Organocatalytic synthesis of sugar‐derived polyesters via ring‐opening alternating copolymerization of anhydrosugar oxetane and anhydrides

Zheng, Lanlan; Feng, Jiabing; Xie, Hongyan; Xu, Zhiguang

doi:10.1002/pol.20230036

Cited by 3 publications

(4 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Additionally, the xylose oxetane has also been used in homopolymerization and other copolymerizations, like with CS 2 , CO 2 , cyclic anhydrides, or isothiocyanates . Xu and co-workers reported the alternating copolymerization of OX and various cyclic anhydrides by the use of a phosphazene base combined with triethyl borane (TEB), yielding several polyesters with good thermal stability …”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, its metal catalytic synthesis method exhibits low activity with a turnover of frequency (TOF) of around 10 h –1 and also causes a brown color (Scheme ) and unpleasant metal residues of the poly(thiocarbonate). Additionally, the xylose oxetane has also been used in homopolymerization and other copolymerizations, like with CS 2 , CO 2 , cyclic anhydrides, or isothiocyanates . Xu and co-workers reported the alternating copolymerization of OX and various cyclic anhydrides by the use of a phosphazene base combined with triethyl borane (TEB), yielding several polyesters with good thermal stability …”

Section: Introductionmentioning

confidence: 99%

“…50 use of a phosphazene base combined with triethyl borane (TEB), yielding several polyesters with good thermal stability. 49 Here, we use alkyl borane to replace (salen)CrCl as an organic Lewis acid for the copolymerization to yield metal-free poly(thiocarbonate) with complete XO-alt-COS repeating units (Scheme 1). The catalytic center of borane possesses a weaker coordination ability and is harder to poison by sulfur than metal Cr.…”

mentioning

confidence: 99%

See 2 more Smart Citations

Organocatalytic Synthesis of Poly(thiocarbonate) from Xylose and Carbonyl Sulfide

Feng,

Liu

et al. 2024

Macromolecules

View full text Add to dashboard Cite

Facile synthesis of sulfur-containing polymers from renewable chemicals or the waste of petrochemical resources remains a grand challenge. Here, we report organocatalytic alternating copolymerization of carbonyl sulfide (COS) and D-xylose oxetane (XO) to produce poly(thiocarbonate). COS is industrially released as a waste gas, while XO is synthesized from biorenewable xylose with an E factor of 2.31 and an atom economy of 30%. The commercially available binary organocatalyst system consists of alkyl borane (as a Lewis acid) and a quaternary ammonium salt (as an initiator). Density functional theory calculations suggest that the Lewis acid of borane can activate XO and stabilize the growing anion. The catalyst system exhibits high activity with turnover frequencies of up to 70 h −1 at 25 °C, affording poly(thiocarbonate) with a welldefined structure, complete alternating sequence, >99% chemoselectivity, and regioregular polymer backbone composed of head-to-tail linkages. Terpolymerization of XO, propylene oxide, and COS yields a series of poly(thiocarbonate) with a largely tunable T g ranging from 26 to 138 °C.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

Organocatalytic Synthesis of Poly(thiocarbonate) from Xylose and Carbonyl Sulfide

Feng,

Liu

et al. 2024

Macromolecules

View full text Add to dashboard Cite

show abstract

“…In this study, we successfully established an organobase-catalyzed ROCOP of oxetanes and cyclic anhydrides, yielding polyesters with perfectly alternating structures, predictable molecular weights, and low dispersities (Figure A) . A broad range of initiators and monomers can be used to conveniently obtain various polyester structures.…”

Section: Introductionmentioning

confidence: 99%

Organobase-Catalyzed Ring-Opening Copolymerization of Cyclic Anhydrides and Oxetanes: Establishment and Application in Block Copolymer Synthesis

Ota,

Suzuki,

Mizukami

et al. 2024

Macromolecules

View full text Add to dashboard Cite

Polyesters are a prominent class of polymer materials. The ring-opening copolymerization (ROCOP) of cyclic anhydrides and cyclic ethers has attracted attention as a method for the precise synthesis of a variety of polyesters. However, epoxides have been the primary cyclic ether employed in this method, and precise polymerization with oxetane has been challenging. This paper accomplished organobase-catalyzed ROCOP of cyclic anhydrides and oxetanes for synthesizing polyesters. By applying t-BuP 2 as a catalyst for the ROCOP of phthalic anhydride (PA) and trimethylene oxide (TO), perfectly alternating P(PA-alt-TO) was obtained with predictive molecular weights ranging from 3000 to 20,000 Da and low dispersities (Đ < 1.16). A kinetic experiment on the ROCOP of PA and TO confirmed the controlled/living nature of the proposed ROCOP system. Furthermore, its remarkable tolerance for various functional groups facilitates the utilization of a wide range of monomers and initiators, resulting in polyesters with distinct glass transition temperatures (T g , −45.4 to 60.8 °C). Moreover, this polymerization process can be seamlessly integrated with other ROCOP processes, such as the ring-opening polymerization of trimethylene carbonate, valerolactone, or L-lactide and the ROCOP of PA/epoxide; this enables the synthesis of polyester-based block copolymers in a one-pot/one-step manner, known as self-switchable polymerization. Consequently, this novel polymerization process expands the scope of the existing ROCOP approaches and paves the way to synthesizing diverse polyesters with tailored material properties.

show abstract

Degradable sugar-derived poly(vinyl ether ester)s by hydroxyl-yne click polymerization

Cui,

Chen,

Wang

et al. 2024

European Polymer Journal

View full text Add to dashboard Cite

Organocatalytic synthesis of sugar‐derived polyesters via ring‐opening alternating copolymerization of anhydrosugar oxetane and anhydrides

Cited by 3 publications

References 46 publications

Organocatalytic Synthesis of Poly(thiocarbonate) from Xylose and Carbonyl Sulfide

Organocatalytic Synthesis of Poly(thiocarbonate) from Xylose and Carbonyl Sulfide

Organobase-Catalyzed Ring-Opening Copolymerization of Cyclic Anhydrides and Oxetanes: Establishment and Application in Block Copolymer Synthesis

Degradable sugar-derived poly(vinyl ether ester)s by hydroxyl-yne click polymerization

Contact Info

Product

Resources

About