Preparation method of water-base alicyclic isocyanate modified polyester light-cured resin

Abstract

The invention relates to a preparation method of a water-base alicyclic isocyanate modified polyester light-cured resin. The water-base alicyclic isocyanate modified polyester light-cured resin is prepared from 1 to 3% of a hyperbranched polyester, 5 to 12% of an acrylic monomer containing hydroxyl, 10 to 18% of an alicyclic isocyanate monomer, 0.02 to 0.3% of dibutyltin dilaurate, 10 to 20% of maleic anhydride, 4 to 10% of N,N-dimethylaniline, 3 to 5% of sodium hydroxide, and 40 to 65% of deionized water; wherein the hyperbranched polyester is obtained via synthesis of DMPA with TMP in the presence of a catalyst. The water-base alicyclic isocyanate modified polyester light-cured resin possesses excellent storage stability; coating films obtained under action of a photoinitiator possesses excellent water resistance, hardness, aging resistance, chemical resistance, and stain resistance, high glossiness, excellent wear resistance, high adhesive force, high fullness, and excellent impact resistance. The water-base alicyclic isocyanate modified polyester light-cured resin can be widely applied to surface radiation coating and protection of wood, metal, zinc alloy, aluminium alloy, magnesium alloy, and plastic products.

Description

technical field

[0001] The invention relates to a preparation method of a light-cured polyester resin, in particular to a water-based alicyclic isocyanate-modified polyester light-cured resin, which belongs to the technical field of synthetic resins. Background technique

[0002] In recent years, environmentally friendly coatings, including high-solids and solvent-free coatings, water-based coatings, powder coatings and light-curing coatings, have achieved rapid development. UV curing has the advantages of fast response, room temperature operation, low energy consumption, no solvent and less pollution. Water-based photocurable polyester has a hyperbranched molecular structure. Introducing hyperbranched polyester into the UV curing system can overcome some shortcomings of linear oligomers, such as severe shrinkage of the coating film, volatilization of diluents, and high toxicity; Water-based light-curing polyester coating, one of the representative curing coatings, has the ...

Examples

Embodiment 1

[0013] a. In the reaction kettle, add 13.5 parts of 2,2-dimethylolpropionic acid and 1.5 parts of trimethylolpropane, pass through nitrogen protection, raise the temperature to 130°C, add 0.1 part of p-toluenesulfonic acid, keep warm After reacting for 4 hours, turn off the nitrogen gas, continue to react for 2 hours, and then cool to 40°C to prepare hyperbranched polyester for later use;

[0014] b. In the reaction kettle, add 10.5 parts of IPDI and 0.06 parts of dibutyltin dilaurate, raise the temperature to 30-40°C, add 5.2 parts of 2-hydroxyethyl acrylate monomer dropwise under stirring, and start sampling after 0.5 hours of reaction Detect the isocyanic acid value, and then take a sample every 0.5h. When the detected isocyanic acid value is 15.5-16.0% NCO, add 1.8 parts of the hyperbranched polyester prepared in step a, and heat up to 50-60°C to continue the reaction When the isocyanic acid value is less than 1%, the temperature is raised to 70-80°C, and when the isocyani...

Embodiment 2

[0017] A, step a is arranged in hyperbranched polyester reference example 1;

[0018] b. In the reaction kettle, add 12 parts of HMDI trimer and 0.06 parts of dibutyltin dilaurate, raise the temperature to 30-40°C, add 5.8 parts of 2-hydroxypropyl acrylate monomer dropwise under stirring, and react for 0.5h Then start sampling to detect the isocyanic acid value, and then take a sample every 0.5h. When the detected isocyanic acid value is 15.5-16.0% NCO, add 2 parts of the hyperbranched polyester prepared in step a, and heat up to 50-60°C , continue to react until the isocyanic acid value is less than 1%, then raise the temperature to 70-80°C, when the isocyanic acid value cannot be detected, proceed to the next step of reaction;

[0019] c. Add 4 parts of butanone to the reaction kettle in step b for stirring. After the dissolution is complete, add 5.2 parts of N,N-dimethylaniline, raise the temperature to 80°C, add 28 parts of 50% maleic anhydride butanone solution dropwise, ...

