CN109608622B - Nonionic water-based polyamide curing agent and preparation method thereof - Google Patents
Nonionic water-based polyamide curing agent and preparation method thereof Download PDFInfo
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- 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
- C08G59/44—Amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/40—Polyamides containing oxygen in the form of ether groups
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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Abstract
The invention discloses a nonionic water-based polyamide curing agent and a preparation method thereof, and is characterized in that low-molecular-weight polyether amine and unsaturated acid anhydride react at 80-100 ℃ under the reflux condition to prepare a polyamide acid intermediate, then excessive alicyclic or aromatic polyamine is dripped at 100-120 ℃ to perform Michael addition reaction to obtain a polyamide acid-polyamine adduct, then the polyamide acid-polyamine adduct intermediate and polyamine are subjected to amidation copolymerization at 180-200 ℃ to prepare a brownish red polyamide curing agent, and finally the polyamide acid-polyamine adduct is cooled to 60 ℃ and added with water to disperse to obtain the nonionic water-based polyamide curing agent with the solid content of 50-60 wt%. The product of the invention has higher amine value and better water solubility, the preparation method is simple and feasible, the conditions are mild, the whole process flow does not contain any organic solvent, and the product is safe, environment-friendly and nontoxic.
Description
Technical Field
The invention belongs to the technical field of water-based paint, and particularly relates to a non-ionic water-based polyamide curing agent and a preparation method thereof.
Background
The traditional solvent type epoxy resin coating has been widely used in industry due to its characteristics of high adhesion, good wear resistance, excellent chemical resistance and solvent resistance, high hardness and the like. However, with the stricter requirements of relevant environmental standards at home and abroad, development of low-VOC (volatile organic compound) waterborne epoxy resin systems and relevant coating products is getting more and more attention and research from scientific research technicians at home and abroad. The water-based epoxy resin coating has excellent physical and chemical properties, is easy to produce, store and construct, has small smell, is safe, environment-friendly and nontoxic, and thus becomes a variety of water-based coatings which are mainly developed. In the development of water-based epoxy resin coatings, however, the curing agent has a large specific gravity for the water-based curing and modification.
The modification methods of the currently common waterborne epoxy resin curing agents can be roughly divided into three types: (1) amidated polyamines are prepared by reacting polyamines with mono-fatty acids; (2) polyamide is formed by condensing polyamine and dimer acid; (3) polyamine-epoxy adducts are obtained by addition of polyamines with epoxy resins. The commonly used modification methods (3) can be roughly classified into the following two types:
a typical modification method is to introduce a polyether structure with better hydrophilicity and longer chain segment on a curing agent structure. For example, chinese invention patent CN101007863A discloses a method for preparing a non-ionic waterborne epoxy resin curing agent, which comprises the steps of carrying out a chain extension reaction on polyether polyol diglycidyl ether or polyether epoxy resin or a mixture of the polyether diglycidyl ether and the polyether epoxy resin with aromatic polyamine or aliphatic polyamine, and then adding epoxy resin for further chain extension reaction to obtain the non-ionic waterborne epoxy resin curing agent. However, the polyether chain segment with larger molecular weight is introduced in the method, and the polyether chain segment does not react with the epoxy resin in a crosslinking way in the process of curing and film forming, so that the mechanical property of a film-forming material is not high, the hardness is lower, and meanwhile, the water resistance of a paint film is reduced due to the existence of the polyether chain segment with better hydrophilicity.
The other modification method is to add organic acid to neutralize and salify to adjust the hydrophilic-lipophilic balance value so as to obtain better emulsifying property and curing property. For example, Chinese patent CN101402720A discloses a method for preparing an ionic waterborne epoxy resin curing agent, which comprises the steps of capping polyethylene polyamine by using a monoepoxy compound, then dropwise adding liquid epoxy resin for chain extension, adding organic acid for neutralization and salt formation, and finally adding water for dilution to obtain the ionic waterborne epoxy resin curing agent. However, the method improves the hydrophilicity of the metal body by neutralizing organic acid into salt, and the metal body is easy to generate flash rust phenomenon by the presence of the organic acid; in addition, the ionic water-based curing agent has certain limitation on the selection of pigments, fillers and auxiliaries due to the addition of the organic acid.
