阅读说明：本技术 一种水性环氧树脂涂料 (Water-based epoxy resin coating ) 是由 刘鹏 于 2018-11-10 设计创作，主要内容包括：本发明涉及一种水性环氧树脂涂料,其特征在于,所述涂料含有阳离子型自乳化水性环氧树脂快干固化剂,该固化剂分子结构中含有亲水性的季铵盐阳离子和非离子长链水性化基团,多元脂肪胺位于所述固化剂的支链位置,能够与环氧树脂起固化反应。固化剂的分子结构中含有重复的亲水性的季铵盐阳离子、非离子长链水性化基团；能够与环氧树脂起固化反应的多元脂肪胺,具有自乳化性,同时多元脂肪胺结构使它与环氧树脂反应的交联密度更高、表干更快,使其具备固化速度快的特点,固化后的环氧树脂具有硬度高、韧性足的优点。(The invention relates to a water-based epoxy resin coating which is characterized by comprising a cationic self-emulsifying water-based epoxy resin quick-drying curing agent, wherein the molecular structure of the curing agent contains hydrophilic quaternary ammonium salt cations and nonionic long-chain water-based groups, and a polybasic aliphatic amine is positioned at the branched chain position of the curing agent and can perform a curing reaction with epoxy resin. The molecular structure of the curing agent contains repeated hydrophilic quaternary ammonium salt cations and nonionic long-chain waterborne groups; the polybasic aliphatic amine capable of performing curing reaction with the epoxy resin has self-emulsifying property, and simultaneously has the characteristics of higher crosslinking density and faster surface drying due to the structure of the polybasic aliphatic amine, so that the polybasic aliphatic amine has the function of fast curing speed, and the cured epoxy resin has the advantages of high hardness and enough toughness.)

1. The water-based epoxy resin coating is characterized by comprising a cationic self-emulsifying water-based quick-drying epoxy resin curing agent, wherein the molecular structure of the curing agent contains hydrophilic quaternary ammonium salt cations and nonionic long-chain water-based groups, and a polybasic aliphatic amine is positioned at the branched chain position of the curing agent and can perform a curing reaction with epoxy resin.

2. The water-based epoxy resin coating as claimed in claim 1, wherein the cationic self-emulsifying water-based epoxy resin quick-drying curing agent is prepared by a free radical polymerization method according to parts by weight, and comprises the following steps:

(1) preparation of a polybasic aliphatic amine monomer: introducing nitrogen and ice bath, adding 10-12 parts of dihydroxy-substituted vinyl monomer into a reaction device, dropwise adding 4-8 parts of sulfonic acid derivative into a reaction kettle while stirring, absorbing acid gas released in the reaction through an alkaline drying tube in the reaction process, keeping the temperature for reaction for 2-5 hours after 30min of dropwise addition, discharging to obtain substitutable alkene, and carrying out ice bath for later use; adding 10-12 parts of polyvinyl polyamine compound into a reaction kettle under an ice bath condition, stirring, dropwise adding 10-12 parts of substitutable alkene into the reaction kettle under a stirring condition, continuously stirring after 1h of dropwise adding, keeping the temperature and reacting for 2-3h, wherein the temperature in the whole process is not more than 5 ℃, obtaining a crude product of a polybasic aliphatic amine monomer, extracting salt in the crude product of the polybasic aliphatic amine monomer by using water as a solvent, repeatedly extracting the upper layer for 3-5 times, and distilling the upper layer to remove water to obtain the polybasic aliphatic amine monomer;

(2) low-temperature catalytic free radical polymerization: uniformly stirring 6-8 parts of cationic monomer, 4-6 parts of branched chain type water-based monomer and 8-15 parts of polybasic aliphatic amine monomer in the step (1) in a mixing device at normal temperature to obtain a dropping liquid a for later use; dissolving 0.5-1 part of initiator in 10 parts of water-soluble solvent to obtain dropping liquid b for later use; adding 15-25 parts of water-soluble solvent into a reactor under the condition of introducing nitrogen, heating to 50-60 ℃, respectively dropwise adding a dropping liquid a and a dropping liquid b into the reactor at constant speed from different dropping grooves, after the dropping of the dropping liquid a and the dropping liquid b is finished within 3-4h, adding 0.05-0.1 part of initiator after the dropping is finished, keeping the temperature, continuing to react for 2-3h, and cooling to room temperature to obtain the cationic self-emulsifying water-based epoxy resin quick-drying curing agent.

