CN107151306B - Hydrolysis-resistant polyester resin capable of being cured by UV and preparation method thereof - Google Patents
Hydrolysis-resistant polyester resin capable of being cured by UV 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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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
- 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
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
- C08G18/2835—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds having less than 5 ether groups
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a UV-curable hydrolysis-resistant polyester resin and a preparation method thereof, wherein the UV-curable hydrolysis-resistant polyester resin is obtained by adding a monomer with an epoxy functional group and a (methyl) acrylate monomer containing fluorine atoms in the free radical solution polymerization process of the polyester resin. By adopting the technical scheme, the prepared polyester resin is added with the photoinitiator and sprayed on an ABS/PC board to be cured into a film, and then a damp-heat aging test is carried out to test the impact resistance, the glossiness and the hardness of the film before and after damp-heat aging, so that the hydrolysis resistance of the polyester resin can be greatly improved.
Description
Technical Field
The invention relates to a preparation method of UV-curable polyester resin used in the wood lacquer industry, in particular to a preparation method of UV-curable hydrolysis-resistant polyester resin.
Background
The Ultraviolet (UV) curing technology has the advantages of rapid curing, low energy consumption, high efficiency, no pollution and the like, completely conforms to the principle of '5E', and is an environment-friendly green technology. One of the advantages of uv curing is that it is solvent free, thus greatly eliminating the pollution of organic volatile VOCs to the environment. However, since the main components used, i.e. the low molecular weight oligomers, generally have a relatively high viscosity, it is necessary to add monomers, i.e. reactive diluents, during use in order to adjust their viscosity and rheology. These reactive diluents still contain VOCs and also have varying degrees of toxicity and irritation. On the other hand, water-based coatings have become one of the main development directions of coatings, the low viscosity and the extremely low VOC which are easy to adjust make the coatings suitable for spraying, and the UV curing water-based coatings combine the advantages of the two and are developed more rapidly in more than ten years; however, the UV-curable water-based paint also has the defects of poor hydrolysis resistance and poor water resistance, so that the wider application of the UV-curable water-based paint is limited.
Disclosure of Invention
In order to solve the technical problem, a monomer containing an epoxy group and a (methyl) acrylic monomer containing a fluorine atom are added in the free radical solution polymerization process of the polyester resin to prepare the hydrolysis-resistant polyester resin capable of being cured by UV.
The invention provides a UV-curable hydrolysis-resistant polyester resin, which has a structural formula shown as the following formula:
wherein the content of the first and second substances,
wherein n is 10-20, m is 10-25, p is 0-10, q is 0-5, and p and q are not 0 at the same time.
Here, B represents a basic group in the amine neutralizing agent; ECA represents an end-capping agent.
The invention also provides a preparation method of the UV-curable hydrolysis-resistant polyester resin, which adopts the technical scheme that:
step (1): according to the mass parts, 10-15 parts of acrylic acid, 9-15 parts of acrylate monomers, 4-6 parts of hydroxyl acrylate monomers, 3-20 parts of (methyl) acrylate monomers containing fluorine atoms, 0.5-0.7 part of peroxide initiators, 0.1-0.3 part of molecular weight regulators and 100-110 parts of solvents are added into a reaction container, free radical polymerization is carried out for 4-5 hours at 100-110 ℃, the temperature is reduced to 65-75 ℃, 4-7 parts of acrylate monomers containing epoxy groups and 0.5-0.7 part of quaternary ammonium salt catalysts are added into the solution, and the reaction is continued until epoxy peaks disappear, so that the acrylic polyester resin is obtained;
step (2): adding 8-11 parts of isophorone diisocyanate, 20-25 parts of polyethylene glycol, 12-16 parts of polyethylene glycol monomethyl ether and 0.05-0.15 part of catalyst dibutyltin dilaurate into the reaction vessel, and reacting at 65-75 ℃ until the NCO value reaches a preset value to obtain a polyurethane resin prepolymer;
and (3): after the acrylic polyester resin and polyurethane resin prepolymer is prepared, 3.5-5 parts of end-capping reagent is added into the reaction vessel, the temperature is controlled to be 65-75 ℃, the reaction is stirred for a period of time until the NCO value is zero, then the temperature is reduced to 45-50 ℃, and 3-4 parts of amine neutralizer is added through high-speed stirring, so that the semitransparent polyester resin emulsion with blue light is obtained.
