Degradable biological-based waterborne emulsion and preparation method thereof

Abstract

The invention discloses a degradable biological-based waterborne emulsion and a preparation method thereof. The preparation method comprises the following steps: carrying out a polymerization reaction on purified L-lactide, epsilon-caprolactone and polyol under the action of a catalyst, to obtain hydroxyl-terminated polyester polyol with the viscosity average molecular weight of 1000-10000; carrying out a reaction of hydroxyl-terminated polyester polyol, diisocyanate and a hydrophilic chain extender under the action of a catalyst, to obtain a prepolymer; and adding an emulsifier and water in the prepolymer, carrying out high-speed stirring emulsification, and carrying out a reaction with a crosslinking agent, to obtain the degradable waterborne emulsion. The degradable biological-based emulsion and the preparation method thereof are novel; the polylactide and caprolactone random copolymer which can be fully biodegradable is obtained, has relatively low glass transition temperature (Tg), has better emulsifying dispersion than polylactide, does not contain organic solvents, is biodegradable, can be widely applied in coatings, adhesives, fabric coating layers and other fields, is a quite good environmental-protection material, and has broad market prospects.

Description

technical field

[0001] The invention belongs to the technical field of biodegradable organic polymers, and in particular relates to a degradable bio-based aqueous emulsion and a preparation method thereof. Background technique

[0002] In recent years, from the perspective of environmental protection, research on biodegradable materials in the natural environment has become increasingly active. Especially polylactic acid, polycaprolactone, polyglycolide, etc. have excellent biocompatibility and degradability, and the source of raw materials is abundant, and the discarded products can be decomposed under the action of microorganisms, water, acid and alkali in nature. , eventually decomposed into water and carbon dioxide, and will not cause any pollution to the environment, but these materials are generally obtained by ring-opening polymerization under a catalyst to obtain thermoplastic polymers, and their hydrophilicity is poor, making it difficult to form aqueous emulsions, ...

Examples

Embodiment 1

[0013] The flask was purged with nitrogen before the reaction. Add 70g of purified L-lactide, 30gε-caprolactone, and 1.5g of ethylene glycol into a 500ml four-neck flask, then add 0.2g of dibutyltin oxide as a catalyst, vacuumize for nitrogen replacement, and under nitrogen protection conditions , raise the temperature to 130°C, react at 130°C for 6h, raise the temperature to 170°C for 5h, then drop to room temperature, add 25g of isophorone diisocyanate (IPDI) to the flask and heat while stirring, Under nitrogen protection, the temperature was raised to 85°C for reaction, and when the NCO content reached 10% of the theoretical value, 5 g of dimethylol acid and 0.1 g of dibutyltin laurate were added to the reaction vessel, and the reaction was carried out at 80°C for 1 hour, and then Add 5.0g of alkylphenol polyoxyethylene ether OP-10 and 280g of water into the flask, stir and emulsify at high speed for 30 minutes, add 5g of triethanolamine, raise the temperature to 50°C, cont...

Embodiment 2

[0016] The flask was purged with nitrogen before the reaction. Add 80g of purified L-lactide, 20gε-caprolactone, and 2g of pentaerythritol into a 500ml four-neck flask, then add 0.15g of the catalyst stannous octoate, vacuumize for nitrogen replacement, and under nitrogen protection conditions, rise Temperature to 135°C, react at 135°C for 5h, raise the temperature to 175°C for 4h, then lower to room temperature, add 25gL-lysine diisocyanate (LDI) to the flask and heat while stirring, under nitrogen protection , the temperature was raised to 85°C for reaction, and when the NCO content reached 10% of the theoretical value, 8 g of sodium ethylenediaminoethanesulfonate and 0.1 g of dibutyltin laurate were added to the reaction vessel, and the reaction was carried out at 80°C for 1 hour, and then Add 5.0g of fatty alcohol polyoxyethylene ether 0-15 and 280g of water into the flask, stir and emulsify at high speed for 30 minutes, add 5g of triethylamine, raise the temperature to 50...

