CN111171309A - Reactive emulsifier, water-based epoxy resin emulsion, preparation and application - Google Patents

Reactive emulsifier, water-based epoxy resin emulsion, preparation and application Download PDF

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CN111171309A
CN111171309A CN202010101602.1A CN202010101602A CN111171309A CN 111171309 A CN111171309 A CN 111171309A CN 202010101602 A CN202010101602 A CN 202010101602A CN 111171309 A CN111171309 A CN 111171309A
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epoxy resin
reactive emulsifier
water
emulsion
resin emulsion
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曾娟娟
韦代东
古伟斌
庄园
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GUANGZHOU CHEMICAL GROUTING COLTD CAS
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    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32Polymers modified by chemical after-treatment
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    • C08G65/333Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/3331Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic
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    • C08G59/00Polycondensates 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
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62Alcohols or phenols
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02Polyglycidyl ethers of bis-phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/04Epoxynovolacs

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Abstract

The invention belongs to the technical field of epoxy resin aquosity, and particularly relates to a reactive emulsifier, an aqueous epoxy resin emulsion, preparation and application. According to the invention, the cardanol-phenolic amine generated by condensation reaction of cardanol, paraformaldehyde and micromolecule polyamine reacts with polyethylene glycol diglycidyl ether to obtain the reactive emulsifier with the cardanol-phenolic end-capped and hydrophilic amine-polyoxyethylene ether-amine structure as the middle chain segment. Then mixing the reactive emulsifier with water to form nano-scale emulsion, and then mixing the nano-scale emulsion with epoxy resin at high speed to prepare the water-based epoxy resin emulsion. The method has the advantages of simple process flow, safe operation, mild reaction and low production cost. The prepared reactive emulsifier has good emulsifying effect, can obtain the water-based epoxy resin emulsion with good stability under the condition of introducing less hydrophilic components, and has excellent mechanical property, adhesion property, water resistance and corrosion resistance when being used as a water-based coating.

Description

Reactive emulsifier, water-based epoxy resin emulsion, preparation and application
Technical Field
The invention belongs to the technical field of epoxy resin aquosity, and particularly relates to a reactive emulsifier, an aqueous epoxy resin emulsion, preparation and application.
Background
Epoxy resin materials have excellent properties such as adhesion, chemical resistance, adhesion, water resistance, stability, and insulation, and thus are widely used in various fields such as paints, composite materials, and adhesives. However, the epoxy resin has high viscosity, is insoluble in water and is easily soluble in organic solvents, so that the traditional epoxy resin coating is solvent-based, contains a large amount of volatile and certain toxic organic solvents, and has high environmental pollution. With the enhancement of environmental awareness of people, the requirements on environment-friendly pollution-free coatings are increasing, and the preparation of environment-friendly pollution-free waterborne epoxy resin is more and more important.
The epoxy resin is made into water by two methods, one is a self-emulsifying method, also called a chemical modification method, which is to graft some hydrophilic groups on the epoxy resin, and the other is an external emulsifier method. The epoxy resin emulsion prepared by the self-emulsifying method has small particle size, but the preparation method is more complex, the controllability is poor and the raw material cost is high. The emulsifier addition method is the most common epoxy resin waterborne technology at present, and the waterborne epoxy resin coating prepared by using the non-reactive emulsifier can reduce the mechanical property, the adhesion property, the water resistance and the corrosion resistance of the coating because the emulsifier does not participate in the curing reaction, particularly the water resistance is greatly reduced, and the coating film is easy to absorb water and turn white. Therefore, it is important to develop reactive emulsifiers for preparing waterborne epoxy resin coatings.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a reactive emulsifier, and the preparation method is characterized in that phenolic amine generated by condensation reaction of cardanol, paraformaldehyde and small-molecule polyamine reacts with polyethylene glycol diglycidyl ether to obtain the lipophilic reactive emulsifier with cardanol aldehyde end capping and hydrophilic middle chain segment in an amine-polyoxyethylene ether-amine structure.
