CN112500524A - Anhydride group modified acrylate resin curing agent, preparation method and application - Google Patents
Anhydride group modified acrylate resin curing agent, preparation method and application Download PDFInfo
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- CN112500524A CN112500524A CN202011574861.2A CN202011574861A CN112500524A CN 112500524 A CN112500524 A CN 112500524A CN 202011574861 A CN202011574861 A CN 202011574861A CN 112500524 A CN112500524 A CN 112500524A
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4238—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof heterocyclic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Abstract
The invention discloses a preparation method of a latent anhydride modified acrylate resin curing agent and application of the resin in latent self-curing epoxy resin paint and coating. Carrying out free radical copolymerization on aliphatic/alicyclic acrylate, alkenyl phenyl derivatives, unsaturated anhydride with a structure containing double bonds, unsaturated aliphatic carboxylic acid and the like in a solvent to synthesize anhydride group modified acrylate resin CAPA; CAPA resin is used as a curing component and then is used in a latent epoxy resin coating system, so that the coating with good room-temperature storage stability can be obtained, and the self-curing of an epoxy resin coating can be realized by heating. The invention introduces the anhydride group into the acrylic resin system through copolymerization reaction, not only successfully converts the solid anhydride into a liquid form which is convenient to use, solves the defects of poor intersolubility reactivity and the like of the micromolecule solid anhydride and the epoxy resin, but also improves the flexibility and other physical and mechanical properties of the epoxy coating by introducing the acrylic resin chain segment.
Description
Technical Field
The invention belongs to the field of latent macromolecular curing agents in resin coatings, and particularly relates to a preparation method of a latent anhydride group modified acrylate resin curing agent and application of the agent in latent self-curing epoxy resin coatings and coatings.
Background
The epoxy resin coating has good adhesive force, strong adhesive property and excellent chemical corrosion resistance, and the cured coating has good electrical insulation performance, so the epoxy resin coating has wide application in the aspects of corrosion prevention and adhesion of chemical equipment, moisture prevention of cables, circuit board encapsulation, encapsulation and insulation of electronic and electrical elements and the like, but the traditional epoxy resin coating can be crosslinked and cured under the action of curing agents such as organic amine, dicyandiamide, hexahydrophthalic anhydride and the like, which can be seen in patents CN104927565A, CN102617984A, CN109988429A, CN109851760A, CN110054965A and the like. Obviously, most of the industrial epoxy resin coatings can only be widely used in a two-component packaging mode of epoxy paint and curing agent, which brings great inconvenience to industrial coating and application.
Latent self-curing epoxyResin coatings, i.e., epoxy resin coating systems that themselves contain latent curing agents. Compared with the traditional two-component, the latent self-curing coating can be cured by heating without adding a curing agent when in use, so that the latent self-curing coating has the advantages of simple packaging, convenient use and the like, and becomes the development direction of epoxy resin coatings and coatings in recent years (see CN111423347A and CN 1594390). For example, CN111423347A has used phenolic aldehyde benzene thiol ester as latent curing agent of epoxy resin, which not only makes the self-curing coating system have longer pot life, but also makes use of the characteristic that thiol released by the dissociation of benzene thiol ester can rapidly initiate the reaction of epoxy resin under the catalysis of tertiary amine after the temperature is raised, thus being especially suitable for the treatment of prepreg; CN1594390 firstly reacts ethyl acetoacetate and aluminum isopropoxide to prepare aluminum tris (ethyl acetoacetate), then n-alkanol is added, the product is cooled, recrystallized, dried and the like to prepare white powder, and then the powder and bisphenol S form a latent coinitiator system which is used for an alicyclic epoxy resin system and can realize medium-temperature curing of epoxy resin; the self-curing resin coating constructed by bisphenol A epoxy resin, diisopropoxy-diethyl-acetoacetate titanate and the like of Tang G and the like has good heat resistance and chemical corrosion resistance, and the coating also has good physical properties (Tang G, Zhang K, Yan Z, et al).Prog. Organ. Coatings, 2017, 102:225-230). However, as can be seen, no report is found in the literature that the carboxylated/anhydride modified acrylate resin is used as a latent curing agent and compounded with epoxy resin and the like to prepare self-curing resin coatings and coatings.