Further, the structure of the (meth) acrylate monomer containing a fluorine atom described in the step (1) is shown as the following formula:
wherein p is 0-10, q is 0-5, and p and q are not 0 at the same time.
Further, the acrylate monomer in the step (1) is methyl acrylate, ethyl acrylate or butyl acrylate.
Further, the hydroxy acrylate monomer in the step (1) is hydroxyethyl acrylate or hydroxypropyl acrylate.
Further, the peroxide initiator in the step (1) is benzoyl peroxide, benzoyl tert-butyl peroxide or methyl ethyl ketone peroxide.
Further, the molecular weight regulator in the step (1) is n-dodecyl mercaptan.
Further, the solvent in the step (1) is one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol methyl ether, propylene glycol ethyl ether or diethylene glycol dimethyl ether.
Further, tetrabutylammonium bromide is selected as the quaternary ammonium salt catalyst in the step (1).
Further, the acrylic ester monomer containing an epoxy group in the step (1) is glycidyl methacrylate.
Further, the neutralizing agent in the step (3) is ammonia, triethylamine or triethanolamine.
Further, the total mass of the (meth) acrylate monomer containing a fluorine atom and the acrylate monomer containing an epoxy group in the step (1) accounts for 8.0-25% of the total mass of the reaction monomers, and specifically, the reaction monomers are acrylic acid, the acrylate monomer, the hydroxy acrylate monomer, the (meth) acrylate monomer containing a fluorine atom, the acrylate monomer containing an epoxy group in the step (1), isophorone diisocyanate, polyethylene glycol monomethyl ether in the step (2), and pentaerythritol triacrylate in the step (3).
Further, the mass ratio of the (methyl) acrylic ester monomer containing fluorine atoms to the acrylic ester monomer containing epoxy groups in the step (1) is (3-1): 1.
By adopting the technical scheme, because the fluorocarbon has extremely low surface tension, fluorine atoms are introduced into the polyester resin to obtain low surface energy, strong hydrophobicity and greatly reduced water absorption rate, thereby improving hydrolysis resistance; in addition, the monomer containing epoxy functional group modifies the property of polyester resin by opening a ring and forming a chain with an epoxy group through a compound containing active hydrogen, thereby improving the hardness and weather resistance of a coating film during resin film forming, and further improving hydrolysis resistance.
Detailed Description
The invention will be further elucidated with reference to the following specific examples.
Example 1
Step (1): adding 15 parts of acrylic acid, 12 parts of butyl acrylate, 6 parts of hydroxypropyl acrylate, 4 parts of trifluoroethyl methacrylate, 0.6 part of benzoyl peroxide, 0.2 part of n-dodecyl mercaptan and 100 parts of diethylene glycol dimethyl ether into a reaction vessel, carrying out free radical polymerization reaction at 110 ℃ for 5 hours, reducing the temperature to 70 ℃, adding 4 parts of glycidyl methacrylate and 0.6 part of tetrabutylammonium bromide into the solution, and continuing the reaction until an epoxy peak disappears to obtain the acrylic polyester resin;
step (2): adding 10.5 parts of isophorone diisocyanate, 25 parts of polyethylene glycol, 15 parts of polyethylene glycol monomethyl ether and 0.1 part of catalyst dibutyltin dilaurate into the reaction vessel, and reacting at 70 ℃ until the NCO value reaches a preset value to obtain a polyurethane resin prepolymer;
wherein n is 10-20, and m is 10-25.
