CN113896896B - Water-based epoxy emulsifier and preparation method and application thereof - Google Patents
Water-based epoxy emulsifier and preparation method and application thereof Download PDFInfo
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- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 104
- 239000004593 Epoxy Substances 0.000 title claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003822 epoxy resin Substances 0.000 claims abstract description 88
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 88
- 239000000839 emulsion Substances 0.000 claims abstract description 70
- 238000003756 stirring Methods 0.000 claims abstract description 37
- 150000001412 amines Chemical class 0.000 claims abstract description 26
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 23
- 229920000570 polyether Polymers 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000007599 discharging Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000012153 distilled water Substances 0.000 claims description 26
- 239000006184 cosolvent Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 11
- 230000008961 swelling Effects 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 abstract description 20
- 238000005338 heat storage Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 239000006185 dispersion Substances 0.000 description 15
- 230000001804 emulsifying effect Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002522 swelling effect Effects 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- -1 polyethylene chain Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- 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
-
- 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
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- 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
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of epoxy resin, and particularly relates to a preparation method and application of a water-based epoxy emulsifier, wherein the raw material formula comprises the following components in parts by weight: 60-80% of polyether amine and 25-40% of epoxy resin. Mixing the two materials, stirring and heating to 120 ℃, reacting for 3 hours, stirring and cooling, cooling to room temperature, and discharging for standby, thus obtaining the emulsifier. The beneficial effects of the invention are as follows: the aqueous epoxy emulsion prepared by the emulsifier has small particle size, good heat storage stability and difficult layering.
Description
Technical Field
The invention belongs to the technical field of epoxy resin, and particularly relates to a water-based epoxy emulsifier, and a preparation method and application thereof.
Background
The water-based epoxy resin (WEP) is widely applied to the fields of heavy corrosion prevention, containers, ships and other coatings due to the characteristics of excellent performance, low price, high safety, environmental friendliness and the like. At present, the preparation methods of the common aqueous epoxy emulsion mainly comprise a mechanical method, a reverse rotation method, a self-emulsifying method and a curing agent emulsifying method. The mechanical method, the self-emulsifying method and the curing agent emulsifying method have the defects of more synthesis steps, high cost and relatively complex process. Compared with the three methods, the reverse rotation method has the advantages of lower cost, simple process, less dosage of emulsifying agent and the like. However, the reverse method also has the defects of high requirement on the emulsifier, easy delamination of the emulsifier from the epoxy resin (EP), great influence on emulsion stability due to operation conditions, and the like. Therefore, it is important to prepare an emulsifier which has good compatibility with EP and good emulsion stability. At present, the common emulsifier mainly uses polyethylene glycol and epoxy resin as raw materials to prepare the corresponding emulsifier, but the emulsifier prepared by the method can cause the problems of larger particle size, poor thermal storage stability, easy layering, easy sedimentation and the like of the prepared epoxy resin in industrial production, and the preparation process of the emulsifier is complex.
Chinese patent CN112898733a provides an aqueous polyhydric phenol type epoxy emulsion and a preparation method thereof, the aqueous polyhydric phenol type epoxy emulsion comprising: 50-75 parts of polyphenol type epoxy resin, 6-8 parts of reactive emulsifier and 55-80 parts of water, wherein the reactive emulsifier is prepared by reacting bisphenol A type epoxy resin, polyphenol type epoxy resin and polyether amine, the emulsifier can be well matched with the polyphenol type epoxy resin, the obtained emulsion has good stability, but three-functional polyether amine is required to be added to enable the polyphenol type epoxy resin to better react, four kinds of polyether amine are required to be mixed, the preparation process is complex, the industrial production process is difficult, the reaction is difficult to control, the emulsifier product is complex, the emulsifying effect on the epoxy resin in the later period is poor, and the emulsion viscosity is large.
