CN115477739A - Preparation method of epoxy active emulsifier, single-component epoxy resin aqueous dispersion and preparation method thereof - Google Patents
Preparation method of epoxy active emulsifier, single-component epoxy resin aqueous dispersion and preparation method thereof Download PDFInfo
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- CN115477739A CN115477739A CN202110597912.1A CN202110597912A CN115477739A CN 115477739 A CN115477739 A CN 115477739A CN 202110597912 A CN202110597912 A CN 202110597912A CN 115477739 A CN115477739 A CN 115477739A
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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
- C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
- C08G59/1411—Polycondensates modified by chemical after-treatment with inorganic compounds containing sulfur
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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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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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
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
Abstract
The invention relates to a preparation method of an epoxy active emulsifier and a preparation method of a single-component epoxy resin aqueous dispersion. Then, an acrylate polymer is grafted in epoxy resin through chemical bonds, and finally, dopamine is selectively added to react with the epoxy resin modified by the acrylate.
Description
Technical Field
The invention belongs to the field of coatings and adhesives, and relates to an epoxy active emulsifier, a single-component epoxy resin aqueous dispersion and a preparation method thereof.
Background
The traditional epoxy resin coating is generally a solvent type, most of organic volatile matters in the traditional epoxy resin coating belong to flammable, explosive and toxic substances, are directly discharged into the atmosphere, can generate light smoke or form acid rain under ultraviolet radiation, and seriously pollute the environment. Prolonged inhalation of such toxic gases by humans can lead to respiratory diseases, fatigue, memory loss or other neurological diseases.
In recent years, laws and regulations concerning environmental pollution restrictions have been followed, in which there are two major problems concerning the emission restrictions of VOCs (content of organic volatile matter in paint) and HAPs (pollutants in harmful air) in the paint industry. This limits the production of solvent-borne coatings, which account for about 53% of the world's coating industry production. Nowadays, the development of coatings towards high-solid and water-based coatings has become a consensus in the coating world, zero VOC or low VOC, and the water-based development of materials has become a research direction of novel materials. The water-based epoxy coating has the advantages of low VOC content, small smell, safe use, water cleaning, mature process technology, environmental protection and energy conservation meeting and the like, and quickly becomes an important development direction of modern coatings.
The traditional water-based epoxy resin coating mainly comprises two components: one component is an epoxy resin water dispersion system (emulsion); the other component is amine curing agent. Aqueous two-component epoxy coatings have found many applications in the market, such as high-performance container primers, primers and intermediate paints for construction machinery and rail transit, architectural coatings, equipment primers, industrial floor coatings, transportation primers, automotive repair primers, and industrial repair primers.
At present, a single-component system widely applied to the field of light corrosion prevention of automobiles mainly uses an acrylic dispersion, but the single-component system has poor corrosion prevention performance, needs high-frequency repeated coating of an anticorrosive paint and brings great troubles to downstream use.
As the aqueous epoxy resin, for example, it is known to prepare an epoxy emulsion by a phase inversion method, mechanical grinding or the like using a conventional nonionic surfactant (also referred to as a nonionic epoxy emulsifier) by means of a mixer, a ball mill or the like. The obtained emulsion has the defects of difficult dispersion and poor water resistance of the emulsion due to large using amount of the emulsifier and high system viscosity; the emulsion system is unstable due to a large amount of free emulsifier, latex particles are easy to aggregate and precipitate, and the storage time is short.
To ameliorate the above disadvantages, publication CN 103249777A proposes to use the reaction of an epoxy composition with an amide composition to prepare an improved epoxy functional nonionic surfactant followed by phase inversion to prepare an aqueous epoxy dispersion with low emulsifier content. The dispersion is matched with a curing agent with a similar structure for use, so that an ideal corrosion resistance effect can be achieved, but the emulsifier has too strong hydrophobicity, so that the particle size of the dispersion is larger (800-950 nm), the stability of the dispersion is poor, and the storage stability of the product is influenced because the 50 ℃ heat storage is less than 10 days.
