CN110669206A - Water-soluble cardanol waterborne epoxy resin curing agent and preparation method and application thereof - Google Patents
Water-soluble cardanol waterborne epoxy resin curing agent and preparation method and application thereof Download PDFInfo
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C217/28—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines
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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
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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Abstract
The invention discloses a water-soluble cardanol waterborne epoxy resin curing agent and a preparation method and application thereof. The preparation method comprises the following steps: enabling a mixed reaction system at least containing cardanol, triethylene tetramine and formaldehyde to carry out Mannich reaction to obtain an intermediate product; and in a protective atmosphere, carrying out ring-opening reaction on the intermediate product and trimethylolpropane triglycidyl ether to obtain the water-soluble cardanol waterborne epoxy resin curing agent. The water-soluble cardanol water-based epoxy resin curing agent has good emulsification and curing performances on epoxy resin, has excellent corrosion resistance, toughness, water resistance and lower toxicity with a cured product of the epoxy resin, is simple in preparation method and process, wide in available source of raw materials, environment-friendly, natural, renewable, small in using amount, good in water solubility, suitable for large-scale production, and can be applied to the field of water-based epoxy resin coatings.
Description
Technical Field
The invention relates to a water-based epoxy resin curing agent, in particular to a water-soluble cardanol water-based epoxy resin curing agent, and a preparation method and application thereof, belonging to the technical field of water-based epoxy resin curing agents.
Background
The epoxy resin has good corrosion resistance, adhesive property, mechanical property and electrical insulation property, and is widely applied to the fields of buildings, traffic, electronics, machinery and the like. When the traditional solvent type epoxy resin is used, an organic solvent is required to be added for dilution, and most of the organic solvents are volatile, so that the environment is polluted and the human health is harmed, and therefore, the development of the low-VOC water-based epoxy resin is very important. The curing agent is one of the key factors influencing the performance of the two-component epoxy coating, and the most important of the epoxy resin curing agent is an amine curing agent which accounts for 71 percent of the total curing agent, so the research on the modification of the amine curing agent is particularly important. The curing agent for the water-based epoxy resin coating mostly adopts polyamine, such as amidoamine, polyamide, epoxy-amine addition product and the like. The two components of the curing agent and the epoxy resin can not be uniformly mixed and can not be well cured, and the key point is the compatibility of the curing agent and the epoxy resin. At present, the existing waterborne epoxy curing agent in the market has good compatibility with epoxy resin, is oily, is not easy to dissolve in water and is not easy to disperse; the water-based epoxy curing agent which is easy to disperse or dissolve in water has great solubility difference with epoxy resin, can not be well mixed uniformly, and can not achieve good curing effect. Therefore, further research and study is required for modification of the aqueous epoxy curing agent.
Disclosure of Invention
The invention mainly aims to provide a water-soluble cardanol waterborne epoxy resin curing agent and a preparation method thereof, so as to overcome the defects of the prior art.
The invention also aims to provide application of the water-soluble cardanol water-based epoxy resin curing agent in preparation of a water-based epoxy resin coating.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a water-soluble cardanol waterborne epoxy resin curing agent, which has the following structural formula:
wherein n is 0, 1 or 2.
The embodiment of the invention also provides a preparation method of the water-soluble cardanol waterborne epoxy resin curing agent, which comprises the following steps:
enabling a mixed reaction system at least containing cardanol, triethylene tetramine and formaldehyde to generate a Mannich reaction to obtain an intermediate product;
and in a protective atmosphere, carrying out ring-opening reaction on the intermediate product and trimethylolpropane triglycidyl ether to obtain the water-soluble cardanol waterborne epoxy resin curing agent.
The embodiment of the invention also provides the water-soluble cardanol waterborne epoxy resin curing agent prepared by the method.
The embodiment of the invention also provides application of the water-soluble cardanol water-based epoxy resin curing agent in preparation of a water-based epoxy resin coating.
The embodiment of the invention also provides a composition which comprises the water-based epoxy resin and the water-soluble cardanol water-based epoxy resin curing agent.
Accordingly, the embodiment of the invention also provides a cured product of the composition.
