Herbaceous plants-derived hydroxycinnamic units for constructing recyclable and controllable copolyesters

Shi, Jia; Wang, Shuizhong; Li, Helong; Song, Guoyong

doi:10.1039/d2gc04372f

Cited by 8 publications

(5 citation statements)

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“…The commercialized preparation of BDO and SA from renewable resources of hemicellulose and cellulose, respectively, has been established recently. − (Scheme ) In this work, a series of fully biobased copolyesters of PBC x BS y were synthesized with CBPC, SA, and BDO, where BC and BS represent the BDO–CBPC and BDO–SA units and x and y represent the molar percentages of CBPC and SA in the copolyesters, respectively. PBC x BS y was synthesized using a two-step melting procedure containing esterification and polycondensation.…”

Section: Resultsmentioning

confidence: 99%

Improving Thermal, Mechanical, and Crystalline Properties of Poly(butylene succinate) Copolyesters from a Renewable Rigid Diester

Yu,

Liu,

Wei

2023

ACS Sustainable Chem. Eng.

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The introduction of rigid cyclic monomers into the poly(butylene succinate) (PBS) backbone is the most common way to elevate its low glass-transition temperature (T g = −30.0 °C). However, the insertion of cyclic units always leads to very poor crystallinity and low molecular weight, which drastically hinder their industrial applications. Herein, a renewable rigid diester N,N′trans-1,4-cyclohexane-bis(pyrrolidone-4-methyl carboxylate) (CBPC) was obtained via Michael addition. CBPC with linked rings had high spatial mobility, resulting in high reaction reactivity. A series of biobased PBC x BS y copolyesters were prepared by melt polycondensation of CBPC with succinic acid and 1,4-butanediol, achieving the high-number-average molecular weight of up to 44.5 kDa. The insertion of CBPC led to higher thermal stability and dramatically enhanced the T g , such that the T g of PBC 80 BS 20 (87.5 °C) surpassed that of PBS (−30.0 °C) over 117.5 °C. Moreover, PBC x BS y showed an unexpected cocrystallization behavior, in which the rigid CBPC with a bulky tricyclic structure could be inserted into the crystal of PBS and formed a homogeneous crystalline structure. The cocrystallization was deeply analyzed by thermodynamic study and density functional theory calculation. Benefiting from the cocrystallization, PBC x BS y showed distinguished mechanical performances, which matched with or excelled those of the commercial polyesters of polyethylene terephthalate, polybutylene terephthalate, and polylactic acid. Accordingly, CBPC could be regarded as an effective biobased building block to spectacularly improve the thermal, mechanical, and crystalline performances of PBS at the same time.

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Section: Resultsmentioning

confidence: 99%

Improving Thermal, Mechanical, and Crystalline Properties of Poly(butylene succinate) Copolyesters from a Renewable Rigid Diester

Yu,

Liu,

Wei

2023

ACS Sustainable Chem. Eng.

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“…In 2023, Shi et al described the synthesis of a series of poly(butylene adipate- co -lignin monomers) (PBAL, Scheme ). Using reductive catalytic fractionation of herbaceous plant biomass, ethyl p -coumarate and ethyl ferulate were isolated. These were subsequently functionalized into dicarboxylic esters (L 1 = coumaric acid-derived diester (R = H); L 2 = ferulic acid-derived diester (R = OMe)) and then copolymerized with adipic acid and butane diol to yield a family of aliphatic–aromatic copolyesters (PBAL 1 (x) L 2 ( y ); M n = 10.6–33.8 kg mol –1 , Đ = 1.3–3.4).…”

Section: Emerging Aromatic and Aromatic–aliphatic Polyestersmentioning

confidence: 99%

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

Shi,

Quinn,

Diment

et al. 2024

Chem. Rev.

