Aliphatic-aromatic copolyester, preparation method and application thereof

Abstract

This invention provides an aliphatic-aromatic copolyester and the preparation and use thereof, and the polymeric monomers comprise compounds selected from aliphatic diacids, naphthenic diacids or the esters, anhydrides, acyl halides thereof; compounds selected from aromatic diacids or the esters, anhydrides, acyl halides thereof; compounds selected from compounds with two functional groups selected from amino groups, mercapto groups or hydroxyl groups, or the derivatives thereof with epoxys, nitrogen-containing heterocyclic rings or sulfur-containing heterocyclic rings; compounds selected from unsaturated acids with at least one carbon-carbon, carbon-oxygen, carbon-nitrogen, or carbon-sulfur double bonds, carbon-carbon or carbon-nitrogen triple bonds or the esters, anhydrides, acyl halides thereof; compounds selected from unsaturated alcohols with at least one carbon-carbon double bonds or carbon-carbon triple bonds or the epoxy derivatives thereof; the aliphatic-aromatic copolyester is obtained by mixing the foregoing polymeric monomers, followed by esterification, condensation polymerization; then polymerizing, grafting and / or coupling the double bonds and / or triple bonds of the monomers with an initiating agent.

Description

technical field

[0001] The invention relates to an aliphatic-aromatic copolyester and its preparation method and application, in particular to a high molecular weight, biodegradable aliphatic-aromatic copolyester and its preparation method and application. Background technique

[0002] At present, polymer materials have penetrated into various fields of people's lives. While it brings convenience to people, it also creates a problem to be solved-"white pollution". Most of the polymer materials currently used cannot be degraded in the environment for a long time, and a large amount of them remain in the environment after use. The pressure on the environment is increasing year by year, destroying the ecological environment of the earth and affecting the recycling of resources. As people are concerned about their living environment, more and more people pay attention to environmentally friendly biodegradable polymer materials.

[0003] There are ester bonds in the main molecul...

Examples

Embodiment 1

[0049] Add 1000ml chloroform, 507.5 grams of terephthaloyl chloride and 387.5 grams of succinoyl chloride in the reaction flask, stir well, add dropwise the mixture of 450 grams of butanediol and 11.6 grams of monoethylene glycol acrylate under stirring, control the reaction temperature at 0~40°C, after the dropwise addition is completed, continue to stir for 60 minutes to complete the reaction. The hydrogen chloride produced in the reaction was absorbed with NaOH solution.

[0050] After the reaction is complete, distill off the chloroform, add 0.5-1 g of tetrabutyl titanate, stir thoroughly for 20 minutes after melting, fill the bottle with nitrogen to replace the air in the bottle, reduce the pressure to 100-1000 Pa, continue to heat up to 180-250 °C, and stir After reacting for 60-120 minutes, light yellow to white polymer 1 was obtained. The GPC method determined that the molecular weight was 65,300 for Mn, 140,400 for Mw, and the molecular weight distribution was 2.15. ...

Embodiment 2

[0052] Add 1000ml of chloroform, 507.5 grams of terephthaloyl chloride, 387.5 grams of succinoyl chloride, and 4.5 grams of acryloyl chloride into the reaction flask and stir evenly, then add dropwise 62 grams of ethylene glycol, 270 grams of butanediol, 95 grams of hexanediol, Mixture of 80 grams of polyethylene glycol, control reaction temperature at 0~40 ℃, dropwise, continue to stir for 60 minutes to make reaction complete. The hydrogen chloride produced in the reaction was absorbed with NaOH solution.

[0053] After the reaction is complete, distill off the chloroform, add 0.5-1 g of tetrabutyl titanate, stir for 20 minutes, fill the bottle with nitrogen to replace the air in the bottle, reduce the pressure to 100-1000 Pa, continue to heat up to 180-250 ° C, and react for 60-120 minutes , to obtain light yellow to white polymer 2. The GPC method determined that the molecular weight was 58,200 for Mn, 134,500 for Mw, and a molecular weight distribution of 2.31.

Embodiment 3

[0055] Add 1000ml of chloroform, 507.5g of terephthaloyl chloride, 457.5g of adipoyl chloride and 4.5g of acryloyl chloride into the reaction bottle, stir evenly, add dropwise a mixture of 441g of butanediol and 100g of polyethylene glycol under stirring to control the reaction The temperature is 0-40°C, after the dropwise addition is completed, the stirring is continued for 60 minutes to complete the reaction. The hydrogen chloride produced in the reaction was absorbed with NaOH solution.