The invention also aims to provide the reactive emulsifier prepared by the preparation method.
The invention also aims to provide application of the reactive emulsifier.
The fourth object of the present invention is to provide an aqueous epoxy resin emulsion comprising the above reactive emulsifier.
The fifth object of the present invention is to provide a method for preparing the above aqueous epoxy resin emulsion.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a reactive emulsifier comprises the following steps:
(1) mixing cardanol and micromolecular polyamine; slowly adding paraformaldehyde into the mixed reactant in batches under the condition of 50-60 ℃ oil bath, and reacting for 0.5-1 h after the addition is finished; then heating to 90-100 ℃, and continuing to react for 3-4 h under the oil bath condition; after the reaction is finished, cooling the reaction system to 50-60 ℃ to stop the reaction, thereby obtaining an intermediate product, namely phenolic aldehyde amine;
(2) slowly adding polyethylene glycol diglycidyl ether to the phenolic aldehyde amine intermediate product prepared in the step (1) in batches, and reacting for 2-4 h at 50-60 ℃ after the addition is finished to obtain a reactive emulsifier;
the small molecular polyamine in the step (1) is preferably at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and polyether amine D-230;
the dosage of the micromolecule polyamine in the step (1) is preferably 1.0-1.2 times of the molar mass of cardanol;
the dosage of the paraformaldehyde in the step (1) is preferably as follows: calculated by the using amount of formaldehyde, the using amount is 1.0-1.1 times of the molar mass of cardanol;
the epoxy value of the polyethylene glycol diglycidyl ether in the step (2) is preferably 0.29-0.4;
the dosage of the polyethylene glycol diglycidyl ether in the step (2) is preferably 0.4-0.6 times of the molar mass of the micromolecular polyamine in the step (1);
a reactive emulsifier, which is prepared by the preparation method;
the application of the reactive emulsifier in the field of paint preparation;
an aqueous epoxy resin emulsion comprising the above reactive emulsifier;
the aqueous epoxy resin emulsion preferably further comprises an epoxy resin, a reactive diluent and water;
the preparation method of the waterborne epoxy resin emulsion comprises the following steps
(1) Slowly adding water into the reactive emulsifier, and stirring for 0.5-1 h at 50-60 ℃ to obtain emulsion a;
(2) diluting the epoxy resin by using an active diluent, and then preheating to 50-60 ℃ to obtain low-viscosity epoxy resin;
(3) slowly adding the emulsion a prepared in the step (1) into the low-viscosity epoxy resin prepared in the step (2) while stirring, and stirring at the rotating speed of 1500-3000 r/min for 15-30 min after the addition is finished to obtain a water-based epoxy resin emulsion;
the amount of the water used in the step (1) is preferably 4-9 times of the mass of the reactive emulsifier;
the using amount of the reactive diluent in the step (2) is preferably 10-15% of the mass of the epoxy resin;
the dosage (total dosage of the reactive diluent and the epoxy resin) of the low-viscosity epoxy resin in the step (2) is preferably 5-5.5 times of the mass of the reactive emulsifier;
the epoxy resin in the step (2) is preferably at least one of E-44, E-51 and F-51;
the reactive diluent in step (2) is preferably at least one of 692, AGE and BGE;
the solid content of the aqueous epoxy resin emulsion in the step (3) is preferably 40-60%;
the solid content of the aqueous epoxy resin emulsion in the step (3) is further preferably (50 +/-2)%;
the water-based epoxy resin emulsion is applied to the fields of waterproof anticorrosive coatings and adhesives;
the water-based epoxy resin emulsion is preferably applied to the fields of waterproof and anticorrosive coatings and adhesives of concrete, metal, woodware and the like;
the reaction principle of the method of the invention is as follows:
firstly, cardanol, paraformaldehyde and micromolecule polyamine are subjected to condensation reaction to generate phenolic aldehyde amine, secondly, the phenolic aldehyde amine is reacted with polyethylene glycol diglycidyl ether to generate an emulsifier with oleophilic two ends and hydrophilic middle chain segment, and a molecular chain of the emulsifier contains secondary amine groups which can continuously react with epoxy resin, so that the emulsifier is a reactive emulsifier.