Compared with the prior art, the invention has the advantages that:
1) the preparation method of the water-soluble cardanol water-based epoxy resin curing agent provided by the invention is simple in process, the used raw materials are easily available and widely available, the cashew phenol water-based epoxy resin curing agent is environment-friendly, natural and renewable, small in using amount and good in water solubility, is suitable for large-scale production, and can be applied to the field of water-based epoxy resin coatings;
2) the water-soluble cardanol water-based epoxy resin curing agent prepared by the invention has good water solubility and is relatively stable;
3) the water-soluble cardanol waterborne epoxy resin curing agent prepared by the invention has the advantages of low-temperature curing or room-temperature curing, and can be cured in a humid environment;
4) the water-soluble cardanol waterborne epoxy resin curing agent prepared by the invention has good emulsification and curing performances on epoxy resin, and has excellent corrosion resistance, toughness, water resistance and lower toxicity with a cured product of the epoxy resin.
Drawings
Fig. 1 is a schematic diagram of a preparation reaction process of a water-soluble cardanol waterborne epoxy resin curing agent in a typical embodiment of the present invention.
Fig. 2 is an infrared spectrum of the water-soluble cardanol based water-borne epoxy resin curing agent in example 1 of the present invention.
Detailed Description
As described above, in view of the defects of the prior art, the inventors of the present invention have made extensive studies and practices to provide a technical solution of the present invention, which is mainly to perform a mannich reaction on cardanol-modified triethylene tetramine, and then perform a ring-opening reaction on trimethylolpropane triglycidyl ether, so as to finally prepare a novel water-soluble cardanol-based waterborne epoxy resin curing agent, which has good emulsification and curing properties on epoxy resin.
Cardanol is a natural renewable resource extracted from cashew nut shell oil, is a green chemical raw material, and the amine curing agent modified by cardanol is introduced with C of cardanol15Side chains, so that it has the advantages of room temperature curing or low temperature curing and being able to cure in a humid environment. The amine curing agent modified by cardanol and the cured product of epoxy resin have excellent corrosion resistance, water resistance, toughness and the like, and are low in toxicity, so that the cardanol modified amine curing agent is a research hotspot in the field of waterborne epoxy resin curing agents. Trimethylolpropane triglycidyl ether is an organic compound containing three epoxy groups, and is used for modifying cardanol amine curing agent, and can improve hydrophilicity of the curing agent, and C of cardanol15The side chain improves the hydrophobicity of the curing agent and the compatibility with epoxy resin, and simultaneously, a large amount of active amine in the product molecule has better curing performance, so that the amphiphilic waterborne epoxy curing agent with better emulsification effect can be obtained.
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of the embodiment of the present invention provides a water-soluble cardanol water-based epoxy resin curing agent, which has a structural formula shown as follows:
wherein n is 0, 1 or 2.
According to the principle of mannich reaction and ring-opening reaction, another aspect of the embodiments of the present invention provides a method for preparing a water-soluble cardanol waterborne epoxy resin curing agent, which comprises:
enabling a mixed reaction system at least containing cardanol, triethylene tetramine and formaldehyde to generate a Mannich reaction to obtain an intermediate product;
and in a protective atmosphere, carrying out ring-opening reaction on the intermediate product and trimethylolpropane triglycidyl ether to obtain the water-soluble cardanol waterborne epoxy resin curing agent.
In some embodiments, the cardanol, triethylene tetramine, and formaldehyde are present in a 1: (1.0-1.5): 1.
in some embodiments, the temperature of the Mannich reaction is from 80 to 120 ℃.
Further, the time of the Mannich reaction is 3-5 h.
In some embodiments, the molar ratio of the intermediate product to trimethylolpropane triglycidyl ether is (3.0-5.0): 1.
in some embodiments, the temperature of the ring-opening reaction is 50 to 80 ℃.
Further, the time of the Mannich reaction is 3-6 h.
Further, the protective atmosphere includes a nitrogen atmosphere and/or an inert gas atmosphere, preferably an argon atmosphere, but is not limited thereto.
In some more specific embodiments, the preparation method may include:
firstly, preheating cardanol and triethylene tetramine at a certain temperature, adding 37% formaldehyde water solution, heating to a certain temperature, and carrying out mannich reaction for a period of time to obtain a reddish brown viscous liquid intermediate product;
and secondly, slowly dropwise adding trimethylolpropane triglycidyl ether into the intermediate product obtained in the first step under the protection of protective gas, carrying out ring-opening reaction at a certain temperature, and after reacting for a period of time, carrying out rotary evaporation to remove unreacted triethylene tetramine, thus obtaining the water-soluble cardanol waterborne epoxy resin curing agent.
