CN111019069B - Water-based epoxy organic silicon acrylate composite resin and preparation method thereof - Google Patents
Water-based epoxy organic silicon acrylate composite resin and preparation method thereof Download PDFInfo
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- CN111019069B CN111019069B CN201911303265.8A CN201911303265A CN111019069B CN 111019069 B CN111019069 B CN 111019069B CN 201911303265 A CN201911303265 A CN 201911303265A CN 111019069 B CN111019069 B CN 111019069B
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/064—Polymers containing more than one epoxy group per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention provides a water-based epoxy organic silicon acrylate composite resin. The invention also provides a preparation method and a reaction route of the waterborne epoxy organic silicon acrylate composite resin. The invention also provides application of the waterborne epoxy organic silicon acrylate composite resin. The prepared resin is suitable for being used outdoors, is mainly engineering mechanical paint, and has the advantages of qualified water resistance, no rust return, strong water solubility, good glossiness and excellent performance.
Description
Technical Field
The invention belongs to the field of synthetic resin, relates to composite resin for engineering machinery paint and a preparation method thereof, and particularly relates to water-based epoxy/organic silicon/acrylate composite resin and a preparation method thereof.
Background
In recent years, with the increasing call for environmental protection, various industries have started to develop towards green environmental protection. With the increasing awareness of environmental protection, the high hazard of Volatile Organic Compound (VOC) emissions from traditional solvent-based coatings is gradually recognized. Therefore, the engineering mechanical paint containing various toxic and harmful substances such as aromatic hydrocarbon and the like is gradually replaced by the environment-friendly water-based engineering mechanical paint by taking the traditional organic compound as a solvent. Because the acrylate resin has the advantages of excellent weather resistance, stain resistance, corrosion resistance and mechanical property, excellent color retention, good film forming property, rich sources, relatively low cost and the like, the acrylate resin is widely used as a main film forming material of engineering machinery paint (coating) at present.
At present, the water resistance, the glossiness and the like of the water-based acrylic resin have larger differences compared with the traditional solvent-based acrylic resin, and the performance requirements of the engineering mechanical paint used outdoors are particularly outstanding. However, due to the use limitation of the conventional solvent type resins, it is urgent to develop satisfactory aqueous acrylic resins having high performance. The following problems may occur in the aqueous engineering machine coating: when spraying is carried out in humid weather, the water resistance of a paint film is poor after drying, the cast iron substrate is easy to rust when meeting water, the glossiness is reduced, and the like; the modified acrylic resin often has reduced water solubility (influences the compatibility with aqueous color paste) or limited improvement of water resistance. If the prior art only adopts the mode of adding the organosilicon coupling agent for modification, the water resistance is not improved enough due to insufficient organosilicon chain length; acrylic acid monomers are consumed when the epoxy resin is used for modification, so that the water solubility of the resin is rapidly reduced; the two-component crosslinking curing acrylic resin has the problems to a certain extent, but is inconvenient to use, is difficult to operate particularly when being used for spraying construction, and seriously influences the application range of the acrylic resin.
For example, the chinese patent CN101775109a discloses a method for preparing epoxy modified silicon-containing water-based acrylic resin and a coating thereof, the resin prepared by the method needs to be crosslinked and cured with amino resin to obtain excellent water resistance, the glossiness is not high, and the operation of a two-component coating is inconvenient.
For example, the Chinese patent CN109233500A discloses a water-based acrylic resin antirust insulating paint and a preparation method thereof, wherein the method comprises the steps of firstly preparing an organic silicon oligomer, then mixing the organic silicon oligomer with epoxy resin for physical modification, and finally grafting the organic silicon oligomer and the epoxy resin onto the water-based acrylic resin through ether bonds on the epoxy resin. The resin has improved water-resistant insulating properties, but is poor in gloss and water solubility.
For example, chinese patent CN107236418A discloses a preparation method of epoxy resin modified water-based acrylic resin, wherein epoxy resin is modified in the method, and although the glossiness is improved, the water resistance and the water solubility are poor. The gloss of the paint film prepared from the resin is 88.
In conclusion, when the single-component waterborne acrylic resin is prepared, the silicone chain length is insufficient through the silicone physical modification, and the characteristics of the silicone cannot be fully exerted; a single chemical modification is also not satisfactory. The existing single-component water-based acrylic resin cannot solve the balance of various performances, particularly water resistance (service performance) and water solubility (paint making performance); in addition, the glossiness of the resin in the current market is not high, and is greatly reduced after meeting water.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a one-component waterborne epoxy/silicone/acrylate composite resin having not only good water solubility and excellent water resistance, but also high gloss, and a method for preparing the same.
To achieve the above and other related objects, a first aspect of the present invention provides an aqueous epoxy silicone acrylate composite resin compound or a salt thereof, the compound having a chemical structure represented by formula I:
in the above-mentioned structural formula, the compound,
R 1 is composed of
Wherein n is 1 ＞0，n 2 ＞0。
R is as defined above 1 In the structural formula, only one end having an ether bond is linked to one end of the compound having a carbonyl group.
The compound of formula I, a carboxylic acid form of the waterborne epoxy silicone acrylate composite resin.
Preferably, the degree of polymerization n in the above formula 1 N is more than 0 and less than 200000000 2 > 0 and < 200000000.