3. The waterborne epoxy resin coating of claim 2, wherein the dihydroxy-substituted vinyl monomer is at least one of 3, 4-dihydroxy-1-butene, cis-1, 4-dihydroxy-2-butene, trans-1, 4-dihydroxy-2-butene, and 2, 3-dihydroxy-1-butene.

4. The waterborne epoxy resin coating of claim 2, wherein the sulfonic acid derivative is at least one of p-toluenesulfonic acid, p-toluenesulfonyl chloride, chlorosulfonic acid, benzenesulfonyl chloride, o-toluenesulfonyl chloride, and o-toluenesulfonic acid.

5. The water-based epoxy resin coating as claimed in claim 2, wherein the alkaline drying tube is at least one of a calcium hydroxide drying tube, a quicklime drying tube and a sodium hydroxide drying tube.

6. The waterborne epoxy resin coating of claim 2, wherein the polyvinyl polyamine compound is at least one of isophorone diamine, trimethyl cyclohexane diamine, ethylene diamine, divinyl triamine, triethylene tetramine, and tetraethylene pentamine.

7. The waterborne epoxy resin coating of claim 2, wherein the cationic monomer is at least one of N, N, N-trimethyl allyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, N, N, N-trimethyl- (1- (4-vinylphenyl)) methyl ammonium chloride, acryloyloxyethyl trimethyl ammonium bromide, methacryloyloxyethyl trimethyl ammonium bromide, N-methyl-2-vinylpyridine chloride, and N-methyl-4-vinylpyridine chloride.

8. The waterborne epoxy resin coating as claimed in claim 2, wherein the branched waterborne monomer is polyethylene glycol methacrylate, polyethylene glycol acrylate, allyl polyethylene glycol or methallyl polyethylene glycol.

9. The water-based epoxy resin coating as claimed in claim 2, wherein the initiator is at least one of hydrogen peroxide, dibenzoyl peroxide, benzoic acid peroxide, azobisisobutyronitrile and azobisisoheptonitrile.

10. The water-based epoxy resin coating of claim 2, wherein the water-soluble solvent is at least one of ethanol, ethylene glycol monobutyl ether and ethylene glycol monomethyl ether.

Technical Field

The invention relates to a water-based epoxy resin, in particular to a water-based epoxy resin coating, and belongs to the technical field of environmental protection.

Background

The epoxy resin structure contains active groups such as epoxy groups, hydroxyl groups, ether bonds and the like, has a plurality of excellent electrical insulation properties, physical and mechanical properties, corrosion resistance and bonding properties, can permeate into various aspects of people's life in a direct or indirect way, and is used in the fields of economy and high technology, such as aerospace, anticorrosive coatings, building materials, industrial floor coatings and the like. Epoxy coatings are generally classified into solvent-based epoxies and waterborne epoxies. With the development of the world economy and science and technology, people are increasingly more conscious of environmental protection. The solvent type epoxy resin is a volatile organic solvent in the production and construction processes, causes serious pollution to the ecological environment of human beings, harms human health and limits the development and application.

Compared with solvent-based coatings, the water-based epoxy coating has the outstanding advantages of safe use, low VOC content, small smell, water cleaning and the like. Therefore, the water-based epoxy self-emulsifying water-based epoxy curing agent is not only a curing agent but also an emulsifier of epoxy resin in essence, and has the technical characteristics that the oleophylic property and the hydrophilic property of the curing agent are improved through modification, so that the curing agent achieves polarity balance. When the epoxy resin, the curing agent and the water are mixed by stirring, a stable dispersed multiphase structure is formed. The existing water-based curing agent has the defects of slow drying speed and low emulsifying efficiency on epoxy resin.

