Highly Regioselective and Alternating Copolymerization of Racemic Styrene Oxide and Carbon Dioxide via Heterogeneous Double Metal Cyanide Complex Catalyst

Wei, Ren‐Jian; Zhang, Xinghong; Du, Binyang; Sun, Ximing; Fan, Zhiqiang; Qi, Guilin

doi:10.1021/ma4004709

Cited by 47 publications

(53 citation statements)

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“…10,13,15,45,48 Here, CO 2 /epoxide copolymers with highly alternating degrees (94.2% ->99%, entries 4−11 in Table 1) were selected for further analysis of regiochemistry because the carbonate anion (−OOCO − ) was the main nucleophilic species attacking the methylene (CH 2 ) or methine (CH) sites to open the epoxide ring (Scheme 2). CO 2 /J copolymerization was highly regioselective under Zn− Co(III) DMCC catalysis 14 and afforded a CO 2 /J copolymer with 90% HT connectivity (50°C). In this instance, the electronwithdrawing phenyl group made the CH site more positive than the CH 2 site, and thus the carbonate anion predominantly attacked the CH site of J (route 1 in Scheme 2) although the CH site had significant steric hindrance due to the phenyl group.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Carbon Dioxide/Epoxide Copolymerization via a Nanosized Zinc–Cobalt(III) Double Metal Cyanide Complex: Substituent Effects of Epoxides on Polycarbonate Selectivity, Regioselectivity and Glass Transition Temperatures

et al. 2015

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In this study, we describe the substituent effect of epoxides on CO 2 / epoxide copolymerization catalyzed by a nanosized zinc−cobalt(III) double metal cyanide complex [Zn−Co(III) DMCC]. The Zn−Co(III) DMCC catalyzed the copolymerization of CO 2 with 11 epoxides with alkyl or aryl groups at 50−60°C within 15 h. The reaction afforded various CO 2 /epoxide copolymers with high epoxide conversion efficiencies up to 100%. The alternating degree (F CO 2 ) of the resulting copolymer was solely decided by the steric hindrance of the substituents of the epoxides regardless of their electron-donating or withdrawing properties. Substituents with large steric hindrances (2, 2-dimethyl, tert-butyl, cyclohexyl, decyl, and benzyl) led to highly alternating degrees (up to 100%). The regioselective CO 2 /epoxide copolymerization was dominated by the electron induction effect of the substituent. The electron-withdrawing substituent such as phenyl and benzyl induced regioselective ring-opening at the methine site of the epoxide. For CO 2 /isobutene oxide copolymerization, the regioselective reaction occurred at the methylene site of the isobutene oxide because of the strong electron-donating ability and steric hindrance of the two methyls of the isobutene oxide. The linear alkyl groups of the epoxides could not induce the regioselective reaction during copolymerization. The glass transition temperatures (T g s) of the CO 2 /epoxide copolymers with linear alkyl substituent groups decreased from +6 to −38°C with increasing alkyl length, but increased from 6 to 84°C with increasing steric hindrance of the epoxide substituents. Thus, various CO 2 /epoxide copolymers with a wide T g range from −38 to +84°C were provided and could be applied as elastomers or plastics.

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Section: ■ Results and Discussionmentioning

confidence: 99%

“…14,16,28,29 Recently, a nanolamellar Zn−Co(III) DMCC was observed to effectively catalyze the alternating copolymerization of CO 2 with epoxides with long side alkyl groups. 30 These results led us to systematically study the substituent effects of the epoxides on the alternating copolymerization of CO 2 /epoxide using this catalyst.…”

Section: ■ Introductionmentioning

confidence: 99%

Carbon Dioxide/Epoxide Copolymerization via a Nanosized Zinc–Cobalt(III) Double Metal Cyanide Complex: Substituent Effects of Epoxides on Polycarbonate Selectivity, Regioselectivity and Glass Transition Temperatures

et al. 2015

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“…This involves a careful tuning of the symmetry of the ligand in the metal complex to create a suitable asymmetric environment around the metal center . The asymmetric structure of the catalyst should induce a specific stereochemistry in the epoxide ring opening step, thus allowing the generation of isotactic poly(propylene carbonate) from racemic propylene oxide . For instance, ( R , R) ‐SalenAlCl ( 5a in Figure ) shows a preference in generating an alkoxide with R ‐configuration as a result of the ring opening of a racemic PO mixture .…”

Section: Synthesis and Characterization Of Polycarbonates Prepared Bymentioning

confidence: 99%

Green polycarbonates prepared by the copolymerization of CO₂ with epoxides

Taherimehr

Pescarmona

2014

J of Applied Polymer Sci

173

139

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Polycarbonates can be prepared by the copolymerization of epoxides with carbon dioxide as an inexpensive, abundant, nontoxic, and renewable feedstock. This review covers the synthesis, the physicochemical properties, and the growing applications of this class of green polymers. The review has been conceived to provide a useful tool for the researchers who are new to this field, as well as to offer an updated overview for those who are already actively working on this topic.