The salt may be formed between the compound and a cation or base, and may typically be a salt formed between the compound, typically an acid (deprotonated) such as an anion, and a cation, preferably an inorganic cation. The salts include salts of the compounds with alkali metals and alkaline earth metals, and salts of the compounds with ammonium cations and the like. In particular, the salts are selected from the group consisting of the salts formed with ammonium cations after deprotonation of the compounds.
Preferably, the salt is a salt of the deprotonated compound with an ammonium cation of the formula:
the second aspect of the invention provides a preparation method of a water-based epoxy organic silicon acrylate composite resin compound, which comprises the steps of adding a polymerization reagent into an epoxy-methacrylate-organic silicon intermediate (1) to carry out free radical polymerization reaction to obtain a required compound (3), wherein the polymerization reagent comprises methyl methacrylate (11), styrene (12), butyl acrylate (13) and acrylic acid (14);
the reaction route is as follows:
in the above-mentioned reaction scheme, the reaction,
R 1 is composed of
Wherein n is 1 ＞0，n 2 ＞0。
Preferably, said compound (3) is hydrolyzed and deprotonated, being able to form a salt (5) with the compound (M) which acquires a proton.
The reaction route is as follows:
in the above-mentioned reaction scheme, the reaction,
R 1 is composed of
Wherein n is 1 ＞0，n 2 ＞0。
More preferably, the proton-obtaining compound (M) is N, N-dimethylethanolamine (4), the structural formula of the N, N-dimethylethanolamine (4) being:
the M causes the compound (3) and the N, N-dimethylethanolamine (4) to perform neutralization and salt formation reaction, and the formed salt can be decomposed into anions in water.
The specific reaction route is as follows:
wherein R is 2 Is composed of
R 1 Is composed of
Wherein n is 1 ＞0，n 2 ＞0。
Further preferably, the weight ratio of the N, N-dimethylethanolamine (4) to the epoxy-methacrylate-silicone intermediate (1) addition is 1 to 6:50. further preferably, the weight ratio of the added N, N-dimethylethanolamine (4) to the added epoxy-methacrylate-silicone intermediate (1) is 2 to 5:50.
more preferably, the reaction temperature is 60-70 ℃.
More preferably, the reaction time is 0.5 to 1h.
The neutralization salification refers to that acrylic acid is subjected to free radical polymerization reaction to enable a polymer chain segment to have carboxyl, and the carboxyl and tertiary amine in the N, N-dimethylethanolamine are subjected to neutralization reaction to generate salification, so that the polymer has water solubility.
More preferably, the neutralization salt-forming reaction is followed by filtration.
Preferably, the above reaction is carried out under a gas blanket provided by nitrogen. The amount of the protective atmosphere is the amount conventionally used in the art for protective atmospheres.
Preferably, the epoxy-methacrylate-silicone intermediate (1) is prepared by the following steps:
a) Carrying out hydrolysis reaction on the organosilicon coupling agent (6) to obtain an organosilicon coupling agent hydrolysate (7);
the reaction route is as follows:
b) Carrying out esterification reaction on epoxy resin (8) and methacrylic acid (9) to obtain epoxy-methacrylate (10);
the reaction route is as follows:
c) Reacting an epoxy group of the organic silicon coupling agent hydrolysate (7) with epoxy-methacrylate (10) to obtain an epoxy-methacrylate-organic silicon intermediate (1);
the reaction route is as follows:
in the above-mentioned reaction scheme, the reaction,
r is one of methyl or ethyl;
R 1 is composed of
Wherein n is 2 ＞0。
More preferably, the preparation of the epoxy-methacrylate-silicone intermediate (1) is carried out under a protective atmosphere, which is nitrogen. The amount of the protective atmosphere is the amount conventionally used in the art for protective atmospheres.
More preferably, in step a), the organosilicon coupling agent (6) is selected from one or a mixture of trimethylethoxysilane and trimethylmethoxysilane.
More preferably, in step a), the water is deionized water.
More preferably, in step a), the weight ratio of the organosilicon coupling agent (6) to water added in the hydrolysis reaction is 20-27:6-8. Further preferably, the weight ratio of the added organosilicon coupling agent (6) to water is 21-26:6.4-7.9.
More preferably, in step A), the reaction temperature of the hydrolysis reaction is between 0 and 15 ℃.
More preferably, in step a), the reaction conditions of the hydrolysis reaction are: stirring speed: 300-400r/min; hydrolysis time: 1-2h.
More preferably, in the step a), the organosilicon coupling agent (6) is subjected to hydrolysis reaction, and then is subjected to reduced pressure and standing.
Further preferably, the reduced pressure conditions are: decompression time: 1-2h; pressure reduction: -0.15 to-0.05 MPa.
Further preferably, the standing is performed at normal temperature. The normal temperature is 20-30 ℃.
Further preferably, the standing time is 2-3h.
More preferably, in step A), the viscosity of the organosilicon coupling agent hydrolysate (7) is from 200 to 400 mPas (25 ℃).
More preferably, in step B), the epoxy resin (8) is epoxy resin E-51.
More preferably, in step B), the weight ratio of the epoxy resin (8) to the methacrylic acid (9) added in the esterification reaction is 30-60:10-20. Further preferably, the weight ratio of the added epoxy resin (8) to the added methacrylic acid (9) is 40-50:15-19. The esterification reaction is the reaction of the epoxy group of the epoxy resin and the carboxyl group of the methacrylic acid. In the esterification reaction, the molar ratio of the added epoxy resin (8) to the added methacrylic acid (9) is 1:1.
more preferably, in step B), the discharged acid value of the epoxy-methacrylate (10) is less than or equal to 5mgKOH/g.