Compared with the prior art, the invention has the following advantages and effects:
(1) the reactive emulsifier in the prior art is mostly prepared by reacting micromolecular amine with water-soluble polyether, then blocking the end by epoxy resin, and neutralizing the end by acid to form salt.
(2) The preparation method of the reactive emulsifier provided by the invention has the advantages of simple process flow and safe operation, and the production cost of the emulsifier is low because the cheap materials such as cardanol and paraformaldehyde are adopted as main raw materials.
(3) The common preparation method of the epoxy resin emulsion is a phase inversion method, namely, the epoxy resin and the emulsifier are uniformly mixed, and then water is slowly added while stirring at a high speed to realize phase inversion. Since the reactive emulsifier of the present invention can react with an epoxy resin, the epoxy resin emulsion prepared by the above conventional phase inversion method has poor stability. The preparation method of the epoxy resin emulsion provided by the invention is that the reactive emulsifier and water are uniformly mixed to prepare uniform emulsion a, and then the emulsion a is slowly added into the epoxy resin to prepare the epoxy resin emulsion by high-speed stirring. The preparation method firstly disperses the reactive emulsifier in water, the reaction probability of the emulsifier and the epoxy resin can be reduced by the water barrier effect, the high-efficiency emulsification effect of the emulsifier is kept, and finally the emulsion with good stability is obtained.
(4) The reactive emulsifier prepared by the invention has good hydrophilicity, can easily realize nanoscale dispersion in water to obtain nanoscale emulsion a, and epoxy resin emulsion particles are separated by a large amount of nanoscale emulsifier colloidal particles and are not easy to aggregate with epoxy resin emulsion prepared by high-speed stirring of the nanoscale emulsion a and the epoxy resin, so that the stability of the waterborne epoxy resin emulsion prepared by the invention is very good.
(5) The reactive emulsifier prepared by the invention can react with epoxy resin and has a toughening effect on the epoxy resin, so that after the waterborne epoxy resin emulsion prepared by the invention is compounded with an epoxy resin curing agent to form a waterborne coating, the mechanical property, the adhesion property, the water resistance and the corrosion resistance of the coating are excellent.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The starting materials described in the examples are all commercially available.
Example 1
(1) Adding 30g of cardanol (0.1mol) and 10g of diethylenetriamine (0.1mol) into a three-neck flask with a mechanical stirring paddle and a condensing tube, heating the three-neck flask to 50 ℃ in a constant-temperature oil bath, slowly adding 3g of paraformaldehyde (the dosage is 0.1mol calculated by the dosage of formaldehyde) in batches into the mixed reactant, and reacting for 1h after the addition is finished; then heating to 90 ℃, and continuing to react for 3 hours under the oil bath condition; after the reaction is finished, cooling the reaction system to 50 ℃ to stop the reaction, thereby obtaining an intermediate product, namely the phenolic aldehyde amine;
(2) slowly adding 37.5g of polyethylene glycol diglycidyl ether (with the epoxy value of 0.32 and the dosage of 0.06mol) into the phenolic aldehyde amine intermediate product prepared in the step (1) in batches, and reacting at 50 ℃ for 2h to obtain 80.5g of reactive emulsifier;
(3) slowly adding water (the amount of the water is 4 times of the mass of the reactive emulsifier, namely 322g) into the reactive emulsifier prepared in the step (2), and stirring for 1h at 50 ℃ to obtain 402.5g of emulsion a;
(4) 350g of epoxy resin E-44 was diluted with 52.5g of reactive diluent 692 and then preheated to 60 ℃ to obtain 402.5g of low viscosity epoxy resin;
(5) and (3) slowly adding the emulsion a prepared in the step (3) into the low-viscosity epoxy resin prepared in the step (4) while stirring, and stirring at the rotating speed of 1500r/min for 30min after the addition is finished to obtain the water-based epoxy resin emulsion with the solid content of 60%.