Disclosure of Invention
In order to solve the problems and the defects of the prior art, the invention provides a nonionic water-based polyamide curing agent and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a nonionic water-based polyamide curing agent comprises the following steps:
(1) preparation of polyamic acid intermediate a: putting low-molecular-weight polyetheramine and unsaturated anhydride into a reaction device, slowly heating to 80-100 ℃ under the conditions of nitrogen protection, stirring, condensation water diversion and reflux, and reacting for 1-2 hours under heat preservation to obtain an unsaturated polyamic acid intermediate a;
(2) addition of intermediate a to polyamine: slowly dripping polyamine into the unsaturated polyamic acid intermediate a to perform Michael addition reaction for 1-2 h, keeping the temperature for reaction for 1-2 h, and controlling the reaction temperature to be 100-120 ℃ to obtain a polyamic acid-polyamine adduct intermediate b;
(3) and (3) polyamidation reaction: carrying out amidation polycondensation reaction on excessive polyamine and the intermediate b for 2-3 h at 180-200 ℃ under the reflux condition, then continuously heating to 200-220 ℃ and carrying out heat preservation reaction for 2-3 h until water is completely evaporated, thus preparing a copolymer polyamide curing agent of the intermediate b and the polyamine;
(4) adding water for dispersion: slowly dripping deionized water into the polyamide curing agent at the temperature of 60 +/-5 ℃ under the condition of high-speed stirring for about 30min to ensure that the solid content is 50-60 wt%, thus obtaining the non-ionic water-based polyamide curing agent.
Further, the low molecular weight polyether amine is selected from one or two of polyether amine D230 and D400.
Further, the unsaturated anhydride is selected from one of nadic anhydride, maleic anhydride and tetrahydrophthalic anhydride.
Further, the polyamine amine is selected from one or a mixture of more of isophorone diamine, 1-methyl-2, 4-cyclohexanediamine, 1, 3-cyclohexanediamine, m-xylylenediamine and p-xylylenediamine.
Further, the polyether amine, the unsaturated anhydride and the polyamine are mixed according to the molar ratio of substances of 1: 1: 1.0 to 1.5.
Furthermore, the solid amine value of the curing agent in the nonionic water-based polyamide curing agent is 160-330 mgKOH/g, and the equivalent of active hydrogen is 100-220 g/mol.
According to the scheme, the non-ionic water-based polyamide curing agent is prepared.
According to the scheme, the waterborne polyamide curing agent is applied to waterborne industrial terrace coatings.
According to the scheme, the waterborne polyamide curing agent is applied to the waterborne metal anticorrosive paint.
Compared with the prior art CN101007863A, the invention has the following outstanding advantages:
(1) the water-based polyamide curing agent prepared by the method does not contain any organic solvent, is easy to produce, store and construct, is safe, environment-friendly and nontoxic, and has simple and feasible preparation method and mild conditions.
(2) The amido polyamine chain segment, the polyether chain segment with low molecular weight, the alicyclic or benzene ring structure and the like in the water-based polyamide curing agent prepared by the invention ensure that a paint film has good physical properties such as substrate wettability, flexibility, hardness and the like and excellent chemical properties such as water resistance, acid and alkali resistance, humidity resistance, salt mist resistance and the like.
Compared with the prior art CN101402720A, the invention has the following outstanding advantages:
(3) the waterborne polyamide curing agent prepared by the invention does not contain organic acid, has wide selectivity on pigments, fillers, additives, base materials and the like, and widens the application field of waterborne epoxy resin.
The water-based polyamide curing agent provided by the invention has the advantages of high amine value, good water solubility, simple and feasible preparation method, mild conditions, no organic solvent in the whole process flow, safety, environmental protection and no toxicity; the amido polyamine chain segment, the low molecular weight polyether chain segment, the alicyclic or benzene ring structure and the like introduced by the water-based polyamide curing agent ensure that a paint film has excellent physical and chemical properties; the waterborne polyamide curing agent is not added with organic acid, has wide selectivity on pigments, fillers, additives, base materials and the like, and widens the application field of waterborne epoxy resin. The nonionic water-based polyamide curing agent provided by the invention can be suitable for industrial floor coatings, metal anticorrosive coatings and the like.
Detailed Description
In order to make the present invention more understandable to those skilled in the art, the following embodiments are provided to further illustrate the present invention, but the present invention is not limited to these embodiments.
Example 1
Putting the polyetheramine D400 and the nadic anhydride into a reaction bottle with a stirrer, a condensation and water separation device, a constant-pressure funnel, nitrogen protection, a thermometer and a heating sleeve, slowly heating to 90 ℃, and continuously stirring in the heating process to fully mix the two components and react for 1.5 hours in a heat preservation way;
slowly heating to 110 ℃, slowly adding isophorone diamine at a constant speed for addition reaction, and after finishing adding dropwise within 1.5h, keeping the temperature for reaction for 2 h;
then heating to 190 ℃ for amidation polycondensation reaction for 2.5h, distilling to remove water, and continuously heating to 210 ℃ for 2h until water is completely evaporated;
and finally, cooling to 60 ℃, dropwise adding deionized water under the condition of high-speed stirring, discharging after dropwise adding is finished for 30min to obtain the brownish red water-based polyamide curing agent a, wherein the solid content is 60wt%, the equivalent weight of active hydrogen of solid is 216g/mol, and the amine value is 168 mgKOH/g.