Chinese patent CN201410828589.4 provides a preparation method of an amide type self-emulsifying water-based epoxy resin curing agent, which comprises the steps of synthesis of an amido polyamine long chain, synthesis of a self-emulsifying water-based epoxy resin curing agent and the like. The molecular structure of the amide self-emulsifying waterborne epoxy resin curing agent prepared by the preparation method simultaneously contains a hydrophilic amido polyamine long-chain structure and a lipophilic bisphenol A resin structure, and does not contain polyether long chains and organic acid; the long-chain structure of the amido polyamine enables the paint film to have good flexibility, acid and alkali resistance and other properties, and the paint film does not contain polyether long chains and organic acid, so that the water resistance of the paint film is improved, and the application field of the water-based epoxy resin is widened; meanwhile, the polyamine structure enables the cross-linking density of a paint film to be high, and the pencil hardness to be high. The curing agent has a disadvantage of slow drying speed due to its amide structure.

Disclosure of Invention

In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a cationic self-emulsifying water-based quick-drying epoxy resin curing agent.

A cation type self-emulsifying water-based epoxy resin quick-drying curing agent is characterized in that the molecular structure of the curing agent contains hydrophilic quaternary ammonium salt cations and nonionic long-chain water-based groups; the polybasic aliphatic amine is positioned at the branched chain position of the curing agent, can perform curing reaction with the epoxy resin, and has higher crosslinking density and faster surface drying when reacting with the epoxy resin.

According to parts by weight, the cation type self-emulsifying water-based epoxy resin quick-drying curing agent adopts a free radical polymerization method and comprises the following steps:

(1) preparation of a polybasic aliphatic amine monomer: introducing nitrogen and ice bath, adding 10-12 parts of dihydroxy-substituted vinyl monomer into a reaction device, dropwise adding 4-8 parts of sulfonic acid derivative into a reaction kettle while stirring, absorbing acid gas released in the reaction through an alkaline drying tube in the reaction process, keeping the temperature for reaction for 2-5 hours after 30min of dropwise addition, discharging to obtain substitutable alkene, and carrying out ice bath for later use; adding 10-12 parts of polyvinyl polyamine compound into a reaction kettle under an ice bath condition, stirring, dropwise adding 10-12 parts of substitutable alkene into the reaction kettle under a stirring condition, continuously stirring after 1h of dropwise adding, keeping the temperature and reacting for 2-3h, wherein the temperature in the whole process is not more than 5 ℃, obtaining a crude product of a polybasic aliphatic amine monomer, extracting salt in the crude product of the polybasic aliphatic amine monomer by using water as a solvent, repeatedly extracting the upper layer for 3-5 times, and distilling the upper layer to remove water to obtain the polybasic aliphatic amine monomer;

(2) low-temperature catalytic free radical polymerization: uniformly stirring 6-8 parts of cationic monomer, 4-6 parts of branched chain type water-based monomer and 8-15 parts of polybasic aliphatic amine monomer in the step (1) in a mixing device at normal temperature to obtain a dropping liquid a for later use; dissolving 0.5-1 part of initiator in 10 parts of water-soluble solvent to obtain dropping liquid b for later use; adding 15-25 parts of water-soluble solvent into a reactor under the condition of introducing nitrogen, heating to 50-60 ℃, respectively dropwise adding a dropping liquid a and a dropping liquid b into the reactor at constant speed from different dropping grooves, after the dropping of the dropping liquid a and the dropping liquid b is finished within 3-4h, adding 0.05-0.1 part of initiator after the dropping is finished, keeping the temperature, continuing to react for 2-3h, and cooling to room temperature to obtain the cationic self-emulsifying water-based epoxy resin quick-drying curing agent.

The dihydroxy-substituted vinyl monomer is at least one of 3, 4-dihydroxy-1-butene, cis-1, 4-dihydroxy-2-butene, trans-1, 4-dihydroxy-2-butene and 2, 3-dihydroxy-1-butene.

