CN113265038B - Tung oil-based modified amine curing agent and preparation method and application thereof - Google Patents
Tung oil-based modified amine curing agent and preparation method and application thereof Download PDFInfo
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- CN113265038B CN113265038B CN202110377743.0A CN202110377743A CN113265038B CN 113265038 B CN113265038 B CN 113265038B CN 202110377743 A CN202110377743 A CN 202110377743A CN 113265038 B CN113265038 B CN 113265038B
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/12—Chemically modified polycondensates
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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
- 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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
- C08G59/623—Aminophenols
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
Abstract
Adding methyl eleostearate, phenol and a catalyst into a reaction container, stirring and heating to react under the condition of continuously introducing nitrogen, cooling, washing and standing, and drying an upper-layer brown viscous liquid by using anhydrous sodium sulfate to obtain a tung oil source phenol addition compound; adding the tung oil source phenol addition compound and polyamine into a reaction container, uniformly mixing and stirring, dropwise adding aldehyde, heating to react after dropwise adding, and removing generated water by reduced pressure distillation to obtain the tung oil-based Mannich base curing agent; and under the stirring state, continuously dropwise adding polyamine into the tung oil-based Mannich base curing agent, heating and refluxing, then carrying out amidation reaction, stopping heating when anhydrous and free amine are evaporated out, and cooling to room temperature to obtain the dark brown viscous tung oil-based modified amine curing agent. The tung oil-based modified amine curing agent has more extensive and uniform distribution of curing reaction active crosslinking points, and can well balance the hardness and flexibility of the coating, so that the coating is tougher.
Description
Technical Field
The invention belongs to the field of thermosetting resin materials, and particularly relates to a tung oil-based modified amine curing agent, and a preparation method and application thereof.
Background
The epoxy resin/curing agent system has good processability, can endow epoxy cured products with higher bonding strength due to the polar groups such as epoxy groups, hydroxyl groups, ether bonds, amine bonds, ester bonds and the like with extremely high activity and higher cohesive force, and can be used as casting materials, laminating materials, adhesives, coatings and the like due to good dimensional stability, low shrinkage, excellent electrical insulation, high mechanical strength, good solvent resistance and the like. The curing agent plays a decisive role in the performance of the epoxy resin anticorrosive coatings, so that a suitable curing agent must be selected. The polyamide curing agent and the epoxy resin can be cured to form a film at normal temperature, and the film has good corrosion resistance, flexibility and recoatability; the cardanol phenolic aldehyde amine curing agent has low viscosity, excellent low-temperature curing performance and excellent water resistance of a coating film, and the cardanol phenolic aldehyde amine curing agent are widely applied to epoxy anticorrosive coatings at present. However, in recent years, the defects of high brittleness and poor impact toughness of the traditional epoxy anticorrosive paint are reflected by the occurrence of a large amount of equipment corrosion in the severe environment with high salt mist and high humidity and heat in the ocean area. In the long-term use process, due to the fact that the ageing degree of the material, the temperature alternation and the humidity alternation influence, microcracks are easy to appear on the material, the shock resistance of the material is reduced, corrosive media permeate into the material and the like, and therefore the use of the polyamide curing agent and the cardanol phenolic aldehyde amine curing agent is gradually limited. The general toughening means directly causes the reduction of the strength, oil resistance and other medium resistance of the cured epoxy resin, so the development of the curing agent for the epoxy resin with higher corrosion resistance and high impact toughness has important significance. The research starts from the design of a molecular structure, integrates the excellent flexibility and corrosion resistance of an amide curing agent and the excellent low-temperature curing property and water resistance of a cardanol phenolic aldehyde amine curing agent into a novel tung oil-based modified amine curing agent, and is expected to be applied to the field of epoxy anticorrosive coatings.