The patent publication CN102933634A proposes a method for preparing a nonionic reactive emulsifier. The method can effectively improve the storage stability of the emulsion, and the nonionic active emulsifier obtained by synthesis participates in the reaction in the process of curing and film forming, thereby improving the water resistance of the coating. However, the emulsifier in the system has too strong hydrophobicity, so that the dosage of the emulsifier is large, the water resistance is poor, and the foaming is serious.
The patent publication CN 1324384A proposes that epoxy resin is dispersed by using a low-temperature and high-temperature nonionic surfactant compounding mode to obtain an emulsion with good storage stability under high-temperature and low-temperature conditions. The above dispersion has a large amount of emulsifier (about 20 wt%), and after coating, since the emulsifier does not participate in the reaction, a large amount of emulsifier is liberated from the system, so that corrosion resistance and water resistance are greatly affected.
In order to reduce the particle size, patent publication CN104520356B further mentions the use of ionic and nonionic emulsifiers for compounding to reduce the particle size of the dispersion. The ionic emulsifier and the nonionic emulsifier are compounded for use, and the small-particle-size dispersion (400-800 nm) can be obtained by using a small amount of the emulsifier. However, the two emulsifiers used in the method are both non-reactive emulsifiers, the emulsifiers do not participate in the reaction in the film forming process, free emulsifiers exist in the system, the resistance and the storage stability of a paint film are influenced, the preparation process is too complex, and the industrial production is difficult.
An acrylic acid modified epoxy resin system is mainly formed by grafting reaction of methylene and acrylic acid in epoxy resin under the condition of catalyst existence, then sodium hydroxide is used for neutralizing acrylic acid to form sodium carboxylate plasma groups, and then single-component epoxy resin aqueous dispersion is obtained through emulsification and dispersion.
Based on the defects of the prior art, an ionic emulsifier needs to be developed for an epoxy resin dispersion, and has the advantages of excellent corrosion and water resistance, good epoxy resin dispersion effect and good stability of the epoxy resin aqueous dispersion.
Disclosure of Invention
The invention aims to provide a preparation method of an epoxy active emulsifier, the obtained emulsifier is a sulfonate ionic active emulsifier, the emulsifying and dispersing effects on epoxy resin are good, the emulsion stability is high, the influence of a sulfonate system on the corrosion resistance of a resin paint film is small, and the adhesion of the paint film to a base material is promoted.
The invention also aims to provide the single-component epoxy resin aqueous dispersion and the preparation method thereof, and the obtained single-component epoxy resin aqueous dispersion has the characteristics of good stability, no need of curing agent crosslinking, excellent corrosion resistance and better impact resistance, and can be used in the fields of coatings, adhesives and the like.
It has been found that 1, in the reaction with an epoxy resin, an aminocarboxylic acid type emulsifier which is frequently used in the field of other water-based paints often causes a gelation phenomenon due to the carboxyl group participating in the reaction, and the reaction cannot be controlled. The sulfamic acid/sulfamate which is generally used has a high melting point (> 300 ℃ C.), and is hardly reacted with an epoxy resin even under very severe conditions. However, it has been surprisingly found that an aqueous solution of sulfamic acid and/or sulfamic acid salt can be reacted with epoxy resin smoothly under mild conditions to obtain the ideal ionic reactive emulsifier. However, after the emulsifier is prepared into the epoxy resin aqueous dispersion containing the emulsifier, the storage temperature is higher than 30 ℃, and the storage time is longer than 30 days, the tertiary amine groups in the emulsifier structure still catalyze the epoxy group reaction, so that the molecular weight of the epoxy resin is increased (verified in GPC), the emulsion stability is damaged, and the epoxy resin is seriously even crosslinked into gel, and the reaction can be delayed but cannot be completely avoided by adding a proper polymerization inhibitor; 2. amine-containing organic substances such as amino carboxylic acid or sulfonic acid react with the epoxy resin, and the structure of a product is difficult to accurately control; 3. amine-containing organic substances such as aminocarboxylic acid or sulfonic acid and the like are generally high in price, so that the cost of the prepared emulsifier is high, the application of the emulsifier in the field of waterborne epoxy is greatly limited, and the waterborne metal corrosion prevention is not facilitated. In order to solve the problems, the invention creatively provides that sulfur dioxide reacts with epoxy resin in the presence of a potassium hydroxide/sodium water solution to prepare an ideal stable sulfonate ion epoxy active emulsifier, and the emulsifier does not contain amino or tertiary amine groups which can react with epoxy groups or can catalyze self polymerization of the epoxy groups, so that the emulsifier structure can be stably stored for a long time no matter at room temperature or not higher than 60 ℃, so that the industrial large-scale production of the emulsifier is possible, and the epoxy resin dispersion obtained by using the emulsifier has excellent stability, and the instability phenomena such as coagulation and the like can be prevented from occurring in 2 months under the storage condition of 50 ℃; meanwhile, compared with sulfamic acid or carboxylate, the sulfur dioxide is extremely low in price, so that the cost of the epoxy active emulsifier is greatly reduced, the cost of the aqueous epoxy dispersion is reduced, and the aquosity of the epoxy resin in the field of metal corrosion prevention can be greatly promoted.
