Recyclable and (Bio)degradable Polyesters in a Circular Plastics Economy

Shi, Changxia; Quinn, Ethan C.; Diment, Wilfred T.; Chen, Eugene Y.-X.

doi:10.1021/acs.chemrev.3c00848

Cited by 29 publications

(6 citation statements)

References 674 publications

(1,462 reference statements)

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“…The specific class of biobased and biodegradable PHAs –(O–CHR–CH 2 –CO) n – has drawn increasing interest as sustainable alternatives to petroleum-based, environmentally persistent polyolefins. − ,− The remarkable properties of biodegradability due to the hydrolysis by enzymes ,,− depend on the structure in the solid state, polymorphic behavior, crystallinity, and thickness of crystalline lamellae, , and in principle, the biodegradability of PHAs could be regulated by modification of the structure . Since PHAs may be synthesized as a carbon reserve by different bacteria, − ,− their composition is variable and depends on the fermentation conditions.…”

Section: Introductionmentioning

confidence: 99%

Crystal Structure of Atactic and Isotactic Poly(3-hydroxy-2,2-dimethylbutyrate): A Chemically Recyclable Poly(hydroxyalkanoate) with Tacticity-Independent Crystallinity

Scoti,

Zhou,

Chen

et al. 2024

Macromolecules

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The crystal structures of isotactic and atactic poly(3-hydroxy-2,2-dimethylbutyrate) (P3H(Me) 2 B) are presented. Samples of atactic P3H(Me) 2 B (at-(R/S)-P3H(Me) 2 B) and of the R and S enantiomers of isotactic P3H(Me) 2 B (it-(R)-P3H(Me) 2 B and it-(S)-P3H(Me) 2 B, respectively) have been synthesized by ring opening polymerization of racemic and chiral dimethyl-butyrolactones employing a superbase catalyst. A 1:1 racemic mixture of the two R and S enantiomers (it-(R,S)-P3H(Me) 2 B) has been also prepared. Both the atactic and the pure enantiomer isotactic polymers crystallize showing identical diffraction patterns, indicating crystallization in the same crystalline form and identical crystal structure. The racemic mixture it-(R,S)-P3H(Me) 2 B also crystallizes giving identical diffraction pattern. This is one of the few examples of crystallization of an atactic polymer despite the configurational disorder and probably it is the first structurally confirmed example of crystallization of atactic and isotactic polymers in the identical crystal structure. This fascinating tacticity-independent crystallinity explains the remarkable thermal and mechanical behaviors of P3H(Me) 2 B, which is thermally stable and melt-processable and chemically recyclable to the monomer. The crystal structure has been resolved by analysis of X-ray powder diffraction and X-ray fiber diffraction of oriented fibers, combined with conformational analysis based on methods of density functional theory. The ordered crystal structure of the isotactic pure enantiomer it-(R)-P3H(Me) 2 B (or it-(S)-P3H(Me) 2 B) is described by chains in a nearly trans-planar conformation with chain axis of 4.7 Å packed in an orthorhombic unit cell with axes a = 13.30 Å, b = 9.99 Å, and c = 4.75 Å according to the chiral space groups P2 1 2 1 2 or P2 1 2 1 2 1 . The atactic polymer at-(R/S)-P3H(Me) 2 B crystallizes in the same orthorhombic unit cell having only slightly larger a axis, a = 13.94 Å, b = 10.03 Å, and c = 4.75 Å, with chains characterized by a disordered succession of R and S monomers and a distorted trans-planar conformation that keeps a straight chain axis and the same periodicity of 4.7 Å of the ordered pure enantiomer. This proposed model of the conformation of at-(R/S)-P3H(Me) 2 B explains the crystallization of the atactic polymer. The crystal structure of at-(R/S)-P3H(Me) 2 B is, therefore, characterized by the packing of disordered chains in nearly trans-planar conformation according to both the chiral space groups P2 1 2 1 2 or P2 1 2 1 2 1 and the achiral space groups Pna2 1 or Pnn2.

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Section: Introductionmentioning

confidence: 99%

Crystal Structure of Atactic and Isotactic Poly(3-hydroxy-2,2-dimethylbutyrate): A Chemically Recyclable Poly(hydroxyalkanoate) with Tacticity-Independent Crystallinity

Scoti,

Zhou,

Chen

et al. 2024

Macromolecules

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“…Poly(ethylene terephthalate) (PET) is widely used as fiber, film, and plastics due to its excellent comprehensive performance and high cost-effectiveness. As the raw material for PET, terephthalic acid (PTA) is basically available from nonrenewable petroleum . In recent years, with the increasing depletion of petrochemical resources, the rational development and utilization of biomass resources for the preparation of chemicals has been of great significance in achieving the sustainable development of the chemical industry. − Among all biobased chemicals, 2,5-furan dicarboxylic acid (FDCA) has a structure similar to that of PTA .…”

Section: Introductionmentioning

confidence: 99%

Fire Retardancy of Poly(ethylene 2,5-furandicarboxylate-co-ethylene terephthalate) Regulated by Phosphinate

Ding,

Zhang,

Zhu

et al. 2024

ACS Appl. Polym. Mater.

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A flame retardant containing two phosphonate structures (DOPO−DP) was synthesized by applying diphenylphosphinic chloride and 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphazephenanthrene-10-oxide. The DOPO−DP was used to modify the flame retardancy of poly(ethylene 2,5-furandicarboxylate-co-ethylene terephthalate) containing (PEFT). DOPO−DP has a high flame-retardant efficiency in PEFT. The UL-94 V0 level is obtained by adding 7 wt % DOPO−DP into PEFT. The fireretardant mode of action is melting away, which is induced by the plasticizing effect of DOPO−DP mainly. In addition, two chain extenders triglycidyl isocyanurate (TGIC) and 2,2′-(1,3-phenylene)-dioxazoline were applied to enhance the mechanical properties of PEFT. DOPO−DP deteriorates the mechanical properties of PEFT while coupling agents improve the bending and impact strength. While the chain expansion effect of TGIC competes with the plasticizing effect of DOPO−DP, excessive TGIC deteriorates the UL-94 rating of PEFT.

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“…Here, we focus on step-growth polymers (SGPs), while recognizing the equal significance of chain-growth polymers. With regards to the delineation and recycling of the latter, it can be referred in these comprehensive reviews. − …”

Section: Introductionmentioning

confidence: 99%

Chemical Recycling of Step-Growth Polymers Guided by Le Chatelier’s Principle

Liu,

2024

ACS Eng. Au

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Recyclable and (Bio)degradable Polyesters in a Circular Plastics Economy

Cited by 29 publications

References 674 publications

Crystal Structure of Atactic and Isotactic Poly(3-hydroxy-2,2-dimethylbutyrate): A Chemically Recyclable Poly(hydroxyalkanoate) with Tacticity-Independent Crystallinity

Crystal Structure of Atactic and Isotactic Poly(3-hydroxy-2,2-dimethylbutyrate): A Chemically Recyclable Poly(hydroxyalkanoate) with Tacticity-Independent Crystallinity

Fire Retardancy of Poly(ethylene 2,5-furandicarboxylate-co-ethylene terephthalate) Regulated by Phosphinate

Chemical Recycling of Step-Growth Polymers Guided by Le Chatelier’s Principle

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