A kind of amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating

Abstract

The invention relates to the technical field of coatings and discloses an amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating. The epoxy resin coating comprises a component A comprising 100 parts of an aqueous epoxy resin emulsion, 5-20 parts of titanium dioxide, 1-2.5 parts of a dispersant, and 0.05-0.2 parts of a defoamer; and a component B comprising 50-70 parts of an amino-terminated ether-containing hyperbranched polyamide. The amino-terminated ether-containing hyperbranched polyamide contains active terminal amino groups, so that the hyperbranched polyamide acts as a curing agent and undergoes a cross-linking and curing reaction with the epoxy resin. The hyperbranched polyamide has a three-dimensional branched network structure and forms a spatially cross-linked interpenetrating network system with the epoxy resin. The hyperbranched polyamide contains flexible ether-containing chain segments and alkyl chain segments, which have a good toughening effect, thereby improving the impact resistance and impact strength of the epoxy resin coating and the cast body thereof, while maintaining relatively high hardness and tensile strength.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, in particular to an amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating. Background Art

[0002] In recent years, toughening modification of water-based epoxy resins and development of new epoxy resin materials have been research hotspots. The curing agent of epoxy resin contains curing hydrogen, which can cross-link and cure with epoxy resin, and has many effects on the performance of the cured coating. At present, the curing agents of epoxy resin mainly include amine curing agents, carboxylic acid curing agents, imidazole curing agents, etc.; among them, polymer curing agents such as polyamides and polyetheramines have better modification effects on epoxy resins.

[0003] Patent CN113461960B discloses synthesizing a hyperbranched epoxy polymer from epoxy resin, trimethylolpropane, and a catalyst; then preparing a mono-blocked polyamine from n-butyl glycidyl ether and a polyamine; and finally, combining the hyperbranched epoxy polymer, epoxy resin, and mono-blocked polyamine to form a modified waterborne epoxy curing agent. This modified waterborne epoxy curing agent, which contains a hyperbranched structure, imparts excellent water resistance, high hardness, and impact resistance to the cured coating. Therefore, using a hyperbranched polymer as a curing agent for epoxy resins is an effective method for improving the performance of epoxy resins. Summary of the Invention

[0004] Technical problem solved: Provides an amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating, which solves the problems of low strength and poor impact resistance of epoxy resin coatings.

[0005] Technical solution:

[0006] A terminal amino group-containing ether-containing hyperbranched polyamide modified epoxy resin coating, characterized by comprising the following raw materials in parts by weight: component A: 100 parts of water-based epoxy resin emulsion, 5-20 parts of titanium dioxide, 1-2.5 parts of dispersant, and 0.05-0.2 parts of defoamer; component B: 50-70 parts of terminal amino group-containing ether-containing hyperbranched polyamide.

[0007] The amino-terminated ether-containing hyperbranched polyamide is prepared according to the following method:

[0008] The structural formula is The ether-containing acrylate monomer and ethylenediamine are added to N,N-dimethylformamide, reacted at a temperature of 110-140 ° C for 10-18 hours, cooled, poured into methanol for precipitation, filtered, washed with ethanol, and dried at 60-70 ° C to obtain terminal amino group-containing ether hyperbranched polyamide.

[0009] Furthermore, the ratio of the acrylate monomer to ethylenediamine is 1 mol: (4.5-5) mol.

[0010] Furthermore, the ether-containing acrylate monomer is prepared according to the following method:

[0011] S1. Add methyl acrylate and 1-amino-3,6,9-trioxa-11-undecanol to methanol, reflux at 55-70°C for 24-36 h in a nitrogen atmosphere, cool, concentrate under reduced pressure, wash with n-hexane, and dry at 40-50°C to obtain intermediate A.

[0012] S2. Add intermediate A and hexamethylene diisocyanate to any one of tetrahydrofuran, 1,4-dioxane or toluene solvents, and reflux in a nitrogen atmosphere at a temperature of 70-100°C for 3-5 hours, cool, concentrate under reduced pressure, wash with n-hexane, and dry at 40-50°C to obtain an ether-containing acrylate monomer.

[0013] Furthermore, the ratio of methyl acrylate to 1-amino-3,6,9-trioxa-11-undecanol is (2.4-3.2) mol:1 mol.

[0014] Furthermore, in S3, the molar ratio of the intermediate A to hexamethylene diisocyanate is (2.2-2.5) mol:1 mol.

