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KR-102961216-B1 - BIO-DEGRADABLE FURAN-BASED COMPOSITE WITH IMPROVED MECHANICAL PROPERTIES AND MANUFACTURING METHOD THEREOF

KR102961216B1KR 102961216 B1KR102961216 B1KR 102961216B1KR-102961216-B1

Abstract

The present invention relates to a furan-based biodegradable composite having significantly improved mechanical properties, in which natural polymer nanofibers are uniformly dispersed and cross-linked, and a method for manufacturing the same.

Inventors

  • 전현열
  • 황성연
  • 박제영
  • 구준모
  • 오동엽
  • 탄부트렁

Assignees

  • 한국화학연구원

Dates

Publication Date
20260507
Application Date
20231215

Claims (11)

  1. A biodegradable composite prepared by polymerizing a furan-based dicarboxylic acid or its derivative, an aliphatic dicarboxylic acid or its derivative, an aliphatic diol, and natural polymer nanofibers; The above natural polymer nanofiber is one or more selected from nanochitin fibers and nanocellulose fibers; The content of the above natural polymer nanofiber is 0.05 to 0.1 weight% with respect to 100 weight% of the total biodegradable composite, and The above-mentioned biodegradable composite has a tensile strength of 70 MPa or more as measured at 25 ℃ with a 1 kN load cell and a crosshead speed of 100 mm/min, and satisfies the following Equation 1: [Equation 1] In the above Equation 1, TS 1 is the tensile strength (MPa) of the biodegradable composite, and TS 0 is the tensile strength (MPa) when polymerized without including the natural polymer nanofiber.
  2. In paragraph 1, A biodegradable complex in which the furan-based dicarboxylic acid is dimethyl furan-2,5-dicarboxylate, dimethyl furan-2,4-dicarboxylate, dimethyl furan-2,3-dicarboxylate, dimethyl furan-3,4-dicarboxylate, diethyl furan-2,5-dicarboxylate, dipropyl furan-2,5-dicarboxylate, 5-(methoxycarbonyl)furan-2-carboxylic acid, 5-(ethoxycarbonyl)furan-2-carboxylic acid, or 5-(methoxycarbonyl)furan-3-carboxylic acid.
  3. In paragraph 1, A biodegradable complex in which the furan-based dicarboxylic acid is dimethyl furan-2,5-dicarboxylate, dimethyl furan-2,4-dicarboxylate, dimethyl furan-2,3-dicarboxylate, dimethyl furan-3,4-dicarboxylate, diethyl furan-2,5-dicarboxylate, or dipropyl furan-2,5-dicarboxylate.
  4. In paragraph 1, The above-mentioned furan-based dicarboxylic acid is a biodegradable complex in which dimethyl furan-2,5-dicarboxylate.
  5. In paragraph 1, A biodegradable complex in which the above-mentioned aliphatic dicarboxylic acid is one or more selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sertive acid, azelaic acid, and sebacic acid.
  6. In paragraph 1, A biodegradable composite in which the aliphatic diol is one or more selected from the group consisting of ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,4-dimethyl-2-ethyl-1,3-hexanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, and 2,2,4-trimethyl-1,6-hexanediol.
  7. In paragraph 1, The above natural polymer nanofiber is a biodegradable composite having an average diameter of 1 to 200 nm and a length of 100 nm to 100 µm.
  8. delete
  9. A step of preparing a mixture composed of a furan-based dicarboxylic acid or a derivative thereof, an aliphatic dicarboxylic acid or a derivative thereof, and an aliphatic diol; A step of dispersing natural polymer nanofibers in the above mixture; and A method for manufacturing a biodegradable composite according to claim 1, comprising the step of polymerizing a mixture in which the above-mentioned natural polymer nanofibers are dispersed.
  10. A step of dispersing natural polymer nanofibers in an aliphatic diol; and A method for manufacturing a biodegradable composite according to claim 1, comprising the step of polymerizing an aliphatic diol in which the above-mentioned natural polymer nanofibers are dispersed, a furan-based dicarboxylic acid or a derivative thereof, and an aliphatic dicarboxylic acid or a derivative thereof by mixing them.
  11. In Paragraph 10, A method for manufacturing a biodegradable composite, wherein the step of dispersing the above natural polymer nanofibers in an aliphatic diol involves adding distilled water in which the above natural polymer nanofibers are dispersed into the above aliphatic diol to disperse them.

