CN112521830A - Silicon modified waterborne epoxy resin emulsion and preparation method thereof - Google Patents
Silicon modified waterborne epoxy resin emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to polysiloxane modified waterborne epoxy resin emulsion and a preparation method thereof, wherein the emulsion is mainly prepared from an epoxy adduct, epoxy resin, a cosolvent and water according to the mass ratio of 0.1-0.2: 1: 0.1-0.2: 0.6-1; wherein the molecular structure of the epoxy adduct has the molecular structure characteristics of both (a) and (b): (a) is a terminal epoxy molecule comprising one siloxy group; (b) is a terminal epoxy molecule containing a polyether segment. The invention improves the adhesive force, water resistance, salt fog resistance and other properties of the existing water-based epoxy resin emulsion, synthesizes an epoxy addition compound (emulsifier) with an organic silicon structure through a chemical modification process, and introduces the organic silicon structure with excellent adhesive force and strong hydrophobicity into a cross-linking system of a paint film, thereby improving the adhesive force, water resistance and salt fog resistance of the paint film.
Description
Technical Field
The application relates to a silicon-modified waterborne epoxy resin emulsion and a preparation method thereof, which are applied to the field of production of metal anticorrosive coatings.
Background
The epoxy resin is one of three general thermosetting resins, has excellent technological properties, mechanical properties and physical properties, and is widely applied to metal anticorrosive coatings. In order to avoid the generation of a large amount of alcohol, ether and ketone organic solvents which cause environmental pollution in the construction process of the traditional epoxy resin anticorrosive paint, water-based epoxy resin and related paint products thereof are developed in recent years to replace the traditional high-pollution solvent-based epoxy anticorrosive paint.
In the related literature reports (for example, CN 108084458A, CN 110577652A, CN 106349906 a) of preparing aqueous epoxy resin emulsion, the process is to use epoxy emulsifier to produce aqueous epoxy resin emulsion under high speed stirring, and the aqueous epoxy resin emulsion obtained by the process is crosslinked with curing agent to form paint film with dense crosslinking structure.
At present, the change of epoxy anticorrosive oil into water has some favorable progress, for example, a water-based epoxy anticorrosive matching is applied to a container coating matching on a large scale. However, in other fields, such as engineering machinery, steel structures and rail transit, the replacement rate of the oily epoxy system is not high. The big reason is that: in some fields with specific performance requirements, such as rail transit coating kits; or under more severe corrosive environments, such as heavy anti-corrosion coating matching (C5), higher performance requirements are provided for the adhesion and corrosion resistance of the coating (HG T5176-. However, the water-based epoxy resin on the current market generally has paint defects such as bubbling and shedding of the prepared paint film in a long-time damp-heat corrosion environment, such as a long-time Neutral Salt Spray Test (NSST). This greatly increases the difficulty of replacing oily epoxy systems with waterborne epoxy systems. The specific reason for the bubbling and the falling of the paint film is analyzed, and the saturated vapor pressure of water is larger than the adhesive force between the paint film and the base material, so that the adhesive force is lost, and the coating is foamed and falls off. The underlying reason for this is the hydrophilic nature of the emulsifier itself. Because in the process of preparing the aqueous epoxy resin emulsion, the hydrophobic epoxy resin needs to be emulsified into the emulsion by means of the epoxy emulsifier with emulsification effect. And the epoxy emulsifier has strong hydrophilicity. The residual emulsifier in the paint film can reduce the water resistance, salt fog resistance and adhesive force of the paint film, thereby directly causing the problems of bubbling, falling off and the like of the paint film.
Therefore, it is desirable to provide a water-based epoxy resin emulsion with better adhesion, water resistance and salt spray resistance and a preparation method thereof.
Disclosure of Invention
In order to improve the performances of the existing waterborne epoxy resin emulsion such as adhesive force, water resistance, salt spray resistance and the like, the application provides the silicon modified waterborne epoxy resin emulsion and the preparation method thereof.
