Preparation method of biodegradable carbon dioxide-based polyester-polycarbonate terpolymer

Abstract

The invention discloses a preparation method of a biodegradable carbon dioxide-based polyester-polycarbonate terpolymer. A commercialized, simple and efficient nonmetal triethyl boron / tetra-n-butyl ammonium chloride catalytic initiation system is used for catalyzing and initiating epoxypropane, carbon dioxide and phthalic anhydride to be subjected to a ternary polymerization reaction, and an aromatic polyester structure with the content of 10%-40% is successfully introduced into a main chain of polymethyl ethylene carbonate (PPC). The terpolymer can have different sequence structures; and haverandom and block structures and the like, the glass transition temperature and the thermal stability of PPC are improved, and a catalytic system does not contain metal components, so that the phthalic anhydride modified PPC has extremely high light transmittance, very high melt viscosity and good foaming performance on the premise of keeping the biodegradability of a PPC material. The method canbe used for synthesizing the modified PPC biodegradable material, and widens the application range of the PPC material.

Description

technical field

[0001] The invention relates to the technical field of polymer materials, in particular to a preparation method of a biodegradable carbon dioxide-based polyester-polycarbonate terpolymer. Background technique

[0002] While petroleum-based polymer materials bring convenience to people's lives, they also cause serious "white pollution". Therefore, the development of biodegradable materials is of great significance; It forces people to seek ways to fix carbon dioxide into useful small molecules or polymer materials.

[0003] Since Professor Shohei Inoue first discovered that propylene oxide and carbon dioxide can carry out copolymerization reaction in 1969, the reaction has been extensively researched and developed. Its product, polymethylethylene carbonate (PPC), is a transparent, fully degradable, environmentally friendly plastic with excellent biocompatibility, high barrier properties and impact toughness, and its elongation at break is 600- 1200%. Howeve...

Examples

Embodiment 1

[0020] With a 50mL autoclave as the reaction vessel, in an anhydrous and oxygen-free environment, 1.0g of phthalic anhydride, 3.92g of propylene oxide, 7.5mg of tetra-n-butylammonium chloride, and 54μL of triethylboron solution were sequentially Put it into a high-pressure reactor, fill it with 1.0MPa carbon dioxide, react at 80°C for 12 hours, release the carbon dioxide pressure after the reaction, dissolve the product with dichloromethane, quench the reaction with dilute hydrochloric acid / methanol solution, and precipitate in ethanol to obtain a polymer , After the polymer is vacuum-dried, do molecular weight testing, nuclear magnetic analysis and thermal performance analysis. m n =52.7kDa, PDI=1.16, polyester content 14.8%, polycarbonate content=81.6%, polyether content=3.6%, T g = 40.5°C.

Embodiment 2

[0022] With a 50mL autoclave as the reaction vessel, in an anhydrous and oxygen-free environment, 2.5g of phthalic anhydride, 4.90g of propylene oxide, 9.4mg of tetra-n-butylammonium chloride, and 200μL of triethylboron solution were sequentially Put it into a high-pressure reactor, fill it with 1.0MPa carbon dioxide, react at 80°C for 12 hours, release the carbon dioxide pressure after the reaction, dissolve the product with dichloromethane, quench the reaction with dilute hydrochloric acid / methanol solution, and precipitate in ethanol to obtain a polymer , After the polymer is vacuum-dried, do molecular weight testing, nuclear magnetic analysis and thermal performance analysis. m n =102.8kDa, PDI=1.35, polyester content 39.9%, polycarbonate content=55.2%, polyether content=4.9%, T g =47.4°C