In order to achieve one aspect of the above object, the present invention provides the following technical solutions:
the preparation method of the epoxy active emulsifier comprises the step of reacting sulfur dioxide serving as a first reaction raw material with epoxy resin in the presence of a sodium/potassium hydroxide aqueous solution to obtain the stable sulfonate ion active emulsifier, wherein the obtained epoxy active emulsifier contains at least one epoxy group from the epoxy resin and at least one sodium/potassium sulfonate group in a molecule.
In the invention, the molar ratio of the total epoxy groups provided by the epoxy resin to sulfur dioxide in the reaction system for preparing the epoxy reactive emulsifier is more than 1, preferably 2-20; the molar ratio of sulfur dioxide to sodium/potassium hydroxide is 1:0.1-1:1, preferably 1.5-1:1.
The presence of water is required in the reaction system in order to smoothly proceed the reaction. In one embodiment, the mass ratio of water (from the aqueous sodium/potassium hydroxide solution) to the sulfur dioxide is not less than 1.
In one embodiment, during the preparation of the emulsifier, sulfur dioxide is passed into an epoxy resin system containing an aqueous sodium/potassium hydroxide solution, wherein the epoxy resin is reacted with an active hydrogen ring-opening epoxy group optionally in the presence of a solvent for reducing the viscosity of the reaction system at a temperature of 50 to 150 ℃, such as 70, 80, 90, 110, 120, 130 or 140 ℃, to obtain the stable sulfonate ion reactive emulsifier, preferably at a temperature of 60 to 100 ℃, more preferably 80 to 100 ℃. In the present invention, "optional" means that it may or may not be present. Solvents useful for reducing the viscosity of the reaction system are conventional and well known in the art and may be, for example, n-butanol, isopropanol, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol propyl ether, benzyl alcohol, acetone, methyl ethyl ketone, and the like. The dosage of the solvent is not more than 2 times of the mass of the epoxy resin in the reaction system.
In the present invention, the epoxy resin contains at least two epoxy groups in the molecule, and these epoxy resins may be saturated or unsaturated, and may be aliphatic, cycloaliphatic, aromatic or heterocyclic epoxy resins, and may further contain a hydroxyl group. They may also contain other substituents which do not cause interfering side reactions under the mixing and reaction conditions, for example alkyl or aryl substituents, ether groups and the like. Preferably, the epoxy resin has an epoxy value of not more than 0.6, preferably not more than 0.55, such as 0.05 to 0.6, preferably 0.1 to 0.55, further preferably polyglycidyl ether.
Preferably, the commonly used polyglycidyl ether epoxy resins may be glycidyl ethers of polyhydric phenols or polyhydric alcohols, such as resorcinol, hydroquinone, 2,2-bis (4 ' -hydroxyphenyl) -propane (bisphenol A), isomer mixtures of dihydroxydiphenyl methane (bisphenol F), 4,4' -dihydroxydiphenylcyclohexane, 4,4' -dihydroxy-3,3 ' -dimethyldiphenylpropane, 4,4' -dihydroxybiphenyl, 4,4' -dihydroxybenzophenone, bis (4 ' -hydroxyphenyl) -1,1-ethane, bis (4 ' -hydroxyphenyl) -1,1-isobutane, bis (4 ' -hydroxy-tert-butylphenyl) -2,2-propane, bis (2-hydroxynaphthyl) -methane, 1,5-dihydroxynaphthalene, tris (4-hydroxyphenyl) -methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, and brominated products of the foregoing.