It is well known that in small amounts of H+Or epoxy group [ -CH (O) CH ] in epoxy resin under the catalysis of carboxyl group2]Can react with-COOH to generate carboxylic ester and generate alcoholic hydroxyl, and the alcoholic hydroxyl can generate ring-opening reaction of anhydride group and further generate carboxyl when meeting anhydride, and the cycle is repeated, and finally complete crosslinking and curing of the epoxy resin can be realized.
However, small molecular acid anhydride is mostly solid at room temperature when used as a latent epoxy resin curing agent, which causes poor solubility or insolubility of the curing agent in epoxy resin, and limits the application of the acid anhydride curing agent in a latent low-temperature or medium-temperature curing epoxy resin system. The polymer containing anhydride group in the structure is prepared by copolymerizing solid unsaturated anhydride and acrylic ester, so that the solid anhydride can be converted into liquid which is convenient to use, and the mutual solubility reactivity of the anhydride and the epoxy resin can be greatly improved. In view of the above, the invention carries out free radical copolymerization on unsaturated anhydride, acrylate, alkenyl phenyl derivatives and the like, thereby not only preparing a novel polyacrylate macromolecule containing a plurality of anhydride groups in the structure, successfully converting solid anhydride into a liquid state which can be mutually dissolved with epoxy resin and is convenient to use, but also using the macromolecule as a latent curing agent for an epoxy resin system, realizing the self-curing of an epoxy resin coating by heating, and having the effects of improving the flexibility of the coating and the like on the basis of keeping the original performance characteristics of the epoxy resin coating.
Disclosure of Invention
Aiming at the defect that a two-component epoxy resin coating system is inconvenient to use, the invention discloses a preparation method of a latent anhydride modified acrylate resin curing agent and an application method of the resin in latent self-curing epoxy resin coatings and coatings. Therefore, the invention adopts the following technical scheme:
a latent anhydride modified acrylate resin curing agent is prepared by the free radical copolymerization reaction of fatty/alicyclic acrylate and alkenyl phenyl derivative, unsaturated anhydride with double bond in structure and unsaturated aliphatic carboxylic acid, or the free radical copolymerization reaction of fatty/alicyclic acrylate and unsaturated anhydride with double bond in structure and unsaturated aliphatic carboxylic acid.
The latent anhydride modified acrylate resin curing agent comprises the following preparation steps:
(1) weighing 30-89.5 parts of acrylic ester, 0-35 parts of alkenyl phenyl derivative, 10-30 parts of unsaturated anhydride with a double bond structure and 0.5-5 parts of unsaturated aliphatic carboxylic acid in sequence according to parts by mass, and uniformly stirring to obtain a monomer mixture A; then, 0.5-3% of initiator is weighed according to the mass part of A, stirred and mixed evenly, and ultrasonic dispersion is carried out for 10-30min to obtain transparent-slightly turbid liquid which is marked as B.
(2) Weighing 70-90% of B by mass, adding 0.5-2% of molecular weight regulator based on A by mass, stirring uniformly, recording as B1, and placing in a dropping funnel for later use.
(3) Adding reaction solvent and 10-30% by mass of B into a reactor equipped with a thermometer, a stirrer and a dropping funnel in sequence, stirring and uniformly mixing, introducing N2Protecting, stirring, heating to 70-80 ℃, reacting for 10-30min, then dropwise adding B1, controlling the dropwise adding speed of B1 to ensure that the dropwise adding is finished within 0.5-2 h, and then continuously preserving the temperature and reacting for 2-6 h. After the reaction is finished, transparent liquid with certain viscosity is obtained, namely the latent anhydride group modified acrylate resin curing agent has solid content of about 50-70%, the content of the anhydride group (calculated by the mole number of the anhydride group contained in each hundred grams of solid resin) is about 0.05-0.27mol/100g (abbreviated as 0.05-0.27%), and the carboxyl value (calculated by the mole number of the carboxyl group contained in each hundred grams of solid resin) is about 0.005-0.025 mol/100g (abbreviated as 0.005-0.025%).