More preferably, in the step B), a polymerization inhibitor and n-tetrabutylammonium bromide are further added in the esterification reaction, and the weight ratio of the epoxy resin (8) to the polymerization inhibitor and the n-tetrabutylammonium bromide is 30-60:0.10-0.30:0.3-0.6. Further preferably, the weight ratio of the epoxy resin (8) to the added polymerization inhibitor and n-tetrabutylammonium bromide is 40-50:0.20-0.25:0.4-0.5. The polymerization inhibitor and the n-tetrabutylammonium bromide are reaction assistants.
More preferably, in step B), the reaction temperature of the esterification reaction is between 90 and 100 ℃.
More preferably, in step B), the mixed reaction conditions of the esterification reaction: reaction time: 1-2h; stirring speed: 300-400r/min.
Further preferably, in step B), the polymerization inhibitor is one or more selected from hydroquinone, p-methoxyphenol and p-hydroxyanisole.
More preferably, in step C), the organosilicon coupling agent hydrolysate (7) and the epoxy-methacrylate (10) are added in a weight ratio of 21-26:40-50. The epoxy group reaction is the reaction of silanol of the hydrolysate of the organosilicon coupling agent and epoxy in epoxy-methacrylate.
More preferably, in step C), tetraisobutyl titanate is further added to the epoxy group reaction, and the weight ratio of the organosilicon coupling agent hydrolysate (7) to the tetraisobutyl titanate is 21-26:0.10-0.35. Further preferably, the weight ratio of the organosilicon coupling agent hydrolysate (7) to the tetraisobutyl titanate is 21-26:0.20-0.25. The tetraisobutyl titanate is a reaction auxiliary agent.
More preferably, in step C), the reaction temperature for the reaction of the epoxide groups is from 140 to 150 ℃.
More preferably, in step C), the mixing reaction conditions for the reaction of the epoxy groups are: reaction time: 3-4h; stirring speed: 300-400r/min.
More preferably, in step C), the epoxy groups are cooled and filtered after reaction.
Preferably, in step 1), in the radical polymerization reaction, the weight ratio of the epoxy-methacrylate-silicone intermediate (1) to the added methyl methacrylate (11), styrene (12), butyl acrylate (13) and acrylic acid (14) is 50:30-55:20-40:4-11:1-6. More preferably, the weight ratio of the epoxy-methacrylate-silicone intermediate (1) to the weight of the methyl methacrylate (11), styrene (12), butyl acrylate (13), acrylic acid (14) additions is 50:40-45:30-35:5-10:2-5.
Preferably, in step 1), the epoxy-methacrylate-silicone intermediate (1) is mixed with dipropylene glycol methyl ether, and the weight ratio of the epoxy-methacrylate-silicone intermediate (1) to the dipropylene glycol methyl ether is 50:70-110. More preferably, the weight ratio of the epoxy-methacrylate-silicone intermediate (1) to dipropylene glycol methyl ether addition is 50:80-100. The dipropylene glycol methyl ether is a solvent of the epoxy-methacrylate-organosilicon intermediate (1).
More preferably, the reaction temperature of the mixed reaction conditions is 140-145 ℃.
More preferably, the reaction conditions of the mixing are: reaction time: 5-6h; stirring speed: 300-400r/min.
Preferably, in the step 1), the polymerization reagent further comprises an initiator and dodecyl mercaptan, and the weight ratio of the methyl methacrylate (11) to the added initiator and dodecyl mercaptan is 30-55:1.0-4.0:0.5-4. More preferably, the ratio by weight of the methyl methacrylate (11) to the initiator, dodecylmercaptan addition, is 40-45:1.2-3.6:1-3.
More preferably, the initiator is one or more selected from di-tert-butyl peroxide, dicumyl peroxide or tert-butyl peroxybenzoate.
Preferably, in step 1), the reaction temperature of the radical polymerization reaction is 148 to 152 ℃.
Preferably, in step 1), the reaction time of the radical polymerization reaction is 1.5-2.5h.
The third aspect of the invention provides an application of a water-based epoxy organic silicon acrylate composite resin compound in preparing a coating.
Preferably, the coating is an engineering machinery paint.
More preferably, the engineering machine paint is a one-component paint. The single-component coating does not need to be added with a curing agent when in use, and is an environment-friendly single-component coating.
Further preferably, the one-component coating is a water-borne modified acrylate coating.
In a fourth aspect, the present invention provides a composition comprising water and the above aqueous epoxy silicone acrylate composite resin compound, or a salt thereof.
According to the waterborne epoxy silicone acrylate composite resin and the preparation method thereof, disclosed by the invention, by a reasonable reaction mode, on the basis of a waterborne acrylic resin, a silicone coupling agent hydrolysate is prepared, then the epoxy resin and methacrylic acid are subjected to esterification reaction to form epoxy-methacrylate, then an epoxy group in the epoxy-methacrylate is reacted with silanol of the silicone coupling agent hydrolysate to obtain an epoxy-methacrylate-silicone intermediate, and finally the epoxy-methacrylate-silicone intermediate is subjected to free radical polymerization with other monomers to prepare the waterborne epoxy/silicone/acrylate composite resin. Has the following beneficial effects:
(1) The resin prepared by the invention can be directly added with water (including other additives) to be mixed to form the water-based modified acrylate coating, and the coating does not need to be added with a curing agent when in use and is an environment-friendly single-component coating.
