CN104961857B - One kind is modified（Methyl）Acrylate and preparation method thereof - Google Patents

Abstract

The invention discloses a modified (meth)acrylate resin, which contains (meth)acrylate chain links, unsaturated double bonds and carboxylic acid groups, unsaturated double bonds and epoxy groups groups and groups of silicones containing double bonds. The invention can be cured in various ways, has the characteristics of high hardness, high toughness, non-adhesion, strong adhesion, good wear resistance, etc., and can be applied in the fields of coatings, inks, adhesives, etc., and the invention also relates to the material method of preparation.

Description

A kind of modified (meth)acrylate resin and preparation method thereof

technical field

The invention belongs to the technical field of organic polymer synthesis, and in particular relates to a multi-curable silicone-modified (meth)acrylate resin and a preparation method thereof. The resin can be applied to heat, ultraviolet light, moisture, and air-cured Coatings, adhesives, inks and other fields.

Background technique

In the prior art, various (meth)acrylate heat-curable and UV-curable resins have been proposed. The cured resin has fast light curing, high hardness of the coating film, good adhesion, good gloss, and chemical resistance. Corrosion and other advantages.

(Meth)acrylate resins cured in two or more ways can generally achieve ideal results, but there is a problem of easy adhesion after one curing, and increasing the molecular weight will increase the viscosity and bring inconvenience to construction. An increase in the degree of crosslinking reduces the toughness. Adding a release layer can solve the above problems, but it will increase the cost. In addition, high hardness and high toughness cannot be maintained at the same time, that is, good adhesion and no adhesion.

Chinese patent CN101665561B discloses a siloxane-modified urethane acrylate hyperbranched oligomer and a preparation method thereof, wherein the multi-curing coating is firstly dehydrating the polyol in vacuum, adding diisocyanate, and synthesizing the polyurethane pre- Polymer, then add hyperbranched polyester, then add hydroxyacrylate and polymerization inhibitor, add catalyst to initiate polymerization, finally add diaminosiloxane and active diluent, react for a period of time, that is, siloxane modified polyurethane acrylic acid Ester hyperbranched oligomers. The siloxane-modified urethane acrylate hyperbranched oligomer is mixed with a photoinitiator, a reactive diluent, a solvent and an auxiliary agent to obtain an ultraviolet light-heat-moisture multiple curing material. The multiple curing material has a viscosity of 200 mPa·s-800 mPa·s and a number average molecular weight of 2000-8000. The oligomers and reactive diluents in this coating contain unsaturated double bonds and can be cured by UV light. UV curing is the main curing method of this coating; thermal curing is based on the heat energy of ultraviolet light to form additional polymerization, and the polymerized units are polyurethane and acrylate; the siloxane contained in it can be cured by moisture, and finally form a polymer interpenetrating network structure. Although the UV-heat-moisture multi-curing material here has multiple curing mechanisms, it is mainly cured by UV light when used, and thermal curing and UV curing must be carried out at the same time. If it is only cured by heating, then It cannot be cured into a film, and moisture curing is also an auxiliary curing method. The UV-heat-moisture multi-cure material has a pencil hardness of 2H. The cured coating obtained by this method is single multiple curing, and after curing and winding, secondary curing cannot be performed in the stamping and setting process, so that the surface modification in the setting process is limited.

Contents of the invention

Problem to be solved by the present invention

In order to overcome the disadvantages of the above-mentioned prior art, the present invention provides a multi-curable (meth)acrylate resin containing silicone and a preparation method thereof, wherein the multi-curable groups include hydroxyl groups, epoxy groups and double bonds. The resin can maintain the hardness, gloss, chemical corrosion resistance and other properties of (meth)acrylate resin, and at the same time overcome the shortcomings of poor toughness and non-wear resistance of the coating film.

The technical scheme adopted in the present invention is:

A modified (meth)acrylate resin, the resin has the following structural formula:

Where M is a (meth)acrylate chain link, including methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, Isobutyl acrylate, methyl crotonate, ethyl crotonate, butyl octadecenoate, ethyl cinnamate, dimethyl maleate, dibutyl maleate, dioctyl maleate , one or more of dimethyl fumarate, diethyl fumarate,

A is a group containing unsaturated double bonds and carboxylic acids, including acrylic acid, methacrylic acid, oleic acid, 2-phenylacrylic acid, 3-phenylacrylic acid, 2-fluoroacrylic acid, 3-(2-furyl)acrylic acid , 3-iodoacrylic acid, benzyl acrylic acid in one or more groups formed,

G is a group containing unsaturated double bonds and epoxy groups, including glycidyl (meth)acrylate monomers or glycidyl (meth)acrylate oligomers or copolymers,

S is an organosilicon group containing a double bond,

n ₁ and n ₂ are integers greater than 1.