Example 2
(1) Adding 30g of cardanol (0.1mol) and 16g of triethylene tetramine (0.11mol) into a three-neck flask with a mechanical stirring paddle and a condensing tube, heating the mixture to 55 ℃ in a constant-temperature oil bath kettle, slowly adding 3.3g of paraformaldehyde (the dosage is 0.11mol calculated by the dosage of formaldehyde) in batches into the mixed reactant, and reacting for 0.5h after the addition is finished; then heating to 95 ℃, and continuing to react for 4 hours under the oil bath condition; after the reaction is finished, cooling the reaction system to 55 ℃ to stop the reaction, thereby obtaining an intermediate product, namely the phenolic aldehyde amine;
(2) slowly adding 33.5g of polyethylene glycol diglycidyl ether (with the epoxy value of 0.3 and the dosage of 0.05mol) into the phenolic aldehyde amine intermediate product prepared in the step (1) in batches, and reacting at 55 ℃ for 3h to obtain 82.8g of reactive emulsifier;
(3) slowly adding water (496.8 g, the amount of which is 6 times of the mass of the reactive emulsifier) into the reactive emulsifier prepared in the step (2), and stirring for 0.5h at 55 ℃ to obtain 579.6g of emulsion a;
(4) adopting 46g of active diluent AGE to dilute 368g of epoxy resin E-51, and then preheating to 55 ℃ to obtain 414g of low-viscosity epoxy resin;
(5) and (3) slowly adding the emulsion a prepared in the step (3) into the low-viscosity epoxy resin prepared in the step (4) while stirring, and stirring at the rotating speed of 2000r/min for 20min after the addition is finished to obtain the water-based epoxy resin emulsion, wherein the solid content of the emulsion is 50%.
Example 3
(1) Adding 30g of cardanol (0.1mol) and 27.6g of polyetheramine D-230(0.12mol) into a three-neck flask with a mechanical stirring paddle and a condensing tube, heating the three-neck flask to 60 ℃ in a constant-temperature oil bath, slowly adding 3g of paraformaldehyde (the dosage is 0.1mol) in batches into the mixed reactant, and reacting for 0.5h after the addition is finished; then heating to 100 ℃, and continuing to react for 3.5h under the oil bath condition; after the reaction is finished, cooling the reaction system to 60 ℃ to stop the reaction, thereby obtaining an intermediate product, namely the phenolic aldehyde amine;
(2) slowly adding 25g of polyethylene glycol diglycidyl ether (with an epoxy value of 0.4 and the using amount of 0.05mol) into the phenolic aldehyde amine as the intermediate product prepared in the step (1) in batches, and reacting at 60 ℃ for 4 hours to obtain 85.6g of reactive emulsifier;
(3) slowly adding water (the amount of water is 9 times of the mass of the reactive emulsifier, namely 770.4g) into the reactive emulsifier prepared in the step (2), and stirring at 60 ℃ for 0.5h to obtain 856g of emulsion a;
(4) 389g of epoxy resin F-51 is diluted by 39g of active diluent BGE, and then preheated to 50 ℃ to obtain 428g of low-viscosity epoxy resin;
(5) and (3) slowly adding the emulsion a prepared in the step (3) into the low-viscosity epoxy resin prepared in the step (4) while stirring, and stirring for 15min at the rotating speed of 3000r/min after the addition is finished to prepare the water-based epoxy resin emulsion, wherein the solid content of the emulsion is 40%.