Polyglycidyl ethers of polyhydric alcohols can also be used, such as ethylene glycol-1,2-diglycidyl ether, propylene glycol-1,2-diglycidyl ether, propylene glycol-1,3-diglycidyl ether, butanediol diglycidyl ether, pentanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, higher polyoxyalkylene glycol diglycidyl ethers (such as higher polyoxyethylene glycol diglycidyl ether and polyoxypropylene glycol diglycidyl ether, mixed polyoxyethylene-propylene glycol diglycidyl ether), polyoxybutylene glycol diglycidyl ether, diglycidyl ethers of glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, polyglycidyl ethers of sorbitol, cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane, and diglycidyl ethers of 2,2-bis (4-hydroxycyclohexyl) propane, castor oil, or polyglycidyl ethers of triglycidyl tris (2-hydroxyethyl) isocyanurate.
In addition, the epoxy resin may also be a polyglycidyl ester of a polycarboxylic acid which is produced by reacting epichlorohydrin or a similar epoxy compound with an aliphatic, cycloaliphatic or aromatic polycarboxylic acid which is oxalic acid, succinic acid, adipic acid, glutaric acid, phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 2,6-naphthalenedicarboxylic acid, and a high-carbon dicarboxylic acid, dimerized or trimerized linolenic acid, or the like. Preferably the diglycidyl esters of adipic acid, phthalic acid and hexahydrophthalic acid.
In order to achieve another aspect of the above object, the present invention adopts the following technical solutions:
a single-component epoxy resin aqueous dispersion and a preparation method thereof are disclosed: slowly dripping acrylic ester into the emulsifier at 90-120 ℃ in the presence of a catalyst, reacting for 4-7 h at constant temperature, optionally adding dopamine, reacting for 1-3 h, and finally slowly dripping deionized water into the system under the high-speed shearing of 1000-1500 r/min to obtain the single-component epoxy resin aqueous dispersion.
In the invention, the catalyst is a thermal initiation type polymerization initiator, such as one or more of azodiisobutyronitrile, ammonium persulfate, potassium persulfate, benzoyl peroxide and benzoyl peroxide tert-butyl ester. Acrylates include, but are not limited to, butyl acrylate, hydroxyethyl acrylate, and the like. The mass ratio of the emulsifier solid (namely, water and organic solvent are removed) to the acrylate is 5:5-9:1, preferably 7:3-9:1. The addition amount of the dopamine is 0-5%, preferably 0.5-3% of the total mass of the emulsifier and the acrylate.
In one embodiment, the method of making results in a one-part epoxy resin aqueous dispersion having a mass ratio of resin solids to solvent of 2:8-7:3, preferably 4:6-7:3; wherein the solvent comprises water and optionally an organic solvent that can be used to dissolve the epoxy resin system. The mass ratio of the organic solvent (which can be derived from the solvent in the epoxy reactive emulsifier) to the water is 0-1:1, preferably 0-1:2; the organic solvent is one or a mixture of more of n-butyl alcohol, isopropanol, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol propyl ether, benzyl alcohol, acetone and butanone.
It will be understood by those skilled in the art that other adjuvants, such as epoxy reactive diluents (added in an amount of 0 to 20% of the dispersion, such as C8-C14 glycidyl ether compositions, phenyl glycidyl ethers, butyl glycidyl ethers), thickeners (e.g., U905, U300, etc., added in an amount of 0 to 5% by weight of the dispersion; defoamers such as foamstar2410, 902w, BYK-024, -033, -028, A1001, etc., added in an amount of 0 to 1% by weight of the dispersion, and other conventional adjuvants, are also typically added to the dispersion, and their addition is well known in the art and will not be described herein.
