CN114479015B - Waterborne epoxy resin curing agent and preparation method and application thereof - Google Patents
Waterborne epoxy resin curing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN114479015B CN114479015B CN202011157968.7A CN202011157968A CN114479015B CN 114479015 B CN114479015 B CN 114479015B CN 202011157968 A CN202011157968 A CN 202011157968A CN 114479015 B CN114479015 B CN 114479015B
- Authority
- CN
- China
- Prior art keywords
- curing agent
- component
- epoxy resin
- resin curing
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/18—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/52—Amino carboxylic acids
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/3331—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic
- C08G65/33313—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic aromatic
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- C08G2150/00—Compositions for coatings
- C08G2150/90—Compositions for anticorrosive coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the field of polymer chemistry, and particularly relates to a waterborne epoxy resin curing agent, a preparation method and application thereof. The aqueous epoxy resin curing agent has the following structural formula:
the aqueous epoxy resin curing agent has good acid-resistant effect, can be applied to the fields of aqueous floors and aqueous steel structure anticorrosive coatings, and has obvious application value.
Description
Technical Field
The invention belongs to the field of polymer chemistry, and particularly relates to a waterborne epoxy resin curing agent, a preparation method and application thereof.
Background
In recent years, along with the driving of national policies and the continuous enhancement of environmental awareness of people, the application of waterborne epoxy resin coatings is more and more widespread, but the waterborne epoxy curing agents prepared from aliphatic amines are mostly used in the market, and the types of waterborne epoxy curing agents prepared from aromatic amines are few.
Aniline, also known as anilin, is an aromatic amine, has poor water solubility, and is one of the most important amine substances. As a common bulk raw material, the aniline has very wide application, and has very important application in the fields of dyes, medicines, resins, rubber vulcanization accelerators and the like. Aniline is low in activity and high in hydrophobicity, and therefore it is difficult to prepare a water-based epoxy curing agent, so that the water-based epoxy curing agent is prepared in a polyaniline form at present, for example, the water-based epoxy curing agent is prepared in a polyaniline form in Chinese patent document CN105647378A, but the water-based curing agent prepared by the aniline is complex in process and poor in film forming performance due to the fact that the polyaniline is high in hydrophobicity and poor in toughness.
Therefore, the research of directly preparing the aqueous epoxy resin curing agent from aniline or modified aniline has important significance.
Disclosure of Invention
The invention aims to provide a waterborne epoxy resin curing agent and a preparation method thereof, wherein the waterborne epoxy resin curing agent is obtained by reacting aniline and aniline derivatives with compounds containing hydrophilic groups such as polyether chain segments and the like under certain conditions and reacting the compounds with paraformaldehyde and polyamine under certain conditions, and further provides application of the epoxy resin curing agent.
The invention is realized by the following technical scheme:
in a first aspect, the present invention provides an aqueous epoxy resin curing agent having the structural formula shown below:
wherein n is 1 or 2;
R 1 、R 2 h, C1 to C10 carboxyl, C1 to C10 ester, C1 to C10 hydroxyl or C1 to C50 polyether segments respectively, but not simultaneously H;
when n is 1, R 3 H, C1 to C10 alkyl, C1When the number n is 2, R is C10 amino, C1-C10 hydroxyl or C1-C10 carboxyl 3 Absence of;
R 4 is H, halogen, C1-C10 alkyl or-CH 2 -NH-R 3 ；R 4’ Is H, halogen, C1-C10 alkyl or-CH 2 -NH-R 3 ；
R 5 ，R 6 Independently of one another, H or halogen.
Preferably, in the aqueous epoxy resin curing agent, R 1 H, C1 to C5 carboxyl, C1 to C8 hydroxyl, C1 to C8 ester group or C2 to C30 polyether chain segment; r is R 2 H, C1 to C5 carboxyl, C1 to C8 hydroxyl, C1 to C8 ester group or C2 to C30 polyether chain segment; when n is 1, R 3 H, C1 to C6 alkyl, C1 to C10 amino, C1 to C5 carboxyl or C1 to C8 hydroxyl, and when n is 2, R 3 Absence of; r is R 4 Is H or-CH 2 -NH-R 3 ；R 4’ Is H or-CH 2 -NH-R 3 ；R 5 ，R 6 H independently of each other.