Disclosure of Invention
The technical problem to be solved is as follows: the invention provides a tung oil-based modified amine curing agent and a preparation method and application thereof, and through molecular structure design, the molecular structure of the tung oil-based modified amine curing agent integrates a long carbon chain flexible structure of tung oil, phenolic hydroxyl, secondary amino, primary amino and polar amide groups of polyamide and other active groups, so that an epoxy cured product coating of the tung oil-based modified amine curing agent integrates excellent flexibility and corrosion resistance of amide, low-temperature curing performance of cardanol phenolic amine and excellent water resistance and can be used as a tung oil-based modified amine curing agent for an anticorrosive coating. Compared with polyamide curing agents and cardanol phenolic aldehyde amine curing agents, the tung oil-based modified amine curing agent has the advantages that the distribution of curing reaction active crosslinking points is wider and uniform, the hardness and flexibility of the coating can be well balanced, and the coating is tougher. In addition, the problem of poor corrosion resistance caused by simple physical mixing of the polyamide curing agent and the phenolic aldehyde amine curing agent can be avoided. Provides a thought and a method for deep processing of the bio-based material tung oil, can widen the application field and improve the added value thereof.
The technical scheme is as follows: the preparation method of the tung oil-based modified amine curing agent comprises the following steps of: the first step is as follows: adding 0.5mol of methyl eleostearate, 0.51-0.55 mol of phenol and a catalyst accounting for 0.3-0.4 wt.% of the methyl eleostearate into a reaction container, stirring and heating to 90-120 ℃ under the state of continuously introducing nitrogen, continuing to react for 2-3 hours at the temperature, naturally cooling to room temperature, sequentially adding 5 wt.% of NaOH aqueous solution and saturated salt solution to wash, standing and layering for 3 times, taking the brown viscous liquid at the upper layer, and drying with anhydrous sodium sulfate to obtain the tung oil source phenol addition product; the second step is that: adding 0.4-0.5 mol of tung oil source phenol adduct and 0.4-0.5 mol of polyamine into a reaction container, uniformly mixing and stirring, then dropwise adding 0.4-0.5 mol of aldehyde, controlling the temperature to be not more than 60 ℃, heating to 85-95 ℃ after dropwise adding, reacting for 3-4 h, and then carrying out reduced pressure distillation to remove generated water to obtain the tung oil-based Mannich base curing agent; the third step: continuously dropwise adding 0.44-0.55 mol of polyamine into the tung oil-based Mannich base curing agent under the stirring state, heating to 135-145 ℃, refluxing and maintaining for 1-2 h, then heating to 180-190 ℃ for amidation reaction and maintaining for 1-2 h, finally maintaining for 1-1.5 h under 0.67-1.33 kPa, stopping heating when anhydrous and free amine are evaporated out, and cooling to room temperature to obtain the dark brown viscous tung oil-based modified amine curing agent.
The phenol in the first step is any one selected from phenol, cresol, p-tert-butylphenol, bisphenol A and maleimide phenol.
The catalyst in the first step is selected from AlCl3A pair of nailsBenzenesulfonic acid, H3PO4Any one of them.
In the second step, the polyamine is at least one selected from hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylylenediamine and 1, 3-cyclohexyldimethylamine.
The aldehyde in the second step is at least one selected from the group consisting of formaldehyde, n-butyraldehyde, isobutyraldehyde, furfural, and benzaldehyde.
In the third step, the polyamine is at least one selected from hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylylenediamine, 4-diaminodicyclohexylmethane and 1, 3-cyclohexyldimethylamine.
The tung oil-based modified amine curing agent prepared by the method.
The tung oil-based modified amine curing agent is applied to preparation of epoxy anticorrosive paint.
Has the advantages that: the tung oil-based modified amine curing agent has good compatibility with epoxy resin and moderate reaction speed. The molecular structure of the coating integrates the long carbon chain flexible structure of tung oil, phenolic hydroxyl, secondary amino, primary amino of phenolic aldehyde amine, polar amide group of polyamide and other active groups, so that the coating of the epoxy cured product integrates excellent flexibility and corrosion resistance of amide and low-temperature curing property and excellent water resistance of cardanol phenolic amine. Compared with polyamide curing agents and cardanol phenolic aldehyde amine curing agents, the tung oil-based modified amine curing agent has the advantages that the distribution of curing reaction active cross-linking points is wider and uniform, the hardness and flexibility of a coating can be well balanced, and the prepared epoxy anticorrosive coating is tougher and has excellent adhesive force, water resistance, oil resistance, humidity resistance, heat resistance and salt mist resistance.