The invention has the beneficial effects that:
1. the ideal stable sulfonate ion epoxy active emulsifier is prepared by reacting sulfur dioxide with epoxy resin in the presence of a sodium hydroxide/potassium hydroxide aqueous solution, and the emulsifier structure does not contain an amino group or a tertiary amine group which can react with an epoxy group or can catalyze the self polymerization of the epoxy group, so that the emulsifier structure can be stably stored for a long time no matter at room temperature or not higher than 60 ℃, the industrial large-scale production of the emulsifier becomes possible, the epoxy resin dispersoid obtained by using the emulsifier has excellent stability, and the instability phenomena such as coagulation and the like can be prevented from occurring for 2 months under the storage condition of 50 ℃ of the dispersoid; compared with sulfamic acid or carboxylate, the use of sulfur dioxide greatly reduces the cost of the epoxy active emulsifier, and then reduces the cost of the aqueous epoxy dispersion, thereby greatly promoting the aquosity of the epoxy resin in the field of metal corrosion prevention.
2. The stable active emulsifier containing the sulfonate group utilizes the acrylate modified single-component epoxy dispersion on the basis, is different from other acrylic modified epoxy, utilizes tertiary amine and acrylic acid as hydrophilic group emulsified resin, does not introduce an acrylic acid structure, and utilizes the sulfonate group as the hydrophilic group to emulsify to obtain the single-component epoxy aqueous dispersion.
3. According to the invention, the dopamine modified single-component epoxy dispersoid has high adhesion of multiple substrates, meanwhile, the phenolic hydroxyl structure of the dopamine modified single-component epoxy dispersoid can catalyze epoxy groups to generate self-crosslinking at higher temperature, and the paint film has the characteristic of excellent corrosion resistance due to double functions of the dopamine modified single-component epoxy dispersoid, has excellent impact resistance, and can be used in the fields of coatings, adhesives and the like.
Detailed Description
The present invention is described in further detail below by way of examples, but it should not be construed that the scope of the present invention is limited to the examples below. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
The following examples/comparative examples use the following sources of materials:
TABLE 1
| Name of substance | Form of the composition | Suppliers of goods | CAS number | Molecular weight |
| Sulfur dioxide | Gas (es) | Wanhua chemistry | 7446-09-5 | 64 |
| Sodium hydroxide | Solid body | Aladdin | 1310-73-2 | 40 |
| Potassium hydroxide | Solid body | Aladdin | 1310-58-3 | 56 |
| Acrylic acid butyl ester | Liquid, method for producing the same and use of the same | Wanhua chemistry | 141-32-2 | 128 |
| Epoxy resin (E12/E44/E51) | Solid/liquid | Linglin chemical | 25068-38-6 | 1400/460/380 |
| Methacrylic acid methyl ester | Liquid, method for producing the same and use of the same | Wanhua chemistry | 80-62-6 | 100 |
| Benzoyl peroxide | Solid body | Qilu petrochemical | 94-36-0 | 242 |
| Propylene glycol methyl ether | Liquid, method for producing the same and use of the same | Dow's disease | 107-98-2 | 90 |
| Acrylic acid | Liquid, method for producing the same and use thereof | Wanhua chemistry | 79-10-7 | 72 |
| Dimethylethanolamine | Liquid, method for producing the same and use thereof | Dow's disease | 108-01-0 | 89 |
The following test methods were used in the examples of the present invention:
(1) Dispersion stability testing and shelf life prediction: GT/T5208;
(2) Neutral salt spray resistance: GB/T1771;
(3) Impact resistance: GB/T1732;
(4) Adhesion force: GB/T9286.
In the following examples/comparative examples, the reagents used were all analytical grade, unless otherwise specified; the content is a mass content unless otherwise specified.
Preparation of epoxy active emulsifier:
example 1a: 32g of sulfur dioxide is added into a mixed system of 700g of epoxy resin E12, 400g of propylene glycol methyl ether and 40g of sodium hydroxide aqueous solution (with the concentration of 50 percent), the temperature is slowly increased to 100 ℃, the mixture is refluxed and stirred at constant temperature for reaction for about 1 hour, and the epoxy value (determined by a hydrochloric acid-acetone method, the same applies below) is tested to basically reach the theoretical epoxy value (0.043 mol/100 g), so that the epoxy active emulsifier is obtained.