The acrylate is C contained in the molecular structure1-18The aliphatic (meth) acrylate and the alicyclic acrylate of the alcohol ester group are mainly selected from one or more of methyl (meth) acrylate, ethyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and the like;
the alkenyl phenyl derivative is a compound such as aromatic olefin and aromatic alkenyl ether which simultaneously contain alkenyl and phenyl functional groups in the structure, and is mainly selected from one of styrene, allyl phenyl ether (also called propenyl phenyl ether), phenyl vinyl ether, benzyl vinyl ether, vinyl benzyl chloride and the like;
the unsaturated anhydride containing double bonds in the structure is one of maleic anhydride, 2-methylene succinic anhydride (also named 2-methylene succinic anhydride), (2-propenyl) succinic anhydride, 2-butenyl succinic anhydride, 2-octenyl succinic anhydride and the like;
the unsaturated aliphatic carboxylic acid is aliphatic carboxylic acid containing polymerizable unsaturated double bonds in a molecular structure, and one of acrylic acid, methacrylic acid, 4-octenoic acid, 13-docosenoic acid and the like is selected;
the molecular weight regulator is thioglycolic acid or dodecyl mercaptan;
the initiator is a compound which can be decomposed by heating to generate free radicals and has good solubility in monomers such as oil phase acrylate, and is preferably one of Benzoyl Peroxide (BPO), Azobisisobutyronitrile (AIBN), percarbonate and the like;
the reaction solvent is a compound such as micromolecular ester, ether ester and aromatic hydrocarbon which have good intersolubility with monomers such as acrylate, anhydride and unsaturated carboxylic acid, and mainly comprises toluene (MB), xylene (DMB), Ethyl Acetate (EA), Butyl Acetate (BA), ethylene glycol monomethyl ether acetate (GMA), propylene glycol monomethyl ether acetate (PMA) and the like, and can be used as a single component or used by randomly mixing two components, and the dosage of the reaction solvent is generally controlled as follows: the mass concentration of the monomer A mixture in the reaction system is about 50-70%.
The latent anhydride modified acrylate resin curing agent is applied to self-curing epoxy resin paint and coating, and comprises the following two steps of paint preparation and coating preparation:
(1) preparation of latent self-curing coating: taking an epoxy resin (E), and according to the mole number of epoxy groups contained in the E: weighing CAPA resin with the mole number of (anhydride group + carboxyl group) about 1: 1-0.8; then, according to the total mass of the solid resin contained in the (E + CAPA), sequentially weighing 25-80 mass percent of the nano pigment and filler, 0.5-2 mass percent of the dispersant and 10-20 mass percent of the diluting solvent based on the total mass of the solid resin of the (E + CAPA); when in proportioning, the E, the nano pigment and filler, the dispersant and the diluent are mixed uniformly, dispersed and ground for 40-60min by a dispersion machine with the rotating speed of 1000r/min, then the latent CAPA curing agent is added and stirred uniformly, and the obtained slurry, namely the latent self-curing coating
(2) Preparing a coating: placing a substrate such as tinplate or glass on a sample table, uniformly coating the latent self-curing coating on the surface of the substrate, leveling for 30min at room temperature, then drying for 20-30min at the temperature of 120-130 ℃, and then curing for 10-30min at the temperature of 150-180 ℃, thus obtaining the coating, namely the epoxy resin coating cured by the anhydride-based modified acrylate.
The epoxy resin (E) is one of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, novolac epoxy resin and the like, the epoxy equivalent (the equivalent of epoxy groups contained in one hundred grams of resin) is about 0.2-0.59, and the viscosity is about 2000-20000 mPa.s.
The nano pigment filler comprises nano titanium dioxide (R902), nano silicon dioxide, barium sulfate and the like, and the dispersant is BYK-161 or BYK-ATU; the coating method is one of spraying, brushing, rolling, bar coating and the like;
the application performance of the self-curing resin coating containing the latent anhydride group modified acrylate resin curing agent is evaluated by the following method: coating adhesion: according to GB/T9286-1998 standard, the electric adhesion tester is used for measuring; impact resistance: reference is made to GB/T1732 + 1993 with an impactor assay; flexibility: measured with a paint film elasticity tester according to the method of GB/T1731-1993; hardness: the pencil hardness was evaluated according to the method of GB/T6739-.