Detailed Description
Parts not mentioned in the text are the same as or can be realized by the prior art. The following are preferred embodiments of the present invention, but the present invention is not limited to the following embodiments, and some modifications to the embodiments will be considered as the protection scope of the present invention.
Example 1
The first step is as follows: adding 146g of methyl eleostearate, 51.7g of phenol and 0.438g of p-toluenesulfonic acid into a 500mL four-neck round-bottom flask, continuously introducing nitrogen, stirring, heating to 90-120 ℃, continuously reacting at the temperature for 2-3 h, naturally cooling to room temperature, sequentially adding 5 wt.% of NaOH aqueous solution and saturated salt solution, washing, standing and layering for 3 times, taking the upper brown viscous liquid, and drying with anhydrous sodium sulfate to obtain 189.3g of methyl eleostearate-phenol adduct.
The second step is that: 154.4g of methyl eleostearate-phenol adduct and 46.4g of hexamethylene diamine are added into a 500mL three-neck round-bottom flask, mixed and stirred uniformly, 32.4g of 37 wt.% formaldehyde aqueous solution is added dropwise, the temperature is controlled to be not more than 60 ℃, after the addition is finished, the temperature is raised to 85-95 ℃, after the reaction is carried out for 3-4 hours, the generated water is removed through reduced pressure distillation, and 203.2g of tung oil-based Mannich base curing agent is obtained.
The third step: and under the stirring state, continuously dropwise adding 51.04g of hexamethylenediamine into the three-neck round-bottom flask in the second step, heating to 135-145 ℃, refluxing and maintaining for 1-2 h, then heating to 180-190 ℃ for amidation reaction and maintaining for 1-2 h, finally maintaining for 1-1.5 h under 0.67-1.33 kPa, stopping heating when anhydrous and free amine are evaporated, and cooling to room temperature to obtain 235.2g of dark brown viscous tung oil-based modified amine curing agent.
Example 2
The first step is as follows: 146g of methyl eleostearate, 59.4g of cresol and H3PO4Adding 0.438g of the mixture into a 500mL four-neck round-bottom flask, continuously introducing nitrogen, starting stirring, heating to 90-120 ℃, continuously reacting at the temperature for 2-3 hours, naturally cooling to room temperature, sequentially adding 5 wt.% of NaOH aqueous solution and saturated saline solution, washing, standing and layering for 3 times, taking the upper brown viscous liquid, and drying with anhydrous sodium sulfate to obtain 197.6g of methyl eleostearate-cresol adduct.
The second step is that: 160.0g of methyl eleostearate-cresol adduct and 41.2g of diethylenetriamine are added into a 500mL three-neck round-bottom flask, mixed and stirred uniformly, 28.8g of n-butyl aldehyde is added dropwise, the temperature is controlled to be not more than 60 ℃, after the dropwise addition is finished, the temperature is raised to 85-95 ℃, after reaction is carried out for 3-4 hours, reduced pressure distillation is carried out to remove generated water, and 219.3g of tung oil-based Mannich base curing agent is obtained.
The third step: and under the stirring state, continuously dropwise adding 59.84g of m-xylylenediamine into the three-neck round-bottom flask in the second step, heating to 135-145 ℃, refluxing and maintaining for 1-2 h, then heating to 180-190 ℃ for amidation reaction and maintaining for 1-2 h, finally maintaining for 1-1.5 h under 0.67-1.33 kPa, stopping heating when anhydrous and free amine are evaporated, and cooling to room temperature to obtain 261.2g of dark brown viscous tung oil-based modified amine curing agent.
Example 3
The first step is as follows: 146g of methyl eleostearate, 82.5g of p-tert-butylphenol and AlCl3Adding 0.438g of the mixture into a 500mL four-neck round-bottom flask, continuously introducing nitrogen, starting stirring, heating to 90-120 ℃, continuously reacting at the temperature for 2-3 hours, naturally cooling to room temperature, sequentially adding 5 wt.% of NaOH aqueous solution and saturated saline solution, washing, standing and layering for 3 times, taking the upper brown viscous liquid, and drying with anhydrous sodium sulfate to obtain 217.6g of methyl eleostearate-p-tert-butylphenol adduct.
