Alternating copolymerization of epoxides with anhydrides initiated by organic bases

Hošťálek, Z.; Trhlíková, Olga; Walterová, Zuzana; Martinez, Thomas; Peruch, Frédéric; Cramail, Henri; Merna, Jan

doi:10.1016/j.eurpolymj.2017.01.002

Cited by 65 publications

(31 citation statements)

References 28 publications

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“…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 . 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 .…”

Section: Introductionmentioning

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 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%

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 most reactive substrate was PA, which yielded a polyester with the highest M n value by using a combination of salphen Cr(III) complex catalyst and bis(triphenylphosphine)iminium chloride (PPNCl) as co-catalyst but no information on thermal properties has been reported. Recently, metal-free initiators for the copolymerization of epoxides with anhydrides are being explored [35,36]. A series of dinuclear complexes, in which two iron(III) amino triphenolate moieties are bridged by a phenylene backbone were synthesized by Jiang [37] for the alternating copolymerization of CHO/PA in the presence of PPNCl with good M n value (33 kg/mol).…”

Section: Introductionmentioning

confidence: 99%

Influence of Co-Catalysts and Polymerization Conditions on Properties of Poly(anhydride-alt-epoxide)s from ROCOP Using Salen Complexes with Different Metals

et al. 2019

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Cyclohexene oxide (CHO) and phthalic anhydride (PA) have been reacted in the presence of commercial salen–type complexes with different metals Cr (1), Al (2), and Mn (3) in combination with 4-(dimethylamino) pyridine (DMAP), bis-(triphenylphosphorydine) ammonium chloride (PPNCl) and bis-(triphenylphosphoranylidene)ammonium azide (PPNN3) as co-catalysts to obtain alternating poly(PA-alt-CHO)s by ring-opening copolymerization (ROCOP). The effect of different reaction conditions (pre-contact between catalyst and co-catalyst, polymerization time) on the productivity, molecular weight and glass transition temperature has been evaluated. By using a 24 h pre-contact, the aliphatic polyesters obtained were characterized by high molecular weight (Mn > 15 kg/mol) and glass transition temperature (Tg) up to 146 °C; the more sustainable metals Al and Mn in the presence of PPNCl give comparable results to Cr. Moreover, biodegradability data of these polyesters and the study of the microstructure reveal that the biodegradability is influenced more by the type of chain linkages rather than by the molecular weight of the polyesters.

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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%

“…Recently, there has been rapidly growing interest in implementing epoxide-based alternating copolymerization using metal-free catalysts [22][23][24][25][26][27][28][29][30][31][32]. The competence and potential of organocatalysts have been fully verified by the achievements of strictly alternating sequence distribution and high activity.…”

Section: Introductionmentioning

confidence: 99%

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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Alternating copolymerization of epoxides with anhydrides initiated by organic bases

Cited by 65 publications

References 28 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

Influence of Co-Catalysts and Polymerization Conditions on Properties of Poly(anhydride-alt-epoxide)s from ROCOP Using Salen Complexes with Different Metals

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

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