Chinese patent CN109384907a provides a method for preparing a waterborne epoxy resin curing agent, which comprises synthesizing an emulsifier which has epoxy groups at both ends and contains both epoxy chain segments and polyethylene chain segments with a polyether amine having only one primary amine through an epoxy resin E51, and is a reactive emulsifier containing active groups. Then removing the grafted amine curing agent, introducing the hydrophilic and lipophilic structure of the emulsifier into the molecular structure of the amine curing agent, and finally end-capping primary amine at two ends. The emulsifier used is an emulsifier prepared by using only one epoxy resin E51 and one polyether amine 2070, and the emulsifier is not used for preparing the aqueous epoxy emulsion.
Chinese patent CN112851967a provides a method for preparing a thermoplastic aqueous epoxy resin emulsion with high molecular weight and single component, wherein the emulsifier is prepared by heating glycidyl ether, small molecular epoxy resin and polyetheramine. The purpose of adding glycidyl ether is to enable the glycidyl ether and epoxy resin to react together with amino groups in polyether amine to generate epoxy emulsifier with smaller relative molecular weight, the emulsifier product prepared by the method is uncontrollable, and the reaction product has complex structure. The technology aims at high molecular weight epoxy resin, and the epoxy emulsion emulsified by the epoxy emulsifier prepared by the method has low solid content (40% -58%), and the viscosity is not described.
The present invention has been made to solve the above problems by developing a novel emulsifier.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the aqueous epoxy emulsifier, the preparation method and the application thereof, and the aqueous epoxy emulsifier can be synthesized in one step without steps, and has the advantages of simple preparation process, easy operation, small particle size, good thermal storage stability and difficult layering.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the aqueous epoxy emulsifier comprises the following components in percentage by weight: 60-80% of polyether amine and 25-40% of epoxy resin.
Preferably, the molecular weight of the polyetheramine is 2000-3100 and the molecular weight of the epoxy resin is 200-500.
Preferably, the polyetheramine is one or both of HUNTSMAN (hensman) M2070, M3085, more preferably M3085.
Preferably, the epoxy resin is one or more of south Asia epoxy resins E51, E20 and E44, and further preferably E51.
Preferably, the preparation steps of the emulsifier are as follows: and (3) weighing polyether amine and epoxy resin according to a proportion, heating to 120 ℃ while stirring, reacting for 3 hours, and cooling to room temperature for standby, thus obtaining the emulsifier.
The invention also aims to provide an aqueous epoxy emulsion, which comprises the following components in parts by weight: 5-8% of the emulsifier, 50-55% of the epoxy resin, 6-10% of the cosolvent and 30-34% of the water.
Preferably, the preparation process of the aqueous epoxy emulsion comprises the following steps:
step one: weighing 5-8% of emulsifier, 50-55% of epoxy resin, 6-10% of cosolvent and 30-34% of water according to a proportion;
step two: mixing epoxy resin and cosolvent, heating to about 80 ℃ and stirring to uniformly mix, swelling for 1h, and transferring into a preheated phase inversion device while the mixture is hot;
step three: stirring at 400-500r/min in a phase inversion device, cooling the resin temperature in the device to 60 ℃, adding an emulsifying agent, slowly dripping distilled water into the device, cooling the device to 400-500r/min after the distilled water is added, cooling the device to room temperature, standing, filtering, and discharging to obtain the epoxy emulsion.
Preferably, the preheating temperature of the phase inversion device is 55 ℃.
Preferably, the cosolvent is propylene glycol monomethyl ether (PM). Because PM has good swelling effect on resin, is easy to dissolve in water, and has little influence on phase inversion in the later period. In addition, PM has low toxicity and strong dissolving power, and has the characteristics of reducing the film forming temperature, promoting the aggregation and film forming and ensuring the good state of the film.
Preferably, the epoxy resin is E44 and E20, and the mass ratio of E44 to E20 is 1:4. the single E20 is solid epoxy resin, the swelling effect is poor in the swelling process, and the E44 is liquid epoxy resin, so that the swelling effect can be improved after the E44 is added, and the emulsion performance can be improved.