The invention has the beneficial effects that: the preparation method comprises the steps of carrying out free radical copolymerization on fat/alicyclic acrylate and alkenyl phenyl derivatives, unsaturated acid anhydride and unsaturated carboxylic acid in a solution, or carrying out copolymerization on the fat/alicyclic acrylate and unsaturated acid anhydride and unsaturated aliphatic carboxylic acid containing double bonds in a structure, and firstly synthesizing latent anhydride modified polyacrylate resin CAPA containing a plurality of anhydride groups and a small amount of carboxyl groups in the structure; then CAPA is taken as a latent high-molecular resin curing agent, the agent and epoxy resin are compounded to prepare self-curing coating and coating, the reaction characteristics of continuous circulation are skillfully utilized, wherein carboxyl carried by side chains of the CAPA of the anhydride group modified polyacrylate resin reacts with epoxy groups in the epoxy resin to release hydroxyl, and the hydroxyl can generate carboxyl when meeting the anhydride groups, so that the thermosetting of the epoxy resin + the latent CAPA resin coating and a coating system can be realized, and the toughening effect of polyacrylate resin chain segments in curing components also has the effects of improving the flexibility of a target coating, improving the impact resistance of the coating and the like. In addition, the invention converts the solid acid anhydride into a liquid form which is convenient to use through reaction, can effectively improve the intersolubility and reactivity of the acid anhydride and the epoxy resin, enlarges the application range of the acid anhydride, and provides a reference idea for solving the application of the solid acid anhydride in the epoxy resin and the low-temperature curing coating.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
(1) Weighing 50.0g of butyl acrylate, 35.0g of styrene, 10.0g of 2-methylene succinic anhydride and 5.0g of docosadienoic acid in sequence according to parts by mass, and uniformly stirring to obtain about 100g of a monomer mixture (A); then, 0.5% by mass of the initiator AIBN based on the part by mass of A and about 0.5g of the initiator AIBN are weighed and mixed with A, and ultrasonic dispersion is carried out for 30min by using an ultrasonic cleaner with the power of 1KW, so that about 100.5g of transparent-slightly turbid liquid (B) is obtained in total.
(2) 90.45g and about 90% of B by mass are weighed, 2% of thioglycolic acid serving as a molecular weight regulator and about 2.0g of thioglycolic acid serving as a molecular weight regulator are added into the mixture, the mixture is stirred and mixed uniformly, and the mixture is marked as B1 and placed into a dropping funnel for later use.
(3) A three-necked flask equipped with a thermometer, a stirrer and a dropping funnel was charged with 42.85gMB/BA solvent (MB: BA mass ratio =1:1) and 10.05g, about 10% by mass of B in this order, stirred and mixed, and N was introduced thereinto2Protecting, stirring, heating to 80 deg.C, reacting for 10min, then adding B1 dropwise, controlling the dropping speed of B1 to make it completely drop in 2h, and keeping the temperature at 80 deg.C for 2 h. After the reaction is finished, the temperature is reduced to room temperature to obtain transparent liquid with certain viscosity, namely latent anhydride modified acrylate resin curing agent-butyl acrylate-co-styrene-co-2-methylenesuccinic anhydride-co-a docosenoic acid copolymer having a solids content of about 70%, an anhydride group content (moles of anhydride groups per hundred grams of solid resin, same below) of about 0.0875%, and a carboxyl group content (moles of carboxyl groups per hundred grams of solid resin, same below) of about 0.0358%.
Example 2
(1) Weighing 30.0g of methacrylic acid dodecyl ester, 25.0g of cyclohexyl acrylate, 14.5g of benzyl vinyl ether, 30.0g of allyl succinic anhydride and 0.5g of acrylic acid in sequence according to parts by mass, and uniformly stirring to obtain 100g of monomer mixture (A); then, 2% by mass of A and about 2.0g of initiator BPO are weighed and mixed with A, and ultrasonic dispersion is carried out for 30min by using an ultrasonic cleaner with the power of 1KW, so as to obtain about 102.0g of transparent liquid (B) in total.
(2) 71.4g and about 70 percent of B by mass are weighed, then 0.5 percent of dodecyl mercaptan of which the amount is 0.5 percent of A by mass and about 0.5 percent of molecular weight regulator are added, stirred and mixed uniformly, and marked as B1, and placed in a dropping funnel for later use.
(3) 100g DMB/EA solvent (DMB: EA mass ratio =3: 2) and 30.6g, about 30% by mass of B were sequentially added to a three-necked flask equipped with a thermometer, a stirrer and a dropping funnel, stirred and mixed, and N was introduced2Protecting, stirring, heating to 70 deg.C, reacting for 30min, then adding B1 dropwise, controlling the dropping speed of B1 to make it completely drop in 0.5h, and keeping the temperature at 70 deg.C for reacting for 6 h. After the reaction is finished, the temperature is reduced to room temperature to obtain transparent liquid with certain viscosity, namely latent anhydride modified acrylate resin curing agent-methacrylic acid decaglycol ester-coCyclohexyl acrylate-co-Benzyl vinyl ether alkene-coAllyl succinic anhydride-coAcrylic copolymers having a solids content of about 50%, an anhydride group content of about 0.213% and a carboxyl group content of about 0.0069%.