Example 4
(1) Adding 30g of cardanol (0.1mol) and 6g of ethylenediamine (0.1mol) into a three-neck flask with a mechanical stirring paddle and a condensing tube, heating the three-neck flask to 50 ℃ in a constant-temperature oil bath, slowly adding 3g of paraformaldehyde (the dosage is 0.1mol calculated by the dosage of formaldehyde) in batches into the mixed reactant, and reacting for 0.5h after the addition is finished; then heating to 90 ℃, and continuing to react for 3 hours under the oil bath condition; after the reaction is finished, cooling the reaction system to 50 ℃ to stop the reaction, thereby obtaining an intermediate product, namely the phenolic aldehyde amine;
(2) adding 41g of polyethylene glycol diglycidyl ether (with an epoxy value of 0.29 and the dosage of 0.06mol) into the phenolic aldehyde amine intermediate product prepared in the step (1) in batches slowly, and reacting at 60 ℃ for 3h to obtain 80g of reactive emulsifier;
(3) slowly adding water (the amount of water is 7 times of the mass of the reactive emulsifier, namely 560g) into the reactive emulsifier prepared in the step (2), and stirring for 0.5h at 60 ℃ to obtain 640g of emulsion a;
(4) diluting 390g of epoxy resin E-44 by adopting 47g of active diluent BGE, and then preheating to 60 ℃ to obtain 437g of low-viscosity epoxy resin;
(5) and (3) slowly adding the emulsion a prepared in the step (3) into the low-viscosity epoxy resin obtained in the step (4) while stirring, and stirring for 20min at the rotating speed of 2500r/min after the addition is finished to obtain the water-based epoxy resin emulsion, wherein the solid content of the emulsion is 52%.
Effects of the embodiment
The stability test results of the waterborne epoxy resin emulsions prepared in examples 1-4 are shown in table 1, and the emulsions do not have a delamination phenomenon, which shows that the epoxy resin emulsions prepared by the invention have good stability and can be stored for more than half a year.
TABLE 1 stability testing of waterborne epoxy resin emulsions
Figure BDA0002387042230000061
The aqueous epoxy resin emulsions prepared in examples 1 to 4 were uniformly mixed with a curing agent (XT 101-B, a phenolic amine curing agent, manufactured by Guangzhou chemical filling of the department of China) to form aqueous epoxy resin coatings. Wherein, the proportion of the emulsion and the curing agent is shown in table 2, the performance of the formed waterborne epoxy resin coating is tested, the test result is shown in table 3, and the adhesion test method is according to ASTM D3359; flexibility test method according to JC/T2217-2014; the water resistance test method refers to GB/T1733-93; salt resistance and acid resistance, wherein the alkali resistance refers to JC/T2217-2014; the surface dry time and the real dry time are according to JC/T2217-2014.
TABLE 2 proportion of aqueous epoxy resin emulsion and curing agent
Figure BDA0002387042230000062
Figure BDA0002387042230000071
As can be seen from Table 3, the waterborne epoxy resin coating prepared by the invention has good adhesive force, good flexibility, excellent water resistance and corrosion resistance, 8-9 h of surface drying time and 15-16 h of actual drying time; and the whole system is a solvent-free system, only water is used as a dispersion medium, and the method is very environment-friendly.
TABLE 3 Properties of waterborne epoxy coatings
Figure BDA0002387042230000072
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of a reactive emulsifier is characterized by comprising the following steps:
(1) mixing cardanol and micromolecular polyamine; slowly adding paraformaldehyde into the mixed reactant in batches under the condition of 50-60 ℃ oil bath, and reacting for 0.5-1 h after the addition is finished; then heating to 90-100 ℃, and continuing to react for 3-4 h under the oil bath condition; after the reaction is finished, cooling the reaction system to 50-60 ℃ to stop the reaction, thereby obtaining an intermediate product, namely phenolic aldehyde amine;
(2) and (2) slowly adding polyethylene glycol diglycidyl ether to the phenolic aldehyde amine intermediate product prepared in the step (1) in batches, and reacting for 2-4 h at 50-60 ℃ after the addition is finished to obtain the reactive emulsifier.
