Controllable Synthesis of Stereoregular Polyesters by Organocatalytic Alternating Copolymerizations of Cyclohexene Oxide and Norbornene Anhydrides

Han, Bing; Zhang, Li; Liu, Binyuan; Dong, Xiaofang; Kim, Il; Duan, Zhongyu; Théato, Patrick

doi:10.1021/acs.macromol.5b00555

Cited by 90 publications

(114 citation statements)

References 63 publications

(24 reference statements)

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“…To today, only a few organic compounds have been successfully employed as efficient catalysts for limited monomers to prepare polyesters by ROAC method. For instance, Theato and Liu demonstrated the success of ROAC of norbornene anhydride and cyclohexene oxide (CHO) with bis(triphenylphosphine)iminium chloride (PPNCl) as catalyst . Later, Merna and coworkers extended this research to phthalic anhydride (PA) and CHO monomers using the same catalyst .…”

Section: Introductionmentioning

confidence: 99%

“…For instance, Theato and Liu demonstrated the success of ROAC of norbornene anhydride and cyclohexene oxide (CHO) with bis(triphenylphosphine)iminium chloride (PPNCl) as catalyst. 9 Later, Merna and coworkers extended this research to phthalic anhydride (PA) and CHO monomers using the same catalyst. 10 On the other hand, phosphazene base t-BuP 1 with a relatively low basicity was used as catalyst for a living ROAC of PA with various epoxides.…”

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confidence: 99%

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Phosphazene/Lewis Acids as Highly Efficient Cooperative Catalyst for Synthesis of High‐Molecular‐Weight Polyesters by Ring‐Opening Alternating Copolymerization of Epoxide and Anhydride

Zhang

Wang

Liu

et al. 2020

Journal of Polymer Science

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The synthesis of high‐molecular‐weight polyesters via the ring‐opening alternating copolymerization (ROAC) of cyclic anhydrides and epoxides using organocatalysts remains a major challenge. In this context, the organic cyclic trimeric phosphazene base (CTPB) was used as an efficient catalyst for the ROAC of phthalic anhydride (PA) with epoxides. It was found that the activity and PA conversion dramatically increased with the addition of triethyl borane (TEB) as a cocatalyst, even a small amount of TEB, for example, 5 mol % relative to CTPB. The molecular structures of obtained polyesters were characterized by nuclear magnetic resonance (1H NMR, 13C NMR) and matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI TOF), which demonstrated the formation of perfectly alternating polyesters with unimodal and narrow molecular weight distributions. Different molecular weight polyesters (up to 118.5 kg mol−1) were facilely prepared by reducing the loading of CTPB and TEB, while the polymerizations were fast (turnover frequency, TOF up to 500 h−1). Thermal analysis of the resulting polymers indicated that the alternating polyesters were amorphous, and their Tgs increased with the increment of molecular weights. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 803–810

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Phosphazene/Lewis Acids as Highly Efficient Cooperative Catalyst for Synthesis of High‐Molecular‐Weight Polyesters by Ring‐Opening Alternating Copolymerization of Epoxide and Anhydride

Zhang

Wang

Liu

et al. 2020

Journal of Polymer Science

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“…The LBs were chosen to span a range of basicity (the pKa values of their conjugate acid LB−H + listed are reported in MeCN, THF, DMSO, or H 2 O, see Table S1 in the Supporting Information) [38,39]: TEEA (pKa cal = 9.03) < TEA (pKa cal = 10.62, pKa MeCN = 18.7) < DBU (pKa MeCN = 24.3) < MTBD (pKa MeCN = 25.4) < t-BuP 1 (pKa MeCN = 26.9) < t-BuP 2 (pKa MeCN = 33.5). TEA, DBU, t-BuP 1 have been previously reported to copolymerize epoxides and anhydrides, but showed low activities [26,28,40]. The equimolar combination of these LBs (TEA, TEEA, t-BuP 2 , DBU) with TEB exhibited improved activity towards the PO/SA copolymerization, and the ester contents of the resultant poly(propylene succinate)s were ≥93%.…”

Section: Resultsmentioning

confidence: 95%

An Investigation of the Organoborane/Lewis Base Pairs on the Copolymerization of Propylene Oxide with Succinic Anhydride

