylate, 2-10% of butyl methacrylate, 3-8% of isooctyl acrylate, 5-15% of methacrylic acid and 1-7% of hydroxypropyl acrylate.
Preferably, the mass ratio of the acrylic monomer to the epoxy ester in the step (2) is 30: 70-70: 30, the amount of the initiator is 1.5-4.5 wt% of the total amount of the acrylic monomer.
In addition, the invention also claims a single-component quick self-drying epoxy ester/acrylic ester composite emulsion prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the high-melting-point hydroxy acid and the organic monobasic fatty acid are esterified with the epoxy resin, so that the softening point of the epoxy ester is improved, the surface drying and actual drying time of the finally obtained epoxy ester/acrylic ester composite emulsion is greatly shortened at normal temperature, and the construction efficiency is favorably improved;
(2) the epoxy ester is grafted and modified by the acrylate monomer to introduce hydrophilic groups, neutralized by triethylamine and emulsified to obtain epoxy ester/acrylate composite emulsion, thereby greatly reducing the VOC content of the epoxy ester, avoiding the use of organic solvents harmful to human bodies and meeting the requirement of environmental protection;
(3) according to the invention, the epoxy ester is subjected to graft modification by the acrylate monomer, and the acrylate component with good weather resistance is introduced, so that the weather resistance of the epoxy ester is improved, and the epoxy ester can be applied to outdoor places.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Although the steps in the present invention are arranged by using reference numbers, the order of the steps is not limited, and the relative order of the steps can be adjusted unless the order of the steps is explicitly stated or other steps are required for the execution of a certain step. It is to be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
Example 1
A preparation method of a single-component quick self-drying epoxy ester/acrylic ester composite emulsion comprises the following steps:
(1) synthesis of epoxy ester: firstly, adding epoxy resin E-44 and ricinoleic acid into a reactor, heating to form a homogeneous phase, then adding a catalyst lithium laurate, reacting at 170 ℃, adding linoleic acid, octadecanoic acid and xylene with the total mass fraction of 5% of reactants when the acid value of the reaction liquid is measured to be less than 5mgKOH/g, heating to 240 ℃ for reaction, cooling to 100 ℃, adding propylene glycol methyl ether acetate, and diluting until the solid content is 70% to obtain epoxy ester; wherein the molar ratio of the epoxy resin to the ricinoleic acid is 1: 1.5, the molar ratio of the epoxy resin to the linoleic acid is 1: 1.5, the molar ratio of the epoxy resin to the octadecanoic acid is 1: 2, the using amount of the catalyst lithium laurate is 1.2 percent of the total amount of homogeneous reactants;
(2) synthesizing acrylic ester monomer modified epoxy ester: adding the epoxy ester obtained in the step (1) into a reactor, heating to 110 ℃, then dropwise adding an acrylate monomer dissolved with three-fourths of dibenzoyl peroxide (BPO) into the epoxy ester for 2.5h, then preserving heat for 0.5h, then dividing the rest of initiator into two equal parts, supplementing one initiator every 0.5h, and preserving heat for 2h after the completion of the supplementing to obtain the acrylate monomer modified epoxy ester; wherein the mass ratio of the acrylic monomer to the epoxy ester is 60: 40, wherein the BPO is used in an amount of 3 wt% of the total amount of the acrylic monomer; the acrylate monomer is a mixture of methyl methacrylate, styrene, butyl acrylate, butyl methacrylate, isooctyl acrylate, methacrylic acid and hydroxypropyl acrylate; the mass ratio of each acrylate monomer in the mixture is respectively as follows: 20% of methyl methacrylate, 30% of styrene, 24% of butyl acrylate, 5% of butyl methacrylate, 8% of isooctyl acrylate, 10% of methacrylic acid and 3% of hydroxypropyl acrylate;
(3) and (3) cooling the acrylate monomer modified epoxy ester obtained in the step (2) to 60 ℃, adding triethylamine for neutralization for 30min, adding water for dispersion for 2h when the neutralization degree is 100%, and adjusting the solid content to 41% to obtain the normal-temperature single-component self-drying epoxy ester/acrylate composite emulsion.