The second step is that: adding 176.8g of methyl eleostearate-p-tert-butylphenol adduct and 58.4g of triethylene tetramine into a 500mL three-neck round-bottom flask, uniformly mixing and stirring, dropwise adding 28.8g of isobutyraldehyde, controlling the temperature to be not more than 60 ℃, heating to 85-95 ℃ after dropwise adding, reacting for 3-4 hours, and then carrying out reduced pressure distillation to remove generated water to obtain 250.2g of tung oil-based Mannich base curing agent.
The third step: and under the stirring state, continuously dropwise adding 59.84g of m-xylylenediamine into the three-neck round-bottom flask in the second step, heating to 135-145 ℃, refluxing and maintaining for 1-2 h, then heating to 180-190 ℃ for amidation reaction and maintaining for 1-2 h, finally maintaining for 1-1.5 h under 0.67-1.33 kPa, stopping heating when anhydrous and free amine are evaporated, and cooling to room temperature to obtain 261.2g of dark brown viscous tung oil-based modified amine curing agent.
Example 4
The first step is as follows: 146g of methyl eleostearate, 125.4g of bisphenol A and AlCl3Adding 0.438g of the mixture into a 500mL four-neck round-bottom flask, starting stirring and heating to 90-120 ℃ under the condition of continuously introducing nitrogen, continuing to react at the temperature for 2-3 hours, naturally cooling to room temperature, and sequentially adding 5 wt.% of NaOH aqueous solutionWashing with saturated saline solution, standing for 3 times, collecting upper brown viscous liquid, and drying with anhydrous sodium sulfate to obtain 252.6g methyl eleostearate-bisphenol A adduct.
The second step is that: adding 208g of methyl eleostearate-bisphenol A adduct and 75.6g of tetraethylenepentamine into a 500mL three-neck round-bottom flask, uniformly mixing and stirring, dropwise adding 38.4g of furfural, controlling the temperature to be not more than 60 ℃, heating to 85-95 ℃ after dropwise adding, reacting for 3-4 hours, and then carrying out reduced pressure distillation to remove generated water to obtain 306.8g of tung oil-based Mannich base curing agent.
The third step: and under the stirring state, continuously dropwise adding 62.48g of 1, 3-cyclohexyldimethylamine into the three-neck round-bottom flask in the second step, heating to 135-145 ℃, refluxing and maintaining for 1-2 h, then heating to 180-190 ℃, carrying out amidation reaction and maintaining for 1-2 h, finally maintaining for 1-1.5 h under 0.67-1.33 kPa, stopping heating when anhydrous and free amine are evaporated, and cooling to room temperature to obtain 352.8g of dark brown viscous tung oil-based modified amine curing agent.
Example 5
The first step is as follows: adding 146g of methyl eleostearate, 51.7g of phenol and 0.438g of p-toluenesulfonic acid into a 500mL four-neck round-bottom flask, continuously introducing nitrogen, stirring, heating to 90-120 ℃, continuously reacting at the temperature for 2-3 h, naturally cooling to room temperature, sequentially adding 5 wt.% of NaOH aqueous solution and saturated salt solution, washing, standing and layering for 3 times, taking the upper brown viscous liquid, and drying with anhydrous sodium sulfate to obtain 189.3g of methyl eleostearate-phenol adduct.
The second step is that: 154.4g of methyl eleostearate-phenol adduct and 75.6g of tetraethylenepentamine are added into a 500mL three-neck round-bottom flask, uniformly mixed and stirred, 42.4g of benzaldehyde is dropwise added, the temperature is controlled to be not more than 60 ℃, after the dropwise addition is finished, the temperature is raised to 85-95 ℃, after reaction is carried out for 3-4 hours, reduced pressure distillation is carried out to remove generated water, and 261.3g of tung oil-based Mannich base curing agent is obtained.