Example 1b: adding 12.8g of sulfur dioxide into a mixed system of 460g of epoxy resin E44, 100g of propylene glycol methyl ether and 11.2g of potassium hydroxide aqueous solution (with the concentration of 50%), slowly heating to 80 ℃, carrying out reflux stirring reaction at constant temperature for about 1h, and testing that the epoxy value basically reaches the theoretical epoxy value (0.33 mol/100 g), thereby obtaining the epoxy active emulsifier.
Example 1c: 6.4g of sulfur dioxide is added into a mixed system of 380g of epoxy resin E51 and 8g of sodium hydroxide aqueous solution (with the concentration of 50 percent), the temperature is slowly increased to 60 ℃, the reaction is carried out for about 1 hour under constant temperature reflux and stirring, and the epoxy value is tested to basically reach the theoretical epoxy value (0.48 mol/100 g), so as to obtain the epoxy active emulsifier.
Preparation of one-component epoxy resin aqueous dispersions
Example 2a: 1172g of the active emulsifier obtained in the embodiment 1a is placed in a flask, the temperature in the flask is maintained at 90 ℃, 9.6g of benzoyl peroxide, 200g of butyl acrylate and 122g of methyl methacrylate are mixed, slowly dropped into the flask, and transferred into a dispersing cup after reacting at constant temperature for 4 hours, and 1215g of deionized water is added under the shearing of 1000r/min, so that the single-component epoxy aqueous dispersion is obtained. The dispersion was measured as follows:
the dispersion particle size was about 410nm (test instrument: zetasizer Nano ZS, test method: dispersion of dispersion in deionized water for testing, the same below);
viscosity: 1500cp (test apparatus: brookfield viscometer DV1, determination method: direct test at 25 ℃, the same applies below);
solid content: 39.6 percent.
Example 2b: putting 577.6g of the active emulsifier obtained in the embodiment 1b into a flask, maintaining the temperature in the flask at 120 ℃, mixing 4.2g of benzoyl peroxide with 32.4g of butyl acrylate and 20g of methyl methacrylate, slowly dripping into the flask, reacting at constant temperature for 6 hours, transferring into a dispersion cup, and adding 119g of deionized water under the shearing of 1500r/min to obtain the single-component epoxy aqueous dispersion. The dispersion was measured as follows:
the dispersion particle size was about 370nm;
viscosity: 900cp;
solid content: 70.0 percent.
Example 2c: 1172g of the active emulsifier obtained in the embodiment 1a is placed in a flask, the temperature in the flask is maintained at 90 ℃, 9.6g of benzoyl peroxide, 200g of butyl acrylate and 122g of methyl methacrylate are mixed, slowly dripped into the flask, after constant temperature reaction for 4 hours, 32g of dopamine is added, after reaction for 3 hours, the mixture is transferred into a dispersion cup, and 1215g of deionized water is added under the shearing of 1000r/min, so that the single-component epoxy aqueous dispersion is obtained.
The dispersion was measured as follows:
the dispersion particle size was about 430nm;
viscosity: 1700cp;
solid content: 40.7 percent.
Example 2d: 394.4g of the reactive emulsifier from example 1c are placed in a flask, the temperature in the flask is maintained at 120 ℃, 0.1g of benzoyl peroxide is mixed with 58.6g of butyl acrylate and 39g of methyl methacrylate, the mixture is slowly dripped into the flask, after the constant temperature reaction for 7 hours, the mixture is transferred into a dispersion cup, and 1134g of deionized water is added under the shearing of 1500r/min, thus obtaining the single-component epoxy aqueous dispersion. The dispersion was measured as follows:
the dispersion particle size is about 380nm;
viscosity: 700cp;
solid content: 30.0 percent.
Example 2e: 1172g of the active emulsifier obtained in the embodiment 1a is placed in a flask, the temperature in the flask is maintained at 90 ℃, 9.6g of benzoyl peroxide, 200g of butyl acrylate and 122g of methyl methacrylate are mixed, slowly dripped into the flask, reacted for 4 hours at constant temperature, 53g of dopamine is added, after 3 hours of reaction, the mixture is transferred into a dispersion cup, and 1215g of deionized water is added under the shearing of 1000r/min, so that the single-component epoxy aqueous dispersion is obtained.