Example 2
A preparation method of a single-component quick self-drying epoxy ester/acrylic ester composite emulsion comprises the following steps:
(1) synthesis of epoxy ester: firstly, adding epoxy resin E-20 and salicylic acid into a reactor, heating to form a homogeneous phase, then adding a catalyst lithium neodecanoate, reacting at 160 ℃, adding linoleic acid, abietic acid and xylene with the total mass fraction of reactants being 5% when the acid value of a reaction solution is measured to be less than 5mgKOH/g, heating to 250 ℃ for reaction, cooling to below 100 ℃ when the acid value is measured to be less than 15mgKOH/g, and adding propylene glycol methyl ether acetate to dilute until the solid content is 70% to obtain epoxy ester; wherein the molar ratio of the epoxy resin to the salicylic acid is 1: 1, the molar ratio of the epoxy resin to the linoleic acid is 1: 1.5, the molar ratio of the epoxy resin to the abietic acid is 1: 1.5, the using amount of the catalyst lithium neodecanoate is 1.5 percent of the total amount of homogeneous reactants;
(2) synthesizing acrylic ester monomer modified epoxy ester: adding the epoxy ester obtained in the step (1) into a reactor, heating to 120 ℃, then dropwise adding an acrylate monomer dissolved with three-fourths TBPB into the epoxy ester for 3 hours, then preserving heat for 0.5 hour, then dividing the rest initiator into two equal parts, supplementing one initiator every 0.5 hour, and preserving heat for 3 hours after supplementing is finished, thus obtaining the acrylate monomer modified epoxy ester; wherein the mass ratio of the acrylic monomer to the epoxy ester is 50: 50, the TBPB accounts for 2 wt% of the total amount of the acrylic monomers; the acrylate monomer is a mixture of methyl methacrylate, styrene, butyl acrylate, butyl methacrylate, isooctyl acrylate, methacrylic acid and hydroxypropyl acrylate; the mass ratio of each acrylate monomer in the mixture is respectively as follows: 25% of methyl methacrylate, 35% of styrene, 20% of butyl acrylate, 3% of butyl methacrylate, 5% of isooctyl acrylate, 8% of methacrylic acid and 4% of hydroxypropyl acrylate;
(3) and (3) cooling the acrylate monomer modified epoxy ester obtained in the step (2) to 65 ℃, adding triethylamine for neutralization for 20min, adding water for dispersion for 2h when the neutralization degree is 110%, and adjusting the solid content to 41% to obtain the normal-temperature single-component self-drying epoxy ester/acrylate composite emulsion.
Example 3
A preparation method of a single-component quick self-drying epoxy ester/acrylic ester composite emulsion comprises the following steps:
(1) synthesis of epoxy ester: firstly, adding epoxy resin E-20 and ricinoleic acid into a reactor, heating to form a homogeneous phase, then adding a catalyst lithium neodecanoate, reacting at 180 ℃, adding linoleic acid, hexadecanoic acid, abietic acid and xylene with the total mass fraction of reactants being 5% when the acid value of a reaction solution is measured to be less than 5mgKOH/g, heating to 250 ℃ for reaction, cooling to below 80 ℃ when the acid value is measured to be less than 15mgKOH/g, and adding propylene glycol methyl ether to dilute until the solid content is 75% to obtain epoxy ester; wherein the molar ratio of the epoxy resin to the linoleic acid is 1: 1.8, the molar ratio of the epoxy resin to the palmitic acid is 1: 1, the molar ratio of the epoxy resin to the abietic acid is 1: 1.2, the using amount of the catalyst lithium neodecanoate is 1.2 percent of the homogeneous reactants;
(2) synthesizing acrylic ester monomer modified epoxy ester: adding the epoxy ester obtained in the step (1) into a reactor, heating to 120 ℃, then dropwise adding an acrylate monomer dissolved with three-quarters of TBPB into the epoxy ester for 2.5, then preserving heat for 0.5h, then dividing the rest of the initiator into two equal parts, supplementing one initiator every 0.5h, and preserving heat for 3h after supplementing is completed to obtain the acrylate monomer modified epoxy ester; wherein the mass ratio of the acrylic monomer to the epoxy ester is 40: 60, the TBPB accounts for 3.5 wt% of the total amount of the acrylic monomers; the acrylate monomer is a mixture of methyl methacrylate, styrene, butyl acrylate, butyl methacrylate, isooctyl acrylate, methacrylic acid and hydroxypropyl acrylate; the mass ratio of each acrylate monomer in the mixture is respectively as follows: 25% of methyl methacrylate, 32% of styrene, 20% of butyl acrylate, 4% of butyl methacrylate, 5% of isooctyl acrylate, 11% of methacrylic acid and 3% of hydroxypropyl acrylate;
(3) and (3) cooling the acrylate monomer modified epoxy ester obtained in the step (2) to 65 ℃, adding triethylamine for neutralization for 20min, adding water for dispersion for 2h when the neutralization degree is 100%, and adjusting the solid content to 41% to obtain the normal-temperature single-component self-drying epoxy ester/acrylate composite emulsion.