According to a second aspect of the present invention, there is provided a method of preparing the above aqueous epoxy resin curing agent, the method comprising reacting the following raw materials to prepare the above aqueous epoxy resin curing agent:
a) Aniline or aniline derivatives
b) Compounds containing carboxyl, hydroxyl, polyether segments or ester groups
R-OH，
R-C(O)-OR’；
c) Formaldehyde solutions (preferred concentration ranges from 20wt% to 40 wt%) or formaldehyde polymers;
d) Monoamines or polyamines;
wherein R is 1 、R 2 H, C1 to C10 carboxyl groups, C1 to C10 ester groups and C1 to C1 respectively0 hydroxy or a C1-C50 polyether segment, but not simultaneously H;
when n is 1, R 3 H, C1 to C10 alkyl, C1 to C10 amino, C1 to C10 hydroxy or C1 to C10 carboxy, R when n is 2 3 Absence of;
R 4 is H, halogen, C1-C10 alkyl or-CH 2 -NH-R 3 ；R 4’ Is H, halogen, C1-C10 alkyl or-CH 2 -NH-R 3 ；
R 5 ，R 6 Independently of each other, H or halogen;
R 7 h, C1 to C10 hydroxyl or C2 to C10 epoxy;
R 8 is H or methyl;
r is C1-C10 alkyl, C1-C10 ester group or C1-C50 polyether chain segment;
r' is C1-C5 alkyl or C1-C5 hydroxyalkyl.
Preferably, in the preparation method of the aqueous epoxy resin curing agent, R 1 H, C1 to C5 carboxyl, C1 to C8 hydroxyl, C1 to C8 ester group or C2 to C30 polyether chain segment; r is R 2 H, C1 to C5 carboxyl, C1 to C8 hydroxyl, C1 to C8 ester group or C2 to C30 polyether chain segment; when n is 1, R 3 H, C1 to C6 alkyl, C1 to C10 amino, C1 to C5 carboxyl or C1 to C8 hydroxyl, and when n is 2, R 3 Absence of; r is R 4 Is H or-CH 2 -NH-R 3 ；R 4’ Is H or-CH 2 -NH-R 3 ；R 5 ，R 6 Are independently of each other H; r is R 7 Is C2-C6 epoxy; r is C1-C5 alkyl, C1-C8 ester group or C2-C30 polyether chain segment.
Preferably, in the above-mentioned method for preparing the aqueous epoxy resin curing agent,
the component a) is at least one selected from aniline, N-methylaniline, N-ethylaniline, halogenated anilines (halogen selected from fluorine, chlorine, bromine, iodine) and alkyl (for example C1-C6 alkyl) substituted anilines, preferably aniline;
the component b) is at least one selected from acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, allyl alcohol, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether;
the component c) is selected from formaldehyde solution, trioxymethylene or paraformaldehyde;
the component d) is at least one selected from aliphatic polyamine and derivatives thereof, alicyclic amine and derivatives thereof and aromatic amine and derivatives thereof; the aliphatic polyamine is at least one selected from ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine and octylenediamine; the alicyclic amine is at least one selected from isophorone diamine, 1, 3-cyclohexanediamine, 4' -diaminodicyclohexylmethane and cyclohexylamine; the aromatic amine is selected from m-xylylenediamine.
Further, the method for preparing the aqueous epoxy resin curing agent comprises the following steps:
(1) Adding the component a) and the component b) with the selected mass into a reaction container, heating (for example, heating to 80-120 ℃) and stirring for reaction (for example, reacting for 2-6 hours) to prepare an intermediate product;
(2) Adding the component c) and the component d) with the selected mass into the reaction container, heating (for example, the reaction temperature is 80-120 ℃) and stirring for reaction (for example, the reaction lasts for 2-6 hours) to prepare a curing agent product;
(3) And cooling the curing agent product (for example, cooling to room temperature), and adding deionized water to obtain the waterborne epoxy resin curing agent.
