Depolymerizable semi-fluorinated polymers for sustainable functional materials

Zhou, Junfeng; Schrage, Briana R.; Yoon, Seiyoung; Wang, Zeyu; Ziegler, Christopher J.; Wang, Junpeng; Chen, Hanlin; Sathe, Devavrat

doi:10.1039/d2py00240j

Cited by 17 publications

(19 citation statements)

References 52 publications

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“…接下来, Wang 等 [178] 详细研究了并环的结构与聚合过程中 T c 的关系, 发现在并环中引入偕二取代基时可以进一步降低聚合反应的 T c , 有利于聚合物解聚回到单体. 此外, Wang 等 [179] 将氟原子(Z-tCBCO-7, 图 23)引入该体系得到可化学回收的疏水性(水接触角为 97.4°)含氟材料.…”

Section: 闭环回收的含硫高分子unclassified

Recent Advances in Monomer Design for Recyclable Polymers

Cai¹,

Liu²,

Tao³

et al. 2022

Acta Chimica Sinica

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The development of modern society highly depends on polymer materials. However, progressive usage and accumulation of polymer products caused the waste of resources and severe environmental issues. To address the abovementioned problem, the development of chemical recycling polymers that could transform the polymers back to monomers and repolymerize to produce polymer materials without value loss is an attractive and important strategy. In recent years, significant advances in the design of "ideal monomers" have enabled the regulation of "polymerization−depolymerization" equilibrium and achieved the closed-loop recycling under mild conditions. This review will focus on the closed-loop recycling of polyesters, polycarbonates, sulfur-containing polymers, and poly(cyclic olefin)s, illustrate the challenges of this field, and provide a perspective on the future development direction.

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Section: 闭环回收的含硫高分子unclassified

Recent Advances in Monomer Design for Recyclable Polymers

Cai¹,

Liu²,

Tao³

et al. 2022

Acta Chimica Sinica

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“…[3][4][5][6][7][8] A promising approach is ring-opening polymerization (ROP) by which the resulting polymers are capable of ring-closing depolymerization (RCD) to regenerate the cyclic monomers. This reversible ring-chain recycling process has recently been demonstrated for various cyclic monomers such as acetals, 9 carbonates, [10][11][12][13] alkenes, [14][15][16][17][18] lactones, [19][20][21][22][23][24][25] thiolactones, [26][27][28][29] and lactams. 30 Such polymerizations are typically driven by the relief of ring strain of small cyclic monomers, leading to a favorable enthalpy change (ΔH p < 0) that overcomes the unfavorable entropy (ΔS p < 0) due to the loss of translational entropy.…”

Section: Introductionmentioning

confidence: 99%

Dithioacetal Polymers Capable of Chemical Recycling to Macrocyclic Monomers and Formation of Vitrimers

Kariyawasam

Rolsma

Yang

2022

Preprint

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Polymers capable of chemical recycling to monomers are highly desirable to produce sustainable materials with a circular economy. We here report a highly efficient ring-chain recycling of polydithioacetal (PDTA) via ring-closing depolymerization (RCD) and entropy-driven ring-opening polymerization (ED-ROP). Pristine PDTAs can be conveniently synthesized via a one-step reaction using 3,4,5-trimethoxybenzaldehyde and α,ω-alkyl dithiols with an acid catalyst. The resulting PDTAs undergo acid-catalyzed RCD with refluxing toluene to yield a mixture of macrocycles of various sizes with conversions of 75-95%. ED-ROP of these macrocyclic monomer mixtures in solution at room temperature affords virgin PDTAs, reaching high conversions of 80-95% within 2 h. Owing to the stability of dithioacetals, PDTAs are far more stable than the acetal counterparts, resisting hydrolysis under both acidic and basic conditions. With a floor temperature below 0 °C, depolymerization is not a concern in the bulk state even in the presence of residual catalysts as polymerization is favored at higher temperatures for ED-ROP. Once crosslinked, the network behaves as a vitrimer enabled by temperature-activated interchain exchange of dithioacetals in the bulk state. The vitrimer depolymerizes into macrocyclic monomers in solvent which can repolymerize to regenerate the vitrimer.

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“…The T g of the polymers can be adjusted from −30 °C to 100 °C by varying the functional groups on cyclobutane, allowing for both elastic and plastic polymeric materials to be prepared [20] . In addition, cis ‐cyclooctene can be isomerized into its trans analogue, which is suitable for living ROMP and allows for the preparation of depolymerizable polymers with diverse architectures, including block copolymers and graft polymers [21–23] …”

Section: Introductionmentioning

confidence: 99%

“…[20] In addition, ciscyclooctene can be isomerized into its trans analogue, which is suitable for living ROMP and allows for the preparation of depolymerizable polymers with diverse architectures, including block copolymers and graft polymers. [21][22][23] A system relevant to tCBCO is trans-benzocyclobutene-fused cyclooctene (M1, Figure 1b), which can be viewed as adding a benzene ring next to cyclobutane in tCBCO. Compared to tCBCO, the synthesis of which requires a photochemical [2 + 2] cycloaddition of 1,5-cis,cis-cyclooctadiene with an olefin and often gives low yield (< 40%), [24] M1 is advantageous in that its synthesis can be conveniently conducted thermally using benzyne and 1,5-cis,trans-cycloooctadiene at high yield.…”

Section: Introductionmentioning

confidence: 99%

Evaluating Trans‐Benzocyclobutene‐Fused Cyclooctene as a Monomer for Chemically Recyclable Polymer

Zhou

Yoon

et al. 2023

Chemistry An Asian Journal

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Chemically recyclable polymers offer a promising solution to address the issues associated with the unsustainable use of plastics by converting the traditional linear plastic economy into a circular one. Central to developing chemically recyclable polymers is to identify the appropriate monomers that enable practical conditions for polymerization and depolymerization and ensure useful stability and material properties. Our group has recently demonstrated that transcyclobutane-fused cyclooctene (tCBCO) meets the abovementioned requirements and is a promising candidate for developing chemically recyclable polymers. Herein, encour-aged by the success with tCBCO, we investigate the thermodynamics of polymerization of a relevant system, trans-benzocyclobutene-fused-cyclooctene, which can be viewed as tCBCO with an additional benzene ring. The study shows that introducing an additional benzene ring favors polymerization and disfavors depolymerization, and the effect is predominantly entropic. The benzo-effect can be leveraged to fine-tune the thermodynamics of polymerization and depolymerization to facilitate the chemical recycling of polymers.

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Depolymerizable semi-fluorinated polymers for sustainable functional materials

Abstract: Fluorinated polymers are important functional materials for a broad range of applications, but the recycling of current fluorinated polymers is challenging. We present the first example of semi-fluorinated polymers that...

Cited by 17 publications

References 52 publications

Recent Advances in Monomer Design for Recyclable Polymers

Recent Advances in Monomer Design for Recyclable Polymers

Dithioacetal Polymers Capable of Chemical Recycling to Macrocyclic Monomers and Formation of Vitrimers

Evaluating Trans‐Benzocyclobutene‐Fused Cyclooctene as a Monomer for Chemically Recyclable Polymer

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