The chemical bond between G and A is formed by the reaction of epoxy and carboxylic acid.

The organosilicon group is one of the following structures:

Wherein R ¹ represents a monovalent hydrocarbon group or a hydrogen atom with 1-20 carbon atoms, and n is an integer greater than 1, and two R ¹ are the same or different groups;

Wherein R ² represents a substituted or unsubstituted straight-chain or branched alkenyl group with 2-20 carbon atoms, and X represents a halogen atom, an alkoxy group, a phenoxy group or an acetoxy group, and the three Xs are the same or different groups;

Wherein R ³ represents a substituted or unsubstituted branched or branched alkenyl group with 2-20 carbon atoms, and R ⁴ represents a monovalent hydrocarbon group, and three R ⁴ are the same or different groups;

Wherein R ⁵ represents a hydrocarbon group or hydrogen atom containing 1-20 carbon atoms, and n is an integer greater than 1, two R ⁵ are the same or different hydrocarbon groups or hydrogen atoms, R ⁶ represents substituted or unsubstituted , a straight-chain or branched alkenyl group with 2-20 carbon atoms, R ⁷ represents hydrogen or a monovalent hydrocarbon group.

A preparation method of modified (meth)acrylate resin, comprising the following steps:

(1) Preparation of (meth)acrylate, glycidyl (meth)acrylate and silicone copolymer intermediates

Under the condition of passing inert gas, heat the solvent 1 to 60°C-90°C, slowly add the mixture of monomer 1, monomer 2, initiator, molecular weight regulator, and organosilicon containing double bonds, for 1 hour- The addition is completed in 6 hours; the system is kept warm for 2 hours to 10 hours, the temperature is raised to 100°C-130°C, and the temperature is kept for 0.5 hours to 4 hours to obtain a copolymer intermediate.

(2) Preparation of modified (meth)acrylate resin

Lower the temperature of the copolymer intermediate obtained in step (1) to below 60°C, pass air or other gases containing oxygen, add monomer 3, polymerization inhibitor, catalyst, then raise the temperature to 70°C-100°C, and keep it warm for 2 hours After -10 hours, the temperature of the system is lowered to below 60°C, adding a polymerization inhibitor and solvent 2 and stirring evenly to obtain a modified (meth)acrylate resin.

The silicones containing double bonds used are silicone monomers containing unsaturated double bonds or macromolecules containing silicones.

The monomer 1 is a (meth)acrylate monomer, including methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate ester, isobutyl methacrylate, methyl crotonate, ethyl crotonate, butyl octadecenoate, ethyl cinnamate, dimethyl maleate, dibutyl maleate, maleic acid One or more of dioctyl esters, dimethyl fumarate, and diethyl fumarate, the monomer 2 is a compound containing unsaturated double bonds and epoxy groups, including glycidol (methyl) Acrylate monomer or oligomer or copolymer of glycidyl (meth)acrylate, the monomer 3 is a compound containing unsaturated double bonds and carboxylic acid groups, including acrylic acid, methacrylic acid, oleic acid , 2-phenylacrylic acid, 3-phenylacrylic acid, 2-fluoroacrylic acid, 3-(2-furyl)acrylic acid, 3-iodoacrylic acid, benzyl acrylic acid, the initiator is Nitrogen initiators, organic peroxygen initiators or oxidation-reduction initiators.

The initiator is azobisisobutyronitrile, azobisisoheptanonitrile, dimethyl azobisisobutyrate, dibenzoyl peroxide, diethylhexyl peroxydicarbonate, tert-butyl peroxide Hydrogen Oxide, Potassium Persulfate, Hydrogen Peroxide, Potassium Permanganate-Oxalic Acid, Cuprous Naphthalate-Dibenzoyl Peroxide, Hydrogen Peroxide-Sodium Thiosulfate.

The molecular weight regulator is aliphatic mercaptan, carbon tetrachloride, dithioester, iodoform, 1-chloro-1-iodane, sodium bisulfite, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid , sodium hypophosphite, sodium formate, the catalyst is triethylamine, triethanolamine, N,N-diethylbenzylamine, tetraethylammonium bromide, tetraethylammonium chloride, triethylammonium One or more of benzyl ammonium chloride, triphenylphosphine, and benzyltriphenylphosphine bromide, and the polymerization inhibitors used are benzoquinone, methylquinone, nitro compounds, aromatic amines, phenols, containing One or more of sulfur compounds, oxygen, sulfur, etc.