As one of more specific embodiments of the present invention, the preparation method may include the following steps:
the water-soluble cardanol waterborne epoxy resin curing agent is synthesized by two steps of reaction, wherein in the first step of reaction, triethylene tetramine and cardanol with a certain proportion are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, a certain amount of 37% formaldehyde aqueous solution is slowly dropped after the mixture is preheated to a certain temperature, and an intermediate product which is a reddish brown viscous liquid is obtained after the mixture is heated to a certain temperature and reacts for a period of time. And the second step of reaction is that a certain amount of intermediate product is added into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, the mixture is stirred in a protective gas atmosphere and heated to a certain temperature, a certain amount of trimethylolpropane triglycidyl ether is slowly dripped into the three-necked flask at the temperature by a separating funnel, unreacted triethylene tetramine is removed by rotary evaporation after the reaction is carried out for a period of time, and reddish brown viscous liquid is obtained, so that the water-soluble cardanol waterborne epoxy resin curing agent is obtained.
The preparation method of the water-soluble cardanol water-based epoxy resin curing agent provided by the invention is simple in process, the used raw materials are easily available and widely available, the cashew phenol water-based epoxy resin curing agent is environment-friendly, natural and renewable, small in using amount and good in water solubility, is suitable for large-scale production, and can be applied to the field of water-based epoxy resin coatings.
In another aspect of the embodiments of the present invention, there is also provided a water-soluble cardanol type waterborne epoxy resin curing agent prepared by the foregoing method.
The water-soluble cardanol waterborne epoxy resin curing agent prepared by the invention has the advantages of low-temperature curing or room-temperature curing, can be cured in a humid environment, has good emulsifying and curing performances, and has excellent corrosion resistance, toughness, water resistance and lower toxicity with a cured product of epoxy resin.
In another aspect of the embodiment of the invention, the application of the water-soluble cardanol water-based epoxy resin curing agent in preparing a water-based epoxy resin coating is also provided.
In another aspect of the embodiments of the present invention, a composition is further provided, which includes a water-based epoxy resin and the water-soluble cardanol water-based epoxy resin curing agent.
Accordingly, another aspect of the embodiments of the present invention also provides a cured product of the aforementioned composition.
By the technical scheme, the water-soluble cardanol water-based epoxy resin curing agent has good emulsifying and curing performances on epoxy resin, has excellent corrosion resistance, toughness, water resistance and lower toxicity with a cured product of the epoxy resin, is simple in preparation method process, wide in available source of used raw materials, environment-friendly, natural and renewable, small in using amount, good in water solubility, suitable for large-scale production, and can be applied to the field of water-based epoxy resin coatings.
In order to further understand the present invention, the technical solutions of the present invention are further described in detail below with reference to several preferred embodiments, but the present invention is not limited to the following embodiments, and those skilled in the art can make insubstantial improvements and modifications within the spirit of the present invention, and still fall within the scope of the present invention.
The experimental materials used in the examples used below were purchased from conventional biochemical reagent stores, unless otherwise specified.
Example 1
The first step of reaction, 1.0mol of cardanol and 1.2mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde water solution is slowly dropped into the bottle after the bottle is preheated to 80 ℃, and an intermediate product which is a reddish brown viscous liquid is obtained after the reaction is carried out for 4 hours after the temperature is raised to 100 ℃. And a second step of reaction, namely adding 4.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating to 60 ℃ in an argon atmosphere, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether at the temperature by using a separating funnel, reacting for 3 hours, and then spirally evaporating to remove unreacted triethylene tetramine to obtain reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 92%. The infrared spectrum of the water-soluble cardanol type waterborne epoxy resin curing agent obtained in the example is shown in fig. 2.
Example 2
The first step of reaction, 1.0mol of cardanol and 1mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde water solution is slowly dropped after the cardanol and the triethylene tetramine are preheated to 80 ℃, the temperature is raised to 100 ℃, and an intermediate product is obtained after reaction for 4 hours, and the intermediate product is reddish brown viscous liquid. And a second step of reaction, namely adding 4.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating to 60 ℃ in an argon atmosphere, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether at the temperature by using a separating funnel, reacting for 3 hours, and then spirally steaming out unreacted triethylene tetramine to obtain a reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 87%.