[0015] Furthermore, the curing method of the amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating is as follows: component A and component B are evenly mixed, first cured at 60-80°C for 1-2 hours, then cured at 100-110°C for 2-4 hours, and finally cured at 120-140°C for 2-4 hours to obtain an epoxy resin coating.

[0016] The technical effect is that the amino-terminated ether-containing hyperbranched polyamide prepared by the present invention contains hydrophilic polyether, amide bond and amino group, so that the hyperbranched polyamide has good hydrophilicity and water solubility, and can be well dispersed in the water-based epoxy resin coating matrix.

[0017] Compared with the traditional polyamide curing agent 651, the amino-terminated ether-containing hyperbranched polyamide of the present invention contains an active amino group, so that it can act as a curing agent and undergo a cross-linking and curing reaction with the epoxy resin. The hyperbranched polyamide has a three-dimensional branched network structure and forms a spatially cross-linked interpenetrating network system with the epoxy resin. In addition, the hyperbranched polyamide contains flexible ether-containing segments and alkyl segments, which have a good toughening effect, improve the impact resistance and impact strength of the epoxy resin paint coating and its cast body, while maintaining a high hardness and tensile strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is the preparation reaction route of intermediate A.

[0019] Figure 2 This is a reaction route for preparing ether-containing acrylate monomers.

[0020] Figure 3 This is a reaction route for preparing amino-terminated ether-containing hyperbranched polyamide. DETAILED DESCRIPTION

[0021] Example 1

[0022] 32 mmol of methyl acrylate and 10 mmol of 1-amino-3,6,9-trioxa-11-undecanol were added to methanol, and the mixture was refluxed at 55°C for 30 h under nitrogen atmosphere. The mixture was cooled, concentrated under reduced pressure, washed with n-hexane, and dried at 40°C to obtain intermediate A.

[0023] 11 mmol of intermediate A and 5 mmol of hexamethylene diisocyanate were added to tetrahydrofuran solvent, and the mixture was refluxed at 70°C for 5 h in a nitrogen atmosphere. The mixture was cooled, concentrated under reduced pressure, washed with n-hexane, and dried at 40°C to obtain an ether-containing acrylate monomer.

[0024] 5 mmol of ether-containing acrylate monomer and 22.5 mmol of ethylenediamine were added to 20 mL of N,N-dimethylformamide, and the reaction was carried out at 120°C for 12 h. After cooling, the solution was poured into methanol for precipitation, filtered, washed with ethanol, and dried at 60°C to obtain amino-terminated ether-containing hyperbranched polyamide.

[0025] Component A: 100 parts of water-based epoxy resin emulsion, 10 parts of titanium dioxide, 1.5 parts of dispersant LW-110, 0.1 parts of defoamer 902w; component B: 50 parts of amino-terminated ether-containing hyperbranched polyamide, mixed evenly, first cured at 80°C for 2 h, then cured at 110°C for 3 h, and finally cured at 120°C for 2 h to obtain an epoxy resin coating.

[0026] Example 2

[0027] Add 24 mmol of methyl acrylate and 10 mmol of 1-amino-3,6,9-trioxa-11-undecanol to methanol, reflux at 70°C for 24 h under nitrogen atmosphere, cool, concentrate under reduced pressure, wash with n-hexane, and dry at 45°C to obtain intermediate A.

[0028] 12.5 mmol of intermediate A and 5 mmol of hexamethylene diisocyanate were added to a toluene solvent, and the mixture was refluxed at 100°C for 4 h in a nitrogen atmosphere. The mixture was cooled, concentrated under reduced pressure, washed with n-hexane, and dried at 45°C to obtain an ether-containing acrylate monomer.

[0029] 5 mmol of ether-containing acrylate monomer and 25 mmol of ethylenediamine were added to 15 mL of N,N-dimethylformamide, and the reaction was carried out at 130°C for 12 hours. After cooling, the solution was poured into methanol for precipitation, filtered, washed with ethanol, and dried at 70°C to obtain amino-terminated ether-containing hyperbranched polyamide.

[0030] Component A: 100 parts of water-based epoxy resin emulsion, 10 parts of titanium dioxide, 1.5 parts of dispersant LW-110, 0.1 parts of defoamer 902w; component B: 55 parts of amino-terminated ether-containing hyperbranched polyamide, mixed evenly, first cured at 60°C for 3 h, then cured at 100°C for 4 h, and finally cured at 140°C for 2 h to obtain an epoxy resin coating.