Preferably, in the above preparation method, the component a) is at least one selected from aniline, N-methylaniline, N-ethylaniline, halogenated anilines (halogen selected from fluorine, chlorine, bromine, iodine) and alkyl (e.g. C1-C6 alkyl) substituted anilines, preferably aniline; the component b) is at least one selected from acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, allyl alcohol, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether; the component c) is selected from formaldehyde solution, trioxymethylene or paraformaldehyde; the component d) is at least one selected from aliphatic polyamine and derivatives thereof, alicyclic amine and derivatives thereof and aromatic amine and derivatives thereof; the aliphatic polyamine is at least one selected from ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine and octylenediamine; the alicyclic amine is at least one selected from isophorone diamine, 1, 3-cyclohexanediamine, 4' -diaminodicyclohexylmethane and cyclohexylamine; the aromatic amine is selected from m-xylylenediamine.
Preferably, in the above preparation process, the molar ratio of component a) to component b) is 1: (0.5 to 2.5), preferably 1: (1-2), for example, may be 1:0.7 or 1:1.6; and/or the molar ratio of component a), component c) to component d) is 1: (0.5-2): (0.5-2), preferably 1 (0.8-1.2): (0.8 to 1.2), for example, may be 1:0.6:0:6, 1:1: 1. 1:1.5:1.5 or 1:1.8:1.8, wherein the molar amount of component c) is based on formaldehyde.
In a third aspect, the invention also provides an application of the aqueous epoxy resin curing agent or the aqueous epoxy resin curing agent prepared by the preparation method in preparation of aqueous paint.
In a fourth aspect, the invention provides a water-based paint, which is prepared from the water-based epoxy resin curing agent or the water-based epoxy resin curing agent prepared by the preparation method.
Methods for preparing waterborne coatings from waterborne epoxy curing agents are well known in the art.
The technical scheme of the invention has the following advantages:
(1) The invention creatively modifies the aniline, and then prepares the aqueous epoxy curing agent by using the aniline and the derivatives thereof through a certain process. The aqueous epoxy curing agent can crosslink with epoxy resin by virtue of active hydrogen on aniline and active hydrogen on a side chain, so that the crosslinking density of the system is increased, and the performance of the system is further improved. The aqueous epoxy resin curing agent has good acid-resistant effect, can be applied to the fields of aqueous floors and aqueous steel structure anticorrosive coatings, and has obvious application value.
(2) The ionic and nonionic aqueous epoxy curing agents can be prepared from compounds containing carboxyl, hydroxyl, ester or polyether structures respectively, and can be suitable for different formula systems.
(3) The invention uses different monoamine or polyamine and amino-containing compound with different structures to prepare the aqueous epoxy resin curing agent with different chain segment lengths, different systems, different mechanical strength and different performances, thereby meeting various application requirements.
(4) The aqueous epoxy resin curing agent can be used alone or in combination with other epoxy resin curing agents, and has wide application range.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is an IR chart of an aqueous epoxy resin curing agent of example 1 of the present invention;
FIG. 2 is an IR chart of the aqueous epoxy resin curing agent of example 2 of the present invention;
FIG. 3 is an IR chart of the aqueous epoxy resin curing agent of example 3 of the present invention;
FIG. 4 is an IR chart of the aqueous epoxy resin curing agent of example 4 of the present invention.
FIG. 5 is an IR chart of the aqueous epoxy resin curing agent of example 5 of the present invention.
Detailed Description
The invention is further illustrated by means of specific examples which are given solely as illustrations of the invention and do not limit the scope thereof.
The names, abbreviations and sources of the main chemicals used in the examples of the present invention are shown in the following table. The reagents used were all chemically pure unless indicated otherwise.