The beneficial effects of the invention are as follows: the aqueous epoxy emulsifier is prepared by adding an amino-containing monomer into a formula, wherein the amino is not only a hydrophilic group but also has high reaction activity, and the amino can react with epoxy resin by increasing the temperature under the condition of no need of adding a catalyst to generate the amphoteric emulsifier with hydrophilicity and lipophilicity.
The emulsifier prepared by the epoxy resin E44 and the polyether amine 3085 according to a certain proportion has better emulsifying effect compared with the emulsifier prepared by the epoxy resin E51 and the polyether amine 2070. Because the molecular weights of the emulsifiers prepared from the different epoxy resin and polyetheramine combinations are greatly different, the molecular weight of polyetheramine 3085 is greater than that of polyetheramine M2070, and the hydrophobic chain segments in the formed emulsifier are longer; also, of the epoxy E51 and E44, E44 is higher in molecular weight. The research of the invention proves that the molecular weight has a larger influence on the emulsifying capacity, and the emulsifying capacity of the emulsifying agent directly leads to larger differences in particle size, stability, viscosity and the like of the aqueous epoxy emulsion.
The emulsifier is prepared by using only two substances in the formula, and auxiliaries such as glycidyl ether and the like are not added, so that the prepared emulsifier has relatively large molecular weight and has good compatibility with epoxy resin. The reaction is carried out at 120 ℃, so that the reaction speed can be ensured, the increase of side reactions and uncontrollable factors with overhigh temperature can be avoided, when the temperature is higher than 120 ℃, the temperature of the system is obviously increased, the color of the product is deepened, and when the temperature is lower than 100 ℃, the reaction is slow, the reaction is not easy to carry out, and the time and the resource are wasted. The epoxy emulsion prepared by the emulsifier has the characteristics of high solid content and low viscosity, the solid content is 58-63%, the viscosity is low, and the epoxy emulsion has only 63KU at 25 ℃. The preparation method can be completed in one step without step synthesis, and has simple preparation process, easy realization of industrial production and low cost.
In the process of preparing the emulsion, the water-based epoxy emulsion with small particle size and good heat storage stability can be prepared by using less emulsifying agent (5-8%) due to the use of the emulsifying agent, the cost is low, and the proper value of the adding amount of the emulsifying agent for preparing the high-solid low-viscosity water-based epoxy emulsion is determined. The invention also determines the proper rotation speed during phase inversion, and the whole distilled water dripping process uses high dispersion rotation speed for stirring, so that the particle size of the obtained aqueous epoxy emulsion is smaller, the particle size of the prepared aqueous epoxy emulsion is D50/D90 (mu m) 0.441/0.875 when the particle size is 1000-1500r/min, and the obtained emulsion has excellent performances of good heat storage stability, difficult layering, difficult sedimentation, low viscosity, high solid content and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples, and it is apparent that the described examples are only some of the examples of the present invention, but not all of the examples. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The aqueous epoxy emulsifier of the embodiment comprises the following formula components in percentage by mass: 67.7% of polyetheramine (M2070) and 32.3% of epoxy resin (E51). And (3) weighing polyether amine and epoxy resin according to the proportion in a four-neck flask, heating to 120 ℃ while stirring, reacting for 3 hours, cooling while stirring, and discharging at room temperature for standby, thus obtaining the emulsifier prepared in the example.
The emulsifier is used for preparing the aqueous epoxy emulsion, and the epoxy emulsion comprises the following components in percentage by mass: 8.3% of the emulsifier, 51.7% of epoxy resin, 8% of cosolvent and 32% of distilled water. The preparation method comprises the following steps:
step one: in a four-necked flask, the epoxy resin (mass ratio of the mixed resin of E44 and E20: 1:4) and the cosolvent (PM) were weighed in the above-mentioned proportions. Heating to about 80deg.C, stirring, and mixing. Then, the temperature is controlled at 80 ℃, swelling is carried out for 1h, and the mixture is transferred to a preheated phase inversion device while the mixture is hot.