Example 3
(1) Weighing 24.0g of methyl acrylate, 30.0g of butyl methacrylate, 20.0g of octadecyl methacrylate, 25.0g of 2-octenyl succinic anhydride and 1.0g of methacrylic acid in sequence according to parts by mass, and uniformly stirring to obtain 100g of a monomer mixture (A); then, 1% by mass of A and about 1.0g of initiator BPO are weighed and mixed with A, and ultrasonic dispersion is carried out for 20min by using an ultrasonic cleaner with the power of 1KW, so as to obtain about 101.0g of transparent liquid (B) in total.
(2) 80.8g and about 80% of B by mass are weighed, 1% of thioglycolic acid serving as a molecular weight regulator and about 1.0g of thioglycolic acid serving as a molecular weight regulator are added into the mixture, the mixture is stirred and mixed uniformly, and the mixture is marked as B1 and placed into a dropping funnel for later use.
(3) Adding 66.67g of BA, 20.2g of B and about 20 percent of B in sequence into a three-necked flask provided with a thermometer, a stirrer and a dropping funnel, stirring and uniformly mixing, introducing N2The protection is carried out on the surface of the steel pipe,stirring, heating to 80 deg.C, reacting for 15min, adding B1 dropwise, controlling the dropping speed of B1 to make it completely drop in 1.5 hr, and keeping the temperature at 80 deg.C for 4 hr. After the reaction is finished, the temperature is reduced to room temperature, 167.67g of transparent liquid with certain viscosity is obtained in total, namely latent anhydride modified acrylate resin curing agent-methyl acrylate-coButyl methacrylate-coOctadecyl methacrylate-co-2-octenyl succinic anhydride-coMethacrylic acid copolymer with a solids content of about 60%, an anhydride group content of about 0.1178% and a carboxyl group content of about 0.0223%.
Example 4
(1) Weighing 44.5g of butyl methacrylate, 30.0g of phenyl vinyl ether, 24.0g of maleic anhydride and 1.5g of acrylic acid in sequence according to parts by mass, and uniformly stirring to obtain 100g of monomer mixture (A); then, 1.2% by mass of the initiator BPO (1.2 g) based on the mass of the component A is weighed and mixed with the component A, and ultrasonic dispersion is carried out for 25min by using an ultrasonic cleaner with the power of 1KW, so as to obtain about 101.2g of transparent liquid (B) in total.
(2) 86.02g and about 85% of B are weighed, 1.5% of thioglycolic acid serving as a molecular weight regulator and about 1.5g of thioglycolic acid serving as A are added, the mixture is stirred and mixed uniformly and is marked as B1, and the mixture is placed in a dropping funnel for later use.
(3) 66.67g of BA/PMA solvent (BA: PMA mass ratio =2:1) and 15.18g of about 15% by mass of B were sequentially charged into a three-necked flask equipped with a thermometer, a stirrer and a dropping funnel, and mixed by stirring and N was introduced2Protecting, stirring, heating to 80 deg.C, reacting for 12min, then adding B1 dropwise, controlling the dropping speed of B1 to make it completely drop in 2h, and keeping the temperature at 80 deg.C for reaction for 3 h. After the reaction is finished, the temperature is reduced to room temperature to obtain transparent liquid with certain viscosity, namely latent anhydride modified acrylate resin curing agent-butyl methacrylate-co-phenyl vinyl ether-co-Maleic anhydride-coAcrylic copolymers having a solids content of about 60%, an anhydride group content of about 0.2413% and a carboxyl group content of about 0.0366%.
Example 5
(1) Weighing 30.0g of butyl acrylate, 24.0g of isobornyl methacrylate, 20.0g of vinylbenzyl chloride, 25.0g of maleic anhydride and 1.0g of acrylic acid in sequence according to parts by mass, and uniformly stirring to obtain 100g of monomer mixture (A); then, 1.5% by mass of the initiator BPO (1.5 g) based on the mass part of the A is weighed and mixed with the A, and ultrasonic dispersion is carried out for 30min by using an ultrasonic cleaner with the power of 1KW, so as to obtain about 101.5g of transparent liquid (B) in total.