Wherein the dosage (mass/g) of the used raw materials is as follows:
example 2
Putting the polyetheramine D400 and maleic anhydride into a reaction bottle with a stirrer, a condensation and water separation device, a constant-pressure funnel, nitrogen protection, a thermometer and a heating sleeve, slowly heating to 85 ℃, and continuously stirring in the heating process to fully mix the two components for heat preservation reaction for 1 h;
slowly heating to 105 ℃, slowly dripping 1-methyl-2, 4-cyclohexanediamine at a constant speed for addition reaction, and keeping the temperature for reaction for 1.5 hours after finishing dripping within 2 hours;
then heating to 185 ℃ for amidation polycondensation reaction for 2h, distilling to remove water, and continuously heating to 205 ℃ for 2h until all water is evaporated;
and finally, cooling to 60 ℃, dropwise adding deionized water under the condition of high-speed stirring, discharging after dropwise adding is finished for 30min to obtain the brownish red water-based polyamide curing agent b, wherein the solid content is 55 wt%, the equivalent weight of active hydrogen of solid is 167g/mol, and the amine value is 212 mgKOH/g.
Wherein the dosage (mass/g) of the used raw materials is as follows:
example 3
Putting the polyetheramine D400 and tetrahydrophthalic anhydride into a reaction bottle with a stirrer, a condensation and water separation device, a constant-pressure funnel, nitrogen protection, a thermometer and a heating sleeve, slowly heating to 95 ℃, and continuously stirring in the heating process to fully mix the two components and react for 1.5 hours with heat preservation;
slowly heating to 115 ℃, slowly adding m-xylylenediamine at a constant speed for addition reaction, and after the addition reaction is finished within 2h, keeping the temperature for 1 h;
then heating to 195 ℃ for amidation polycondensation reaction for 2.5h, distilling to remove water, and continuously heating to 215 ℃ for 2h until water is completely evaporated;
and finally, cooling to 60 ℃, dropwise adding deionized water under the condition of high-speed stirring, discharging after dropwise adding is finished for 30min to obtain the brownish red water-based polyamide curing agent c, wherein the solid content is 58 wt%, the equivalent weight of active hydrogen of solid is 169g/mol, and the amine value is 205 mgKOH/g.
Wherein the dosage (mass/g) of the used raw materials is as follows:
example 4
Putting the polyetheramine D230 and the nadic anhydride into a reaction bottle with a stirrer, a condensation and water separation device, a constant-pressure funnel, nitrogen protection, a thermometer and a heating sleeve, slowly heating to 80 ℃, and continuously stirring in the heating process to fully mix the two components and react for 1h under heat preservation;
slowly heating to 115 ℃, slowly adding 1, 3-cyclohexanediamine dropwise at a constant speed for addition reaction, and keeping the temperature for reaction for 1.5h after dropwise addition is finished within 2 h;
then heating to 180 ℃ for amidation polycondensation reaction for 2h, distilling to remove water, and continuously heating to 205 ℃ for 2.5h until water is completely evaporated;
and finally, cooling to 60 ℃, dropwise adding deionized water under the condition of high-speed stirring, discharging after dropwise adding is finished for 30min to obtain the brownish red water-based polyamide curing agent d, wherein the solid content is 56 wt%, the equivalent weight of active hydrogen of solid is 125g/mol, and the amine value is 273 mgKOH/g.
Wherein the dosage (mass/g) of the used raw materials is as follows:
example 5
Putting the polyetheramine D230 and maleic anhydride into a reaction bottle with a stirrer, a condensation and water separation device, a constant-pressure funnel, nitrogen protection, a thermometer and a heating sleeve, slowly heating to 100 ℃, and continuously stirring in the heating process to fully mix the two components for heat preservation reaction for 2 hours;
slowly heating to 120 ℃, slowly dripping p-xylylenediamine at a constant speed for addition reaction, and keeping the temperature for 1.5h after finishing dripping within 2 h;
then heating to 200 ℃ for amidation polycondensation reaction for 3h, distilling to remove water, and continuously heating to 220 ℃ for 2h until water is completely evaporated;
and finally, cooling to 60 ℃, dropwise adding deionized water under the condition of high-speed stirring, discharging after dropwise adding is finished for 30min to obtain the brownish red water-based polyamide curing agent e, wherein the solid content is 54 wt%, the equivalent weight of active hydrogen of solid is 103g/mol, and the amine value is 327 mgKOH/g.