Step two: transferring the swollen epoxy resin into a phase inversion device preheated to 55 ℃ by circulating water while the swollen epoxy resin is hot, stirring the epoxy resin at a rotating speed of 400-500r/min, reducing the temperature of the resin in the device to 60 ℃, and adding an emulsifying agent. The dispersion speed is increased to 1200r/min, and the weighed distilled water is slowly dripped. After distilled water is added completely, the circulating water is removed to reduce the dispersion rotating speed to 400-500r/min, the temperature is reduced, the emulsion is cooled to room temperature, and the epoxy emulsion is obtained after standing and filtering and discharging.
Example 2
The aqueous epoxy emulsifier of the embodiment comprises the following formula components in percentage by mass: polyether amine (M2070) 64.6%, epoxy resin (E44) 35.4%. And (3) weighing polyether amine and epoxy resin according to a proportion in a four-neck flask, heating to 120 ℃ while stirring, reacting for 3 hours, cooling while stirring, and discharging at room temperature for standby, thus obtaining the emulsifier.
The emulsifier is used for preparing the aqueous epoxy emulsion, and the epoxy emulsion comprises the following components in percentage by mass: 8.3% of the obtained emulsifier, 51.7% of epoxy resin, 8% of cosolvent and 32% of distilled water. The preparation method comprises the following steps:
step one: in a four-necked flask, epoxy resin (mass ratio of mixed resin of E44 and E20: 1:4) and cosolvent (PM) were weighed in proportion. Heating to about 80deg.C, stirring, and mixing. Then, the temperature is controlled at 80 ℃, swelling is carried out for 1h, and the mixture is transferred to a preheated phase inversion device while the mixture is hot.
Step two: transferring the swollen epoxy resin into a phase inversion device preheated to 55 ℃ by circulating water, stirring at a rotating speed of 400-500r/min, cooling the resin temperature in the device to 60 ℃, and adding a self-made emulsifier according to a formula. Then, the dispersion rotation speed was increased to 1200r/min, and the weighed distilled water was slowly dropped. After distilled water is added completely, the circulating water is removed to reduce the dispersion rotating speed to 400-500r/min, the temperature is reduced, the emulsion is cooled to room temperature, and the epoxy emulsion is obtained after standing and filtering and discharging.
Example 3
The aqueous epoxy emulsifier of the embodiment comprises the following formula components in percentage by mass: 76.0% of polyetheramine (M3085) and 24.0% of epoxy resin (E51). And (3) weighing polyether amine and epoxy resin according to a proportion in a four-neck flask, heating to 120 ℃ while stirring, reacting for 3 hours, cooling while stirring, and discharging at room temperature for standby, thus obtaining the emulsifier.
The emulsifier is used for preparing the aqueous epoxy emulsion, and the epoxy emulsion comprises the following components in percentage by mass: 7.4% of the emulsifier, 52.6% of epoxy resin, 8% of cosolvent and 32% of distilled water. The preparation is carried out according to the following preparation process.
Step one: in a four-necked flask, epoxy resin (mass ratio of mixed resin of E44 and E20: 1:4) and cosolvent (PM) were weighed in proportion. Heating to about 80deg.C, stirring, and mixing. Then, the temperature is controlled at 80 ℃, swelling is carried out for 1h, and the mixture is transferred to a preheated phase inversion device while the mixture is hot.
Step two: transferring the swollen epoxy resin into a phase inversion device preheated to 55 ℃ by circulating water, stirring at a rotating speed of 400-500r/min, cooling the resin temperature in the device to 60 ℃, and adding a self-made emulsifier according to a formula. Then, the dispersion rotational speed was increased to 1500r/min, and the weighed distilled water was slowly dropped. After distilled water is added completely, the circulating water is removed to reduce the dispersion rotating speed to 400-500r/min, the temperature is reduced, the emulsion is cooled to room temperature, and the epoxy emulsion is obtained after standing and filtering and discharging.