The sulfonic acid derivative is at least one of p-toluenesulfonic acid, p-toluenesulfonyl chloride, chlorosulfonic acid, benzenesulfonyl chloride, o-toluenesulfonyl chloride and o-toluenesulfonic acid.

The alkaline drying tube is at least one of a calcium hydroxide drying tube, a quicklime drying tube and a sodium hydroxide drying tube.

The polyvinyl polyamine compound is at least one of isophorone diamine, trimethyl cyclohexane diamine, ethylene diamine, divinyl triamine, triethylene tetramine and tetraethylene pentamine

The cationic monomer is at least one of N, N, N-trimethyl allyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride, N, N, N-trimethyl- (1- (4-vinyl phenyl)) methyl ammonium chloride, acryloyloxyethyl trimethyl ammonium bromide, methacryloyloxyethyl trimethyl ammonium bromide, N-methyl-2-vinylpyridine chloride and N-methyl-4-vinylpyridine chloride.

The branched chain type water-based monomer is polyethylene glycol methacrylate, polyethylene glycol acrylate, allyl polyethylene glycol and methallyl polyethylene glycol, and the relative molecular weight of the branched chain type water-based monomer is 600-1200.

The initiator is at least one of hydrogen peroxide, dibenzoyl peroxide, benzoic acid peroxide, azobisisobutyronitrile and azobisisoheptonitrile.

The water-soluble solvent is at least one of ethanol, ethylene glycol monobutyl ether and ethylene glycol monomethyl ether.

Compared with the prior art, the invention has the following advantages or beneficial effects: (1) according to the invention, the polybasic aliphatic amine monomer is synthesized through the substitution reaction of the dihydroxy-substituted vinyl monomer, and the amine value of the monomer is higher; (2) the polybasic aliphatic amine monomer is used as a reaction type catalyst for free radical polymerization, and reduces the temperature of polymerization reaction while participating in polymerization as a monomer; (3) the molecular structure of the quick-drying curing agent contains repeated hydrophilic quaternary ammonium salt cations and nonionic long-chain waterborne groups; the polybasic aliphatic amine capable of performing curing reaction with the epoxy resin has self-emulsifying property, has the characteristics of higher crosslinking density and higher surface drying speed due to the structure of the polybasic aliphatic amine, and has the advantages of high hardness and enough toughness after being cured by the method.

Detailed Description

A cationic self-emulsifying waterborne epoxy resin fast-drying curing agent of the present invention is further described with reference to the following examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.

Example 1

A cation type self-emulsifying water-based epoxy resin quick-drying curing agent contains hydrophilic quaternary ammonium salt cations and nonionic long-chain water-based groups in the molecules; the polybasic aliphatic amine which can perform curing reaction with the epoxy resin is positioned at the branched chain position of the curing agent, and the crosslinking density and the surface drying speed of the reaction with the epoxy resin are higher.

The free radical polymerization method of the cationic self-emulsifying water-based epoxy resin quick-drying curing agent comprises the following steps of:

(1) preparation of a polybasic aliphatic amine monomer: introducing nitrogen and ice bath, adding 12 parts of 3, 4-dihydroxy-1-butene into a reaction device, dropwise adding 8 parts of paratoluensulfonyl chloride into a reaction kettle while stirring, absorbing acid gas released in the reaction through a calcium hydroxide drying tube in the reaction process, keeping the temperature for reaction for 5 hours after 30min of dropwise addition, discharging to obtain substitutable alkene, and carrying out ice bath for later use; adding 12 parts of isophorone diamine into a reaction kettle under an ice bath condition, stirring, dropwise adding 12 parts of substitutable alkene into the reaction kettle under a stirring condition, continuously stirring and carrying out heat preservation reaction for 3 hours after 1 hour of dropwise adding is finished, wherein the temperature in the whole process is not more than 5 ℃, obtaining a crude product of a polybasic aliphatic amine monomer, extracting salt in the crude product of the polybasic aliphatic amine monomer by using water as a solvent, repeatedly extracting the upper layer for 5 times, and distilling the upper layer to remove water to obtain the polybasic aliphatic amine monomer.