The dispersion was measured as follows:
the dispersion particle size was about 460nm;
viscosity: 1900cp;
solid content: 40.8 percent.
Example 2f: 1172g of the active emulsifier obtained in the embodiment 1a is placed in a flask, the temperature in the flask is maintained at 90 ℃, 9.6g of benzoyl peroxide, 200g of butyl acrylate and 122g of methyl methacrylate are mixed, slowly dripped into the flask, 5.4g of dopamine is added after constant temperature reaction for 4 hours, the mixture is transferred into a dispersion cup after 3 hours of reaction, 1215g of deionized water is added under the shearing of 1000r/min, and the single-component epoxy aqueous dispersion is obtained.
The dispersion was measured as follows:
the dispersion particle size was about 430nm;
viscosity: 1700cp;
solid content: 39.8 percent.
Comparative example 2g: mixing 700g of epoxy resin E12 and 400g of propylene glycol methyl ether, injecting the mixture into a flask, maintaining the temperature in the flask at 90 ℃, mixing 9.6g of benzoyl peroxide with 52g of acrylic acid, 200g of butyl acrylate and 122g of methyl methacrylate, slowly dripping the mixture into the flask, reacting at constant temperature for 4 hours, adding 64g of dimethylethanolamine, reacting at 50 ℃ for 1 hour, transferring the mixture into a dispersion cup, and adding 1147g of deionized water under the shearing of 1000r/min to obtain the single-component epoxy aqueous dispersion. The dispersion was measured as follows:
the dispersion particle size was about 390nm;
viscosity: 1130cp;
solid content: 40.0 percent.
Performance testing of the one-component epoxy resin aqueous dispersions:
TABLE 2
The waterborne epoxy anti-rust paint prepared according to the table 2 is coated on a carbon steel plate with polished surface by the thickness of 70-80 mu m, and is baked for 30 minutes at 80 ℃ after being leveled for 10-15 minutes at room temperature, and is cured for 7 days at 25 ℃ to obtain a single-component epoxy paint film. The neutral salt spray resistance is determined according to the GB/T1771 standard. Within the specified test time (200 h), the blank of the plate surface is required to be rustless and not to be foamed, the corrosion and foaming width diffusion at the cut of the plate surface is less than 2mm, namely 5 minutes can be defined, the blank of the plate surface is not rusty, a small amount of bubbles are formed, the corrosion and foaming width diffusion at the cut of the plate surface is less than 2mm, 4 minutes is defined, the blank of the plate surface is rusty and foamed, and the corrosion and foaming width diffusion at the cut of the plate surface is less than 2mm, and 3 minutes is defined. The results are shown in Table 3.
TABLE 3
From the comparison of the above properties, it can be seen that the one-component aqueous epoxy dispersion obtained with the sulfonic acid and/or sulfonate-containing reactive emulsifier is effective in improving the dispersion stability and improving the salt spray resistance of the product.
Claims (10)
1. The preparation method of the epoxy active emulsifier is characterized in that sulfur dioxide and epoxy resin react in the presence of a proper amount of sodium hydroxide/potassium hydroxide aqueous solution to obtain the epoxy active emulsifier.
2. The process according to claim 1, wherein the epoxy resin provides a molar ratio of the total amount of epoxy groups to sulfur dioxide of greater than 1, preferably from 2 to 20; and/or the molar ratio of sulfur dioxide to sodium/potassium hydroxide is 1:0.5-1:1.
3. The method according to claim 1 or 2, wherein the mass ratio of water to the sulfur dioxide is not less than 1.
4. A method according to any one of claims 1-3, wherein sulfur dioxide is passed into an epoxy resin system containing aqueous sodium/potassium hydroxide, wherein the epoxy group opening reaction with active hydrogen is carried out at a temperature of 50-150 ℃ optionally in the presence of a solvent for reducing the viscosity of the reaction system, preferably at a temperature of 60-100 ℃, to obtain the epoxy reactive emulsifier, wherein the solvent is one or more of n-butanol, isopropanol, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol propyl ether, benzyl alcohol, acetone, butanone.
5. The production method according to any one of claims 1 to 4, wherein the epoxy resin has at least two epoxy groups in a molecule, and preferably has an epoxy value of 0.05 to 0.6, preferably 0.1 to 0.55.