Example 4
The aqueous epoxy emulsifier of the embodiment comprises the following formula components in percentage by mass: 73.1% of polyetheramine (M3085) and 26.9% of epoxy resin (E44). And (3) weighing polyether amine and epoxy resin according to a proportion in a four-neck flask, heating to 120 ℃ while stirring, reacting for 3 hours, cooling while stirring, and discharging at room temperature for standby, thus obtaining the emulsifier.
The emulsifier is used for preparing the aqueous epoxy emulsion, and the epoxy emulsion comprises the following components in percentage by mass: 5.5% of the obtained emulsifier, 54.5% of epoxy resin, 8% of cosolvent and 32% of distilled water. The preparation method comprises the following steps:
step one: in a four-necked flask, epoxy resin (mass ratio of mixed resin of E44 and E20: 1:4) and cosolvent (PM) were weighed in proportion. Heating to about 80deg.C, stirring, and mixing. Then, the temperature is controlled at 80+/-3 ℃, swelling is carried out for 1h, and the mixture is transferred to a preheated phase inversion device when the mixture is hot.
Step two: transferring the swollen epoxy resin into a phase inversion device preheated to 55+/-2 ℃ by circulating water while the swollen epoxy resin is hot, stirring at a rotating speed of 400-500r/min, cooling the resin in the device to 60+/-5 ℃, and adding a self-made emulsifier according to a formula. Then, the dispersion rotation speed was increased to 1200r/min, and the weighed distilled water was slowly dropped. After distilled water is added completely, the circulating water is removed to reduce the dispersion rotating speed to 400-500r/min, the temperature is reduced, the emulsion is cooled to room temperature, and the epoxy emulsion is obtained after standing and filtering and discharging.
Example 5
The aqueous epoxy emulsifier of the embodiment comprises the following formula components in percentage by mass: 73.1% of polyetheramine (M3085) and 26.9% of epoxy resin (E44). And (3) weighing polyether amine and epoxy resin according to a proportion in a four-neck flask, heating to 120 ℃ while stirring, reacting for 3 hours, cooling while stirring, and discharging at room temperature for standby, thus obtaining the emulsifier.
The emulsifier is used for preparing the aqueous epoxy emulsion, and the epoxy emulsion comprises the following components in percentage by mass: 6.4% of the emulsifier, 53.6% of epoxy resin, 8% of cosolvent and 32% of distilled water. The preparation method comprises the following steps:
step one: in a four-necked flask, epoxy resin (mass ratio of mixed resin of E44 and E20: 1:4) and cosolvent (PM) were weighed in proportion. Heating to about 80deg.C, stirring, and mixing. Then, the temperature is controlled at 80+/-3 ℃, swelling is carried out for 1h, and the mixture is transferred to a preheated phase inversion device when the mixture is hot.
Step two: transferring the swollen epoxy resin into a phase inversion device preheated to 55+/-2 ℃ by circulating water while the swollen epoxy resin is hot, stirring at a rotating speed of 400-500r/min, cooling the resin in the device to 60+/-5 ℃, and adding a self-made emulsifier according to a formula. Then, the dispersion rotation speed was increased to 1200r/min, and the weighed distilled water was slowly dropped. After distilled water is added completely, the circulating water is removed to reduce the dispersion rotating speed to 400-500r/min, the temperature is reduced, the emulsion is cooled to room temperature, and the epoxy emulsion is obtained after standing and filtering and discharging.