(2) 76.13g and about 75% of B are weighed, 1.0% of thioglycolic acid serving as a molecular weight regulator and about 1.0g of thioglycolic acid serving as A are added, the mixture is stirred and mixed uniformly and is marked as B1, and the mixture is placed in a dropping funnel for later use.
(3) A three-necked flask equipped with a thermometer, a stirrer and a dropping funnel was charged with 66.67g of MB/BA solvent (MB: BA mass ratio =1:1) and 25.38g of B in an amount of about 25% by mass in this order, stirred and mixed, and charged with N2Protecting, stirring, heating to 80 deg.C, reacting for 10min, then adding B1 dropwise, controlling the dropping speed of B1 to make it completely drop in 1h, and keeping the temperature at 80 deg.C for reacting for 4 h. After the reaction is finished, the temperature is reduced to room temperature to obtain transparent liquid with certain viscosity, namely latent anhydride modified acrylate resin curing agent-butyl acrylate-coIsobornyl methacrylate-co-vinylbenzyl chloride-coMaleic anhydride-coAcrylic copolymer having a solids content of about 55%, an anhydride group content of about 0.2525% and a carboxyl group content of about 0.0246%.
The CAPA resins prepared in examples 1-5 were applied with epoxy resin E20 as an example, and the specific application procedure was as follows:
(1) preparing a paint vehicle: taking 100g of epoxy resin E20 solution (containing 60g of solid resin and 0.12mol of epoxy group) with the solid content of about 60%, according to the mole number of the epoxy group contained in E20: weighing CAPA-1-CAPA-5 resins prepared in example 1-5 according to the proportion of the mole number of (anhydride groups and carboxyl groups) in CAPA resin being about 1:0.8, then adding 50 mass percent of nano pigment filler titanium dioxide, 1 mass percent of BYK-161 dispersant and 20 mass percent of toluene (MB)/Butyl Acetate (BA) diluent solvent according to the total mass percent of solid resin contained in epoxy resin E20+ CAPA (the mass ratio of MB: BA is about 1: 1); when the paint is prepared, firstly, uniformly mixing the epoxy resin E20 with the nano titanium dioxide, BYK-161 and MB/BA, dispersing and grinding for 60min by using a dispersion machine with the rotating speed of 1000r/min, then adding the measured latent CAPA-1-CAPA-5 resin curing agents, and uniformly stirring to obtain the epoxy resin paint containing the latent CAPA curing agents.
(2) Coating preparation and performance evaluation: placing the polished clean tinplate on a sample table, uniformly spraying an epoxy resin coating containing a latent CAPA resin curing agent on the surface of a base material, leveling for 30min at room temperature, baking for 30min at 120 ℃, curing for 20min at 180 ℃, obtaining a cured coating, namely an epoxy resin coating obtained after curing anhydride-based modified acrylate, and balancing a coating sample for 24h at room temperature of 25 +/-2 ℃ and relative humidity of 48 +/-2% to perform performance measurement. Coating adhesion: the test is carried out by an electric adhesion tester according to the GB/T9286-.
TABLE 1 Properties of the coatings of examples 1-5
Note: examples 1-5 coating raw material usage, example 1: 100g of 60% E20+ 111.22g of 70% CAPA-1+ 68.93g of TiO2+2.21g BYK-161, example 2: 100g of 60% E20+ 87.31g of 50% CAPA-2+51.83gTiO2+1.65g BYK-161, example 3: 100g of 60% E20+ 114.2g of 60% CAPA-3+64.26g TiO2+2.1g BYK-161, example 4: 100g of 60% E20+ 57.57g of 60% CAPA-4+59.09g TiO2+1.5g BYK-161; example 5: 100g of 60% E20+ 62.98g of 55% CAPA-5+47.32g TiO2+1.5gBYK-161
As can be seen from Table 1, the CAPA resin serving as a latent curing agent can realize the thermosetting of a CAPA resin and epoxy resin coating system, the hardness of the cured coating can reach 2-4H (the highest reaches 4H), the adhesive force reaches 1-3 grades, the impact resistance reaches 45-70cm (the highest reaches 70 cm), the flexibility reaches 1-3cm (the smallest reaches 1 cm), and the coating integrally shows a good application effect.