The solvent 1 and solvent 2 are ethanol, isopropanol, butanol, benzyl alcohol, ether, tetrahydrofuran, dioxane, acetone, butanone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, One or more of benzene, toluene, xylene, diethylene glycol methyl ether, propylene glycol monomethyl ether, and ethoxyethyl ether, wherein solvent 1 and solvent 2 can be the same solvent or different solvent.

Compared with prior art, the beneficial effect of the present invention is:

1. The present invention introduces organosilicon groups into the molecular chain of (meth)acrylate resin, changes the original configuration and conformation of the molecular chain, reduces brittleness, increases flexibility, and overcomes the problem of methacrylate monomer copolymerization materials The disadvantage of high brittleness.

2. Introduce three curing groups, hydroxyl, epoxy and unsaturated double bonds. Hydroxyl can be thermally cured, epoxy can be thermally cured, ultraviolet light can initiate cationic curing, and double bonds can be ultraviolet-induced free radical curing. At the same time, the polymer Contains silicone. The resin of the present invention has three curing groups, which can be cured in various ways, and can be cured by heat, ultraviolet light, moisture, and air step by step. One or two groups can be selected to be cured first to obtain a flexible material without adhesion. The time interval between secondary processing and secondary processing can be longer for storage. During secondary processing, it can be fully cured to obtain a material with high hardness and good toughness. , to increase the scope of surface modification during secondary processing. The curing process is easy to control, which can effectively reduce the large curing shrinkage and oxygen resistance in single UV curing. In addition, it maintains properties such as hardness, gloss, and chemical corrosion resistance, and at the same time overcomes the shortcomings of the coating film such as poor toughness and non-wear resistance.

3. The modified (meth)acrylate resin of the present invention can be used in coatings, adhesives, inks and other fields.

4. When synthesizing resin intermediates, the method of continuous feeding can be used to avoid feeding in batches or adding a part of the material first and then continuously adding the remaining raw materials. In the copolymerization of (meth)acrylate monomers, due to the reactivity ratio Different, each monomer is polymerized into the macromolecule and distributed unevenly, which leads to the problem of performance degradation, which is beneficial to reduce the molecular weight distribution index.

detailed description

The modified (meth)acrylate resin provided by the present invention is a (meth)acrylic acid equivalent weight of 100 g/eq-300 g/eq, a hydroxyl value of 20 mgKOH/g-500 mgKOH/g, and an epoxy value of 0.1 mol/100g-6mol/100g, a copolymer resin with a silicone weight content of 0.1%-50% and a molecular weight of 5000-100000, the multiple curing groups include hydroxyl groups, epoxy groups and double bonds. The present invention will be described in detail below.

<monomer>

Monomer 1 used in the present invention is a (meth)acrylate monomer, including but not limited to methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate , butyl methacrylate, isobutyl methacrylate, methyl crotonate, ethyl crotonate, butyl octadecenoate, ethyl cinnamate, dimethyl maleate, dibutyl maleate One or more of esters, dioctyl maleate, dimethyl fumarate, and diethyl fumarate.

The monomer 2 used in the present invention is a compound containing epoxy groups and unsaturated double bonds, including but not limited to glycidyl (meth)acrylate monomers or glycidyl (meth)acrylate oligomers or copolymers things.

The monomer 3 used in the present invention is a monomer containing a carboxyl group and a double bond, including but not limited to acrylic acid, methacrylic acid, oleic acid, 2-phenylacrylic acid, 3-phenylacrylic acid, 2-fluoroacrylic acid, 3-( One or more of 2-furyl)acrylic acid, 3-iodoacrylic acid, and benzyl acrylic acid.

<Silicone>

The silicone used can be a silicone monomer containing unsaturated double bonds or a macromolecule containing silicone. The silicone group is shown in the following structure:

Wherein R ¹ represents a monovalent hydrocarbon group or a hydrogen atom with 1-20 carbon atoms, and n is an integer greater than 1, and two R ¹ can be the same or different groups;

Wherein R ² represents a substituted or unsubstituted straight-chain or branched alkenyl group with 2-20 carbon atoms, and X represents a halogen atom, an alkoxy group, a phenoxy group or an acetoxy group, and three Xs can be are the same or different groups;

Wherein R ³ represents a substituted or unsubstituted branched or branched alkenyl group with 2-20 carbon atoms, and R ⁴ represents a monovalent hydrocarbon group, and the three R ⁴ may be the same or different groups;

Wherein R ⁵ represents a hydrocarbon group or hydrogen atom containing 1-20 carbon atoms, and n is an integer greater than 1, two R ⁵ can be the same or different hydrocarbon groups or hydrogen atoms, R ⁶ represents substituted or unsubstituted , a straight-chain or branched alkenyl group with 2-20 carbon atoms, and R ⁷ represents hydrogen or a monovalent hydrocarbon group.