Example 6
The aqueous epoxy emulsifier of the embodiment comprises the following formula components in percentage by mass: 73.1% of polyetheramine (M3085) and 26.9% of epoxy resin (E44). And (3) weighing polyether amine and epoxy resin according to a proportion in a four-neck flask, heating to 120 ℃ while stirring, reacting for 3 hours, cooling while stirring, and discharging at room temperature for standby, thus obtaining the emulsifier.
The emulsifier is used for preparing the aqueous epoxy emulsion, and the epoxy emulsion comprises the following components in percentage by mass: 7.4% of the emulsifier, 52.6% of epoxy resin, 8% of cosolvent and 32% of distilled water. The preparation is carried out according to the following preparation process.
Step one: in a four-necked flask, epoxy resin (mass ratio of mixed resin of E44 and E20: 1:4) and cosolvent (PM) were weighed in proportion. Heating to about 80deg.C, stirring, and mixing. Then, the temperature is controlled at 80 ℃, swelling is carried out for 1h, and the mixture is transferred to a preheated phase inversion device while the mixture is hot.
Step two: transferring the swollen epoxy resin into a phase inversion device preheated to 55 ℃ by circulating water, stirring at a rotating speed of 400-500r/min, cooling the resin temperature in the device to 60 ℃, and adding a self-made emulsifier according to a formula. Then, the dispersion rotational speed was increased to 1500r/min, and the weighed distilled water was slowly dropped. After distilled water is added completely, the circulating water is removed to reduce the dispersion rotating speed to 400-500r/min, the temperature is reduced, the emulsion is cooled to room temperature, and the epoxy emulsion is obtained after standing and filtering and discharging.
Example 7
The aqueous epoxy emulsifier of the embodiment comprises the following formula components in percentage by mass: 73.1% of polyetheramine (M3085) and 26.9% of epoxy resin (E44). And (3) weighing polyether amine and epoxy resin according to a proportion in a four-neck flask, heating to 120 ℃ while stirring, reacting for 3 hours, cooling while stirring, and discharging at room temperature for standby, thus obtaining the emulsifier.
The emulsifier is used for preparing the aqueous epoxy emulsion, and the epoxy emulsion comprises the following components in percentage by mass: 8.3% of the obtained emulsifier, 52.6% of epoxy resin, 8% of cosolvent and 32% of distilled water. The preparation method comprises the following steps:
step one: in a four-necked flask, epoxy resin (mass ratio of mixed resin of E44 and E20: 1:4) and cosolvent (PM) were weighed in proportion. Heating to about 80deg.C, stirring, and mixing. Then, the temperature is controlled at 80+/-3 ℃, swelling is carried out for 1h, and the mixture is transferred to a preheated phase inversion device when the mixture is hot.
Step two: transferring the swollen epoxy resin into a phase inversion device preheated to 55+/-2 ℃ by circulating water while the swollen epoxy resin is hot, stirring at a rotating speed of 400-500r/min, cooling the resin in the device to 60+/-5 ℃, and adding a self-made emulsifier according to a formula. Then, the dispersion rotation speed was increased to 1200r/min, and the weighed distilled water was slowly dropped. After distilled water is added completely, the circulating water is removed to reduce the dispersion rotating speed to 400-500r/min, the temperature is reduced, the emulsion is cooled to room temperature, and the epoxy emulsion is obtained after standing and filtering and discharging.
The aqueous epoxy emulsions obtained in examples 1 to 7 were subjected to solid content measurement, viscosity measurement and thermal storage stability test by the following test methods; the effect of different emulsifiers on the particle size of the epoxy emulsion and the effect of the addition of the emulsifier on the particle size of the epoxy emulsion were studied, and the test results are shown in tables 1 and 2.
Solid content measurement method reference: GB1725-79 paint solids content assay;
the viscosity measurement method comprises the following steps: a rotary viscometer DV2T (brookfield company);
the thermal storage stability test method comprises the following steps: and the thermal storage stability is poor when the thermal storage is stored at 60 ℃ for 30 days to observe whether layering exists.