Chen

Yang

et al. 2020

Molecules

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The copolymerization of biorenewable succinic anhydride (SA) with propylene oxide (PO) is a promising way to synthesize biodegradable aliphatic polyesters. However, the catalytic systems for this reaction still deserve to be explored because the catalytic activity of the reported catalysts and the molecular weights of produced polyesters are unsatisfied. Herein, we investigate the copolymerization of SA with PO catalyzed by the organoborane/base pairs. The types of Lewis bases, organoboranes, and their loadings all have a large impact on the activity and selectivity of the copolymerization. High ester content of >99% was achieved when performed the PO/SA copolymerization using triethyl borane (TEB)/phosphazene base P1-t-Bu (t-BuP1) pair with a molar ratio of 1/1 at 30–80 °C. Using TEB/t-BuP1 pair with the molar ratio of 4/1 at 80 °C, the turnover of frequency (TOF) was up to 128 h−1 and clearly higher than the known TOF values (0.5–34 h−1) of the PO/SA copolymerization by previously reported catalysts. The number-average molecular weights (Mns) of the resultant polyesters reached up to 20.4 kg/mol when copolymerization was carried out using TEB/t-BuP1 (1/1, in molar ratio) at 30 °C.

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“…The stereochemical structure of polymers is a critical factor to consider when tuning their properties. For example, cis ‐poly(CHO‐ alt ‐NA) (NA=norbornene anhydride) has a higher T g value of 129.8 °C than the analogue trans ‐polymer (115.9 °C) with a similar molecular weight . Furthermore, catalyzed by enantiopure bimetallic complexes, the main‐chain chiral poly(CHO‐ alt ‐PA) was semicrystalline with a melting endothermic peak at 221 °C, whereas the achiral polymer was amorphous …”

Section: Introductionmentioning

confidence: 99%

“…For example, cis-poly(CHOalt-NA) (NA = norbornene anhydride) has ah igher T g value of 129.8 8Ct han the analogue trans-polymer (115.9 8C) with as imilar molecular weight. [17] Furthermore, catalyzed by enantiopure bimetallic complexes,t he main-chain chiral poly(CHO-alt-PA) was semicrystalline with am elting endothermic peak at 221 8C, whereas the achiral polymer was amorphous. [6b] Metal Salen or Salph complexes employed in the coupling of epoxides and CO 2 were mainly coordinated with Co, Cr,a nd Al, of which Al complexes are usually employed for the cycloadditiono ft erminal epoxides with CO 2.…”

Section: Introductionmentioning

confidence: 99%

Preparation and Thermal Properties of Polycarbonates/esters Catalyzed by Using Dinuclear Salph‐Al from Ring‐Opening Polymerization of Epoxide Monomers

Zhou

Duan

et al. 2017

Chemistry An Asian Journal

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A dinuclear Salph-Al complex/bis(triphenylphosphine)iminium chloride catalyst system was synthesized and employed for cyclohexene oxide (CHO) and CO copolymerization. The catalyst system had an excellent selectivity of 99 % for carbonate linkages and the resultant poly(cyclohexene carbonate) (PCHC) had a high glass transition temperature (T ) of 123.8 °C and a thermal decomposition temperature (5 % weight loss; T ) of 265 °C. Furthermore, this catalyst system was active in the polymerization of phthalic anhydride (PA) and epoxides. Poly(CHO-alt-PA) was completely alternating, and had improved thermal properties (T =142.7 and T =295 °C) compared with PCHC. The T values of the polyesters could be adjusted by addition of PO to the CHO/PA reaction system. For the CHO/PO/PA terpolymerization, CHO and PO participated concurrently and proportionally in the chain growth and the obtained terpolyesters had tunable T values from 62.8 to 142.7 °C depending on the CHO/PO feed ratio.

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Controllable Synthesis of Stereoregular Polyesters by Organocatalytic Alternating Copolymerizations of Cyclohexene Oxide and Norbornene Anhydrides

Cited by 90 publications

References 63 publications

Phosphazene/Lewis Acids as Highly Efficient Cooperative Catalyst for Synthesis of High‐Molecular‐Weight Polyesters by Ring‐Opening Alternating Copolymerization of Epoxide and Anhydride

Phosphazene/Lewis Acids as Highly Efficient Cooperative Catalyst for Synthesis of High‐Molecular‐Weight Polyesters by Ring‐Opening Alternating Copolymerization of Epoxide and Anhydride

An Investigation of the Organoborane/Lewis Base Pairs on the Copolymerization of Propylene Oxide with Succinic Anhydride

Preparation and Thermal Properties of Polycarbonates/esters Catalyzed by Using Dinuclear Salph‐Al from Ring‐Opening Polymerization of Epoxide Monomers

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