Description

Biodegradable furan-based composite with improved mechanical properties and method for manufacturing the same The present invention relates to a biodegradable furan-based composite having improved mechanical properties and a method for manufacturing the same. Currently commercialized resins, such as polyethylene and polypropylene, generally utilize petroleum-based monomers. Due to their poor biodegradability in nature, they pose a problem of adverse environmental impact when disposed of after use. However, petroleum-based resins possess excellent mechanical properties, such as durability, leading to a gradual increase in the proportion of products utilizing them. This is emerging as a problem that must be addressed, particularly in today's world where environmental issues are paramount; consequently, there is a global demand for research and development of eco-friendly materials capable of replacing petroleum-based resins. One method for this purpose is to synthesize biodegradable resins using biomass or petroleum-based monomers. As an example, biodegradable polyesters can be biodegraded when their ester functional groups undergo hydrolysis upon exposure to external water and air. Specifically, examples of such polyesters include PBAT (poly butylene adipate terephthalate), PBS (poly butylene succinate), and PLA (poly lactic acid). However, these biodegradable polyesters show inferiority to petroleum-based resins in terms of mechanical properties, commercial value or marketability, and price competitiveness. In particular, there is a problem in that mechanical properties, such as tensile strength and elongation, are significantly inferior to those of petroleum-based resins, so research and development to solve this is urgent. The present invention will be described in detail below. Meanwhile, embodiments of the present invention may be modified in various different forms, and the scope of the present invention is not limited to the embodiments described below. Furthermore, embodiments of the present invention are provided to more completely explain the present invention to those with average knowledge in the relevant technical field. Moreover, throughout the specification, the term "comprising" any component means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Additionally, the singular form includes the plural form unless specifically stated otherwise in the text. One aspect of the present invention provides a biodegradable composite prepared by polymerizing a furan-based dicarboxylic acid or a derivative thereof, an aliphatic dicarboxylic acid or a derivative thereof, an aliphatic diol, and a natural polymer nanofiber. In this case , the furan-based dicarboxylic acid or its derivative may be used without special limitation as long as it is a dicarboxylic acid compound or its derivative containing a furan ( C₄H₄O ) ring, and may also be a mixture of two or more different furan-based dicarboxylic acids or their derivatives. For example, the furan-based dicarboxylic acid or its derivative may be in a form in which a substituent, such as an alkyl, cycloalkyl, or heterocycloalkyl, which is typically substituted independently on each of the two carboxyl groups or each of the carboxyl groups, is attached to the furan ring. Additionally, for example, a substituent, such as -OH, -CN, -NH₂ , -NO₂ , halogen, alkyl, alkoxy, cycloalkyl, or heterocycloalkyl, which is typically substituted, may be further attached to the furan ring. Specifically, examples may include dimethyl furan-2,5-dicarboxylate, dimethyl furan-2,4-dicarboxylate, dimethyl furan-2,3-dicarboxylate, dimethyl furan-3,4-dicarboxylate, diethyl furan-2,5-dicarboxylate, dipropyl furan-2,5-dicarboxylate, 5-(methoxycarbonyl)furan-2-carboxylic acid, dipropyl furan-2,5-dicarboxylate, 5-(ethoxycarbonyl)furan-2-carboxylic acid, or 5-(methoxycarbonyl)furan-3-carboxylic acid, but are not necessarily limited thereto. A composite polymerized from a furan-based compound according to one aspect of the present invention is effective because the reinforcing effect of nanofibers is further enhanced due to the reduction in crystallinity caused by using a furan-based compound compared to using a terephthalic compound. In addition, since furan-based compounds can be derived from biomass, it is possible to manufacture 100% bio-based biodegradable plastics using the biodegradable composite according to the present invention. The aliphatic dicarboxylic acid in the above aliphatic dicarboxylic acid or its derivative is not particularly limited, but may be one or more selected from, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, serbenic acid, azelaic acid, and sebacic acid. The above aliphatic diols are not particularly limited, but may be one or more selected from, for example, ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5