<initiator>

As the initiator of the synthesis reaction, including but not limited to initiators such as azobisisobutyronitrile, azobisisoheptanonitrile, dimethyl azobisisobutyrate and other azo initiators; dibenzoyl peroxide , diethylhexyl peroxydicarbonate, tert-butyl hydroperoxide and other organic peroxygen initiators; potassium persulfate, hydrogen peroxide and other inorganic peroxygen initiators; potassium permanganate-oxalic acid, naphthalene Copper-dibenzoyl peroxide, hydrogen peroxide-sodium thiosulfate and other oxidation-reduction initiators.

<solvent>

Solvent 1 and solvent 2 can include alcohols such as ethanol, isopropanol, butanol, and benzyl alcohol; ethers such as ether, tetrahydrofuran, and dioxane; ketones such as acetone, butanone, and cyclohexanone; ethyl acetate , propyl acetate, butyl acetate and other lipids; benzene, toluene, xylene and other aromatics; diethylene glycol methyl ether, propylene glycol monomethyl ether, ethoxy ether and other ether alcohols or Multiple, solvent 1 and solvent 2 can be the same solvent or different solvents.

<Molecular weight regulator>

As the molecular weight regulator of the synthesis reaction, including but not limited to aliphatic mercaptan, carbon tetrachloride, dithioester, iodoform, 1-chloro-1-iodane, sodium bisulfite, mercaptoethanol, mercaptopropanol, One or more of thioglycolic acid, mercaptopropionic acid, sodium hypophosphite, sodium formate, etc.

<Inhibitor>

As a polymerization inhibitor, one or more of benzoquinone, methoquinone, nitro compounds, aromatic amines, phenols, sulfur compounds, oxygen, sulfur, etc. can be selected.

<catalyst>

As a catalyst for the synthesis reaction, including but not limited to triethylamine, triethanolamine, N,N-diethylbenzylamine and other tertiary amines; tetraethylammonium bromide, tetraethylammonium chloride, triethylbenzyl chloride quaternary ammonium salts such as amines; one or more of phosphines such as triphenylphosphine and benzyltriphenylphosphine bromide.

<film base>

The base film of the present invention is used to support the resin protection layer, so the base film should have appropriate mechanical properties. Examples of materials used for base films include polyesters including polyethylene terephthalate, polyethylene naphthalate, etc., polyethylene, polypropylene, polyamide, polyimide, alkyl poly(methyl) Acrylates, (meth)acrylate copolymers, cellulose triacetate, cellulose diacetate, polyvinyl chloride-vinyl acetate copolymers, polytetrafluoroethylene, and polytrifluoroethylene. Preferred are polyethylene terephthalate and polyethylene naphthalate. The thickness of the base film may be 10 μm to 300 μm, and the material used for the base film may be modified or unmodified resin. The basement surface can be corona, plasma treated or left untreated.

The preparation method of resin of the present invention comprises the following steps:

(1) Preparation of (meth)acrylate, glycidyl (meth)acrylate and silicone copolymer intermediates

Under the condition of passing inert gas, heat the solvent 1 to 60°C-90°C, slowly add the mixture of monomer 1, monomer 2, initiator, molecular weight regulator, and organosilicon containing double bonds, for 1 hour- The addition is completed in 6 hours; the system is kept warm for 2 hours to 10 hours, the temperature is raised to 100°C-130°C, and the temperature is kept for 0.5-4 hours to obtain a copolymer intermediate.

(2) Preparation of modified (meth)acrylate resin

Lower the temperature of the copolymer intermediate obtained in step (1) to below 60°C, pass air or other gases containing oxygen, add monomer 3, polymerization inhibitor, catalyst, then raise the temperature to 70°C-100°C, and keep it warm for 2 hours After -10 hours, the temperature of the system is lowered to below 60°C, adding a polymerization inhibitor and solvent 2 and stirring for another 30 minutes to obtain a modified (meth)acrylate resin.

The modified (meth)acrylate resin of the present invention is coated on a base material to form a coating film, which is semi-cured at 100°C for 30 seconds and cured by 1200mJ/ ^cm2 energy ultraviolet light to obtain a cured coating.

Evaluation method

<Measurement of Pencil Hardness>

Pencil hardness was measured according to the method given in GB/T 6739-2006 Paints and varnishes - Pencil method for the determination of paint film hardness, with a load of 750g and a Japanese Mitsubishi pencil.