(2) The resin prepared by the invention introduces the organic silicon chain and the epoxy resin into the acrylic resin, thereby improving the water resistance, the glossiness, the water solubility and other comprehensive properties of the resin. Compared with the coating prepared by the prior art, the prepared coating has better water resistance (no rust return), water solubility and higher glossiness, and is suitable for preparing coatings used outdoors, in particular engineering machinery paints.
(3) The existing waterborne acrylic resin is often modified singly, or modified by organic silicon or epoxy resin, the preparation method firstly carries out chemical modification on the epoxy resin and then carries out chemical modification on the organic silicon through a reasonable mode, double modification of the organic silicon and the epoxy resin is completed, the defects of single modification and physical modification are overcome, and the prepared resin has better comprehensive performance.
(4) According to the invention, the epoxy-methacrylate-organosilicon intermediate is prepared firstly, and then acrylic acid and other monomers are added for free radical polymerization, so that acrylic acid is added after the acrylic acid is not consumed, and the epoxy-methacrylate-organosilicon intermediate can be completely aminated to form salt without affecting the water solubility of the resin; the prepared epoxy-methacrylate-organosilicon intermediate contains hydroxyl, so that the hydrophilicity of the resin is increased, and the water solubility meets the paint preparation requirement; moreover, when the water paint prepared by the resin is formed into a film, long-chain organic silicon and epoxy resin in the resin component can migrate to the surface of the film layer to improve the water resistance.
(5) The invention overcomes the defects of overlarge viscosity, difficult operation and the like caused by simultaneously directly modifying the acrylate resin by using the epoxy resin and the organic silicon resin, and the prepared resin has good leveling property and high glossiness. The water-based epoxy/organic silicon/acrylate composite resin prepared by the technology is qualified in water resistance, free of rust return, high in water solubility of not less than 0.62, high in glossiness of not less than 92 and excellent in performance.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The raw materials used in the present invention are commercially available raw materials for preparing resins, and any modification or change made to the present invention will fall within the scope of the present invention.
In the present invention, all parts and percentages are by weight unless otherwise specified. In the following examples, the amounts are in parts by weight. The equipment and raw materials used are all available on the market or commonly used in the field. The methods in the following examples are conventional in the art unless otherwise specified.
The specific test method of the performance test project of the waterborne epoxy organic silicon acrylate composite resin prepared by the invention is as follows:
1) And (3) water resistance measurement: the measurement was carried out according to the method B (immersion boiling water test) of the GB/T1733-1993 "test method for Water resistance of paint film".
2) And (3) water solubility determination: at 23 ℃, taking a certain amount of resin, slowly adding deionized water into the resin under stirring, stirring for 30min, standing for a period of time, and observing whether the resin is completely dissolved. The relative size of the water solubility of the resin is expressed by the mass ratio of the resin to the deionized water when the resin is completely dissolved in the deionized water.
3) And (3) rust return measurement: according to GB/T1727-1992 paint film general preparation method, resin is sprayed on tinplate, the tinplate is placed at 23 ℃ for 24 hours, and then the tinplate is soaked in deionized water for 48 hours, and whether the rust return phenomenon occurs or not is observed.
4) And (3) measuring the glossiness: the determination was carried out according to the GB/T1743-1979 "gloss determination method".
Example 1
(1) Under the protection of nitrogen, 21 parts of trimethylethoxysilane and 6.4 parts of water are mixed in a four-neck flask under the stirring of 350r/min at the temperature of 0 ℃, hydrolyzed for 1.5h, decompressed and removed from low molecular compounds under the pressure of-0.10 MPa for 1.5h, and kept stand for 2h, thus obtaining the organic silicon coupling agent hydrolysate with the viscosity of 350 mPas (25 ℃).
(2) Under the protection of nitrogen, 40 parts of epoxy resin E-51 and 15 parts of methacrylic acid are mixed in a four-neck flask, 0.2 part of hydroquinone and 0.4 part of n-tetrabutylammonium bromide are added, the temperature is slowly increased to 90 ℃, the esterification reaction is carried out for 2 hours under the stirring of the rotating speed of 350r/min, and the epoxy-methacrylate is prepared after the acid value is less than 5mgKOH/g.
(3) Under the protection of nitrogen, 21 parts of organosilicon coupling agent hydrolysate, 40 parts of epoxy-methacrylate and 0.2 part of tetraisobutyl titanate are added into a four-neck flask, the temperature is slowly increased to 140 ℃, the mixture reacts for 3 hours under the stirring of the rotating speed of 350r/min, and the epoxy-methacrylate-organosilicon intermediate is obtained after cooling and filtering.
(4) After 40 parts of methyl methacrylate, 30 parts of styrene, 10 parts of butyl acrylate, 5 parts of acrylic acid, 1.2 parts of di-tert-butyl peroxide and 1 part of dodecyl mercaptan were mixed, a mixed solution was obtained.
(5) Adding 100 parts of dipropylene glycol methyl ether and 50 parts of epoxy-methacrylate-organosilicon intermediate into a four-neck flask, heating to 140 ℃, dropwise adding the mixed solution under stirring at the rotating speed of 350r/min, dropwise adding for 5 hours in total, heating to 150 ℃, performing free radical polymerization for 2 hours, finally cooling to 65 ℃, dropwise adding 5 parts of N, N-dimethylethanolamine for neutralization for 0.5 hour, salifying, and filtering to obtain a final product: sample # 1 of waterborne epoxy/silicone/acrylate composite resin.