Wherein the dosage (mass/g) of the used raw materials is as follows:
preparing the aqueous polyamide curing agents a, b, c, d and E and a commercially available aqueous epoxy resin E51 emulsion into industrial floor paint according to indexes, and carrying out performance index test according to the chemical industry standard HG/T5057-2016 of the aqueous epoxy floor paint after the coating is cured, wherein the test results are as follows:
TABLE 1
Preparing the waterborne polyamide curing agents a, b, c, d and E and a commercially available waterborne epoxy resin E20 emulsion into a metal anticorrosive paint according to indexes, and after the coating is cured, performing performance index test according to a waterborne epoxy resin anticorrosive paint chemical industry standard HG/T4759-2014, wherein the test results are as follows:
TABLE 2
As shown in the above tables 1 and 2, the nonionic water-based polyamide curing agent prepared by the method has excellent physical and chemical properties, good mechanical properties such as wear resistance, impact resistance, hardness and adhesion, excellent chemical properties such as water resistance, humidity resistance, acid and alkali resistance and salt spray resistance, flat and smooth paint film, good flash rust inhibition and short curing time, and can be widely applied to the fields of industrial floor coatings, metal anticorrosive coatings and the like.
Although the present invention has been described in detail and illustrated with reference to the examples, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full scope of the invention.
Claims (7)
1. A preparation method of a nonionic water-based polyamide curing agent is characterized by comprising the following steps:
(1) preparation of polyamic acid intermediate a: putting low-molecular-weight polyetheramine and unsaturated anhydride into a reaction device, slowly heating to 80-100 ℃ under the conditions of nitrogen protection, stirring, condensation water diversion and reflux, and reacting for 1-2 hours under heat preservation to obtain an unsaturated polyamic acid intermediate a;
(2) addition of intermediate a to polyamine: slowly dripping polyamine into the unsaturated polyamic acid intermediate a to perform Michael addition reaction for 1-2 h, keeping the temperature for reaction for 1-2 h, and controlling the reaction temperature to be 100-120 ℃ to obtain a polyamic acid-polyamine adduct intermediate b;
(3) and (3) polyamidation reaction: carrying out amidation polycondensation reaction on excessive polyamine and the intermediate b for 2-3 h at 180-200 ℃ under the reflux condition, then continuously heating to 200-220 ℃ and carrying out heat preservation reaction for 2-3 h until water is completely evaporated, thus preparing a copolymer polyamide curing agent of the intermediate b and the polyamine;
the polyamine is selected from one or more of isophorone diamine, 1-methyl-2, 4-cyclohexanediamine, 1, 3-cyclohexanediamine, m-xylylenediamine and p-xylylenediamine; the molar ratio of the polyether amine to the unsaturated anhydride to the polyamine is 1: 1: 1.0 to 1.5;
(4) adding water for dispersion: slowly dripping deionized water into the polyamide curing agent at the temperature of 60 +/-5 ℃ under the condition of high-speed stirring for about 30min to ensure that the solid content is 50-60 wt%, thus obtaining the non-ionic water-based polyamide curing agent.
2. The method for preparing a nonionic aqueous polyamide curing agent according to claim 1, characterized in that: the low molecular weight polyether amine is selected from one or a mixture of two of polyether amines D230 and D400.
3. The method for preparing a nonionic aqueous polyamide curing agent according to claim 1, characterized in that: the unsaturated anhydride is selected from one of nadic anhydride, maleic anhydride and tetrahydrophthalic anhydride.
4. The method for preparing a nonionic aqueous polyamide curing agent according to claim 1, characterized in that: the solid amine value of the curing agent in the nonionic water-based polyamide curing agent is 160-330 mgKOH/g, and the equivalent weight of active hydrogen is 100-220 g/mol.
5. A non-ionic aqueous polyamide curing agent prepared by the preparation method of any one of claims 1 to 4.
6. Use of the aqueous polyamide curing agent of claim 5 in an aqueous industrial floor coating.
7. The use of the aqueous polyamide curing agent of claim 5 in an aqueous metal anticorrosive coating.
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| CN112457190B (en) * | 2020-10-27 | 2022-08-12 | 航天材料及工艺研究所 | Dimer acid modified polyether polyamine compound, preparation method and application thereof |
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| CN104583321B (en) * | 2012-08-14 | 2016-07-06 | 三菱瓦斯化学株式会社 | Polyether-polyamide compositions |
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Denomination of invention: A non-ionic waterborne polyamide curing agent and its preparation method Effective date of registration: 20221026 Granted publication date: 20210302 Pledgee: Industrial and Commercial Bank of China Limited Dongxiang sub branch Pledgor: Jiangxi Gaoxin Frontier Technology Co.,Ltd. Registration number: Y2022980019789 |
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