The third step: under the stirring state, continuously dropwise adding 92.4g of 4, 4-diaminodicyclohexylmethane into the three-neck round-bottom flask in the second step, heating to 135-145 ℃, refluxing and maintaining for 1-2 h, then heating to 180-190 ℃ for amidation reaction and maintaining for 1-2 h, finally maintaining for 1-1.5 h under 0.67-1.33 kPa, stopping heating when anhydrous and free amine are evaporated, and cooling to room temperature to obtain 330.2g of dark brown viscous tung oil-based modified amine curing agent.
Example 6
The first step is as follows: adding 146g of methyl eleostearate and 94.5g of maleimide phenol into a 500mL four-neck round-bottom flask, continuously introducing nitrogen, stirring, heating to 150-160 ℃, continuously reacting at the temperature for 2-3 h, naturally cooling to room temperature, sequentially adding 5 wt.% of NaOH aqueous solution and saturated saline solution, washing, standing and layering for 3 times, taking the upper brown viscous liquid, and drying with anhydrous sodium sulfate to obtain 237.9g of methyl eleostearate-maleimide phenol adduct.
The second step is that: 192.4g of methyl eleostearate-maleimide phenol adduct and 58.4g of triethylene tetramine are added into a 500mL three-neck round-bottom flask, mixed and stirred uniformly, 32.4g of 37 wt.% formaldehyde water solution is dripped, the temperature is controlled to be not more than 60 ℃, after dripping is finished, the temperature is raised to 85-95 ℃, reaction is carried out for 3-4 hours, reduced pressure distillation is carried out to remove generated water, and 251.8g of tung oil-based Mannich base curing agent is obtained.
The third step: and under the stirring state, continuously dropwise adding 62.48g of 1, 3-cyclohexyldimethylamine into the three-neck round-bottom flask in the second step, heating to 135-145 ℃, refluxing and maintaining for 1-2 h, then heating to 180-190 ℃, carrying out amidation reaction and maintaining for 1-2 h, finally maintaining for 1-1.5 h under 0.67-1.33 kPa, stopping heating when anhydrous and free amine are evaporated, and cooling to room temperature to obtain 296.1g of dark brown viscous tung oil-based modified amine curing agent.
Example 7
The first step is as follows: adding 146g of methyl eleostearate, 51.7g of phenol and 0.438g of p-toluenesulfonic acid into a 500mL four-neck round-bottom flask, continuously introducing nitrogen, stirring, heating to 90-120 ℃, continuously reacting at the temperature for 2-3 h, naturally cooling to room temperature, sequentially adding 5 wt.% of NaOH aqueous solution and saturated salt solution, washing, standing and layering for 3 times, taking the upper brown viscous liquid, and drying with anhydrous sodium sulfate to obtain 189.3g of methyl eleostearate-phenol adduct.
The second step is that: 154.4g of methyl eleostearate-phenol adduct and 54.4g of m-xylylenediamine are added into a 500mL three-neck round-bottom flask, uniformly mixed and stirred, 42.4g of benzaldehyde is dropwise added, the temperature is controlled to be not more than 60 ℃, after the dropwise addition is finished, the temperature is raised to 85-95 ℃, after reaction is carried out for 3-4 hours, reduced pressure distillation is carried out to remove generated water, and 240.2g of tung oil-based Mannich base curing agent is obtained.
The third step: and under the stirring state, continuously dropwise adding 83.16g of tetraethylenepentamine into the three-neck round-bottom flask in the second step, heating to 135-145 ℃, refluxing and maintaining for 1-2 h, then heating to 180-190 ℃ for amidation reaction and maintaining for 1-2 h, finally maintaining for 1-1.5 h under 0.67-1.33 kPa, stopping heating when anhydrous and free amine are evaporated, and cooling to room temperature to obtain 301.2g of dark brown viscous tung oil-based modified amine curing agent.