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“…Zn‐Co(III) DMCC used in this study was same with that in our recently reported works . It had nanolamellar structure with thicknesses of about 20–80 nm, which endowed it high surface area (653 m 2 g −1 ), but did not dissolve into the reactants.…”

Section: Resultsmentioning

confidence: 78%

“…A typical nanolamellar Zn‐Co(III) DMCC catalyst was synthesized and characterized to our previous work: an amount of ZnCl 2 (8.0 g) was dissolved in the mixed solution of de‐ionized water (10 mL) and tert ‐BuOH (10 mL). K 3 Co(CN) 6 (6.6 g) dissolved in 10 mL de‐ionized water and was added into ZnCl 2 solution drop by drop over 30 min at 30 °C under vigorous stirring.…”

Section: Methodsmentioning

confidence: 99%

Efficient solvent‐free alternating copolymerization of CO₂ with 1, 2‐epoxydodecane and terpolymerization with styrene oxide via heterogeneous catalysis

Zhang

Wei

Zhang

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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The alternating copolymerization of CO2 with the terminated epoxides anchoring long alkyl groups is rarely reported because of their low reactivity and polycarbonate selectivity. This work describes a well‐controlled solvent‐free copolymerization of CO2 with 1, 2‐epoxydodecane (EDD) with a long electron‐donating alkyl group via the catalysis of Zn‐Co(III) double metal cyanide complex catalyst. The productivity of the catalyst was up to 2406 g polymer/g Zn, that is, EDD conversion was 99.2%. The alternating degree of CO2‐EDD copolymers were more than 99% and had high number‐average molecular weights (Mns) of >100 kg mol−1, while only 1.0 wt % 4‐decyl‐1,3‐dioxolan‐2‐one (DC) were detected. Moreover, by introducing styrene oxide (SO) with electron‐withdrawing phenyl group into EDD‐CO2 copolymerization system, a new random terpolymer with either electron‐withdrawing or electron‐donating side groups was produced with single glass transition temperatures (Tgs) in a wide range from 3 to 56 °C, which might be potentially used as biodegradable elastomers or plastics. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 737–744

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Highly Regioselective and Alternating Copolymerization of Racemic Styrene Oxide and Carbon Dioxide via Heterogeneous Double Metal Cyanide Complex Catalyst

Cited by 47 publications

References 50 publications

Carbon Dioxide/Epoxide Copolymerization via a Nanosized Zinc–Cobalt(III) Double Metal Cyanide Complex: Substituent Effects of Epoxides on Polycarbonate Selectivity, Regioselectivity and Glass Transition Temperatures

Carbon Dioxide/Epoxide Copolymerization via a Nanosized Zinc–Cobalt(III) Double Metal Cyanide Complex: Substituent Effects of Epoxides on Polycarbonate Selectivity, Regioselectivity and Glass Transition Temperatures

Green polycarbonates prepared by the copolymerization of CO₂ with epoxides

Efficient solvent‐free alternating copolymerization of CO₂ with 1, 2‐epoxydodecane and terpolymerization with styrene oxide via heterogeneous catalysis

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Highly Regioselective and Alternating Copolymerization of Racemic Styrene Oxide and Carbon Dioxide via Heterogeneous Double Metal Cyanide Complex Catalyst

Cited by 47 publications

References 50 publications

Carbon Dioxide/Epoxide Copolymerization via a Nanosized Zinc–Cobalt(III) Double Metal Cyanide Complex: Substituent Effects of Epoxides on Polycarbonate Selectivity, Regioselectivity and Glass Transition Temperatures

Carbon Dioxide/Epoxide Copolymerization via a Nanosized Zinc–Cobalt(III) Double Metal Cyanide Complex: Substituent Effects of Epoxides on Polycarbonate Selectivity, Regioselectivity and Glass Transition Temperatures

Green polycarbonates prepared by the copolymerization of CO2 with epoxides

Efficient solvent‐free alternating copolymerization of CO2 with 1, 2‐epoxydodecane and terpolymerization with styrene oxide via heterogeneous catalysis

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Green polycarbonates prepared by the copolymerization of CO₂ with epoxides

Efficient solvent‐free alternating copolymerization of CO₂ with 1, 2‐epoxydodecane and terpolymerization with styrene oxide via heterogeneous catalysis