Example 4
A preparation method of a single-component quick self-drying epoxy ester/acrylic ester composite emulsion comprises the following steps:
(1) synthesis of epoxy ester: firstly, adding epoxy resins E-44 and E-20 and ricinoleic acid into a reactor, heating to form a homogeneous phase, then adding a catalyst lithium neodecanoate, reacting at 180 ℃, adding linoleic acid, myristic acid, abietic acid and xylene with the total mass fraction of 5% of reactants when the acid value of a reaction solution is measured to be less than 5mgKOH/g, heating to 250 ℃ for reaction, cooling to below 80 ℃ when the acid value is measured to be less than 15mgKOH/g, and adding 25% of propylene glycol methyl ether to prepare epoxy ester; wherein the mass ratio of E-44 to E-20 is 80: 20, the molar ratio of the epoxy resin to the ricinoleic acid is 1: 1.8, the molar ratio of the epoxy resin to the linoleic acid is 1: 1.3, the molar ratio of the epoxy resin to the myristic acid is 1: 0.5, the molar ratio of the epoxy resin to the abietic acid is 1: 1.5, the dosage of the catalyst organic lithium is 1 percent of that of the homogeneous reactants;
(2) synthesizing acrylic ester monomer modified epoxy ester: adding the epoxy ester obtained in the step (1) into a reactor, heating to 120 ℃, then dropwise adding an acrylate monomer dissolved with three-fourths TBPB into the epoxy ester for 3 hours, then preserving heat for 0.5 hour, then dividing the rest initiator into two equal parts, supplementing one initiator every 0.5 hour, and preserving heat for 3 hours after supplementing is finished, thus obtaining the acrylate monomer modified epoxy ester; wherein the mass ratio of the acrylic monomer to the epoxy ester is 50: 50, the TBPB accounts for 3 wt% of the total amount of the acrylic monomers; the acrylate monomer is a mixture of methyl methacrylate, styrene, butyl acrylate, butyl methacrylate, isooctyl acrylate, methacrylic acid and hydroxypropyl acrylate; the mass ratio of each acrylate monomer in the mixture is respectively as follows: 25% of methyl methacrylate, 35% of styrene, 18% of butyl acrylate, 4% of butyl methacrylate, 5% of isooctyl acrylate, 10% of methacrylic acid and 3% of hydroxypropyl acrylate;
(3) and (3) cooling the acrylate monomer modified epoxy ester obtained in the step (2) to 60 ℃, adding triethylamine for neutralization for 30min, adding water for dispersion for 2h when the neutralization degree is 100%, and adjusting the solid content to 41% to obtain the normal-temperature single-component self-drying epoxy ester/acrylate composite emulsion.