<Measurement of Abrasion Resistance>

Abrasion resistance is measured according to HG/T 4302-2012 Surface Hardened Polyester Film Abrasion Resistance Test Method, using 0000# steel wool with a load of 100 grams.

<Measurement of Adhesion>

Use a scratcher to draw 100 small grids of 1mm×1mm on the surface of the resin film, and use the 600 transparent tape produced by 3M Company of the United States to paste the small grids seamlessly, then quickly peel off the tape at an angle of 60°, and observe the small grids. Whether the grid edge is peeled off.

If there is no missing cell, the result is recorded as 5B; if 0-5 cells are missing, the result is recorded as 4B; if 5-15 cells are missing, the result is recorded as 3B; if 15-35 cells are missing, the result is It is recorded as 2B; if 35-65 small grids fall off, the result is recorded as 1B; if the number of small grids falls off is more than 65, the result is recorded as 0B.

<Measurement of Flexibility>

Flexibility is measured according to GB/T1731-1993 paint film flexibility test method.

<Measurement of Adhesion>

Blocking property is determined according to HG/T 2914-1997 film and base anti-blocking properties.

The present invention will be described in detail below in conjunction with specific examples, but the implementation of the present invention is not limited by these examples.

Example 1

Synthesis of modified (meth)acrylate resin intermediates

In the reaction device equipped with a stirrer, condenser tube, nitrogen gas introduction tube, and thermometer, nitrogen gas is passed, 300 parts of butyl acetate are added, the temperature is raised to 80°C, the air in the reaction device is fully removed, and 300 parts of pre-configured Glycidyl methacrylate (hereinafter referred to as GMA), 75 parts of methyl methacrylate (hereinafter referred to as MMA), 37 parts of γ-methacryloxypropyl trimethoxysilane, 12 parts of azobisiso A mixed solution composed of butyronitrile (hereinafter referred to as AIBN) and 1.5 parts of lauryl mercaptan (hereinafter referred to as DDM) was slowly added dropwise for 3 hours and kept warm for 5 hours. Then, the mixture in the reaction device was blown into nitrogen. Raise the temperature to 120° C., keep the temperature for 2 hours, and cool down to obtain a modified (meth)acrylate resin intermediate.

Preparation of modified (meth)acrylate resin

Lower the temperature of the above resin intermediate to 60°C, ventilate with air, and add 122 parts of acrylic acid (hereinafter referred to as AA), 0.8 parts of methylbenzoquinone (hereinafter referred to as MEHQ), and 0.9 parts of triphenylphosphine (hereinafter referred to as TPP) pre-configured Mix the solution, slowly raise the temperature to 90°C, continue to introduce air, keep the temperature for 8 hours, cool down to below 60°C, add 0.4 parts of MEHQ, 250 parts of methyl ethyl ketone, and fully stir for 30 minutes to obtain a modified (meth)acrylate resin.

Example 2

Synthesis of modified (meth)acrylate resin intermediates

In the reaction device equipped with a stirrer, condenser tube, nitrogen gas inlet tube, and thermometer, nitrogen gas is passed, 300 parts of butyl acetate are added, the temperature is raised to 60°C, the air in the reaction device is fully removed, and 85.7 parts of pre-configured A mixed solution composed of GMA, 226 parts of MMA, 37 parts of γ-methacryloxypropyltrimethoxysilane, 12 parts of AIBN, and 1.5 parts of DDM was slowly added dropwise for 6 hours and kept warm for 2 hours. Then, the reaction device The mixture in the mixture was heated to 130° C. under the condition of feeding nitrogen gas, kept at a temperature of 0.5 hour, and cooled to obtain a modified (meth)acrylate resin intermediate.

Synthesis of modified (meth)acrylate resin

Cool the above resin intermediate to 60°C, blow in air, add the pre-configured 10.9 parts of AA, 0.4 parts of MEHQ, 0.5 parts of TPP mixed solution, slowly raise the temperature to 70°C, continue to pass in air, keep warm for 10 hours, and cool down to 60 Below ℃, add 0.2 parts of MEHQ and 74 parts of methyl ethyl ketone, and stir thoroughly for 30 minutes to obtain a modified (meth)acrylate resin.

Example 3

Synthesis of modified (meth)acrylate resin intermediates

In the reaction device equipped with a stirrer, condenser tube, nitrogen gas introduction tube, and thermometer, nitrogen gas is passed, 300 parts of butyl acetate are added, the temperature is raised to 90°C, the air in the reaction device is fully removed, and 214.3 parts of pre-configured A mixed solution consisting of GMA, 192.6 parts of butyl methacrylate (abbreviated as BMA), 37 parts of γ-methacryloxypropyltrimethoxysilane, 12 parts of AIBN, and 1.5 parts of DDM was slowly added dropwise for 1 hour , keep warm for 2 hours, and then, raise the temperature of the mixture in the reaction device to 100° C. under the condition of blowing nitrogen, keep it warm for 0.5 hour, cool down, and modify the (meth)acrylate resin intermediate.