TABLE 1
Example 1
The preparation method of the aqueous epoxy resin curing agent comprises the following steps: (1) 9.3g (0.1 mol) of aniline and 30g (0.053 mol) of polyethylene glycol diglycidyl ether are added into a three-port reaction vessel, stirred uniformly, heated to 80 ℃ and reacted for 2 hours to obtain an intermediate product; (2) 3g of paraformaldehyde (containing 0.1mol of formaldehyde) and 6g (0.1 mol) of ethylenediamine are added into the three-port reaction vessel in the step (1) and reacted for 2 hours under stirring at 80 ℃ to prepare a curing agent product; (3) And cooling the curing agent product to room temperature, and adding 46.5g of deionized water to obtain the waterborne epoxy resin curing agent, wherein the theoretical structural formula is shown as below, and the IR chart is shown as in figure 1. The IR diagram analysis shows that the actual structural formula is the same as the theoretical structural formula.
Example 2
The preparation method of the aqueous epoxy resin curing agent comprises the following steps: (1) 9.3g (0.1 mol) of aniline and 56g (0.1 mol) of polyethylene glycol diglycidyl ether are added into a three-port reaction vessel, stirred uniformly, heated to 120 ℃ and reacted for 4 hours to obtain an intermediate product; (2) 6g of paraformaldehyde (containing 0.2mol of formaldehyde) and 20.6g (0.2 mol) of diethylenetriamine are added into a three-port reaction vessel in the step (1) and reacted for 4 hours under stirring at 120 ℃ to prepare a curing agent product; (3) And cooling the curing agent product to room temperature, and adding 87.7g of deionized water to obtain the waterborne epoxy resin curing agent. The theoretical structural formula is shown below, and the IR chart is shown in FIG. 2. The IR diagram analysis shows that the actual structural formula is the same as the theoretical structural formula.
Example 3
The preparation method of the aqueous epoxy resin curing agent comprises the following steps: (1) 9.3g (0.1 mol) of aniline and 7.2g (0.1 mol) of acrylic acid are added into a three-port reaction vessel, stirred uniformly, heated to 80 ℃ and reacted for 2 hours to obtain an intermediate product; (2) 3g of paraformaldehyde (containing 0.1mol of formaldehyde) and 6g (0.1 mol) of ethylenediamine are added into the three-port reaction vessel in the step (1) and reacted for 4 hours under stirring at 80 ℃ to prepare a curing agent product; (3) And cooling the curing agent product to room temperature, and adding 23.7g of deionized water to obtain the waterborne epoxy resin curing agent. The theoretical structural formula is shown below, and the IR chart is shown in FIG. 3. The IR diagram analysis shows that the actual structural formula is the same as the theoretical structural formula.
Example 4
The preparation method of the aqueous epoxy resin curing agent comprises the following steps: (1) 9.3g (0.1 mol) of aniline and 23.2g (0.2 mol) of hydroxyethyl acrylate are added into a three-port reaction vessel, stirred uniformly, heated to 80 ℃ and reacted for 2 hours to obtain an intermediate product; (2) 3g of paraformaldehyde (containing 0.1mol of formaldehyde) and 6g (0.1 mol) of ethylenediamine are added into the three-port reaction vessel in the step (1) and reacted for 4 hours under stirring at 80 ℃ to prepare a curing agent product; (3) And cooling the curing agent product to room temperature, and adding 39.7g of deionized water to obtain the waterborne epoxy resin curing agent. The theoretical structural formula is shown below, and the IR chart is shown in FIG. 4. The IR diagram analysis shows that the actual structural formula is the same as the theoretical structural formula.
Example 5
The preparation method of the aqueous epoxy resin curing agent comprises the following steps: (1) 9.3g (0.1 mol) of aniline and 30g (0.053 mol) of polyethylene glycol diglycidyl ether are added into a three-port reaction vessel, stirred uniformly, heated to 80 ℃ and reacted for 2 hours to obtain an intermediate product; (2) 6g of paraformaldehyde (containing 0.2mol of formaldehyde) and 12g (0.2 mol) of ethylenediamine are added into the three-port reaction vessel in the step (1) and reacted for 2 hours under stirring at 80 ℃ to prepare a curing agent product; (3) The curing agent product is cooled to room temperature, 53.7g of deionized water is added, and the waterborne epoxy resin curing agent is obtained, the theoretical structural formula of the waterborne epoxy resin curing agent is shown as below, and the IR chart is shown as figure 5. The IR diagram analysis shows that the actual structural formula is the same as the theoretical structural formula.