[0031] Example 3

[0032] Add 28 mmol of methyl acrylate and 10 mmol of 1-amino-3,6,9-trioxa-11-undecanol to methanol, reflux at 60°C for 24 h in a nitrogen atmosphere, cool, concentrate under reduced pressure, wash with n-hexane, and dry at 40°C to obtain intermediate A.

[0033] 12 mmol of intermediate A and 5 mmol of hexamethylene diisocyanate were added to tetrahydrofuran solvent, and the mixture was refluxed at 70°C for 4 h in a nitrogen atmosphere. The mixture was cooled, concentrated under reduced pressure, washed with n-hexane, and dried at 40°C to obtain an ether-containing acrylate monomer.

[0034] 5 mmol of ether-containing acrylate monomer and 23 mmol of ethylenediamine were added to 20 mL of N,N-dimethylformamide, and the reaction was carried out at 140°C for 10 h. After cooling, the solution was poured into methanol for precipitation, filtered, washed with ethanol, and dried at 70°C to obtain amino-terminated ether-containing hyperbranched polyamide.

[0035] Component A: 100 parts of water-based epoxy resin emulsion, 10 parts of titanium dioxide, 1.5 parts of dispersant LW-110, 0.1 parts of defoamer 902w; component B: 60 parts of amino-terminated ether-containing hyperbranched polyamide, mixed evenly, first cured at 70°C for 1 hour, then cured at 110°C for 2 hours, and finally cured at 140°C for 4 hours to obtain an epoxy resin coating.

[0036] Example 4

[0037] 24 mmol of methyl acrylate and 10 mmol of 1-amino-3,6,9-trioxa-11-undecanol were added to methanol, and the mixture was refluxed at 55°C for 36 h under nitrogen atmosphere. The mixture was cooled, concentrated under reduced pressure, washed with n-hexane, and dried at 40°C to obtain intermediate A.

[0038] 12.5 mmol of intermediate A and 5 mmol of hexamethylene diisocyanate were added to 1,4-dioxane solvent, and the mixture was refluxed at 90 °C for 4 h in a nitrogen atmosphere. The mixture was cooled, concentrated under reduced pressure, washed with n-hexane, and dried at 40 °C to obtain an ether-containing acrylate monomer.

[0039] 5 mmol of ether-containing acrylate monomer and 22.5 mmol of ethylenediamine were added to 20 mL of N,N-dimethylformamide, and the reaction was carried out at 120°C for 10 h. After cooling, the solution was poured into methanol for precipitation, filtered, washed with ethanol, and dried at 70°C to obtain amino-terminated ether-containing hyperbranched polyamide.

[0040] Component A: 100 parts of water-based epoxy resin emulsion, 10 parts of titanium dioxide, 1.5 parts of dispersant LW-110, 0.1 parts of defoamer 902w; component B: 65 parts of amino-terminated ether-containing hyperbranched polyamide, mixed evenly, first cured at 60°C for 2 h, then cured at 110°C for 2 h, and finally cured at 130°C for 4 h to obtain an epoxy resin coating.

[0041] Example 5

[0042] 24 mmol of methyl acrylate and 10 mmol of 1-amino-3,6,9-trioxa-11-undecanol were added to methanol, and the mixture was refluxed at 60°C for 36 h under nitrogen atmosphere. The mixture was cooled, concentrated under reduced pressure, washed with n-hexane, and dried at 50°C to obtain intermediate A.

[0043] 12 mmol of intermediate A and 5 mmol of hexamethylene diisocyanate were added to a toluene solvent, and the mixture was refluxed at 100 °C for 4 h in a nitrogen atmosphere. The mixture was cooled, concentrated under reduced pressure, washed with n-hexane, and dried at 50 °C to obtain an ether-containing acrylate monomer.

[0044] 5 mmol of ether-containing acrylate monomer and 25 mmol of ethylenediamine were added to 15 mL of N,N-dimethylformamide, and the reaction was carried out at 140 °C for 10 h. After cooling, the solution was poured into methanol for precipitation, filtered, washed with ethanol, and dried at 60 °C to obtain amino-terminated ether-containing hyperbranched polyamide.