Synthesis of modified (meth)acrylate resin

Cool the above resin intermediate to 60°C, blow in air, add the pre-configured 17.4 parts of AA, 0.4 parts of MEHQ, 0.5 parts of TPP mixed solution, slowly raise the temperature to 110°C, continue to pass in air, keep it warm for 2 hours, and cool down to 60 Below ℃, add 0.2 parts of MEHQ and 176 parts of methyl ethyl ketone, and stir thoroughly for 30 minutes to obtain a modified (meth)acrylate resin.

Example 4

Synthesis of modified (meth)acrylate resin intermediates

In the reaction device equipped with a stirrer, condenser tube, nitrogen gas introduction tube, and thermometer, pass nitrogen gas, add 300 parts of butyl acetate, raise the temperature to 75 ° C, fully remove the air in the reaction device, and start slowly dropwise adding 300 parts of pre-configured A mixed solution consisting of GMA, 15 parts of MMA, 222 parts of γ-methacryloxypropyltrimethoxysilane, 12 parts of AIBN, and 1.5 parts of DDM was slowly added dropwise for 4 hours and kept for 7 hours. Then, the reaction device The mixture in the mixture was heated to 120° C. under the condition of feeding nitrogen gas, kept for 1 hour, and cooled to obtain a modified (meth)acrylate resin intermediate.

Synthesis of modified (meth)acrylate resin

Cool the above resin intermediate to 60°C, blow in air, add the pre-configured 122 parts of AA, 0.4 part of MEHQ, 0.5 part of TPP mixed solution, slowly raise the temperature to 80°C, continue to pass in air, keep warm for 6 hours, and cool down to 60 Below ℃, add 0.2 parts of MEHQ and 359 parts of methyl ethyl ketone, and stir thoroughly for 30 minutes to obtain a modified (meth)acrylate resin.

Example 5

Proceed in the same manner as in Example 1, except that 37 parts of acryltrimethoxysilane (A-151, American Carbon Union) are used to replace 37 parts of γ-methacryloxypropyl in Example 1 Trimethoxysilane.

Comparative example 1

In the reaction device equipped with a stirrer, condenser tube, air inlet tube, and thermometer, ventilate the air, add 520 parts of bisphenol A epoxy resin, heat to 100 ° C, add 95 parts of AA, 1.23 parts of TPP and 1.85 parts of TPP prepared in advance Part of MEHQ mixed solution, reacted for 5 hours, obtained epoxy acrylate monoester;

In the reaction device equipped with a stirrer, condenser tube, air inlet tube, and thermometer, blow nitrogen, add 87 parts of toluene diisocyanate, heat to 60 ° C, add 142 parts of pre-prepared hydroxyl silicone oil (hydroxyl content 6%) and 0.3 parts of dibutyltin dilaurate mixed solution, continue to react for 2.5 hours after the dropwise addition, add 29 parts of hydroxyethyl acrylate and 0.05 parts of MEHQ prepared in advance, heat up the reaction to 100 ° C, react for 2 hours, and get -NCO at one end group of urethane acrylates.

The above-mentioned epoxy acrylate monoester and polyurethane acrylate were mixed and reacted at 90° C. for 4 hours to obtain a modified epoxy acrylate resin.

Coating production

Add 2 parts of N3300, 93 parts of methyl ethyl ketone, 2.5 parts of 184, 1.3 parts of UV6992 to 100 parts of the obtained multi-curable silicone modified (meth)acrylate resin, mix well, coat and form a film, 100 ° C, 30s semi-curing, 1200mJ/cm ² energy UV curing, to obtain a cured coating. The test performance is shown in Table 1.

Comparative example 2

Synthesis of modified (meth)acrylate resin intermediates

In a reaction device equipped with a stirrer, a condenser tube, a nitrogen gas inlet tube, and a thermometer, nitrogen was passed, and 75 parts of butyl acetate, 75 parts of GMA, 18.7 parts of MMA, 9.3 parts of acryltrimethoxysilane, 3 parts of AIBN and 0.4 parts of DDM mixture, fully remove the air in the reaction device, raise the temperature to 75 ° C, keep it warm for 1 hour, start to slowly add 225 parts of GMA, 56.5 parts of MMA, 28 parts of acryltrimethoxysilane, 9 parts of AIBN, 1.1 parts of a mixed solution composed of lauryl mercaptan DDM, slowly added dropwise for 4 hours, and kept warm for 7 hours, then, the mixture in the reaction device was heated up to 120°C under the condition of feeding nitrogen, kept warm for 1 hour, cooled and lowered to obtain the improved Permanent (meth)acrylate resin intermediate.