Embodiment 3

[0024] With a 50mL autoclave as the reaction vessel, in an anhydrous and oxygen-free environment, 1.0g of phthalic anhydride, 4.0g of propylene oxide, 7.5mg of tetra-n-butylammonium chloride, and 54μL of triethylboron solution were sequentially Put it into a high-pressure reactor, fill it with 3.0MPa carbon dioxide, react at 80°C for 12 hours, release the carbon dioxide pressure after the reaction, dissolve the product with dichloromethane, quench the reaction with dilute hydrochloric acid / methanol solution, and precipitate in ethanol to obtain a polymer , After the polymer is vacuum-dried, do molecular weight testing, nuclear magnetic analysis and thermal performance analysis. m n =61.2kDa, PDI=1.27, polyester content 33.4%, polycarbonate content=60.8%, polyether content=5.8%, T g = 45.6°C.

technical field

[0001] The invention relates to the technical field of polymer materials, in particular to a preparation method of a biodegradable carbon dioxide-based polyester-polycarbonate terpolymer. Background technique

[0002] While petroleum-based polymer materials bring convenience to people's lives, they also cause serious "white pollution". Therefore, the development of biodegradable materials is of great significance; It forces people to seek ways to fix carbon dioxide into useful small molecules or polymer materials.

[0003] Since Professor Shohei Inoue first discovered that propylene oxide and carbon dioxide can carry out copolymerization reaction in 1969, the reaction has been extensively researched and developed. Its product, polymethylethylene carbonate (PPC), is a transparent, fully degradable, environmentally friendly plastic with excellent biocompatibility, high barrier properties and impact toughness, and its elongation at break is 600- 1200%. Howeve...

Examples

Embodiment 1

[0020] With a 50mL autoclave as the reaction vessel, in an anhydrous and oxygen-free environment, 1.0g of phthalic anhydride, 3.92g of propylene oxide, 7.5mg of tetra-n-butylammonium chloride, and 54μL of triethylboron solution were sequentially Put it into a high-pressure reactor, fill it with 1.0MPa carbon dioxide, react at 80°C for 12 hours, release the carbon dioxide pressure after the reaction, dissolve the product with dichloromethane, quench the reaction with dilute hydrochloric acid / methanol solution, and precipitate in ethanol to obtain a polymer , After the polymer is vacuum-dried, do molecular weight testing, nuclear magnetic analysis and thermal performance analysis. m n =52.7kDa, PDI=1.16, polyester content 14.8%, polycarbonate content=81.6%, polyether content=3.6%, T g = 40.5°C.

Embodiment 2

[0022] With a 50mL autoclave as the reaction vessel, in an anhydrous and oxygen-free environment, 2.5g of phthalic anhydride, 4.90g of propylene oxide, 9.4mg of tetra-n-butylammonium chloride, and 200μL of triethylboron solution were sequentially Put it into a high-pressure reactor, fill it with 1.0MPa carbon dioxide, react at 80°C for 12 hours, release the carbon dioxide pressure after the reaction, dissolve the product with dichloromethane, quench the reaction with dilute hydrochloric acid / methanol solution, and precipitate in ethanol to obtain a polymer , After the polymer is vacuum-dried, do molecular weight testing, nuclear magnetic analysis and thermal performance analysis. m n =102.8kDa, PDI=1.35, polyester content 39.9%, polycarbonate content=55.2%, polyether content=4.9%, T g =47.4°C

Embodiment 3

[0024] With a 50mL autoclave as the reaction vessel, in an anhydrous and oxygen-free environment, 1.0g of phthalic anhydride, 4.0g of propylene oxide, 7.5mg of tetra-n-butylammonium chloride, and 54μL of triethylboron solution were sequentially Put it into a high-pressure reactor, fill it with 3.0MPa carbon dioxide, react at 80°C for 12 hours, release the carbon dioxide pressure after the reaction, dissolve the product with dichloromethane, quench the reaction with dilute hydrochloric acid / methanol solution, and precipitate in ethanol to obtain a polymer , After the polymer is vacuum-dried, do molecular weight testing, nuclear magnetic analysis and thermal performance analysis. m n =61.2kDa, PDI=1.27, polyester content 33.4%, polycarbonate content=60.8%, polyether content=5.8%, T g = 45.6°C.

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