[0045] Component A: 100 parts of water-based epoxy resin emulsion, 10 parts of titanium dioxide, 1.5 parts of dispersant LW-110, 0.1 parts of defoamer 902w; component B: 70 parts of amino-terminated ether-containing hyperbranched polyamide, mix them evenly, first cure at 70°C for 2 hours, then cure at 100°C for 4 hours, and finally cure at 140°C for 3 hours to obtain an epoxy resin coating.

[0046] Comparative Example 1

[0047] Component A: 100 parts of water-based epoxy resin emulsion, 10 parts of titanium dioxide, 1.5 parts of dispersant LW-110, 0.1 parts of defoamer 902w; component B: 50 parts of polyamide curing agent 651, mixed evenly, first cured at 80℃ for 2 h, then cured at 110℃ for 3 h, and finally cured at 120℃ for 2 h to obtain epoxy resin coating.

[0048] The amino-terminated ether-containing hyperbranched polyamide was added to distilled water and stirred thoroughly to prepare solutions with different mass fractions. The solutions were allowed to stand for 48 h and the state of the solutions was observed.

[0049]

[0050] The amino-terminated ether-containing hyperbranched polyamide has good hydrophilicity and water solubility and can be dispersed uniformly and stably in an aqueous medium.

[0051] The performance test of epoxy resin coating is as follows:

[0052] Pencil hardness is tested according to GB / T 6739-2006.

[0053] Adhesion is tested according to GB / T 9286-2021 standard.

[0054] Impact resistance is tested according to GB / T 1732-2020 standard.

[0055]

[0056] Mix component A: water-based epoxy resin emulsion, titanium dioxide, dispersant LW-110, defoamer 902w; component B: polyamide curing agent 651, mix well, pour into a mold for casting, and heat cure. Test the impact strength and tensile strength according to the methods of GB / T2571-1995 and GB / T2567-2008.

[0057]

[0058] Compared with polyamide curing agent 651, the impact strength of epoxy resin reaches 21.4-32.0 kJ / m when amino-terminated ether-containing hyperbranched polyamide is used as epoxy resin curing agent. 2 , the tensile strength reaches 58.6-69.7MPa.

Claims

1. An amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating, characterized in that: The invention comprises the following raw materials in parts by weight: component A: 100 parts of waterborne epoxy resin emulsion, 5-20 parts of titanium dioxide, 1-2.5 parts of dispersant, 0.05-0.2 parts of defoamer; component B: 50-70 parts of amino-terminated ether-containing hyperbranched polyamide; The amino-terminated ether-containing hyperbranched polyamide is prepared according to the following method: The structural formula is The ether-containing acrylate monomer and ethylenediamine are added to N,N-dimethylformamide to react to obtain an amino-terminated ether-containing hyperbranched polyamide.

2. The amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating according to claim 1, wherein The ratio of the acrylic acid ester monomer to ethylenediamine is 1 mol: (4.5-5) mol.

3. The amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating according to claim 1, wherein The reaction is carried out at a temperature of 110-140°C for 10-18 hours.

4. The amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating according to claim 1, wherein The ether-containing acrylate monomer is prepared according to the following method: S1. Add methyl acrylate and 1-amino-3,6,9-trioxa-11-undecanol to methanol under nitrogen atmosphere, and reflux at 55-70°C for 24-36 hours to obtain intermediate A. S2. Adding intermediate A and hexamethylene diisocyanate to the solvent in a nitrogen atmosphere, and reacting to obtain an ether-containing acrylate monomer.

5. The amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating according to claim 4, wherein The ratio of the methyl acrylate to 1-amino-3,6,9-trioxa-11-undecanol is (2.4-3.2) mol:1 mol.

6. The amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating according to claim 4, wherein The solvent in S2 includes tetrahydrofuran, 1,4-dioxane or toluene.

7. The amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating according to claim 4, wherein In the above-mentioned S2, the molar ratio of the intermediate A to hexamethylene diisocyanate is (2.2-2.5) mol:1 mol.

8. The amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating according to claim 4, wherein The S2 reaction is refluxed at a temperature of 70-100° C. for 3-5 h.

9. A method for curing the amino-terminated ether-containing hyperbranched polyamide modified epoxy resin coating according to claim 1: uniformly mixing component A and component B, first curing at 60-80°C for 1-2 hours, then curing at 100-110°C for 2-4 hours, and finally curing at 120-140°C for 2-4 hours to obtain an epoxy resin coating.

Images