And (3): after acrylic polyester resin and polyurethane resin prepolymers are prepared, 4.5 parts of end-capping agent pentaerythritol triacrylate is added into the reaction vessel, the temperature is controlled at 70 ℃, the reaction is stirred for a period of time until the NCO value is zero, then the temperature is reduced to 50 ℃, and 3.8 parts of triethylamine aqueous solution is added through high-speed stirring, so that semitransparent polyester resin emulsion with blue light is obtained.
Wherein n is 10-20, and m is 10-25.
Taking 35g of the self-made polyester resin emulsion, 10g of deionized water, 0.5g of an antifoaming agent EFKA2721, 0.5g of a leveling assistant BYK-348, 0.5g of a wetting agent BYK168, 1g of an adhesion promoter DH7340, 1.2g of a photoinitiator BASF IRGACURE184, and 1.3g of a photoinitiator BASF IRGACURE 2959, stirring and mixing for 0.5 hour at room temperature to prepare the coating.
Example 2
Step (1): adding 13.7 parts of acrylic acid, 11 parts of butyl acrylate, 5.6 parts of hydroxypropyl acrylate, 10 parts of octafluoropentyl methacrylate, 0.6 part of benzoyl peroxide, 0.2 part of n-dodecyl mercaptan and 100 parts of diethylene glycol dimethyl ether into a reaction vessel, carrying out free radical polymerization reaction for 5 hours at 110 ℃, reducing the temperature to 70 ℃, adding 5 parts of glycidyl methacrylate and 0.6 part of tetrabutylammonium bromide into the solution, and continuously reacting until epoxy groups disappear to obtain the acrylic polyester resin;
step (2): adding 9.5 parts of isophorone diisocyanate, 22.5 parts of polyethylene glycol, 14.5 parts of polyethylene glycol monomethyl ether and 0.1 part of catalyst dibutyltin dilaurate into the reaction vessel, and reacting at 70 ℃ until the NCO value reaches a preset value to obtain a polyurethane resin prepolymer;
and (3): after acrylic polyester resin and polyurethane resin prepolymers are prepared, 4.2 parts of end-capping agent pentaerythritol triacrylate is added into the reaction vessel, the temperature is controlled at 70 ℃, the reaction is stirred for a period of time until the NCO value is zero, then the temperature is reduced to 50 ℃, and 3.8 parts of triethylamine aqueous solution is added through high-speed stirring, so that semitransparent polyester resin emulsion with blue light is obtained.
Taking 35g of the self-made polyester resin emulsion, 10g of deionized water, 0.5g of an antifoaming agent EFKA2721, 0.5g of a leveling assistant BYK-348, 0.5g of a wetting agent BYK168, 1g of an adhesion promoter DH7340, 1.2g of a photoinitiator BASF IRGACURE184, and 1.3g of a photoinitiator BASF IRGACURE 2959, stirring and mixing for 0.5 hour at room temperature to prepare the coating.
Example 3
Step (1): adding 12 parts of acrylic acid, 9.7 parts of butyl acrylate, 4.9 parts of hydroxypropyl acrylate, 18.6 parts of trifluoroethyl methacrylate, 0.6 part of benzoyl peroxide, 0.2 part of n-dodecyl mercaptan and 100 parts of diethylene glycol dimethyl ether into a reaction vessel, carrying out free radical polymerization reaction for 5 hours at 110 ℃, reducing the temperature to 70 ℃, adding 6.2 parts of glycidyl methacrylate and 0.6 part of tetrabutylammonium bromide into the solution, and continuously reacting until an epoxy peak disappears to obtain the acrylic polyester resin;
step (2): adding 8.5 parts of isophorone diisocyanate, 20 parts of polyethylene glycol, 12.5 parts of polyethylene glycol monomethyl ether and 0.1 part of catalyst dibutyltin dilaurate into the reaction vessel, and reacting at 70 ℃ until the NCO value reaches a preset value to obtain a polyurethane resin prepolymer;
and (3): after acrylic polyester resin and polyurethane resin prepolymers are prepared, 3.6 parts of end-capping agent pentaerythritol triacrylate is added into the reaction vessel, the temperature is controlled at 70 ℃, the reaction is stirred for a period of time until the NCO value is zero, then the temperature is reduced to 50 ℃, and 3.8 parts of triethylamine aqueous solution is added through high-speed stirring, so that semitransparent polyester resin emulsion with blue light is obtained.