Example 2
(1) 24 parts of trimethylmethoxysilane and 7.1 parts of water are mixed in a four-neck flask at 5 ℃ under the protection of nitrogen and with stirring at the rotating speed of 350r/min, hydrolyzed for 1.5h, then the low molecular compound is removed under the reduced pressure of-0.10 MPa for 1.5h, and the mixture is kept stand for 2.5h, thus obtaining the hydrolysate of the organosilicon coupling agent with the viscosity of 400 mPas (25 ℃).
(2) Under the protection of nitrogen, 45 parts of epoxy resin E-51 and 17 parts of methacrylic acid are mixed in a four-neck flask, 0.23 part of p-hydroxyanisole and 0.45 part of n-tetrabutylammonium bromide are added, the temperature is slowly raised to 95 ℃, esterification reaction is carried out for 1.5 hours under the stirring of the rotation speed of 350r/min, and the epoxy-methacrylate is prepared after the material is discharged when the acid value is less than 5mgKOH/g.
(3) Under the protection of nitrogen, 24 parts of organosilicon coupling agent hydrolysate, 45 parts of epoxy-methacrylate and 0.23 part of tetraisobutyl titanate are added into a four-neck flask, the temperature is slowly raised to 145 ℃, the mixture reacts for 3.5 hours under the stirring of the rotating speed of 350r/min, and the epoxy-methacrylate-organosilicon intermediate is obtained after cooling and filtering.
(4) After 45 parts of methyl methacrylate, 30 parts of styrene, 5 parts of butyl acrylate, 5 parts of acrylic acid, 2.4 parts of dicumyl peroxide and 2 parts of dodecyl mercaptan were mixed, a mixed solution was obtained.
(5) Adding 90 parts of dipropylene glycol methyl ether and 50 parts of epoxy-methacrylate-organosilicon intermediate into a four-neck flask, heating to 143 ℃, dropwise adding the mixed solution under stirring at the rotating speed of 350r/min, dropwise adding for 5.5 hours in total, heating to 150 ℃, performing free radical polymerization for 2 hours, finally cooling to 65 ℃, dropwise adding 5 parts of N, N-dimethylethanolamine for neutralization for 0.75 hour, salifying, and filtering to obtain a final product: sample # 2 of waterborne epoxy/silicone/acrylate composite resin.
Example 3
(1) Under the protection of nitrogen, 13 parts of trimethylethoxysilane and 7.9 parts of water are mixed in a four-neck flask under the stirring of 350r/min at the temperature of 15 ℃, hydrolyzed for 1.5h, decompressed and removed from low molecular compounds under the pressure of-0.10 MPa for 1.5h, and kept stand for 3h, thus obtaining the organic silicon coupling agent hydrolysate with the viscosity of 200 mPas (25 ℃).
(2) Under the protection of nitrogen, 50 parts of epoxy resin E-51 and 19 parts of methacrylic acid are mixed in a four-neck flask, 0.25 part of p-methoxyphenol and 0.5 part of n-tetrabutylammonium bromide are added, the temperature is slowly increased to 100 ℃, the esterification reaction is carried out for 1 hour under the stirring of the rotating speed of 350r/min, and the epoxy-methacrylate is prepared after the acid value is less than 5mgKOH/g.
(3) Under the protection of nitrogen, 26 parts of organosilicon coupling agent hydrolysate, 50 parts of epoxy-methacrylate and 0.25 part of tetraisobutyl titanate are added into a four-neck flask, the temperature is slowly raised to 150 ℃, the mixture reacts for 4 hours under the stirring of the rotating speed of 350r/min, and the epoxy-methacrylate-organosilicon intermediate is obtained after cooling and filtering.
(4) After 40 parts of methyl methacrylate, 35 parts of styrene, 10 parts of butyl acrylate, 2 parts of acrylic acid, 3.6 parts of tert-butyl peroxybenzoate and 3 parts of dodecyl mercaptan were mixed, a mixed solution was obtained.
(5) Adding 80 parts of dipropylene glycol methyl ether and 50 parts of epoxy-methacrylate-organosilicon intermediate into a four-neck flask, heating to 145 ℃, dropwise adding the mixed solution under stirring at the rotating speed of 350r/min, dropwise adding for 6 hours totally, heating to 150 ℃, performing free radical polymerization for 2 hours, finally cooling to 65 ℃, dropwise adding 2 parts of N, N-dimethylethanolamine for neutralization for 1 hour, salifying and filtering to obtain a final product: waterborne epoxy/silicone/acrylate composite resin sample # 3.
Example 4
(1) A hydrolysate of the organosilicon coupling agent having a viscosity of 350 mPas (25 ℃) was prepared under the same conditions as in step (1) of example 1.
(2) Under the protection of nitrogen, 40 parts of epoxy resin E-51 and 15 parts of methacrylic acid are mixed in a four-neck flask, 0.1 part of hydroquinone, 0.1 part of p-methoxyphenol and 0.4 part of n-tetrabutylammonium bromide are added, the temperature is slowly increased to 90 ℃, the esterification reaction is carried out for 2 hours under the stirring of the rotating speed of 350r/min, and the epoxy-methacrylate is prepared after the material is discharged when the acid value is less than 5mgKOH/g.