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Polyesters carrying polar main-chain ester linkages exhibit distinct material properties for diverse applications and thus play an important role in today's plastics economy. It is anticipated that they will play an even greater role in tomorrow's circular plastics economy that focuses on sustainability, thanks to the abundant availability of their biosourced building blocks and the presence of the main-chain ester bonds that can be chemically or biologically cleaved on demand by multiple methods and thus bring about more desired end-of-life plastic waste management options. Because of this potential and promise, there have been intense research activities directed at addressing recycling, upcycling or biodegradation of existing legacy polyesters, designing their biorenewable alternatives, and redesigning future polyesters with intrinsic chemical recyclability and tailored performance that can rival today's commodity plastics that are either petroleum based and/or hard to recycle. This review captures these exciting recent developments and outlines future challenges and opportunities. Case studies on the legacy polyesters, poly(lactic acid), poly(3-hydroxyalkanoate)s, poly(ethylene terephthalate), poly(butylene succinate), and poly(butylene-adipate terephthalate), are presented, and emerging chemically recyclable polyesters are comprehensively reviewed.

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“…The distinctive aromatic backbone of lignin makes it a potentially valuable feedstock for producing functional polymers with a lowcarbon footprint, and this approach could also add significant profitability to biorefinery. [6,14,41] As the RCF develops, utilizing lignin-depolymerized monomers (not model compounds or lignin-mimics) to produce designer chemicals and materials has become a reality recently. [3,20,28,34,41,[47][48][49] Because these methoxyand alkyl-adorned lignin monomers are seldom used in current chemical and material industries, the search for new routes for fabricating lignin-derivable polymers is still a motivating aspiration.…”

Section: Lignin Derivable Polyestersmentioning

confidence: 99%

“…The “lignin‐first” biorefining approach, where lignin in biomass matrix is preferentially extracted and depolymerized, together with the preservation of (hemi)cellulose biopolymers, has demonstrated the fullest utilization of lignocellulose. [ 14 ] This approach is generally carried out in the presence of a transition metal catalyst under a reduced atmosphere, being termed as reductive catalytic fractionation (RCF). [ 15 , 16 , 17 ] The transition metal catalysts, which dominate the cleavage of lignin linkages and subsequent stabilization steps, have been evolved rapidly in the last decade.…”

Section: Introductionmentioning

confidence: 99%

Harnessing Atomically Dispersed Cobalt for the Reductive Catalytic Fractionation of Lignocellulose

Li,

Ma,

Gao

et al. 2024

Advanced Science

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The reductive catalytic fractionation (RCF) of lignocellulose, considering lignin valorization at design time, has demonstrated the entire utilization of all lignocellulose components; however, such processes always require catalysts based on precious metals or high‐loaded nonprecious metals. Herein, the study develops an ultra‐low loaded, atomically dispersed cobalt catalyst, which displays an exceptional performance in the RCF of lignocellulose. An approximately theoretical maximum yield of phenolic monomers (48.3 wt.%) from lignin is realized, rivaling precious metal catalysts. High selectivity toward 4‐propyl‐substituted guaiacol/syringol facilitates their purification and follows syntheses of highly adhesive polyesters. Lignin nanoparticles (LNPs) are generated by simple treatment of the obtained phenolic dimers and oligomers. RCF‐resulted carbohydrate pulp are more obedient to enzymatic hydrolysis. Experimental studies on lignin model compounds reveal the concerted cleavage of Cα–O and Cβ–O pathway for the rupture of β‐O‐4 structure. Overall, the approach involves valorizing products derived from lignin biopolymer, providing the opportunity for the comprehensive utilization of all components within lignocellulose.

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Herbaceous plants-derived hydroxycinnamic units for constructing recyclable and controllable copolyesters

Abstract: Lignin represents the most abundant renewable aromatic resource, and monophenolics from which would serve as promising monomers for the synthetic aromatic polymers in a sustainable manner. Hererin, we report that...

Cited by 8 publications

References 61 publications

Improving Thermal, Mechanical, and Crystalline Properties of Poly(butylene succinate) Copolyesters from a Renewable Rigid Diester

Improving Thermal, Mechanical, and Crystalline Properties of Poly(butylene succinate) Copolyesters from a Renewable Rigid Diester

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

Harnessing Atomically Dispersed Cobalt for the Reductive Catalytic Fractionation of Lignocellulose

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