Taking 35g of the self-made polyester resin emulsion, 10g of deionized water, 0.5g of an antifoaming agent EFKA2721, 0.5g of a leveling assistant BYK-348, 0.5g of a wetting agent BYK168, 1g of an adhesion promoter DH7340, 1.2g of a photoinitiator BASF IRGACURE184, and 1.3g of a photoinitiator BASF IRGACURE 2959, stirring and mixing for 0.5 hour at room temperature to prepare the coating.
Comparative example
Step (1): adding 15 parts of acrylic acid, 12 parts of butyl acrylate, 6 parts of hydroxypropyl acrylate, 8 parts of methyl methacrylate, 0.6 part of benzoyl peroxide, 0.2 part of n-dodecyl mercaptan and 100 parts of diethylene glycol dimethyl ether into a reaction vessel, carrying out free radical polymerization reaction for 5 hours at 110 ℃, reducing the temperature to 70 ℃, and adding 0.6 part of tetrabutylammonium bromide to obtain acrylic polyester resin;
step (2): adding 10.5 parts of isophorone diisocyanate, 25 parts of polyethylene glycol, 15 parts of polyethylene glycol monomethyl ether and 0.1 part of catalyst dibutyltin dilaurate into the reaction vessel, and reacting at 70 ℃ until the NCO value reaches a preset value to obtain a polyurethane resin prepolymer;
and (3): after acrylic polyester resin and polyurethane resin prepolymers are prepared, 4.5 parts of end-capping agent pentaerythritol triacrylate is added into the reaction vessel, the temperature is controlled at 70 ℃, the reaction is stirred for a period of time until the NCO value is zero, then the temperature is reduced to 50 ℃, and 3.8 parts of triethylamine aqueous solution is added through high-speed stirring, so that semitransparent polyester resin emulsion with blue light is obtained.
Taking 35g of the self-made polyester resin emulsion, 10g of deionized water, 0.5g of an antifoaming agent EFKA2721, 0.5g of a leveling assistant BYK-348, 0.5g of a wetting agent BYK168, 1g of an adhesion promoter DH7340, 1.2g of a photoinitiator BASF IRGACURE184, and 1.3g of a photoinitiator BASF IRGACURE 2959, stirring and mixing for 0.5 hour at room temperature to prepare the coating.
The coatings prepared in example 1, example 2, example 3 and comparative example were respectively sprayed on an ABS/PC substrate, after UV curing, the ABS/PC substrate was placed in a damp heat test aging oven at a temperature of 40 ℃ and a humidity of 98%, and after aging for 120 hours, the impact strength (height 60cm, weight 2kg), gloss at 60 ℃ and hardness of the coating film before and after aging were measured, and the test results were as follows:
as can be seen from the table, the thermal-humid aging test is carried out to test the impact strength, the glossiness and the hardness of the coating film before and after the thermal-humid aging test, and the monomer with the epoxy functional group and the (methyl) acrylic ester monomer containing the fluorine atom are found to greatly improve the hydrolysis resistance of the polyester resin.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (7)
1. A UV-curable hydrolysis-resistant polyester resin, characterized in that it has the following structural formula:
wherein the content of the first and second substances,
wherein n is 10-20, m is 10-25, p is 0-10, q is 0-5, and p and q can not be 0 at the same time;
wherein B represents a basic group in the amine neutralizing agent, and ECA represents an end-capping agent.