(3) An epoxy-methacrylate-silicone intermediate was prepared under the same conditions as in step (3) in example 1.
(4) 45 parts of methyl methacrylate, 35 parts of styrene, 5 parts of butyl acrylate, 2 parts of acrylic acid, 0.5 part of di-tert-butyl peroxide, 0.5 part of dicumyl peroxide and 1 part of dodecyl mercaptan are mixed to obtain a mixed solution.
(5) Adding 80 parts of dipropylene glycol methyl ether and 50 parts of epoxy-methacrylate-organosilicon intermediate into a four-neck flask, heating to 140 ℃, dropwise adding the mixed solution under stirring at the rotating speed of 350r/min, dropwise adding for 5 hours in total, heating to 150 ℃, performing free radical polymerization for 2 hours, finally cooling to 65 ℃, dropwise adding 2 parts of N, N-dimethylethanolamine for neutralization for 0.75 hour, salifying, and filtering to obtain a final product: waterborne epoxy/silicone/acrylate composite resin sample # 4.
Example 5
(1) A hydrolysate of the organosilicon coupling agent having a viscosity of 400 mPas (25 ℃) was prepared under the same conditions as in step (1) of example 2.
(2) Under the protection of nitrogen, 45 parts of epoxy resin E-51 and 17 parts of methacrylic acid are mixed in a four-neck flask, 0.13 part of p-methoxyphenol, 0.1 part of p-hydroxyanisole and 0.45 part of n-tetrabutylammonium bromide are added, the temperature is slowly raised to 95 ℃, the esterification reaction is carried out for 1.5 hours under the stirring of the rotation speed of 350r/min, and the epoxy-methacrylate is obtained after the acid value is less than 5mgKOH/g.
(3) An epoxy-methacrylate-silicone intermediate was prepared under the same conditions as in step (3) in example 2.
(4) 42 parts of methyl methacrylate, 35 parts of styrene, 8 parts of butyl acrylate, 3 parts of acrylic acid, 1 part of di-tert-butyl peroxide, 1 part of tert-butyl peroxybenzoate and 2 parts of dodecyl mercaptan are mixed to obtain a mixed solution.
(5) Adding 90 parts of dipropylene glycol methyl ether and 50 parts of epoxy-methacrylate-organosilicon intermediate into a four-neck flask, heating to 143 ℃, dropwise adding the mixed solution under stirring at the rotating speed of 350r/min, dropwise adding for 5.5 hours in total, heating to 150 ℃, performing free radical polymerization for 2 hours, finally cooling to 65 ℃, dropwise adding 3 parts of N, N-dimethylethanolamine for neutralization for 0.5 hour, salifying, and filtering to obtain a final product: waterborne epoxy/silicone/acrylate composite resin sample # 5.
Example 6
(1) A hydrolysate of the organosilicon coupling agent having a viscosity of 200 mPas (25 ℃) was prepared under the same conditions as in step (1) of example 3.
(2) Under the protection of nitrogen, 50 parts of epoxy resin E-51 and 19 parts of methacrylic acid are mixed in a four-neck flask, 0.15 part of hydroquinone, 0.1 part of p-hydroxyanisole and 0.5 part of n-tetrabutylammonium bromide are added, the temperature is slowly raised to 100 ℃, esterification reaction is carried out for 1 hour under the stirring of the rotating speed of 350r/min, and the epoxy-methacrylate is obtained after the material is discharged when the acid value is less than 5mgKOH/g.
(3) An epoxy-methacrylate-silicone intermediate was prepared under the same conditions as in step (3) in example 3.
(4) 44 parts of methyl methacrylate, 33 parts of styrene, 10 parts of butyl acrylate, 2 parts of acrylic acid, 1.5 parts of di-tert-butyl peroxide and 1.5 parts of dodecyl mercaptan are mixed to obtain a mixed solution.
(5) Adding 100 parts of dipropylene glycol methyl ether and 50 parts of epoxy-methacrylate-organosilicon intermediate into a four-neck flask, heating to 145 ℃, dropwise adding the mixed solution under stirring at the rotating speed of 350r/min, dropwise adding for 6 hours in total, heating to 150 ℃, performing free radical polymerization for 2 hours, finally cooling to 65 ℃, dropwise adding 2 parts of N, N-dimethylethanolamine for neutralization for 0.5 hour, salifying, and filtering to obtain a final product: waterborne epoxy/silicone/acrylate composite resin sample # 6.
Example 7
(1) A hydrolysate of the organosilicon coupling agent having a viscosity of 350 mPas (25 ℃) was prepared under the same conditions as in step (1) of example 1.
(2) Under the protection of nitrogen, 40 parts of epoxy resin E-51 and 15 parts of methacrylic acid are mixed in a four-neck flask, 0.2 part of hydroquinone and 0.4 part of n-tetrabutylammonium bromide are added, the temperature is slowly increased to 90 ℃, the esterification reaction is carried out for 2 hours under the stirring of the rotating speed of 350r/min, and the epoxy-methacrylate is prepared after the acid value is less than 5mgKOH/g.
(3) An epoxy-methacrylate-silicone intermediate was prepared under the same conditions as in step (3) in example 1.