Example 3
The first step of reaction, 1.0mol of cardanol and 1.5mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde water solution is slowly dropped into the bottle after the bottle is preheated to 80 ℃, and an intermediate product which is a reddish brown viscous liquid is obtained after the reaction is carried out for 4 hours after the temperature is raised to 100 ℃. And a second step of reaction, namely adding 4.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating to 60 ℃ in an argon atmosphere, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether at the temperature by using a separating funnel, reacting for 3 hours, and then spirally evaporating to remove unreacted triethylene tetramine to obtain reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 90%.
Example 4
The first step of reaction, 1.0mol of cardanol and 1.2mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde water solution is slowly dropped into the bottle after the bottle is preheated to 80 ℃, and an intermediate product which is a reddish brown viscous liquid is obtained after the reaction is carried out for 4 hours after the temperature is raised to 100 ℃. And a second step of reaction, namely adding 3.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating to 60 ℃ in an argon atmosphere, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether at the temperature by using a separating funnel, reacting for 3 hours, and then spirally evaporating to remove unreacted triethylene tetramine to obtain reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 86%.
Example 5
The first step of reaction, 1.0mol of cardanol and 1.2mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde water solution is slowly dropped into the bottle after the bottle is preheated to 80 ℃, and an intermediate product which is a reddish brown viscous liquid is obtained after the reaction is carried out for 4 hours after the temperature is raised to 100 ℃. And a second step of reaction, namely adding 5.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating to 60 ℃ in an argon atmosphere, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether at the temperature by using a separating funnel, reacting for 3 hours, and then spirally evaporating to remove unreacted triethylene tetramine to obtain reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 92%.
Example 6
The first step of reaction, 1.0mol of cardanol and 1.2mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde aqueous solution is slowly dropped after the cardanol and the triethylene tetramine are preheated to 80 ℃, and an intermediate product is obtained after reaction for 4 hours at the temperature and is a reddish brown viscous liquid. And a second step of reaction, namely adding 4.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating to 60 ℃ in an argon atmosphere, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether at the temperature by using a separating funnel, reacting for 3 hours, and then spirally evaporating to remove unreacted triethylene tetramine to obtain reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 80%.
Example 7
The first step of reaction, 1.0mol of cardanol and 1.2mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde water solution is slowly dropped into the bottle after the bottle is preheated to 80 ℃, and an intermediate product which is a reddish brown viscous liquid is obtained after the reaction is carried out for 4 hours after the temperature is raised to 120 ℃. And a second step of reaction, namely adding 4.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating to 60 ℃ in an argon atmosphere, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether at the temperature by using a separating funnel, reacting for 3 hours, and then spirally evaporating to remove unreacted triethylene tetramine to obtain reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 91%.
Example 8
The first step of reaction, 1.0mol of cardanol and 1.2mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde water solution is slowly dropped into the bottle after the bottle is preheated to 80 ℃, and an intermediate product which is a reddish brown viscous liquid is obtained after the reaction is carried out for 3 hours after the temperature is raised to 100 ℃. And a second step of reaction, namely adding 4.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating to 60 ℃ in an argon atmosphere, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether at the temperature by using a separating funnel, reacting for 5 hours, and then spirally steaming out unreacted triethylene tetramine to obtain reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 91%.
Example 9
The first step of reaction, 1.0mol of cardanol and 1.2mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde water solution is slowly dropped into the bottle after the bottle is preheated to 80 ℃, and an intermediate product which is a reddish brown viscous liquid is obtained after the reaction is carried out for 5 hours after the temperature is raised to 100 ℃. And a second step of reaction, namely adding 4.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating to 60 ℃ in an argon atmosphere, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether at the temperature by using a separating funnel, reacting for 4 hours, and then spirally steaming out unreacted triethylene tetramine to obtain a reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 90%.
Example 10
The first step of reaction, 1.0mol of cardanol and 1.2mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde water solution is slowly dropped into the bottle after the bottle is preheated to 80 ℃, and an intermediate product which is a reddish brown viscous liquid is obtained after the reaction is carried out for 4 hours after the temperature is raised to 100 ℃. And a second step of reaction, namely adding 4.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating to 50 ℃ in an argon atmosphere, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether at the temperature by using a separating funnel, reacting for 6 hours, and then spirally steaming out unreacted triethylene tetramine to obtain reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 78%.