The epoxy ester/acrylate composite emulsions prepared in examples 1-4 and commercially available waterborne epoxy esters were prepared into waterborne varnishes which were sprayed on tinplate to test the properties of the paint films, wherein the surface dry time of the paint films was measured according to the touch method in GB/T1728-1979 (1989), the adhesion of the paint films was measured according to GB/T9286-1998 and the cross-cut method, the hardness of the paint films was measured according to GB/T6739-2006 and the QHQ pencil hardness tester, the water resistance of the paint films was measured according to GB/T1733-1993, and the salt spray resistance of the paint films was measured according to GB/T1771-91, with the test results shown in Table 1.
TABLE 1
In conclusion, when the epoxy ester is synthesized, the softening point of the epoxy ester is greatly improved by introducing the hydroxy acid with high melting point and the organic monobasic fatty acid under the condition of keeping the advantages of the epoxy ester; and then, adopting an acrylate monomer to graft epoxy ester to introduce a hydrophilic group, adding triethylamine to neutralize, and adding to disperse to obtain the epoxy ester/acrylate composite emulsion. Firstly, the VOC of the invention is low, and completely meets the requirement of environmental protection; secondly, the invention has fast surface drying and short adhesive force display time, and can effectively improve the construction efficiency; the paint has good water resistance and rain wash resistance in the initial stage, and is suitable for construction in rainy days; has better salt spray resistance and can be used in the field of metal corrosion prevention.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principles of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a single-component quick self-drying epoxy ester/acrylic ester composite emulsion is characterized by comprising the following steps:
(1) synthesis of epoxy ester: firstly, adding epoxy resin and hydroxy acid into a reactor, heating to form a homogeneous reactant, then adding a catalyst organic lithium, reacting at 160-190 ℃, adding organic monobasic fatty acid and xylene which accounts for 3-6% of the total mass of the homogeneous reactant until the acid value of a reaction solution is measured to be less than 5mgKOH/g, then heating to 230-260 ℃ for reaction, cooling to 80-100 ℃, adding a solvent to dilute until the solid content is 60-80% to obtain epoxy ester when the acid value is measured to be less than 15 mgKOH/g;
(2) synthesizing acrylic ester monomer modified epoxy ester: adding the epoxy ester obtained in the step (1) into a reactor, heating to 110-130 ℃, then dropwise adding an acrylate monomer dissolved with three-fourths of initiator into the epoxy ester for 2.5-3 h, then preserving heat for 0.5h, then dividing the rest of initiator into two equal parts, supplementing one initiator every 0.5h, and preserving heat for 2-3 h after supplementing is finished, thus obtaining the acrylate monomer modified epoxy ester;
(3) and (3) cooling the acrylate monomer modified epoxy ester obtained in the step (2) to 60-65 ℃, adding triethylamine for neutralization for 20-30 min, adding water for dispersion for 1.5-2 h when the neutralization degree is 90-120%, and adjusting the solid content to 41% to obtain the normal-temperature single-component self-drying epoxy ester/acrylate composite emulsion.
2. The method according to claim 1, wherein the epoxy resin in step (1) is one or more of E-51, E-44, E-20 or E-12; the hydroxy acid is one or more of salicylic acid and derivatives thereof, 2-hydroxypropionic acid or ricinoleic acid and derivatives thereof.
3. The method according to claim 1, wherein the organic lithium in step (1) is one or more of lithium laurate or lithium neodecanoate.
4. The method according to claim 1, wherein the organic monobasic fatty acid in the step (1) is any one or more of eleostearic acid, linoleic acid, oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, or abietic acid, and derivatives thereof.
5. The process according to claim 1, wherein the molar ratio of epoxy resin to hydroxy acid in step (1) is 1: 0.5-2.5, wherein the molar ratio of the epoxy resin to the organic monobasic fatty acid is 1: 1-4, and the dosage of the catalyst organic lithium is 0.5-2 wt% of the total weight of the homogeneous reactants.
6. The method according to claim 1, wherein the solvent in step (1) is any one or more of ethylene glycol monobutyl ether, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
7. The method according to claim 1, wherein the initiator in the step (2) is any one or more of dibenzoyl peroxide (BPO) or benzoyl peroxide tert-butyl ester (TBPB).