The aqueous epoxy resin curing agent prepared in examples 1 to 5, a commercial aqueous epoxy resin curing agent and an epoxy resin emulsion wanpro0901 are respectively and uniformly mixed according to a certain proportion, then a paint film template is scraped and coated, and an acid resistance test is carried out, wherein the test method is the medium-C method of GB/T9274-1988 paint and varnish liquid medium resistance test, and the specific test results are shown in Table 2.
TABLE 2
| Numbering device | Resistant to 10% H 2 SO 4 (d) |
| Example 1 | 10 |
| Example 2 | 12 |
| Example 3 | 7 |
| Example 4 | 8 |
| Example 5 | 12 |
| Commercially available curing agents | 3 |
As can be seen from the test results in Table 2, the epoxy resin cured product paint films prepared by the aqueous epoxy resin curing agent in the embodiments 1-5 have good acid resistance, completely meet the application requirements of the epoxy resin terrace material, and have certain application fields.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (11)
1. The aqueous epoxy resin curing agent is characterized by having the following structural formula:
wherein n is 1 or 2;
R 1 、R 2 h, C1 to C10 carboxyl, C1 to C10 ester, C1 to C10 hydroxyl or C1 to C50 polyether segments respectively, but not simultaneously H;
when n is 1, R 3 H, C1 to C10 alkyl, C1 to C10 amino, C1 to C10 hydroxy or C1 to C10 carboxy, R when n is 2 3 Absence of;
R 4 is H, halogen, C1-C10 alkyl or-CH 2 -NH-R 3 ；R 4’ Is H, halogen, C1-C10 alkyl or-CH 2 -NH-R 3 ；
R 5 ，R 6 Independently of one another, H or halogen.
2. The aqueous epoxy resin curing agent according to claim 1, wherein R 1 H, C1 to C5 carboxyl, C1 to C8 hydroxyl or C2 to C30 polyether chain segments; r is R 2 H, C1 to C5 carboxyl, C1 to C8 hydroxyl or C2 to C30 polyether chain segments; when n is 1, R 3 H, C1 to C6 alkyl, C1 to C10 amino, C1 to C5 carboxyl or C1 to C8 hydroxyl, or R when n is equal to 2 3 Absence of; r is R 4 Is H or-CH 2 -NH-R 3 ；R 4’ Is H or-CH 2 -NH-R 3 ；R 5 ，R 6 H independently of each other.
3. A method of preparing the aqueous epoxy resin curing agent of claim 1, comprising reacting the following materials to prepare the aqueous epoxy resin curing agent:
a) Aniline or aniline derivatives
b) Compounds containing carboxyl, hydroxyl, polyether segments or ester groups
R-OH
R-C(O)-OR’；
c) Formaldehyde solutions or formaldehyde polymers;
d) Monoamines or polyamines;
wherein R is 1 、R 2 H, C1 to C10 carboxyl, C1 to C10 ester, C1 to C10 hydroxyl or C1 to C50 polyether segments respectively, but not simultaneously H;
when n is 1, R 3 H, C1 to C10 alkyl, C1 to C10 amino, C1 to C10 hydroxy or C1 to C10 carboxy, R when n is 2 3 Absence of;
R 4 is H, halogen, C1-C10 alkyl or-CH 2 -NH-R 3 ；R 4 ' is H, halogen, C1-C10 alkyl or-CH 2 -NH-R 3 ；
R 5 ，R 6 Independently of each other, H or halogen;
R 7 h, C1 to C10 hydroxyl or C2 to C10 epoxy;
R 8 is H or methyl;
r is C1-C10 alkyl, C1-C10 ester group or C1-C50 polyether chain segment;
r' is C1-C5 alkyl or C1-C5 hydroxyalkyl.