(2) Low-temperature catalytic free radical polymerization: uniformly stirring 6 parts of methacryloyloxyethyl trimethyl ammonium chloride, 4 parts of polyethylene glycol acrylate and 8 parts of the polybasic aliphatic amine monomer obtained in the step (1) in a mixing device at normal temperature to obtain a dropping liquid a for later use; dissolving 0.5 part of dibenzoyl peroxide in 10 parts of ethylene glycol monomethyl ether to obtain a dropping liquid b for later use; adding 15 parts of ethylene glycol monomethyl ether into a reactor under the condition of introducing nitrogen, heating to 50 ℃, respectively dropwise adding a dropping liquid a and a dropping liquid b into the reactor at a constant speed from different dropwise adding grooves, finishing dropwise adding the dropping liquid a and the dropping liquid b simultaneously for 3 hours, adding 0.05 part of dibenzoyl peroxide after finishing dropwise adding, keeping the temperature, continuing to react for 2 hours, and cooling to room temperature to obtain the cationic self-emulsifying water-based epoxy resin quick-drying curing agent.

Example 2

A cation type self-emulsifying water-based epoxy resin quick-drying curing agent contains hydrophilic quaternary ammonium salt cations and nonionic long-chain water-based groups in the molecules; the polybasic aliphatic amine which can perform curing reaction with the epoxy resin is positioned at the branched chain position of the curing agent, and the crosslinking density and the surface drying speed of the reaction with the epoxy resin are higher.

The free radical polymerization method of the cationic self-emulsifying water-based epoxy resin quick-drying curing agent comprises the following steps of:

(1) preparation of a polybasic aliphatic amine monomer: introducing nitrogen and ice bath, adding 10 parts of 2, 3-dihydroxy-1-butene into a reaction device, dropwise adding 4 parts of chlorosulfonic acid into a reaction kettle while stirring, absorbing acid gas released in the reaction through a sodium hydroxide drying tube in the reaction process, keeping the temperature for 2 hours after 30min of dropwise addition is finished, discharging to obtain substitutable alkene, and carrying out ice bath for later use; adding 10 parts of tetraethylenepentamine into a reaction kettle under the ice bath condition, stirring, dropwise adding 10 parts of substitutable alkene into the reaction kettle under the stirring condition, continuously stirring and carrying out heat preservation reaction for 2 hours after 1 hour of dropwise adding is finished, wherein the temperature in the whole process is not more than 5 ℃, obtaining a crude product of the polybasic aliphatic amine monomer, extracting salt in the crude product of the polybasic aliphatic amine monomer by using water as a solvent, repeatedly extracting the upper layer for 3 times, and distilling the upper layer to remove water to obtain the polybasic aliphatic amine monomer.

(2) Low-temperature catalytic free radical polymerization: stirring 7 parts of N, N, N-trimethyl allyl ammonium chloride, 5 parts of methyl allyl polyethylene glycol (the relative molecular weight is 1200) and 12 parts of the polybasic aliphatic amine monomer in the step (1) uniformly in a mixing device at normal temperature to obtain a dropping liquid a for later use; dissolving 0.8 part of azodiisoheptanonitrile in 10 parts of ethylene glycol monobutyl ether to obtain a dropping liquid b for later use; adding 19 parts of ethylene glycol monobutyl ether into a reactor under the condition of introducing nitrogen, heating to 56 ℃, respectively dropwise adding a dropping liquid a and a dropping liquid b into the reactor at a constant speed from different dropwise adding grooves, finishing dropwise adding the dropping liquid a and the dropping liquid b simultaneously within 3.5h, adding 0.07 part of azodiisoheptonitrile after finishing dropwise adding, keeping the temperature, continuing to react for 2.6h, and cooling to room temperature to obtain the cationic self-emulsifying water-based epoxy resin quick-drying curing agent.