Synthesis of modified (meth)acrylate resin

Cool the above resin intermediate to 60°C, blow in air, add the pre-configured 122 parts of AA, 0.4 part of MEHQ, 0.5 part of TPP mixed solution, slowly raise the temperature to 80°C, continue to pass in air, keep warm for 6 hours, and cool down to 60 Below ℃, add 0.2 parts of MEHQ and 359 parts of methyl ethyl ketone, and stir thoroughly for 30 minutes to obtain a modified (meth)acrylate resin.

Table 1 Performance Index

Test items Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Pencil hardness after heat curing 4B 4B 3B 4B 3B B 2B Pencil hardness after UV curing 3H 2H 2H 2H 3H 2H 2H Adhesion 5B 4B 4B 5B 5B 2B 4B Flexibility after heat curing Φ2mm Φ2mm Φ2mm Φ2mm Φ2mm Φ5mm Φ2mm wear resistance >100 >100 >100 >100 >100 20 80 Blocking (after heat curing) √ √ √ √ √ x x Blocking (after UV curing) √ √ √ √ √ √ √

Evaluation Judgment: Adhesion: "×" indicates adhesion, "√" indicates no adhesion, and "△" indicates very few adhesions.

The modified (meth)acrylate resin obtained by the present invention can be cured step by step. After the first step of curing, it has plasticity and no adhesion. It does not need to add a release layer for winding. After winding, it can be processed and shaped to make products. , After the coating film is cured by ultraviolet light, it has high pencil hardness and good wear resistance. As can be seen from the data in Table 1, the resin obtained by the present invention has low pencil hardness after heat curing, all below 2B, good flexibility after heat curing, meeting the requirements of Φ2mm wire rod, and relatively high pencil hardness after ultraviolet light curing; material Good anti-blocking and wear-resistant effects. The compound that provides epoxy group in comparative example 1 adopts bisphenol A type epoxy resin, and the pencil hardness of the synthesized resin is high after thermosetting, is unfavorable for winding and processing, adopts to add a batch of material first and then continue in comparative example 2 If it is prepared by adding the remaining raw materials, the overall performance of the obtained resin will decrease.

Claims (9)