Embodiment 3

[0019] The flask was purged with nitrogen before the reaction. Add 75g of purified L-lactide, 25gε-caprolactone, and 1.5g of ethylene glycol into a 500ml four-neck flask, then add 0.2g of catalyst dibutyltin oxide, vacuumize for nitrogen replacement, under nitrogen protection conditions , raise the temperature to 130°C, react at 130°C for 6h, raise the temperature to 170°C for 5h, then drop to room temperature, add 25g of isophorone diisocyanate (IPDI) to the flask and heat while stirring, Under the protection of nitrogen, the temperature was raised to 85°C for reaction. When the NCO content reached 10% of the theoretical value, 5g of N-methyldiethanolamine and 0.1g of dibutyltin laurate were added to the reaction vessel, and the reaction was carried out at 80°C for 1 hour. Then add 5.0g of isomeric tridecyl alcohol polyoxyethylene ether and 280g of water to the flask, stir and emulsify at high speed for 30 minutes, add 5g of triethanolamine, raise the temperature to 50°C, con...

technical field

[0001] The invention belongs to the technical field of biodegradable organic polymers, and in particular relates to a degradable bio-based aqueous emulsion and a preparation method thereof. Background technique

[0002] In recent years, from the perspective of environmental protection, research on biodegradable materials in the natural environment has become increasingly active. Especially polylactic acid, polycaprolactone, polyglycolide, etc. have excellent biocompatibility and degradability, and the source of raw materials is abundant, and the discarded products can be decomposed under the action of microorganisms, water, acid and alkali in nature. , eventually decomposed into water and carbon dioxide, and will not cause any pollution to the environment, but these materials are generally obtained by ring-opening polymerization under a catalyst to obtain thermoplastic polymers, and their hydrophilicity is poor, making it difficult to form aqueous emulsions, ...

Examples

Embodiment 1

[0013] The flask was purged with nitrogen before the reaction. Add 70g of purified L-lactide, 30gε-caprolactone, and 1.5g of ethylene glycol into a 500ml four-neck flask, then add 0.2g of dibutyltin oxide as a catalyst, vacuumize for nitrogen replacement, and under nitrogen protection conditions , raise the temperature to 130°C, react at 130°C for 6h, raise the temperature to 170°C for 5h, then drop to room temperature, add 25g of isophorone diisocyanate (IPDI) to the flask and heat while stirring, Under nitrogen protection, the temperature was raised to 85°C for reaction, and when the NCO content reached 10% of the theoretical value, 5 g of dimethylol acid and 0.1 g of dibutyltin laurate were added to the reaction vessel, and the reaction was carried out at 80°C for 1 hour, and then Add 5.0g of alkylphenol polyoxyethylene ether OP-10 and 280g of water into the flask, stir and emulsify at high speed for 30 minutes, add 5g of triethanolamine, raise the temperature to 50°C, cont...

Embodiment 2

[0016] The flask was purged with nitrogen before the reaction. Add 80g of purified L-lactide, 20gε-caprolactone, and 2g of pentaerythritol into a 500ml four-neck flask, then add 0.15g of the catalyst stannous octoate, vacuumize for nitrogen replacement, and under nitrogen protection conditions, rise Temperature to 135°C, react at 135°C for 5h, raise the temperature to 175°C for 4h, then lower to room temperature, add 25gL-lysine diisocyanate (LDI) to the flask and heat while stirring, under nitrogen protection , the temperature was raised to 85°C for reaction, and when the NCO content reached 10% of the theoretical value, 8 g of sodium ethylenediaminoethanesulfonate and 0.1 g of dibutyltin laurate were added to the reaction vessel, and the reaction was carried out at 80°C for 1 hour, and then Add 5.0g of fatty alcohol polyoxyethylene ether 0-15 and 280g of water into the flask, stir and emulsify at high speed for 30 minutes, add 5g of triethylamine, raise the temperature to 50...

Embodiment 3

[0019] The flask was purged with nitrogen before the reaction. Add 75g of purified L-lactide, 25gε-caprolactone, and 1.5g of ethylene glycol into a 500ml four-neck flask, then add 0.2g of catalyst dibutyltin oxide, vacuumize for nitrogen replacement, under nitrogen protection conditions , raise the temperature to 130°C, react at 130°C for 6h, raise the temperature to 170°C for 5h, then drop to room temperature, add 25g of isophorone diisocyanate (IPDI) to the flask and heat while stirring, Under the protection of nitrogen, the temperature was raised to 85°C for reaction. When the NCO content reached 10% of the theoretical value, 5g of N-methyldiethanolamine and 0.1g of dibutyltin laurate were added to the reaction vessel, and the reaction was carried out at 80°C for 1 hour. Then add 5.0g of isomeric tridecyl alcohol polyoxyethylene ether and 280g of water to the flask, stir and emulsify at high speed for 30 minutes, add 5g of triethanolamine, raise the temperature to 50°C, con...