TABLE 1 influence of different emulsifiers on the particle size of epoxy emulsions
The size of the particle size is a relatively visual standard for judging whether the aqueous epoxy emulsion is stable or not. As can be seen from Table 1, the emulsifying effect of the emulsifier prepared from polyetheramine M3085 by particle size comparison is significantly better than that of polyetheramine M2070. Comparing the data obtained in examples 1-6, the emulsion of example 6 had a smaller particle size than the emulsion of the other examples, so it was found that the emulsifying effect of the emulsifier prepared from polyetheramine M3085 and epoxy resin E44 was better than the emulsifying effect of the emulsifier prepared in the other examples, and therefore the emulsifying effect of the emulsifier prepared in example 6 was the best.
TABLE 2 influence of the emulsifier addition on the particle size of the epoxy emulsion
| Example of implementation | Emulsifier addition/% | Particle size D50/D90 (μm) | viscosity/KU | Thermal storage stability |
| Example 4 | 5.5 | 1.226/2.815 | 59 | Non-layering |
| Example 5 | 6.4 | 0.972/1.650 | 60 | Non-layering |
| Example 6 | 7.4 | 0.441/0.875 | 63 | Non-layering |
| Example 7 | 8.3 | 0.893/1.634 | 60 | Non-layering |
As can be seen from the effects of the amounts of the different emulsifiers added in Table 2 on the particle size, the aqueous epoxy emulsion prepared in example 6 had the smallest particle size, and thus the aqueous epoxy emulsion of example 6 had the best emulsification effect.
From the above examples, it is clear that the particle size of the aqueous epoxy emulsion prepared by the reverse method is much smaller than the emulsifier prepared by the reaction of polyetheramine M3085 with epoxy resin. And the particle size of the aqueous epoxy emulsion prepared by the reverse rotation method is smaller than that of the emulsifier prepared by the polyether amine M3085 and the epoxy resin E44. Thus, the best combination is polyetheramine M3085 with epoxy E44.
The foregoing detailed description of the embodiments of the invention has been presented only to illustrate the preferred embodiments of the invention and should not be taken as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (4)
1. An aqueous epoxy emulsion, characterized in that: the formula comprises the following components in parts by weight: 5-8% of emulsifying agent, 50-55% of epoxy resin, 6-10% of cosolvent and 30-34% of water; wherein the epoxy resin is mixed resin of E44 and E20, and the mass ratio of E44 to E20 is 1:4, a step of;
wherein the emulsifier formula comprises the following components in percentage by weight: 60-80% of polyether amine and 25-40% of epoxy resin; the polyether amine in the emulsifier is M3085, and the epoxy resin is epoxy resin E44; the preparation steps of the emulsifier are as follows: and (3) weighing polyether amine and epoxy resin according to a proportion, heating to 120 ℃ while stirring, reacting for 3 hours, and cooling to room temperature for standby, thus obtaining the emulsifier.
2. The aqueous epoxy emulsion of claim 1, wherein: the cosolvent is propylene glycol monomethyl ether.
3. The aqueous epoxy emulsion of claim 1, wherein: the preparation process of the aqueous epoxy emulsion comprises the following steps:
step one: weighing 5-8% of emulsifier, 50-55% of epoxy resin, 6-10% of cosolvent and 30-34% of water according to a proportion;
step two: mixing epoxy resin and cosolvent, heating to about 80 ℃ and stirring to uniformly mix, swelling for 1h, and transferring into a preheated phase inversion device while the mixture is hot;
step three: stirring at 400-500r/min in a phase inversion device, cooling the resin temperature in the device to 60 ℃, adding an emulsifying agent, slowly dripping distilled water into the device, cooling the device to 400-500r/min after the distilled water is added, cooling the device to room temperature, standing, filtering, and discharging to obtain the epoxy emulsion.
4. The aqueous epoxy emulsion of claim 3, wherein: the preheating temperature of the phase inversion device was 55 ℃.
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