The technical scheme of the application is as follows:
a silicon modified waterborne epoxy resin emulsion is mainly prepared from an epoxy adduct, epoxy resin, a cosolvent and water according to a mass ratio of 0.1-0.2: 1: 0.1-0.2: 0.6-1;
wherein the molecular structure of the epoxy adduct has the molecular structure characteristics of both (a) and (b):
(a) is a terminal epoxy molecule comprising one siloxy group;
(b) is a terminal epoxy molecule comprising a polyether segment;
the polyether segment in (b) is at least one polyether molecule with the weight-average molecular weight of at least 2000, and the molecule is polyethylene glycol, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene monomethyl ether or polyoxyethylene polyoxypropylene block copolymerization monomethyl ether;
the epoxy resin is an epoxy resin with the weight-average molecular weight of 300-3000.
According to the silicon modified waterborne epoxy resin emulsion, an epoxy adduct with an organic silicon structure is used, and the organic silicon structure with excellent adhesive force and strong hydrophobicity is introduced into a crosslinking system of a paint film through a chemical modification process. On one hand, the organic silicon structure not only can enhance the adhesive force, particularly the wet adhesive force, between a paint film and a base material, but also can participate in chemical crosslinking, so that the crosslinking compactness of the paint film is improved; on the other hand, the silicone structure can improve the water resistance of the paint film.
The structure of the epoxy adduct is shown as a general formula (I)
General formula (II)
General formula (III)
Or general formula (IV)
Wherein n in the general formula is 0 or an integer of 1 to 10, and m is an integer of 50 to 250.
The molecular structure of the epoxy adduct disclosed by the scheme is designed to be half hydrophilic and the other half lipophilic, so that the epoxy adduct has an emulsifying effect. The epoxy group and the siloxy group which can participate in the crosslinking reaction are simultaneously contained in the chain, in the process of curing and film forming, the epoxy group can be chemically reacted with an amine curing agent, and the siloxy group can be chemically reacted with the hydroxyl on the surface of the steel substrate and can also be reacted with each other, so that the epoxy adduct (namely the emulsifier) disclosed by the scheme plays a role of an emulsifier on one hand, and on the other hand, the epoxy adduct becomes a part of a crosslinking system after film forming and plays a role of improving the crosslinking density.
The epoxy adduct is mainly prepared from a silane coupling agent, hydrophilic polyether polyol, a catalyst and epoxy resin according to a mass ratio of 0.01-0.1: 0.8-3.5: 0.0025-0.005: 1.
An epoxy adduct with an organic silicon structure is synthesized by a chemical modification process, and the organic silicon structure with excellent adhesive force and strong hydrophobicity is introduced into a crosslinking system of a paint film, so that the adhesive force, the water resistance and the salt spray resistance of the paint film are improved.
The epoxy resin in the epoxy adduct preparation component and the epoxy resin in the silicon modified waterborne epoxy resin emulsion preparation component are both bisphenol A type epoxy resin, and the catalyst is boron trifluoride diethyl etherate;
the silane coupling agent is one of 3-isocyanatopropyl trimethoxy silane, 3-isocyanatopropyl triethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3- (2-aminoethyl) -aminopropyl trimethoxy silane, 3- (2-aminoethyl) -aminopropyl triethoxy silane, 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3- (2, 3-epoxypropoxy) propyl triethoxy silane or (3-triethoxysilylpropyl) succinic anhydride;
the hydrophilic polyether polyol is one of polyethylene glycol, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene monomethyl ether or polyoxyethylene polyoxypropylene block copolymerization monomethyl ether, and the weight average molecular weight of the hydrophilic polyether polyol is 2000-10000.
The epoxy resin of the preferred class has a plurality of outstanding excellent properties after being cured, such as strong adhesion to various materials, particularly metals, strong chemical corrosion resistance, high mechanical strength, good corrosion resistance and the like. The preferred catalyst boron trifluoride diethyl etherate is a common Lewis acid catalyst and has good catalytic action on the reaction between hydroxyl and epoxy. The preferred silane coupling agent has a functional group that can react with the bisphenol a type epoxy resin, and can be smoothly linked to the molecular chain of the bisphenol a type epoxy resin by appropriate process conditions. The preferred hydrophilic polyether polyols have excellent hydrophilicity and a wide range of molecular weights. And the hydrophilic and oleophilic values of the epoxy adduct can be flexibly adjusted by selecting the proportion between the polyoxyethylene chain segment and the polyoxypropylene chain segment and different molecular weights, so that a structure with optimal emulsifying property is obtained. The preferred hydrophilic polyether polyols of weight average molecular weight have the best emulsifying properties.