[0056] After the reaction is complete, distill off the chloroform, add 0.5-1 g of tetrabutyl titanate, stir thoroughly for 20 minutes after melting, fill the bottle with nitrogen to replace the air in the bottle, reduce the pressure to 100-1000 Pa, continue to heat up to 180-250 °C, and stir After 60-120 minutes of reaction, polymer 3 was obtained. The GPC method determined that the molecular weight was 49,600 for Mn, 137,900 for Mw, and the molecular weight distribution was 2.78.

technical field

[0001] The invention relates to an aliphatic-aromatic copolyester and its preparation method and application, in particular to a high molecular weight, biodegradable aliphatic-aromatic copolyester and its preparation method and application. Background technique

[0002] At present, polymer materials have penetrated into various fields of people's lives. While it brings convenience to people, it also creates a problem to be solved-"white pollution". Most of the polymer materials currently used cannot be degraded in the environment for a long time, and a large amount of them remain in the environment after use. The pressure on the environment is increasing year by year, destroying the ecological environment of the earth and affecting the recycling of resources. As people are concerned about their living environment, more and more people pay attention to environmentally friendly biodegradable polymer materials.

[0003] There are ester bonds in the main molecul...

Examples

Embodiment 1

[0049] Add 1000ml chloroform, 507.5 grams of terephthaloyl chloride and 387.5 grams of succinoyl chloride in the reaction flask, stir well, add dropwise the mixture of 450 grams of butanediol and 11.6 grams of monoethylene glycol acrylate under stirring, control the reaction temperature at 0~40°C, after the dropwise addition is completed, continue to stir for 60 minutes to complete the reaction. The hydrogen chloride produced in the reaction was absorbed with NaOH solution.

[0050] After the reaction is complete, distill off the chloroform, add 0.5-1 g of tetrabutyl titanate, stir thoroughly for 20 minutes after melting, fill the bottle with nitrogen to replace the air in the bottle, reduce the pressure to 100-1000 Pa, continue to heat up to 180-250 °C, and stir After reacting for 60-120 minutes, light yellow to white polymer 1 was obtained. The GPC method determined that the molecular weight was 65,300 for Mn, 140,400 for Mw, and the molecular weight distribution was 2.15. ...

Embodiment 2

[0052] Add 1000ml of chloroform, 507.5 grams of terephthaloyl chloride, 387.5 grams of succinoyl chloride, and 4.5 grams of acryloyl chloride into the reaction flask and stir evenly, then add dropwise 62 grams of ethylene glycol, 270 grams of butanediol, 95 grams of hexanediol, Mixture of 80 grams of polyethylene glycol, control reaction temperature at 0~40 ℃, dropwise, continue to stir for 60 minutes to make reaction complete. The hydrogen chloride produced in the reaction was absorbed with NaOH solution.

[0053] After the reaction is complete, distill off the chloroform, add 0.5-1 g of tetrabutyl titanate, stir for 20 minutes, fill the bottle with nitrogen to replace the air in the bottle, reduce the pressure to 100-1000 Pa, continue to heat up to 180-250 ° C, and react for 60-120 minutes , to obtain light yellow to white polymer 2. The GPC method determined that the molecular weight was 58,200 for Mn, 134,500 for Mw, and a molecular weight distribution of 2.31.

Embodiment 3

[0055] Add 1000ml of chloroform, 507.5g of terephthaloyl chloride, 457.5g of adipoyl chloride and 4.5g of acryloyl chloride into the reaction bottle, stir evenly, add dropwise a mixture of 441g of butanediol and 100g of polyethylene glycol under stirring to control the reaction The temperature is 0-40°C, after the dropwise addition is completed, the stirring is continued for 60 minutes to complete the reaction. The hydrogen chloride produced in the reaction was absorbed with NaOH solution.

[0056] After the reaction is complete, distill off the chloroform, add 0.5-1 g of tetrabutyl titanate, stir thoroughly for 20 minutes after melting, fill the bottle with nitrogen to replace the air in the bottle, reduce the pressure to 100-1000 Pa, continue to heat up to 180-250 °C, and stir After 60-120 minutes of reaction, polymer 3 was obtained. The GPC method determined that the molecular weight was 49,600 for Mn, 137,900 for Mw, and the molecular weight distribution was 2.78.

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