Embodiment 3

[0021] The water-based cycloaliphatic isocyanate-modified polyester photocurable resin prepared in the embodiment of the present invention is formulated into a water-based UV varnish, and the formula is as follows: 62-70 parts of water-based cycloaliphatic isocyanate-modified polyester photocurable resin, photoinitiator 4.2 part, 0.2 part of defoaming agent, 0.3 part of substrate wetting agent, 0.2 part of leveling agent, make up deionized water to 100; and water-based TDI modified polyester photocurable resin (comparative example) according to the above formula to make water-based UV For the varnish, the performance of the coating film was compared and tested according to the relevant national standards, and the coating film was cured by radiation for 10 seconds. The test results are shown in Table 1.

[0022] Table 1: Coating film performance test results

technical field

[0001] The invention relates to a preparation method of a light-cured polyester resin, in particular to a water-based alicyclic isocyanate-modified polyester light-cured resin, which belongs to the technical field of synthetic resins. Background technique

[0002] In recent years, environmentally friendly coatings, including high-solids and solvent-free coatings, water-based coatings, powder coatings and light-curing coatings, have achieved rapid development. UV curing has the advantages of fast response, room temperature operation, low energy consumption, no solvent and less pollution. Water-based photocurable polyester has a hyperbranched molecular structure. Introducing hyperbranched polyester into the UV curing system can overcome some shortcomings of linear oligomers, such as severe shrinkage of the coating film, volatilization of diluents, and high toxicity; Water-based light-curing polyester coating, one of the representative curing coatings, has the ...

Examples

Embodiment 1

[0013] a. In the reaction kettle, add 13.5 parts of 2,2-dimethylolpropionic acid and 1.5 parts of trimethylolpropane, pass through nitrogen protection, raise the temperature to 130°C, add 0.1 part of p-toluenesulfonic acid, keep warm After reacting for 4 hours, turn off the nitrogen gas, continue to react for 2 hours, and then cool to 40°C to prepare hyperbranched polyester for later use;

[0014] b. In the reaction kettle, add 10.5 parts of IPDI and 0.06 parts of dibutyltin dilaurate, raise the temperature to 30-40°C, add 5.2 parts of 2-hydroxyethyl acrylate monomer dropwise under stirring, and start sampling after 0.5 hours of reaction Detect the isocyanic acid value, and then take a sample every 0.5h. When the detected isocyanic acid value is 15.5-16.0% NCO, add 1.8 parts of the hyperbranched polyester prepared in step a, and heat up to 50-60°C to continue the reaction When the isocyanic acid value is less than 1%, the temperature is raised to 70-80°C, and when the isocyani...

Embodiment 2

[0017] A, step a is arranged in hyperbranched polyester reference example 1;

[0018] b. In the reaction kettle, add 12 parts of HMDI trimer and 0.06 parts of dibutyltin dilaurate, raise the temperature to 30-40°C, add 5.8 parts of 2-hydroxypropyl acrylate monomer dropwise under stirring, and react for 0.5h Then start sampling to detect the isocyanic acid value, and then take a sample every 0.5h. When the detected isocyanic acid value is 15.5-16.0% NCO, add 2 parts of the hyperbranched polyester prepared in step a, and heat up to 50-60°C , continue to react until the isocyanic acid value is less than 1%, then raise the temperature to 70-80°C, when the isocyanic acid value cannot be detected, proceed to the next step of reaction;

[0019] c. Add 4 parts of butanone to the reaction kettle in step b for stirring. After the dissolution is complete, add 5.2 parts of N,N-dimethylaniline, raise the temperature to 80°C, add 28 parts of 50% maleic anhydride butanone solution dropwise, ...

Embodiment 3

[0021] The water-based cycloaliphatic isocyanate-modified polyester photocurable resin prepared in the embodiment of the present invention is formulated into a water-based UV varnish, and the formula is as follows: 62-70 parts of water-based cycloaliphatic isocyanate-modified polyester photocurable resin, photoinitiator 4.2 part, 0.2 part of defoaming agent, 0.3 part of substrate wetting agent, 0.2 part of leveling agent, make up deionized water to 100; and water-based TDI modified polyester photocurable resin (comparative example) according to the above formula to make water-based UV For the varnish, the performance of the coating film was compared and tested according to the relevant national standards, and the coating film was cured by radiation for 10 seconds. The test results are shown in Table 1.

[0022] Table 1: Coating film performance test results