The cosolvent is one or any combination of more than two of ethylene glycol butyl ether, ethylene glycol, propylene glycol methyl ether, dipropylene glycol butyl ether, isopropanol or alcohol ester twelve.
On one hand, the preferable cosolvent can reduce the viscosity of the system in the emulsification process and is beneficial to phase inversion; on the other hand, the storage stability of the aqueous epoxy emulsion can be improved.
The epoxy resin for preparing the epoxy adduct and the epoxy resin for preparing the silicon modified waterborne epoxy resin emulsion are one or any combination of more than two of epoxy resin E-06, epoxy resin E-12, epoxy resin E-20, epoxy resin E-44 or epoxy resin E-51.
The preferable epoxy resin can remarkably improve the paint film adhesive force, water resistance and salt spray resistance of the prepared silicon modified water-based epoxy resin emulsion.
The preparation method of the silicon modified waterborne epoxy resin emulsion comprises the following steps of sequentially carrying out:
1) adding the epoxy adduct, the epoxy resin and the cosolvent into an emulsifying device, heating to 40-80 ℃, and stirring until the mixture is uniformly mixed;
2) slowly dripping water into the mixture obtained in the step 1) within 0.5-3 hours at the temperature of 40-80 ℃, shearing and emulsifying at the rotating speed of 500-4000 rpm, cooling to 30-50 ℃, and continuously stirring for 0.5-1.5 hours to obtain the silicon modified waterborne epoxy resin emulsion.
The preparation method of the epoxy adduct comprises the following steps of sequentially carrying out:
1) in N2Under protection, carrying out vacuum dehydration on the hydrophilic polyether polyol at the temperature of 120-140 ℃ for 1-3 hours, then cooling to 100-120 ℃, adding the epoxy resin, stirring for 5-30 minutes, and till the epoxy resin is completely melted;
2) adding a catalyst into the mixture obtained in the step 1), uniformly mixing, carrying out heat preservation reaction at 60-140 ℃ for 1-4 h to obtain a colorless transparent product, and then cooling to 50-100 ℃;
3) adding a silane coupling agent into the product obtained in the step 2), and reacting for 1-3 hours at the temperature of 70-90 ℃ to obtain the epoxy adduct.
The preparation method of the silicon modified waterborne epoxy resin emulsion comprises 2 steps:
firstly, obtaining an epoxy adduct (emulsifier) through a chemical reaction between a silane coupling agent, hydrophilic polyether polyol and epoxy resin;
secondly, the epoxy resin is dispersed into aqueous epoxy resin emulsion by an emulsification process.
The preparation method is simple and quick in steps, and the prepared silicon modified water-based epoxy resin emulsion paint film is good in adhesive force, water resistance and salt spray resistance.
The water is preferably deionized water.
In the step 2) of the method for preparing the silicon modified waterborne epoxy resin emulsion, the time for dropwise adding water and shearing and emulsifying is 1-2 hours, and the rotating speed is 1000-3000 r/min; the mixing temperature in the step 1) of the method for preparing the silicon modified waterborne epoxy resin emulsion is 50-70 ℃, and the temperature of the mixture in the step 2) is 50-70 ℃ when water is dripped.
Detailed Description
The technical solution of the present application will be described in detail with reference to the following examples.
Example 1
The silicon modified waterborne epoxy resin emulsion mainly comprises an epoxy adduct, epoxy resin, a cosolvent and water according to a mass ratio of 0.15: 1: 0.15: 0.8, preparing;
wherein the molecular structure of the epoxy adduct has the molecular structure characteristics of both (a) and (b):
(a) is a terminal epoxy molecule comprising one siloxy group;
(b) is a terminal epoxy molecule comprising a polyether segment;
the polyether segment in (b) is at least one polyethylene glycol molecule having a molecular weight of 4000.