1. A modified (meth)acrylate resin, characterized in that it has at least the following structural units: M, S, G, M, S, and G are present in the main chain through monomer copolymerization, and A is combined with G The reaction between the functional groups is grafted on the main chain; among them, M is derived from (meth)acrylate monomers, including methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, methyl methacrylate , ethyl methacrylate, butyl methacrylate, and isobutyl methacrylate, A is a monomer containing unsaturated double bonds and carboxylic acid, including acrylic acid, methacrylic acid, oleic acid , 2-phenylacrylic acid, 3-phenylacrylic acid, 2-fluoroacrylic acid, 3-(2-furyl)acrylic acid, 3-iodoacrylic acid, benzyl acrylic acid, G derived from containing unsaturated Monomers with double bonds and epoxy groups, including glycidyl (meth)acrylate monomers, S derived from silicones containing double bonds; the chemical bond between G and A is formed by the reaction of epoxy groups and carboxylic acids; The modified (meth)acrylate resin contains hydroxyl groups, epoxy groups and double bonds on branch chains; the epoxy value is 0.1 mol/100g-6mol/100g. 2. The modified (meth)acrylate resin according to claim 1, characterized in that, the main chain structure of the modified (meth)acrylate resin also includes Ethyl enoate, butyl octadecenoate, ethyl cinnamate, dimethyl maleate, dibutyl maleate, dioctyl maleate, dimethyl fumarate, diethyl fumarate One or more structural units of esters. 3. The modified (meth)acrylate resin according to claim 1, wherein the silicone containing double bonds is shown in one of the following structures: Wherein R ¹ represents a monovalent hydrocarbon group or a hydrogen atom with 1-20 carbon atoms, and n is an integer greater than 1, two R ¹ can be the same or different groups, and at least one of the two R ¹ contains double bond; Wherein R ² represents a substituted or unsubstituted linear or branched alkenyl group with 2-20 carbon atoms, and X represents a halogen atom, an alkoxy group, a phenoxy group or an acetoxy group, and the three Xs can be are the same or different groups; Wherein R ³ represents a substituted or unsubstituted linear or branched alkenyl group with 2-20 carbon atoms, and R ⁴ represents a monovalent hydrocarbon group, and the three R ⁴ may be the same or different groups; Wherein R ⁵ represents a hydrocarbon group or hydrogen atom containing 1-20 carbon atoms, and n is an integer greater than 1, two R ⁵ can be the same or different hydrocarbon groups or hydrogen atoms, R ⁶ represents substituted or unsubstituted , a linear or branched alkenyl group with 2-20 carbon atoms, R ⁷ represents hydrogen or a monovalent hydrocarbon group. 4. a preparation method of modified (meth)acrylate resin as claimed in claim 1, is characterized in that, comprises the following steps: (1) Preparation of copolymer intermediate Under the condition of passing inert gas, heat the solvent 1 to 60°C-90°C, slowly add the mixture of monomer 1, monomer 2, initiator, molecular weight regulator, and organosilicon containing double bonds, for 1 hour- The addition is completed in 6 hours; the system is kept warm for 2 hours to 10 hours, heated to 100°C-130°C, and kept warm for 0.5 hours to 4 hours to obtain a copolymer intermediate; wherein monomer 1 corresponds to the formation of M in claim 1, monomer 2 corresponds to forming G in claim 1; (2) Preparation of modified (meth)acrylate resin Lower the temperature of the copolymer intermediate obtained in step (1) to below 60°C, pass air or other gases containing oxygen, add monomer 3, polymerization inhibitor, catalyst, then raise the temperature to 70°C-100°C, and keep it warm for 2 hours - After 10 hours, the temperature of the system is lowered to below 60°C, adding a polymerization inhibitor and solvent 2 and stirring evenly to obtain a modified (meth)acrylate resin; wherein monomer 3 corresponds to A in claim 1. 5. the preparation method of modified (meth)acrylate resin according to claim 4, is characterized in that, described monomer 1 is (meth)acrylate monomer, comprises methyl acrylate, ethyl acrylate , butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, the monomer 2 contains Monomers with saturated double bonds and epoxy groups, including glycidyl (meth)acrylate monomers, and the monomer 3 is monomers containing unsaturated double bonds and carboxylic acid groups, including acrylic acid, methacrylic acid, One or more of oleic acid, 2-phenylacrylic acid, 3-phenylacrylic acid, 2-fluoroacrylic acid, 3-(2-furyl) acrylic acid, 3-iodoacrylic acid, benzyl acrylic acid, the initiator It is an azo initiator, an organic peroxy initiator or an oxidation-reduction initiator. 6. The preparation method of modified (meth)acrylate resin according to claim 4, characterized in that, in step (1) during the preparation of the copolymer intermediate, the mixture of monomers also includes butene Methyl crotonate, ethyl crotonate, butyl octadecenoate, ethyl cinnamate, dimethyl maleate, dibutyl maleate, dioctyl maleate, dimethyl fumarate, One or more of diethyl fumarate. 7. the preparation method of modified (meth)acrylate resin according to claim 4, is characterized in that, described initiator is azobisisobutyronitrile, azobisisoheptanonitrile, azobisisobutyronitrile Dimethyl peroxide, dibenzoyl peroxide, diethylhexyl peroxydicarbonate, tert-butyl hydroperoxide, potassium persulfate, hydrogen peroxide, potassium permanganate-oxalic acid, cuprous naphthenate-peroxide Dibenzoyl Oxide, Hydrogen Peroxide-Sodium Thiosulfate. 8. the preparation method of modified (meth)acrylate resin according to claim 4, is characterized in that, described molecular weight regulator is aliphatic mercaptan, carbon tetrachloride, dithioester, iodoform, 1 -one or more of chloro-1-iodane, sodium bisulfite, mercaptoethanol, mercaptopropanol, mercaptoacetic acid, mercaptopropionic acid, sodium hypophosphite, sodium formate, and the catalyst is triethylamine, triethanolamine, One of N,N-diethylbenzylamine, tetraethylammonium bromide, tetraethylammonium chloride, triethylbenzylamine chloride, triphenylphosphine, benzyltriphenylphosphine bromide or more, and the polymerization inhibitor used is one or more of benzoquinone, methoquinone, nitro compounds, aromatic amines, phenols, sulfur-containing compounds, oxygen, and sulfur. 9. the preparation method of modified (meth)acrylate resin according to claim 4, is characterized in that, described solvent 1 and solvent 2 are ethanol, isopropanol, butanol, benzyl alcohol, ether, tetrahydrofuran, Dioxane, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, benzene, toluene, xylene, diethylene glycol methyl ether, propylene glycol monomethyl ether, ethoxyethyl ether One or more of, wherein, solvent 1 and solvent 2 are the same solvent, or different solvents.