4. A method according to claim 3, wherein R 1 H, C1 to C5 carboxyl, C1 to C8 hydroxyl, C1 to C8 ester group or C2 to C30 polyether chain segment; r is R 2 H, C1 to C5 carboxyl, C1 to C8 hydroxyl, C1 to C8 ester group or C2 to C30 polyether chain segment; when n is 1, R 3 H, C1 to C6 alkyl, C1 to C10 amino, C1 to C5 carboxyl or C1 to C8 hydroxyl, and when n is 2, R 3 Absence of; r is R 4 Is H or-CH 2 -NH-R 3 ；R 4’ Is H or-CH 2 -NH-R 3 ；R 5 ，R 6 Are independently of each other H; r is R 7 Is C2-C6 epoxy; r is C1-C5 alkyl, C1-C8 ester group or C2-C30 polyether chain segment.
5. The method of claim 3, wherein the step of,
the component a) is at least one selected from aniline, N-methylaniline, N-ethylaniline, halogenated aniline and alkyl aniline;
the component b) is at least one selected from acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, allyl alcohol, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether;
the component c) is selected from formaldehyde solution, trioxymethylene or paraformaldehyde;
the component d) is at least one selected from aliphatic polyamine, alicyclic amine and aromatic amine; the aliphatic polyamine is at least one selected from ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine and octylenediamine; the alicyclic amine is at least one selected from isophorone diamine, 1, 3-cyclohexanediamine, 4' -diaminodicyclohexylmethane and cyclohexylamine; the aromatic amine is selected from m-xylylenediamine.
6. The method of claim 5, wherein component a) is aniline.
7. A method according to any one of claims 3-5, characterized in that the method comprises:
(1) Adding the component a) and the component b) with the selected mass into a reaction vessel, heating to 80-120 ℃, and reacting for 2-6 h under stirring to obtain an intermediate product;
(2) Adding the component c) and the component d) with the selected mass into the reaction container, heating and stirring to react for 2-6 h, wherein the reaction temperature is 80-120 ℃, and preparing a curing agent product;
(3) And cooling the curing agent product, and adding deionized water to obtain the waterborne epoxy resin curing agent.
8. The process according to any one of claims 3 to 5, wherein the molar ratio of component a) to component b) is 1: (0.5-2.5); and/or the number of the groups of groups,
the molar ratio of component a), component c) to component d) is 1: (0.5-2): (0.5-2), wherein the molar amount of component c) is calculated as formaldehyde.
9. The process of claim 8 wherein the molar ratio of component a) to component b) is 1: (1-2); and/or the number of the groups of groups,
the mol ratio of the component a), the component c) and the component d) is 1 (0.8-1.2): (0.8-1.2).
10. Use of the aqueous epoxy resin curing agent of any one of claims 1-2 or the aqueous epoxy resin curing agent prepared by the method of any one of claims 3-9 in the preparation of an aqueous coating.
11. An aqueous coating material, characterized in that the aqueous epoxy resin curing agent is prepared by adopting the aqueous epoxy resin curing agent in any one of claims 1-2 or the aqueous epoxy resin curing agent prepared by the method in any one of claims 3-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011157968.7A CN114479015B (en) | 2020-10-26 | 2020-10-26 | Waterborne epoxy resin curing agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011157968.7A CN114479015B (en) | 2020-10-26 | 2020-10-26 | Waterborne epoxy resin curing agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114479015A CN114479015A (en) | 2022-05-13 |
| CN114479015B true CN114479015B (en) | 2023-05-26 |
Family
ID=81470513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011157968.7A Active CN114479015B (en) | 2020-10-26 | 2020-10-26 | Waterborne epoxy resin curing agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114479015B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5936011A (en) * | 1995-05-09 | 1999-08-10 | Mitsubishi Gas Chemical Company, Inc. | Modified polyamine, aqueous epoxy resin curing agent using the same and process for producing thereof |