The structure of the epoxy adduct is a general formula (I), wherein n in the general formula is 0 or an integer of 1-10, and m is an integer of 50-250;
the epoxy adduct is mainly prepared from a silane coupling agent, hydrophilic polyether polyol, a catalyst and epoxy resin according to a mass ratio of 0.08:2.8:0.003: 1.
The epoxy resin in the epoxy adduct preparation component and the epoxy resin in the silicon modified waterborne epoxy resin emulsion preparation component are both bisphenol A type epoxy resin E-20, and the catalyst is boron trifluoride diethyl etherate;
the silane coupling agent is 3-isocyanate propyl trimethoxy silane;
the hydrophilic polyether polyol is polyethylene glycol with the weight-average molecular weight of 4000.
The cosolvent is ethylene glycol butyl ether.
The preparation method of the silicon modified waterborne epoxy resin emulsion comprises the following steps of sequentially carrying out:
1) adding the epoxy adduct, the epoxy resin and the cosolvent into an emulsifying device, and stirring at 80 ℃ until the mixture is uniformly mixed;
2) slowly dripping water into the mixture obtained in the step 1) within 3 hours at the temperature of 80 ℃, carrying out shearing emulsification for 1.5 hours at the rotating speed of 2000 r/min, then cooling to 50 ℃, and continuously stirring for 1 hour to obtain the silicon modified waterborne epoxy resin emulsion.
The preparation method of the epoxy adduct comprises the following steps of sequentially carrying out:
1) in N2Under protection, carrying out vacuum dehydration on hydrophilic polyether polyol at 120 ℃ for 1 hour, then cooling to 100 ℃, adding epoxy resin, stirring for 5 minutes until the epoxy resin is completely melted;
2) adding a catalyst into the mixture obtained in the step 1), uniformly mixing, carrying out heat preservation reaction at 100 ℃ for 3 hours to obtain a colorless transparent product, and then cooling to 80 ℃;
3) adding a silane coupling agent into the product obtained in the step 2), and carrying out heat preservation reaction for 2h at the temperature of 80 ℃ to obtain an epoxy adduct.
Example 2
The silicon modified waterborne epoxy resin emulsion mainly comprises an epoxy adduct, epoxy resin, a cosolvent and water according to a mass ratio of 0.12: 1: 0.1: 0.6 is prepared;
wherein the molecular structure of the epoxy adduct has the molecular structure characteristics of both (a) and (b):
(a) is a terminal epoxy molecule comprising one siloxy group;
(b) is a terminal epoxy molecule comprising a polyether segment;
the polyether segment in (b) is at least one polyethylene glycol molecule with the molecular weight of 6000.
The structure of the epoxy adduct is a general formula (II), wherein n in the general formula is 0 or an integer of 1-10, and m is an integer of 50-250.
The epoxy adduct is mainly prepared from a silane coupling agent, hydrophilic polyether polyol, a catalyst and epoxy resin according to a mass ratio of 0.1:0.8:0.0025: 1.
The epoxy resin in the epoxy adduct preparation component and the epoxy resin in the silicon modified waterborne epoxy resin emulsion preparation component are both bisphenol A type epoxy resin, the epoxy resin for preparing the epoxy adduct is epoxy resin E-44, the epoxy resin for preparing the silicon modified waterborne epoxy resin emulsion is epoxy resin E-20, and the catalyst is boron trifluoride diethyl etherate;
the silane coupling agent is (3-triethoxysilylpropyl) succinic anhydride;
the hydrophilic polyether polyol is polyethylene glycol with the weight-average molecular weight of 6000.
The cosolvent is ethylene glycol.
The preparation method of the silicon modified waterborne epoxy resin emulsion comprises the following steps of sequentially carrying out:
1) adding the epoxy adduct, the epoxy resin and the cosolvent into an emulsifying device, heating to 60 ℃, and stirring until the mixture is uniformly mixed;
2) slowly dripping water into the mixture obtained in the step 1) within 1.5 hours at the temperature of 60 ℃, carrying out shearing emulsification for 1 hour at the rotating speed of 3000 r/min, then cooling to 40 ℃, and continuously stirring for 0.5 hour to obtain the silicon modified waterborne epoxy resin emulsion.
The preparation method of the epoxy adduct comprises the following steps of sequentially carrying out:
1) in N2Under protection, carrying out vacuum dehydration on the hydrophilic polyether polyol at 130 ℃ for 1.5 hours, then cooling to 110 ℃, adding the epoxy resin, stirring for 6 minutes until the epoxy resin is completely melted;
2) adding a catalyst into the mixture obtained in the step 1), uniformly mixing, carrying out heat preservation reaction at 60 ℃ for 1h to obtain a colorless transparent product, and then cooling to 50 ℃;
3) adding a silane coupling agent into the product obtained in the step 2), and carrying out heat preservation reaction for 1h at 70 ℃ to obtain an epoxy adduct.
Example 3
The silicon modified waterborne epoxy resin emulsion mainly comprises an epoxy adduct, epoxy resin, a cosolvent and water according to a mass ratio of 0.12: 1: 0.1: 0.6 is prepared;
wherein the molecular structure of the epoxy adduct has the molecular structure characteristics of both (a) and (b):
(a) is a terminal epoxy molecule comprising one siloxy group;
(b) is a terminal epoxy molecule comprising a polyether segment;
the polyether segment in (b) is at least one polyoxyethylene monomethyl ether molecule with the molecular weight of 6000.
The structure of the epoxy adduct is a general formula (III), wherein n in the general formula is 0 or an integer of 1-10, and m is an integer of 50-250.
The epoxy adduct is mainly prepared from a silane coupling agent, hydrophilic polyether polyol, a catalyst and epoxy resin according to a mass ratio of 0.01-0.5: 0.8:0.0025: 1.
The epoxy resin in the epoxy adduct preparation component and the epoxy resin in the silicon modified waterborne epoxy resin emulsion preparation component are both bisphenol A type epoxy resin E-20, and the catalyst is boron trifluoride diethyl etherate;
the silane coupling agent is 3-isocyanate propyl triethoxysilane;
the hydrophilic polyether polyol is polyoxyethylene monomethyl ether with the weight-average molecular weight of 5000.
The cosolvent is alcohol ester twelve.
The preparation method of the silicon modified waterborne epoxy resin emulsion comprises the following steps of sequentially carrying out:
1) adding the epoxy adduct, the epoxy resin and the cosolvent into an emulsifying device, heating to 60 ℃, and stirring until the mixture is uniformly mixed;
2) slowly dripping water into the mixture obtained in the step 1) within 1.5 hours at the temperature of 60 ℃, carrying out shearing emulsification for 2 hours at the rotating speed of 3000 r/min, then cooling to 40 ℃, and continuously stirring for 1 hour to obtain the silicon modified waterborne epoxy resin emulsion.
The preparation method of the epoxy adduct comprises the following steps of sequentially carrying out:
1) in N2Under protection, carrying out vacuum dehydration on hydrophilic polyether polyol at 140 ℃ for 3 hours, then cooling to 120 ℃, adding epoxy resin, stirring for 15 minutes until the epoxy resin is completely melted;
2) adding a catalyst into the mixture obtained in the step 1), uniformly mixing, carrying out heat preservation reaction at 60 ℃ for 1h to obtain a colorless transparent product, and then cooling to 50 ℃;
3) adding a silane coupling agent into the product obtained in the step 2), and carrying out heat preservation reaction for 1h at 70 ℃ to obtain an epoxy adduct.
Example 4
The silicon modified waterborne epoxy resin emulsion mainly comprises an epoxy adduct, epoxy resin, a cosolvent and water according to a mass ratio of 0.12: 1: 0.1: 0.6 is prepared;
wherein the molecular structure of the epoxy adduct has the molecular structure characteristics of both (a) and (b):
(a) is a terminal epoxy molecule comprising one siloxy group;
(b) is a terminal epoxy molecule comprising a polyether segment;
the polyether segment in (b) is at least one polyoxyethylene monomethyl ether molecule having a molecular weight of 5000.
The structure of the epoxy adduct is a general formula (III), wherein n in the general formula is 0 or an integer of 1-10, and m is an integer of 50-250.
The epoxy adduct is mainly prepared from a silane coupling agent, hydrophilic polyether polyol, a catalyst and epoxy resin according to a mass ratio of 0.01-0.5: 0.8:0.0025: 1.