(4) After 40 parts of methyl methacrylate, 30 parts of styrene, 10 parts of butyl acrylate, 3 parts of acrylic acid, 0.6 part of dicumyl peroxide, 0.6 part of tert-butyl peroxybenzoate and 1 part of dodecyl mercaptan were mixed, a mixed solution was obtained.
(5) Adding 100 parts of dipropylene glycol methyl ether and 50 parts of epoxy-methacrylate-organosilicon intermediate into a four-neck flask, heating to 140 ℃, dropwise adding the mixed solution under stirring at the rotating speed of 350r/min, dropwise adding for 5 hours in total, heating to 150 ℃, performing free radical polymerization for 2 hours, finally cooling to 65 ℃, dropwise adding 3 parts of N, N-dimethylethanolamine for neutralization for 0.5 hour, salifying, and filtering to obtain a final product: waterborne epoxy/silicone/acrylate composite resin sample # 7.
Example 8
(1) A hydrolysate of the organosilicon coupling agent having a viscosity of 400 mPas (25 ℃) was prepared under the same conditions as in step (1) of example 2.
(2) Under the protection of nitrogen, 45 parts of epoxy resin E-51 and 17 parts of methacrylic acid are mixed in a four-neck flask, 0.1 part of hydroquinone, 0.7 part of p-methoxyphenol, 0.6 part of p-hydroxyanisole and 0.45 part of n-tetrabutylammonium bromide are added, the temperature is slowly raised to 95 ℃, the esterification reaction is carried out for 1.5 hours under the stirring of the rotating speed of 350r/min, and the epoxy-methacrylate is prepared after the material is discharged when the acid value is less than 5mgKOH/g.
(3) An epoxy-methacrylate-silicone intermediate was prepared under the same conditions as in step (3) in example 2.
(4) After 45 parts of methyl methacrylate, 30 parts of styrene, 5 parts of butyl acrylate, 3 parts of acrylic acid, 2.4 parts of dicumyl peroxide, 2 parts of tert-butyl peroxybenzoate and 2 parts of dodecyl mercaptan were mixed, a mixed solution was obtained.
(5) Adding 90 parts of dipropylene glycol methyl ether and 50 parts of epoxy-methacrylate-organosilicon intermediate into a four-neck flask, heating to 143 ℃, dropwise adding the mixed solution under stirring at the rotating speed of 350r/min, dropwise adding for 5.5 hours in total, heating to 150 ℃, performing free radical polymerization for 2 hours, finally cooling to 65 ℃, dropwise adding 3 parts of N, N-dimethylethanolamine for neutralizing for 1 hour, salifying, and filtering to obtain a final product: waterborne epoxy/silicone/acrylate composite resin sample # 8.
Example 9
(1) A hydrolysate of the organosilicon coupling agent having a viscosity of 200 mPas (25 ℃) was prepared under the same conditions as in step (1) of example 3.
(2) Under the protection of nitrogen, 50 parts of epoxy resin E-51 and 19 parts of methacrylic acid are mixed in a four-neck flask, 0.25 part of p-methoxyphenol and 0.5 part of n-tetrabutylammonium bromide are added, the temperature is slowly increased to 100 ℃, the esterification reaction is carried out for 1 hour under the stirring of the rotating speed of 350r/min, and the epoxy-methacrylate is prepared after the acid value is less than 5mgKOH/g.
(3) An epoxy-methacrylate-silicone intermediate was prepared under the same conditions as in step (3) in example 3.
(4) 44 parts of methyl methacrylate, 33 parts of styrene, 10 parts of butyl acrylate, 5 parts of acrylic acid, 1.2 parts of di-tert-butyl peroxide, 1.2 parts of dicumyl peroxide, 1.2 parts of tert-butyl peroxybenzoate and 3 parts of dodecyl mercaptan are mixed to obtain a mixed solution.
(5) Adding 80 parts of dipropylene glycol methyl ether and 50 parts of epoxy-methacrylate-organosilicon intermediate into a four-neck flask, heating to 145 ℃, dropwise adding the mixed solution under stirring at the rotating speed of 350r/min, dropwise adding for 6 hours in total, heating to 150 ℃, performing free radical polymerization for 2 hours, finally cooling to 65 ℃, dropwise adding 5 parts of N, N-dimethylethanolamine for neutralization for 1 hour, salifying, and filtering to obtain a final product: waterborne epoxy/silicone/acrylate composite resin sample # 9.
The water-based epoxy/silicone/acrylate composite resin samples No. 1-9 obtained in examples 1-9 were tested for water resistance, water solubility, rust return, and gloss, and compared with a commercially available ordinary water-based acrylic resin (water-based acrylic resin aqueous solution type: PQ 673), and the test structures are shown in Table 1.