Example 11
The first step of reaction, 1.0mol of cardanol and 1.2mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde water solution is slowly dropped into the bottle after the bottle is preheated to 80 ℃, and an intermediate product which is a reddish brown viscous liquid is obtained after the reaction is carried out for 4 hours after the temperature is raised to 100 ℃. And a second step of reaction, namely adding 4.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating to 80 ℃ in an argon atmosphere, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether at the temperature by using a separating funnel, reacting for 3 hours, and then spirally steaming out unreacted triethylene tetramine to obtain a reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 87%.
Example 12
The first step of reaction, 1.0mol of cardanol and 1.2mol of triethylene tetramine are added into a three-mouth bottle provided with a thermometer, a water separator and a stirring magneton, 1.0mol of 37% formaldehyde water solution is slowly dropped into the bottle after the bottle is preheated to 80 ℃, and an intermediate product which is a reddish brown viscous liquid is obtained after the reaction is carried out for 4 hours after the temperature is raised to 100 ℃. And a second step of reaction, namely adding 4.0mol of intermediate product into a three-necked flask provided with a stirring magneton, a protective gas guide pipe and a thermometer, stirring and heating the mixture to 70 ℃ in the atmosphere of argon, slowly dropwise adding 1.0mol of trimethylolpropane triglycidyl ether into the mixture at the temperature by using a separating funnel, reacting for 3 hours, and then spirally steaming out unreacted triethylene tetramine to obtain reddish brown viscous liquid, namely the water-soluble cardanol waterborne epoxy resin curing agent, wherein the yield is 90%.
Comparative example 1
Epoxy resin E51 was used as a comparative example.
The water-soluble cardanol water-based epoxy resin curing agent of examples 1 to 12 and the coating cured by epoxy resin E51 in the same ratio were subjected to various performance tests, and the obtained test results were as follows:
as can be seen from the data of examples 1-12, the yields were highest when examples 1, 3, 5, 7, 9, 12 were applied, with the best performance being obtained with the coating of example 1 and epoxy E51 in the specified ratios, the best example.
As can be seen from the data of example 1 and comparative example 1, the coating performance of example 1 is better.
In conclusion, the water-soluble cardanol waterborne epoxy resin curing agent provided by the invention has good emulsification and curing performances on epoxy resin, has excellent corrosion resistance, toughness, water resistance and lower toxicity with a cured product of the epoxy resin, is simple in preparation method and process, wide in available raw materials, environment-friendly, natural and renewable, low in usage amount, good in water solubility, suitable for large-scale production, and can be applied to the field of waterborne epoxy resin coatings.
In addition, the inventors of the present invention also conducted experiments using other materials and conditions listed in the present specification with reference to examples 1 to 12, and the corresponding effects were also achieved, and water-soluble cardanol based aqueous epoxy resin curing agent-to-epoxy resin having good emulsification and curing properties were obtained.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The water-soluble cardanol waterborne epoxy resin curing agent is characterized by having the following structural formula:
wherein n is 0, 1 or 2.
2. A preparation method of a water-soluble cardanol waterborne epoxy resin curing agent is characterized by comprising the following steps:
enabling a mixed reaction system at least containing cardanol, triethylene tetramine and formaldehyde to carry out Mannich reaction to obtain an intermediate product;
and in a protective atmosphere, carrying out ring-opening reaction on the intermediate product and trimethylolpropane triglycidyl ether to obtain the water-soluble cardanol waterborne epoxy resin curing agent.
3. The method of claim 2, wherein: the mol ratio of the cardanol to the triethylene tetramine to the formaldehyde is 1: (1.0-1.5): 1; and/or the molar ratio of the intermediate product to the trimethylolpropane triglycidyl ether is (3.0-5.0): 1.
4. the method of claim 2, wherein: the temperature of the Mannich reaction is 80-120 ℃, and the time is 3-5 h.
5. The method of claim 2, wherein: the temperature of the ring-opening reaction is 50-80 ℃, and the time is 3-6 h.
6. The method of claim 2, wherein: the protective atmosphere comprises a nitrogen atmosphere and/or an inert gas atmosphere; preferably, the inert gas atmosphere is an argon atmosphere.
7. A water soluble cardanol based waterborne epoxy resin curing agent prepared by the method of any one of claims 2 to 6.
8. Use of the water-soluble cardanol type aqueous epoxy resin curing agent as claimed in claim 1 or 7 for preparing an aqueous epoxy resin paint.
9. A composition characterized by comprising a water-based epoxy resin and the water-soluble cardanol type water-based epoxy resin curing agent described in claim 1 or 7; preferably, the composition is a waterborne epoxy coating.
10. A cured product of the composition according to claim 9.
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