2. The method for preparing a reactive emulsifier according to claim 1, wherein:
the micromolecular polyamine in the step (1) is at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and polyether amine D-230.
3. The method for preparing a reactive emulsifier according to claim 1, wherein:
the dosage of the micromolecular polyamine in the step (1) is 1.0-1.2 times of the molar mass of cardanol;
the dosage of the paraformaldehyde in the step (1) is as follows: calculated by the dosage of formaldehyde, the dosage is 1.0-1.1 times of the molar mass of cardanol.
4. The method for preparing a reactive emulsifier according to claim 1, wherein:
the epoxy value of the polyethylene glycol diglycidyl ether in the step (2) is 0.29-0.4;
the dosage of the polyethylene glycol diglycidyl ether in the step (2) is 0.4-0.6 times of the molar mass of the micromolecular polyamine in the step (1).
5. A reactive emulsifier, which is prepared by the preparation method of any one of claims 1 to 4.
6. An aqueous epoxy resin emulsion comprising the reactive emulsifier of claim 5, an epoxy resin, a reactive diluent and water.
7. The method for preparing an aqueous epoxy resin emulsion according to claim 6, comprising the steps of:
(1) slowly adding water into the reactive emulsifier, and stirring for 0.5-1 h at 50-60 ℃ to obtain emulsion a;
(2) diluting the epoxy resin by using an active diluent, and then preheating to 50-60 ℃ to obtain low-viscosity epoxy resin;
(3) and (3) slowly adding the emulsion a prepared in the step (1) into the low-viscosity epoxy resin prepared in the step (2) while stirring, and stirring at the rotating speed of 1500-3000 r/min for 15-30 min after the addition is finished to obtain the water-based epoxy resin emulsion.
8. The method for preparing an aqueous epoxy resin emulsion according to claim 7, characterized in that:
the amount of the water used in the step (1) is 4-9 times of the mass of the reactive emulsifier.
9. The method for preparing an aqueous epoxy resin emulsion according to claim 7, characterized in that:
the using amount of the reactive diluent in the step (2) is 10-15% of the mass of the epoxy resin.
10. The method for preparing an aqueous epoxy resin emulsion according to claim 7, characterized in that:
the amount of the low-viscosity epoxy resin in the step (2) is 5-5.5 times of the mass of the reactive emulsifier.
CN202010101602.1A 2020-02-19 2020-02-19 Reactive emulsifier, water-based epoxy resin emulsion, preparation and application Pending CN111171309A (en)

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CN112646200A (en) * 2020-12-18 2021-04-13 深圳市彩田化工有限公司 Green preparation process of epoxy resin emulsion
CN113061233A (en) * 2021-03-05 2021-07-02 卡德莱化工(珠海)有限公司 Waterborne emulsion epoxy curing agent and preparation method and application thereof
CN113416462A (en) * 2021-04-14 2021-09-21 常熟耐素生物材料科技有限公司 Plant polyene phenol modified zinc-rich coating and preparation method thereof
CN115572235A (en) * 2022-10-10 2023-01-06 大连理工大学 Preparation method of cardanol aldehyde amine curing agent

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CN112646200A (en) * 2020-12-18 2021-04-13 深圳市彩田化工有限公司 Green preparation process of epoxy resin emulsion
CN113061233A (en) * 2021-03-05 2021-07-02 卡德莱化工(珠海)有限公司 Waterborne emulsion epoxy curing agent and preparation method and application thereof
CN113416462A (en) * 2021-04-14 2021-09-21 常熟耐素生物材料科技有限公司 Plant polyene phenol modified zinc-rich coating and preparation method thereof
CN115572235A (en) * 2022-10-10 2023-01-06 大连理工大学 Preparation method of cardanol aldehyde amine curing agent

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Application publication date: 20200519