TABLE 1
| Name (R) | Water resistance (boiling water 1 h) | Water solubility | Glossiness (60 degree) | Return rust test |
| Resin sample No. 1 | Qualified | 0.93 | 92 | Non-return rust |
| Resin sample No. 2 | Qualified | 0.97 | 93 | Non-return rust |
| Resin sample No. 3 | Qualified | 0.69 | 96 | Non-return rust |
| Resin sample No. 4# | Qualified | 0.62 | 94 | Non-return rust |
| Resin sample No. 5 | Qualified | 0.83 | 95 | Non-return rust |
| Resin sample No. 6 | Qualified | 0.67 | 95 | Non-return rust |
| Resin sample 7# | Qualified | 0.78 | 92 | Non-return rust |
| Resin sample No. 8# | Qualified | 0.85 | 93 | Non-return rust |
| Resin sample 9# | Qualified | 1.01 | 94 | Non-return rust |
| Common water-based acrylic resin on the market | Fail to be qualified | 0.60 | 88 | Back rust |
As shown in Table 1, compared with the common water-based acrylic resin on the market, the water-based epoxy/silicone/acrylate composite resin prepared by the invention has better water resistance, no rust return, better water solubility and higher glossiness, and is suitable for preparing coatings for outdoor use, in particular engineering mechanical paints.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention. Those skilled in the art can make various changes, modifications and equivalent arrangements, which are equivalent to the embodiments of the present invention, without departing from the spirit and scope of the present invention, and which may be made by utilizing the techniques disclosed above; meanwhile, any changes, modifications and variations of the above-described embodiments, which are equivalent to those of the technical spirit of the present invention, are within the scope of the technical solution of the present invention.
Claims (9)
1. A compound or salt thereof, wherein the compound has a chemical structure according to formula I:
in the above-mentioned structural formula, the compound,
R 1 is composed of
Wherein n is 1 ＞0，n 2 ＞0；
The salt is selected from the group consisting of a deprotonated compound and a salt of an ammonium cation;
the ammonium cation is a compound having the following chemical formula:
2. the method for preparing a compound according to claim 1, wherein a polymerization reagent comprising methyl methacrylate (11), styrene (12), butyl acrylate (13), acrylic acid (14) is added to the epoxy-methacrylate-silicone intermediate (1) to perform radical polymerization to obtain the desired compound (3);
the reaction route is as follows:
in the above-mentioned reaction scheme, the reaction,
R 1 is composed of
Wherein n is 1 ＞0，n 2 ＞0。
3. The preparation process according to claim 2, characterized in that the epoxy-methacrylate-silicone intermediate (1) is prepared by the following steps:
a) Carrying out hydrolysis reaction on the organosilicon coupling agent (6) to obtain an organosilicon coupling agent hydrolysate (7);
the reaction route is as follows:
b) Carrying out esterification reaction on epoxy resin (8) and methacrylic acid (9) to obtain epoxy-methacrylate (10);
the reaction route is as follows:
c) Reacting an epoxy group of the organic silicon coupling agent hydrolysate (7) with epoxy-methacrylate (10) to obtain an epoxy-methacrylate-organic silicon intermediate (1);
the reaction route is as follows:
in the above-mentioned reaction scheme, the reaction,
r is one of methyl or ethyl;
R 1 is composed of
4. The method of claim 3, wherein step A) comprises any one or more of the following conditions:
a1 The organosilicon coupling agent (6) is selected from one or two of trimethylethoxysilane or trimethylmethoxysilane;
a2 In the hydrolysis reaction, the weight ratio of the organosilicon coupling agent (6) to water is 20-27:6-8;
a3 The reaction temperature of the hydrolysis reaction is 0 to 15 ℃.
5. The method of claim 3, wherein step B) comprises any one or more of the following conditions:
b1 The epoxy resin (8) is epoxy resin E-51;
b2 In the esterification reaction, the weight ratio of the added epoxy resin (8) to the added methacrylic acid (9) is 30-60:10-20 parts of;
b3 And) adding a polymerization inhibitor and n-tetrabutylammonium bromide in the esterification reaction, wherein the weight ratio of the epoxy resin (8) to the polymerization inhibitor and the n-tetrabutylammonium bromide is 30-60:0.10-0.30:0.3-0.6; the polymerization inhibitor is one or more of hydroquinone, p-methoxyphenol and p-hydroxyanisole;
b4 The reaction temperature of the esterification reaction is 90 to 100 ℃.
6. The method of claim 3, wherein step C) comprises any one or more of the following conditions:
c1 In the reaction of the epoxy groups, the organosilicon coupling agent hydrolysate (7) and the epoxy-methacrylate (10) are added in a weight ratio of 21-26:40-50;
c2 Tetraisobutyl titanate is also added in the reaction of the epoxy groups, and the weight ratio of the organic silicon coupling agent hydrolysate (7) to the tetraisobutyl titanate is 21-26:0.10-0.35;
c3 ) the reaction temperature of the epoxy group reaction is 140 to 150 ℃.
7. The method of claim 2, further comprising any one or more of the following conditions:
d1 In the radical polymerization reaction, the weight ratio of the epoxy-methacrylate-organosilicon intermediate (1) to the added methyl methacrylate (11), styrene (12), butyl acrylate (13), acrylic acid (14) is 50:30-55:20-40:4-11:1-6;
d2 The epoxy-methacrylate-silicone intermediate (1) is mixed with dipropylene glycol methyl ether, and the weight ratio of the addition of the epoxy-methacrylate-silicone intermediate (1) to dipropylene glycol methyl ether is 50:70-110;
d3 The polymerization reagent also comprises an initiator and dodecyl mercaptan, wherein the weight ratio of the methyl methacrylate (11) to the added initiator and dodecyl mercaptan is 30-55:1.0-4.0:0.5 to 4; the initiator is selected from one or more of di-tert-butyl peroxide, dicumyl peroxide or tert-butyl peroxybenzoate;
d4 The reaction temperature of the radical polymerization reaction is 148 to 152 ℃.
8. Use of a compound according to claim 1, or a salt thereof, in the preparation of a coating.
9. A composition comprising water and the compound of claim 1, or a salt thereof.
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