6. A method for preparing a single-component epoxy resin aqueous dispersion, which is characterized in that acrylic ester mixed with a catalyst is added into the emulsifier of any one of claims 1 to 5 at the temperature of 90-120 ℃, the mixture is reacted for 4-7 hours at constant temperature, dopamine is optionally added, the reaction lasts for 1-3 hours, and finally, water is added for dispersion under high-speed shearing, preferably under the high-speed shearing of 1000-1500 r/min, so that the single-component epoxy resin aqueous dispersion is obtained.
7. The method according to claim 6, wherein the mass ratio of the emulsifier solid to the acrylate is 5:5-9:1, preferably 7:3 to 9:1.
8. the preparation method according to claim 6 or 7, characterized in that the catalyst is a thermal initiation catalyst, preferably one or more of azobisisobutyronitrile, ammonium persulfate, potassium persulfate, benzoyl peroxide and benzoyl peroxide tert-butyl ester, and the dosage of the catalyst is 0.1-8% of the mass of the acrylic ester; and/or the acrylate is one or more of methyl acrylate, methyl methacrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl acrylate and isobornyl (meth) acrylate.
9. The method according to any one of claims 6 to 8, wherein dopamine is added in an amount of 0 to 5%, preferably 0.5 to 3%, based on the sum of the mass of the emulsifier and the mass of the acrylate.
10. The one-component epoxy resin aqueous dispersion obtained by the process according to any one of claims 6 to 9, wherein the mass ratio of resin solids to solvent is 2:8-7:3, wherein the solvent comprises water and optionally an organic solvent which can be used to dissolve the epoxy resin system; the mass ratio of the organic solvent to the water is 0-1:1, and preferably, the organic solvent is one or a mixture of n-butanol, isopropanol, propylene glycol methyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol propyl ether, benzyl alcohol, acetone and butanone.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117551273A (en) * | 2024-01-12 | 2024-02-13 | 深圳先进电子材料国际创新研究院 | Functional auxiliary agent for underfill, preparation method and application thereof |
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| GB811693A (en) * | 1956-04-19 | 1959-04-08 | Shawinigan Chem Ltd | Improvements in and relating to surface-active materials |
| GB821961A (en) * | 1955-12-05 | 1959-10-14 | Shawinigan Chem Ltd | Emulsion polymerization process and product thereof |
| US4518723A (en) * | 1982-08-05 | 1985-05-21 | Cl Industries, Inc. | Curable epoxy resin compositions and use in preparing formed, shaped, filled bodies |
| US4668745A (en) * | 1986-06-04 | 1987-05-26 | The Dow Chemical Company | Reaction products of sulfur dioxide and epoxy-containing materials |
| CN111378095A (en) * | 2018-12-29 | 2020-07-07 | 万华化学集团股份有限公司 | Emulsifier preparation method, emulsifier, epoxy resin aqueous dispersion and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB821961A (en) * | 1955-12-05 | 1959-10-14 | Shawinigan Chem Ltd | Emulsion polymerization process and product thereof |
| GB811693A (en) * | 1956-04-19 | 1959-04-08 | Shawinigan Chem Ltd | Improvements in and relating to surface-active materials |
| US4518723A (en) * | 1982-08-05 | 1985-05-21 | Cl Industries, Inc. | Curable epoxy resin compositions and use in preparing formed, shaped, filled bodies |
| US4668745A (en) * | 1986-06-04 | 1987-05-26 | The Dow Chemical Company | Reaction products of sulfur dioxide and epoxy-containing materials |
| CN111378095A (en) * | 2018-12-29 | 2020-07-07 | 万华化学集团股份有限公司 | Emulsifier preparation method, emulsifier, epoxy resin aqueous dispersion and preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117551273A (en) * | 2024-01-12 | 2024-02-13 | 深圳先进电子材料国际创新研究院 | Functional auxiliary agent for underfill, preparation method and application thereof |
| CN117551273B (en) * | 2024-01-12 | 2024-04-05 | 深圳先进电子材料国际创新研究院 | Functional auxiliary agent for underfill, preparation method and application thereof |
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