The epoxy resin in the epoxy adduct preparation component and the epoxy resin in the silicon modified waterborne epoxy resin emulsion preparation component are both bisphenol A type epoxy resin, the epoxy resin for preparing the epoxy adduct is epoxy resin E-20, the epoxy resin for preparing the silicon modified waterborne epoxy resin emulsion is epoxy resin E-44, and the catalyst is boron trifluoride diethyl etherate;
the silane coupling agent is 3-aminopropyl triethoxysilane;
the hydrophilic polyether polyol is polyoxyethylene monomethyl ether with the weight-average molecular weight of 5000.
The cosolvent is isopropanol.
The preparation method of the silicon modified waterborne epoxy resin emulsion comprises the following steps of sequentially carrying out:
1) adding the epoxy adduct, the epoxy resin and the cosolvent into an emulsifying device, heating to 60 ℃, and stirring until the mixture is uniformly mixed;
2) slowly dripping water into the mixture obtained in the step 1) within 1.5 hours at the temperature of 60 ℃, carrying out shearing emulsification for 1 hour at the rotating speed of 3000 r/min, then cooling to 40 ℃, and continuously stirring for 0.5 hour to obtain the silicon modified waterborne epoxy resin emulsion.
The preparation method of the epoxy adduct comprises the following steps of sequentially carrying out:
1) in N2Under protection, carrying out vacuum dehydration on hydrophilic polyether polyol at 120 ℃ for 1 hour, then cooling to 80 ℃, adding epoxy resin, stirring for 15 minutes until the epoxy resin is completely melted;
2) adding a catalyst into the mixture obtained in the step 1), uniformly mixing, carrying out heat preservation reaction at 60 ℃ for 1h to obtain a colorless transparent product, and then cooling to 50 ℃;
3) adding a silane coupling agent into the product obtained in the step 2), and carrying out heat preservation reaction for 1h at 70 ℃ to obtain an epoxy adduct.
Experimental data:
the test method comprises the following steps: the silicon-modified waterborne epoxy resin emulsion of each example was mixed with Epikure8545-w52 curing agent of Hexion corporation, USA (the ratio of the mole number of active hydrogen of the curing agent to the mole number of epoxy group of waterborne epoxy resin was designed to be 0.8), sprayed on the surface of sand washing steel plate (treatment grade is Sa2.5), the thickness of paint film was 80 + -5 microns, baked at 80 ℃ for 30 minutes, and cured in standard environment for 7 days, and then neutral salt spray test was performed according to HG/T5176-2017 waterborne anticorrosive paint for steel structure.
TABLE 1 Properties of the present silicon-modified waterborne epoxy resin emulsion
As can be seen from the above table, the silicon-modified waterborne epoxy resin emulsion prepared by the raw materials and the process route has excellent adhesive force and salt spray resistance.
The silicon-modified waterborne epoxy resin emulsion and the preparation method thereof described herein are not limited to the above examples, and any modification or replacement according to the principles of the present disclosure is within the scope of the present disclosure.
Claims (9)
1. A silicon modified waterborne epoxy resin emulsion is characterized in that: the epoxy resin is mainly prepared from an epoxy adduct, epoxy resin, a cosolvent and water according to a mass ratio of 0.1-0.2: 1: 0.1-0.2: 0.6-1;
wherein the molecular structure of the epoxy adduct has the molecular structure characteristics of both (a) and (b):
(a) is a terminal epoxy molecule comprising one siloxy group;
(b) is a terminal epoxy molecule comprising a polyether segment;
the polyether segment in (b) is at least one polyether molecule with the weight-average molecular weight of at least 2000, and the molecule is polyethylene glycol, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene monomethyl ether or polyoxyethylene polyoxypropylene block copolymerization monomethyl ether;
the epoxy resin is an epoxy resin with the weight-average molecular weight of 300-3000.
2. The silicon-modified aqueous epoxy resin emulsion according to claim 1, characterized in that: the structure of the epoxy adduct is shown as a general formula (I)
General formula (II)
General formula (III)
Or general formula (IV)
Wherein n in the general formula is 0 or an integer of 1 to 10, and m is an integer of 50 to 250.
