Hexacyanometalate Salt Complexes as Catalysts for Epoxide Polymerizations

Herold, R. J.; Livigni, R. A.

doi:10.1021/ba-1973-0128.ch015

Cited by 22 publications

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“…For example, the ratio of primary to secondary hydroxyl groups of pFA‐PO polyol (entry 1) is 9:91. This is a typical value for poly(propylene oxide)‐based polyols obtained via potassium hydroxide or DMC catalysis. Since pFA‐OH end groups are completely primary by definition, this result points out that the formation of a triblock ABA structure with pFA acting as starter takes place.…”

Section: Resultsmentioning

confidence: 86%

Facile synthesis of formaldehyde‐based polyether(‐carbonate) polyols

Langanke

Hofmann

Gürtler

et al. 2015

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

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Paraformaldehyde (pFA) was utilized as an abundant building block to synthesize remarkably stable liquid pFA‐poly(alkoxy) and pFA‐poly(alkoxy)(carbonate) triblock polyols by graft oligomerization of epoxides and variable amounts of CO2. The resulting tailor‐made oligo diols are highly interesting precursors. They are partially made from alternative feedstock and are well suited as starting materials for state‐of‐the‐art polyurethane chemistry. Moreover, this study demonstrates the general feasibility of a novel polyether polyol process with a significantly reduced epoxide demand.

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Section: Resultsmentioning

confidence: 86%

Facile synthesis of formaldehyde‐based polyether(‐carbonate) polyols

Langanke

Hofmann

Gürtler

et al. 2015

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

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“…Crystallization of the dried DMC was determined by an X‐ray diffractometer. The essence of DMC with high activity is amorphous, this means the lower crystallinity of DMC is, the higher its catalytic activity is 43–48. Figure 3 shows X‐ray diffraction pattern of Complex 1 ground for 14 min had the same crystal pattern with that prepared in solution.…”

Section: Resultsmentioning

confidence: 96%

Double metal cyanide complexes synthesized by solvent‐free grinding method for copolymerization of CO₂ and propylene oxide

Zhang

Lin

Cheng

et al. 2011

J of Applied Polymer Sci

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Two active double metal cyanide (DMC) complexes were successfully synthesized by solvent-free grinding method. Their structures were characterized by FTIR spectrometer and X-ray diffractometer. The results showed that Complex 1 (double metal cyanide complex with K 3 Fe(CN) 6 and ZnCl 2 ) and Complex 2 (double metal cyanide complex with K 3 Fe(CN) 6 and Zn(CH 3 COO) 2 ) had the same structures, crystal forms, and lower crystallinity as both of them synthesized by conventional solvent-based methods, respectively. Investigations on grinding conditions indicated that Complex 1 ground 14 min at a high grinding strength could achieve low crystallinity and showed substantially amorphous structures. Two speculated structures of DMC were given. The alternating copolymerization of CO 2 and propylene oxide with Complex 1 as catalyst obtained anticipated poly(propylene carbonate) (PPC) with very high catalytic activity. The PPC produced by optimized Complex 1 has molecular weight (M n ) up to 98,000 and narrow polydispersity of 1.93 with more than 90% carbonate linkages. Compared with Complex 1, Complex 2 displayed low catalytic activity but high selectivity mainly due to the electron atmosphere and strong steric hindrance. V C 2011Wiley Periodicals, Inc. J Appl Polym Sci 123: [977][978][979][980][981][982][983][984][985] 2012

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“…[25][26][27][28] As a general rule, the polyether polyols obtained by anionic, cationic, and coordinative ring opening polymerization have a narrower dipersity (M w /M n ¼ 1.05-1.3) than the polyether polyols obtained by the polycondensation processes (M w /M n ¼ 2.5-2.8). The practice of polyurethane fabrication proved that polyether polyols with high M n and low dispersity give much better physico-mechanical properties in the resulting polyurethane than the polyether polyols with low M n and broad dispersity, especially in the area of elastic polyurethanes, i.e., elastomers and flexible foams.…”

Section: Synthesis Of Poly(propylene Oxide)mentioning

confidence: 99%

Application of Dipotassium Glycoxides–Activated 18-Crown-6 for the Synthesis of Poly(propylene oxide) with Increased Molar Mass

Grobelny

Matlengiewicz

Golba

et al. 2014

International Journal of Polymer Analysis and Characterization

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Mono-and dipotassium salts of dipropylene glycol were applied for the polymerization of propylene oxide in mild conditions, i.e., tetrahydrofuran solution at ambient temperature. The structure of polymers was investigated by use of 13 C NMR and MALDI-TOF techniques. The structure depends strongly on the kind of initiator and additives that are used such as coronand 18-crown-6 and dipropylene glycol. The lowest unsaturation, represented by allyloxy starting groups, has the polymer obtained by use of monopotassium salt without the ligand. The highest unsaturation degree is for the polymer synthesized in the presence of dipotassium salt-activated 18-crown-6. This polymer, obtained at high initial monomer concentration and low initial concentration of initiator, consists of two fractions, i.e., a low molar mass fraction (M n ¼ 9400) containing mainly macromolecules with alkoxide starting and end groups and a much higher molar mass fraction (M n ¼ 29500 g/mol) containing macromolecules with allyloxy starting groups and alkoxide or hydroxyl end groups. Addition of free glycol to this system decreases the molar mass of polymers. Similar results were obtained by use of dipotassium salts of other glycols. The mechanisms of the studied processes are discussed.

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Hexacyanometalate Salt Complexes as Catalysts for Epoxide Polymerizations

Cited by 22 publications

References 0 publications

Facile synthesis of formaldehyde‐based polyether(‐carbonate) polyols

Facile synthesis of formaldehyde‐based polyether(‐carbonate) polyols

Double metal cyanide complexes synthesized by solvent‐free grinding method for copolymerization of CO₂ and propylene oxide

Application of Dipotassium Glycoxides–Activated 18-Crown-6 for the Synthesis of Poly(propylene oxide) with Increased Molar Mass

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Hexacyanometalate Salt Complexes as Catalysts for Epoxide Polymerizations

Cited by 22 publications

References 0 publications

Facile synthesis of formaldehyde‐based polyether(‐carbonate) polyols

Facile synthesis of formaldehyde‐based polyether(‐carbonate) polyols

Double metal cyanide complexes synthesized by solvent‐free grinding method for copolymerization of CO2 and propylene oxide

Application of Dipotassium Glycoxides–Activated 18-Crown-6 for the Synthesis of Poly(propylene oxide) with Increased Molar Mass

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Double metal cyanide complexes synthesized by solvent‐free grinding method for copolymerization of CO₂ and propylene oxide