Example 3

A cation type self-emulsifying water-based epoxy resin quick-drying curing agent contains hydrophilic quaternary ammonium salt cations and nonionic long-chain water-based groups in the molecules; the polybasic aliphatic amine which can perform curing reaction with the epoxy resin is positioned at the branched chain position of the curing agent, and the crosslinking density and the surface drying speed of the reaction with the epoxy resin are higher.

The free radical polymerization method of the cationic self-emulsifying water-based epoxy resin quick-drying curing agent comprises the following steps of:

(1) preparation of a polybasic aliphatic amine monomer: introducing nitrogen and ice bath, adding 10.5 parts of trans-1, 4-dihydroxy-2-butene into a reaction device, dropwise adding 5 parts of p-toluenesulfonic acid into a reaction kettle under the stirring condition, absorbing acid gas released in the reaction through a quick lime drying tube in the reaction process, keeping the temperature for reacting for 4 hours after 30min of dropwise adding is finished, discharging to obtain substitutable alkene, and carrying out ice bath for later use; adding 11 parts of trimethyl cyclic hexanediamine into a reaction kettle under the ice bath condition, stirring, dropwise adding 10.5 parts of substitutable alkene into the reaction kettle under the stirring condition, continuously stirring and carrying out heat preservation reaction for 2.5 hours after 1 hour of dropwise adding is finished, wherein the temperature in the whole process is not more than 5 ℃, obtaining a crude product of the polybasic aliphatic amine monomer, extracting salt in the crude product of the polybasic aliphatic amine monomer by using water as a solvent, repeatedly extracting the upper layer for 4 times, and distilling the upper layer to remove water to obtain the polybasic aliphatic amine monomer.

(2) Low-temperature catalytic free radical polymerization: uniformly stirring 8 parts of N-methyl-4-vinylpyridine chloride, 6 parts of methylallyl polyethylene glycol (with the relative molecular weight of 800) and 15 parts of the polybasic aliphatic amine monomer in the step (1) in a mixing device at normal temperature to obtain a dropping liquid a for later use; dissolving 1 part of hydrogen peroxide in 10 parts of ethanol to obtain a dropping liquid b for later use; adding 25 parts of ethanol into a reactor under the condition of introducing nitrogen, heating to 60 ℃, respectively dropwise adding a dropwise adding liquid a and a dropwise adding liquid b into the reactor at a constant speed from different dropwise adding grooves, finishing dropwise adding the two simultaneously for 4 hours, adding 0.1 part of hydrogen peroxide after finishing dropwise adding, keeping the temperature, continuing to react for 3 hours, and cooling to room temperature to obtain the cationic self-emulsifying water-based epoxy resin quick-drying curing agent.

Purchasing a certain brand of waterborne epoxy curing agent (comparative example) on the market, respectively adding 20 parts by weight of examples 1-3 and the comparative example into 35 parts of water, respectively marking as No. 1, No. 2, No. 3 and No. 4, respectively adding 25 parts of commercially available epoxy resin E-51 into the mixture after uniform dispersion, uniformly dispersing and emulsifying the mixture at a high speed, then adding 0.4 part of waterborne polyether modified organic silicon flatting agent into the mixture, and uniformly dispersing the mixture to obtain the epoxy floor paint, wherein the physical properties are shown in Table 1; taking out behind the epoxy terrace paint of 1-4 and rolling and coating on the cement board surface, the coating thickness through brushing 3 times to 1-4 is 50 microns +/-5 microns, and test performance is as following table 2 after the coating is completely cured:

table 1: performance Table of epoxy floor paint formulated in examples and comparative examples

Table 2: paint film performance table of epoxy floor paint prepared in examples and comparative examples

	Hardness of pencil	Adhesion force	Irradiating with ultraviolet lamp for 12h
				Example 1	2H	Level 0	Colorless and transparent
Example 2	2H	Level 0	Colorless and transparent
				Example 3	2H	Level 0	Colorless and transparent
Comparative example	HB	Level 0	Yellowish, colorless and transparent

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the following claims.