2. A method for preparing the UV-curable hydrolysis-resistant polyester resin of claim 1, which comprises the following steps:
step (1): according to the mass parts, 10-15 parts of acrylic acid, 9-15 parts of acrylate monomers, 4-6 parts of hydroxyl acrylate monomers, 3-20 parts of (methyl) acrylate monomers containing fluorine atoms, 0.5-0.7 part of peroxide initiators, 0.1-0.3 part of molecular weight regulators and 100-110 parts of solvents are added into a reaction container, free radical polymerization is carried out for 4-5 hours at 100-110 ℃, the temperature is reduced to 65-75 ℃, 4-7 parts of acrylate monomers containing epoxy groups and 0.5-0.7 part of quaternary ammonium salt catalysts are added into the solution, and the reaction is continued until epoxy peaks disappear, so that acrylic polyester resin is obtained, wherein the acrylate monomers containing epoxy groups are glycidyl methacrylate;
step (2): adding 8-11 parts of isophorone diisocyanate, 20-25 parts of polyethylene glycol, 12-16 parts of polyethylene glycol monomethyl ether and 0.05-0.15 part of catalyst dibutyltin dilaurate into the reaction vessel, and reacting at 65-75 ℃ until the NCO value reaches a preset value to obtain a polyurethane resin prepolymer;
and (3): after the acrylic polyester resin and polyurethane resin prepolymer is prepared, 3.5-5 parts of end-capping reagent is added into the reaction vessel, the temperature is controlled to be 65-75 ℃, the reaction is stirred for a period of time until the NCO value is zero, then the temperature is reduced to 45-50 ℃, and 3-4 parts of amine neutralizer is added through high-speed stirring, so that the semitransparent polyester resin emulsion with blue light is obtained.
3. The method for preparing a UV-curable hydrolysis-resistant polyester resin according to claim 2, wherein the structure of the (meth) acrylate monomer containing a fluorine atom in the step (1) is represented by the following formula:
wherein p is 0-10, q is 0-5, and p and q are not 0 at the same time.
4. The method of claim 2, wherein the acrylate monomer in step (1) is methyl acrylate, ethyl acrylate or butyl acrylate, the hydroxy acrylate monomer is hydroxyethyl acrylate or hydroxypropyl acrylate, the peroxide initiator is benzoyl peroxide, benzoyl peroxide tert-butyl ester or methyl ethyl ketone peroxide, the molecular weight regulator is n-dodecyl mercaptan, the solvent is one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol methyl ether, propylene glycol ethyl ether or diethylene glycol dimethyl ether, and the quaternary ammonium salt catalyst is tetrabutylammonium bromide.
5. The method of claim 2, wherein the neutralizing agent in step (3) is ammonia, triethylamine or triethanolamine.
6. The method of claim 2, wherein the sum of the mass of the (meth) acrylate monomer containing a fluorine atom and the acrylate monomer containing an epoxy group in step (1) is 8.0 to 25% of the total mass of the reaction monomers.
7. The method for preparing the UV-curable hydrolysis-resistant polyester resin according to claim 2, wherein the mass ratio of the (meth) acrylate monomer containing a fluorine atom to the acrylate monomer containing an epoxy group in the step (1) is (3-1: 1).
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| CN201710483008.1A CN107151306B (en) | 2017-06-22 | 2017-06-22 | Hydrolysis-resistant polyester resin capable of being cured by UV and preparation method thereof |
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| JP7447484B2 (en) * | 2019-12-26 | 2024-03-12 | ａｒｔｉｅｎｃｅ株式会社 | Resin composition and laminate |
| CN112029067A (en) * | 2020-09-08 | 2020-12-04 | 珠海市金团化学品有限公司 | Photo-curing water-based acrylic acid dispersion and preparation method and application thereof |
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