Claims (10)
1. The preparation method of the latent anhydride modified acrylate resin curing agent is characterized by comprising the following steps:
1) weighing 30-89.5 parts of acrylic ester, no more than 35 parts of alkenyl phenyl derivative, 10-30 parts of unsaturated anhydride containing double bonds and 0.5-5 parts of unsaturated aliphatic carboxylic acid in sequence by mass, and uniformly stirring to obtain a monomer mixture A; then weighing 0.5-3% of initiator by mass of A, uniformly stirring, and ultrasonically dispersing for 10-30min, wherein the mark is B; the alkenyl phenyl derivative is aromatic olefin or aromatic alkenyl ether with the structure containing alkenyl and phenyl functional groups; the unsaturated acid anhydride containing double bonds is a compound containing unsaturated double bonds and anhydride groups in a molecular structure; the unsaturated aliphatic carboxylic acid is carboxylic acid with polymerizable unsaturated double bond in the molecular structure;
2) taking 70-90% of the total mass of B, adding a molecular weight regulator accounting for 0.5-2% of the mass of A, and uniformly stirring to obtain B1;
3) adding reaction solvent and 10-30% of total mass of B into reactor, stirring, introducing N2Protecting, stirring, heating to 70-80 ℃, and reacting for 10-30 min; dropwise adding B1, controlling the dropwise adding speed of B1 to ensure that the solution is completely added within 0.5-2 h, and then continuing to perform heat preservation reaction for 2-6 h; and (4) obtaining the latent anhydride modified acrylic ester resin CAPA curing agent after the reaction is finished.
2. The method of claim 1, wherein the acrylate is C1-18Aliphatic acrylic acid ester of (1), C1-18Aliphatic methacrylates or alicyclic acrylates.
3. The method of claim 2, wherein the acrylate is one or more of methyl methacrylate, ethyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, dodecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate.
4. The method of claim 1, wherein the alkenylphenyl derivative is one selected from the group consisting of styrene, allyl phenyl ether, phenyl vinyl ether, benzyl vinyl ether, and vinylbenzyl chloride.
5. The method of claim 1, wherein the unsaturated anhydride containing a double bond is one of maleic anhydride, 2-methylene succinic anhydride, (2-propenyl) succinic anhydride, 2-butenyl succinic anhydride, and 2-octenyl succinic anhydride.
6. The method of claim 1, wherein the unsaturated aliphatic carboxylic acid is one of acrylic acid, methacrylic acid, and 4-octenoic acid.
7. A latent anhydride-modified acrylate resin curing agent obtainable by the process according to any one of claims 1 to 6.
8. The curing agent according to claim 7, wherein the curing agent has a solid content of 50 to 70%, a molar amount of anhydride groups per hundred grams of solid resin of 0.05 to 0.27mol/100g, and a molar amount of carboxyl groups per hundred grams of solid resin of 0.005 to 0.025 mol/100 g.
9. A latent self-curing coating, characterized in that it is obtained by a process comprising the steps of:
taking an epoxy resin E, and mixing the epoxy resin E and the curing agent according to claim 7 or 8, wherein the molar ratio of the total epoxy groups in the epoxy resin to the total anhydride groups and carboxyl groups in the curing agent is 1: (1-0.8) weighing a curing agent; taking the total mass of the raw materials as a reference, weighing 25-80 parts of nano pigment filler, 0.5-2 parts of dispersant and 10-20 parts of diluent for each 100 parts of the total mass of the epoxy resin E and the curing agent;
when in burdening, firstly, the epoxy resin E is uniformly mixed with the nano pigment filler, the dispersant and the diluent solvent, dispersed and ground for 40-60min by a dispersion machine with the rotating speed of 1000r/min, then the curing agent is added, and the mixture is uniformly stirred to obtain the latent self-curing coating.
10. A method of curing a coating according to claim 9, comprising the steps of: and (3) taking a clean coating substrate, uniformly coating the latent self-curing coating on the surface of the substrate, leveling at room temperature for 30min, drying at the temperature of 120-130 ℃ for 20-30min, and curing at the temperature of 150-180 ℃ for 10-30min to obtain the epoxy resin coating after the anhydride-based modified acrylate is cured.
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| CN113121737A (en) * | 2021-04-30 | 2021-07-16 | 鞍山润德精细化工有限公司 | Solid polyacrylate resin containing anhydride functional group and preparation and use method thereof |
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