8. The method according to claim 1, wherein the acrylic monomer in the step (2) is a mixture of methyl methacrylate, styrene, butyl acrylate, butyl methacrylate, isooctyl acrylate, methacrylic acid and hydroxypropyl acrylate; the mass fractions of the various acrylate monomers in the mixture are respectively as follows: 15-30% of methyl methacrylate, 15-40% of styrene, 15-25% of butyl acrylate, 2-10% of butyl methacrylate, 3-8% of isooctyl acrylate, 5-15% of methacrylic acid and 1-7% of hydroxypropyl acrylate.
9. The method of claim 1, wherein the acrylic monomer to epoxy ester mass ratio in step (2) is about 30: 70-70: 30, the amount of the initiator is 1.5-4.5 wt% of the total amount of the acrylic monomer.
10. A one-component fast-drying epoxy ester/acrylate composite emulsion prepared by the preparation method of any one of claims 1-9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0967425A (en) * | 1995-09-04 | 1997-03-11 | Toyo Ink Mfg Co Ltd | Esterified modified epoxy resin, aqueous epoxy resin composition containing the same and water-based coating material |
| JP2006089560A (en) * | 2004-09-22 | 2006-04-06 | Hitachi Chem Co Ltd | Water-based resin composition and coating material using the same |
| CN102358815A (en) * | 2011-07-25 | 2012-02-22 | 上海电动工具研究所 | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method |
| CN103665271A (en) * | 2013-12-06 | 2014-03-26 | 江苏柏鹤涂料有限公司 | Acrylic acid-epoxy ester hybrid resin and coatings thereof |
| CN104497224A (en) * | 2014-12-04 | 2015-04-08 | 北京金汇利应用化工制品有限公司 | Low-acid-value and low-VOC aqueous acrylic acid and fatty acid modified epoxy resin |
| CN104513343A (en) * | 2014-12-04 | 2015-04-15 | 北京金汇利应用化工制品有限公司 | Preparation method for low acid value and low VOC waterborne acrylic acid and fatty acid modified epoxy resin |
| CN108570131A (en) * | 2017-03-10 | 2018-09-25 | 北京金汇利应用化工制品有限公司 | The preparation method of the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin |
-
2019
- 2019-11-22 CN CN201911158074.7A patent/CN110894265B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0967425A (en) * | 1995-09-04 | 1997-03-11 | Toyo Ink Mfg Co Ltd | Esterified modified epoxy resin, aqueous epoxy resin composition containing the same and water-based coating material |
| JP2006089560A (en) * | 2004-09-22 | 2006-04-06 | Hitachi Chem Co Ltd | Water-based resin composition and coating material using the same |
| CN102358815A (en) * | 2011-07-25 | 2012-02-22 | 上海电动工具研究所 | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method |
| CN103665271A (en) * | 2013-12-06 | 2014-03-26 | 江苏柏鹤涂料有限公司 | Acrylic acid-epoxy ester hybrid resin and coatings thereof |
| CN104497224A (en) * | 2014-12-04 | 2015-04-08 | 北京金汇利应用化工制品有限公司 | Low-acid-value and low-VOC aqueous acrylic acid and fatty acid modified epoxy resin |
| CN104513343A (en) * | 2014-12-04 | 2015-04-15 | 北京金汇利应用化工制品有限公司 | Preparation method for low acid value and low VOC waterborne acrylic acid and fatty acid modified epoxy resin |
| CN108570131A (en) * | 2017-03-10 | 2018-09-25 | 北京金汇利应用化工制品有限公司 | The preparation method of the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin |
Non-Patent Citations (1)
| Title |
|---|
| 王明晶 等: "水性丙烯酸改性环氧酯防腐涂料的研制", 《中国涂料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876936A (en) * | 2021-03-30 | 2021-06-01 | 海顺易漆富新材料(佛山)有限公司 | Waterborne epoxy ester modified acrylate emulsion for woodware and preparation method thereof |
| CN112876936B (en) * | 2021-03-30 | 2021-12-17 | 海顺易漆富新材料(佛山)有限公司 | Waterborne epoxy ester modified acrylate emulsion for woodware and preparation method thereof |
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| CN110894265B (en) | 2023-02-14 |
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