3. The silicon-modified aqueous epoxy resin emulsion according to claim 2, characterized in that: the epoxy adduct is mainly prepared from a silane coupling agent, hydrophilic polyether polyol, a catalyst and epoxy resin according to a mass ratio of 0.01-0.1: 0.8-3.5: 0.0025-0.005: 1.
4. The silicon-modified aqueous epoxy resin emulsion according to claim 3, characterized in that: the epoxy resin in the epoxy adduct preparation component and the epoxy resin in the silicon modified waterborne epoxy resin emulsion preparation component are both bisphenol A type epoxy resin, and the catalyst is boron trifluoride diethyl etherate;
the silane coupling agent is one of 3-isocyanatopropyl trimethoxy silane, 3-isocyanatopropyl triethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3- (2-aminoethyl) -aminopropyl trimethoxy silane, 3- (2-aminoethyl) -aminopropyl triethoxy silane, 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3- (2, 3-epoxypropoxy) propyl triethoxy silane or (3-triethoxysilylpropyl) succinic anhydride;
the hydrophilic polyether polyol is one of polyethylene glycol, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene monomethyl ether or polyoxyethylene polyoxypropylene block copolymerization monomethyl ether, and the weight average molecular weight of the hydrophilic polyether polyol is 2000-10000.
5. The silicon-modified aqueous epoxy resin emulsion according to claim 1, characterized in that: the cosolvent is one or any combination of more than two of ethylene glycol butyl ether, ethylene glycol, propylene glycol methyl ether, dipropylene glycol butyl ether, isopropanol or alcohol ester twelve.
6. The silicon-modified aqueous epoxy resin emulsion according to claim 4, characterized in that: the epoxy resin for preparing the epoxy adduct and the epoxy resin for preparing the silicon modified waterborne epoxy resin emulsion are one or any combination of more than two of epoxy resin E-06, epoxy resin E-12, epoxy resin E-20, epoxy resin E-44 or epoxy resin E-51.
7. The method for producing the silicon-modified aqueous epoxy resin emulsion according to any one of claims 1 to 6, characterized in that: comprises the following steps which are carried out in sequence:
1) adding the epoxy adduct, the epoxy resin and the cosolvent into an emulsifying device, heating to 40-80 ℃, and stirring until the mixture is uniformly mixed;
2) slowly dripping water into the mixture obtained in the step 1) within 0.5-3 hours at the temperature of 40-80 ℃, shearing and emulsifying at the rotating speed of 500-4000 rpm, cooling to 30-50 ℃, and continuously stirring for 0.5-1.5 hours to obtain the silicon modified waterborne epoxy resin emulsion.
8. The method for preparing the silicon-modified aqueous epoxy resin emulsion according to claim 7, wherein: the preparation method of the epoxy adduct comprises the following steps of sequentially carrying out:
1) in N2Under protection, carrying out vacuum dehydration on the hydrophilic polyether polyol at the temperature of 120-140 ℃ for 1-3 hours, then cooling to 100-120 ℃, adding the epoxy resin, stirring for 5-30 minutes, and till the epoxy resin is completely melted;
2) adding a catalyst into the mixture obtained in the step 1), uniformly mixing, carrying out heat preservation reaction at 60-140 ℃ for 1-4 h to obtain a colorless transparent product, and then cooling to 50-100 ℃;
3) adding a silane coupling agent into the product obtained in the step 2), and reacting for 1-3 hours at the temperature of 70-90 ℃ to obtain the epoxy adduct.
9. The method for preparing the silicon-modified aqueous epoxy resin emulsion according to claim 7, wherein: in the step 2) of the method for preparing the silicon modified waterborne epoxy resin emulsion, the time for dropwise adding water and shearing and emulsifying is 1-2 hours, and the rotating speed is 1000-3000 r/min; the mixing temperature in the step 1) of the method for preparing the silicon modified waterborne epoxy resin emulsion is 50-70 ℃, and the temperature of the mixture in the step 2) is 50-70 ℃ when water is dripped.
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| CN115260890A (en) * | 2022-08-19 | 2022-11-01 | 张滨 | Silane modified epoxy waterborne polyurethane steel structure anticorrosive paint |
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