Example 8
Preparation of resin A component: adding 50 parts of epoxy resin E51, 27.4 parts of epoxy resin E20, 15 parts of epoxy modified carboxyl terminated nitrile rubber, 5 parts of epoxy diluent AGE, 2 parts of coupling agent KH560, 0.2 part of flatting agent AFCONA3034, 0.2 part of defoaming agent BYK530, 0.2 part of wetting dispersant BYK903, a proper amount of talcum powder, mica powder and zinc phosphate into a plastic tank, and dispersing at a high speed until the system is uniform.
Example 9
The tung oil-based modified amine curing agent obtained in the example 1 and the resin A component are weighed according to an equivalent ratio, mixed and stirred uniformly, the mixture is coated on a tinplate by a coating device, the thickness of a paint film is 50 mu m, and the curing conditions are as follows: room temperature/24 h +80 ℃/3 h.
The test results are shown in tables 1 and 2.
Example 10
The tung oil-based modified amine curing agent obtained in the example 6 and the resin A component are weighed according to an equivalent ratio, mixed and stirred uniformly, the mixture is coated on a tinplate by a coating device, the thickness of a paint film is 50 mu m, and the curing conditions are as follows: room temperature/24 h +80 ℃/3 h.
The test results are shown in tables 1 and 2.
Comparative example 1
Weighing and mixing the cardanol phenolic aldehyde amine curing agent and the resin A component according to an equivalent ratio, uniformly stirring, coating the mixture on a tinplate by using a film coater, wherein the thickness of a paint film is 50 micrometers, and the curing conditions are as follows: room temperature/24 h +80 ℃/3 h.
The test results are shown in tables 1 and 2.
TABLE 1 comparison of the mechanical properties of the paint films of the examples and of the comparative examples
TABLE 2 comparison of the corrosion protection properties of the paint films of the examples and comparative examples
Claims (3)
1. The preparation method of the tung oil-based modified amine curing agent is characterized by comprising the following steps of: the first step is as follows: adding 146g of methyl eleostearate, 51.7g of phenol and 0.438g of p-toluenesulfonic acid into a 500mL four-neck round-bottom flask, continuously introducing nitrogen, stirring, heating to 90-120 ℃, continuously reacting at the temperature for 2-3 h, naturally cooling to room temperature, sequentially adding 5 wt% of NaOH aqueous solution and saturated salt solution, washing, standing and layering for 3 times, taking the upper brown viscous liquid, and drying with anhydrous sodium sulfate to obtain 189.3g of methyl eleostearate-phenol adduct; the second step is that: 154.4g of methyl eleostearate-phenol adduct and 46.4g of hexamethylene diamine are added into a 500mL three-neck round-bottom flask, mixed and stirred uniformly, 32.4g of 37 wt.% aqueous formaldehyde solution is dripped, the temperature is controlled to be not more than 60 ℃, after dripping is finished, the temperature is raised to 85-95 ℃, reaction is carried out for 3-4 h, reduced pressure distillation is carried out to remove generated water, and 203.2g of tung oil-based Mannich base curing agent is obtained; the third step: and under the stirring state, continuously dropwise adding 51.04g of hexamethylenediamine into the three-neck round-bottom flask in the second step, heating to 135-145 ℃, refluxing and maintaining for 1-2 h, then heating to 180-190 ℃ for amidation reaction and maintaining for 1-2 h, finally maintaining for 1-1.5 h under 0.67-1.33 kPa, stopping heating when anhydrous and free amine are evaporated, and cooling to room temperature to obtain 235.2g of dark brown viscous tung oil-based modified amine curing agent.
2. The tung oil-based modified amine curing agent prepared by the method of claim 1.
3. Use of the tung oil-based modified amine curing agent of claim 2 in the preparation of an epoxy anticorrosive coating.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101348563A (en) * | 2008-09-17 | 2009-01-21 | 中昊晨光化工研究院 | Tough mannich base curing agent and preparation thereof |
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| 桐油及其衍生物的改性在高分子材料中的应用进展;黄坤等;《化工进展》;20081005;第27卷(第10期);第1588-1592页 * |
| 桐酸甲酯改性酚醛胺的合成与性能研究;夏建陵等;《粘接》;20010820;第22卷(第04期);第1-3页 * |
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