| CN105504296A (en) * | 2015-12-29 | 2016-04-20 | 江苏丰彩新型建材有限公司 | Non-ionic waterborne epoxy curing agent and preparing method thereof |
| CN105713183A (en) * | 2016-02-02 | 2016-06-29 | 江苏丰彩新型建材有限公司 | Epoxy resin curing agent and preparation method thereof |
| WO2018212766A1 (en) * | 2017-05-16 | 2018-11-22 | Evonik Degussa Gmbh | Epoxy curing agents, compositions and uses thereof |
| CN110156957A (en) * | 2019-05-29 | 2019-08-23 | 上海骁鹏新材料科技有限公司 | Aqueous epoxy curing agent and its preparation method and application |
| CN110563927A (en) * | 2019-10-10 | 2019-12-13 | 杭州崇成科技有限公司 | Water-based epoxy resin curing agent and preparation method thereof |
-
2020
- 2020-10-26 CN CN202011157968.7A patent/CN114479015B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5936011A (en) * | 1995-05-09 | 1999-08-10 | Mitsubishi Gas Chemical Company, Inc. | Modified polyamine, aqueous epoxy resin curing agent using the same and process for producing thereof |
| CN105504296A (en) * | 2015-12-29 | 2016-04-20 | 江苏丰彩新型建材有限公司 | Non-ionic waterborne epoxy curing agent and preparing method thereof |
| CN105713183A (en) * | 2016-02-02 | 2016-06-29 | 江苏丰彩新型建材有限公司 | Epoxy resin curing agent and preparation method thereof |
| WO2018212766A1 (en) * | 2017-05-16 | 2018-11-22 | Evonik Degussa Gmbh | Epoxy curing agents, compositions and uses thereof |
| CN110156957A (en) * | 2019-05-29 | 2019-08-23 | 上海骁鹏新材料科技有限公司 | Aqueous epoxy curing agent and its preparation method and application |
| CN110563927A (en) * | 2019-10-10 | 2019-12-13 | 杭州崇成科技有限公司 | Water-based epoxy resin curing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114479015A (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11597796B2 (en) | Ionic aqueous epoxy curing agent, preparation method therefor and use thereof | |
| CN106987194B (en) | Nonionic waterborne epoxy resin emulsion, nonionic waterborne epoxy curing agent, preparation methods of nonionic waterborne epoxy resin emulsion and nonionic waterborne epoxy curing agent and waterborne epoxy resin varnish | |
| US5369152A (en) | Urethane modified waterborne dispersions | |
| US4066592A (en) | Zwitterion-containing compositions | |
| JPS6079072A (en) | Water-dispersible binder for cationic electrodeposition paint lacquer, manufacture and electrodeposition | |
| JPS61166874A (en) | Adhesive and/or coating composition | |
| JPH02103272A (en) | Cathodic deposition paint binder and its manufacture | |
| JPS6241543B2 (en) | ||
| CN112225879B (en) | Modified amine curing agent and preparation method thereof | |
| JP2008247958A (en) | Aqueous epoxy resin composition | |
| CN115947930A (en) | Water-based cationic epoxy curing agent and preparation method thereof | |
| CN113956442B (en) | Preparation method of polyurethane modified nonionic aqueous amine epoxy resin curing agent | |
| CN114605616B (en) | Quick-drying nonionic water-based epoxy curing agent, and preparation method and application thereof | |
| CN109679017B (en) | Single-component aqueous acrylic acid dispersion and preparation method thereof | |
| CN114479015B (en) | Waterborne epoxy resin curing agent and preparation method and application thereof | |
| CN112341604B (en) | Emulsion type epoxy curing agent and preparation method thereof | |
| US4191674A (en) | Zwitterion-containing compositions | |
| JPH0578604A (en) | Manufacture of pigment paste resin for cathodic deposition coating composition | |
| JPS62127360A (en) | Coating composition for resin | |
| CN1187420C (en) | Process for producing pigment dispersing resin of positive ion electroplating paint | |
| CN105705545A (en) | Cationic alkyd resins | |
| CN110804364B (en) | Preparation method of high throwing power emulsion | |
| EP0930348B1 (en) | Basic cationic electrodeposition coating composition and method for its production | |
| CN113683754B (en) | Epoxy curing agent and preparation method and application thereof | |
| CN110483786B (en) | Aniline trimer modified sulfonate type waterborne epoxy curing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |