Zinc adipate/tertiary amine catalytic system: efficient synthesis of high molecular weight poly(propylene carbonate)

Tang, Lei; Xiao, Min; Xu, Yongjian; Wang, Shuanjin; Ye, Meng

doi:10.1007/s10965-013-0190-9

Cited by 24 publications

(18 citation statements)

References 29 publications

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“…Zinc adipate was prepared from zinc oxide and adipic acid as described in previous work . Typically, adipic acid of 98 mmol and zinc oxide of 100 mmol were dissolved in 150 mL toluene using a round‐bottom flask.…”

Section: Methodsmentioning

confidence: 99%

“…Hence, heterogeneous zinc di‐carboxylate is a promising catalyst for commercial applications, due to its relatively high efficiency, high stability, easy preparation and low cost. More recently, we have paid much attention to zinc adipate (ZnAA) the high cost effective zinc dicarboxylate catalyst . Because of adipic acid is a kind of cheap and large scale industrial product when compared with other dicarboxylate acid.…”

Section: Introductionmentioning

confidence: 99%

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One-pot synthesis of terpolymers with long l -lactide rich sequence derived from propylene oxide, CO₂ , and l -lactide catalyzed by zinc adipate

Tang

Luo

Xiao

et al. 2015

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

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We report here an efficient one‐port synthesis of terpolymers from PO, CO2, and l‐lactide (LLA) with long LLA rich sequence using the cheapest zinc adipate as catalyst. The copolymerizations were carried out under various experimental conditions to find out the optimal conditions. The terpolymer yields increase significantly from 151 to 417 (g polymer per g zinc) by the introduction of LLA as a third monomer. The polycarbonate moiety selectivity increases by nearly 60% at relatively high polymerization temperature (80 °C). Moreover, the differences in reaction kinetic of polycarbonate and polyester moieties were observed by in situ infrared monitoring. As confirmed by XRD and DSC, the synthesized terpolymers are a kind of semicrystalline polymer in which the crystalline PLA segment function as strong noncovalent crosslinking domains. Consequently, it exhibits much better thermal properties as well as remarkable higher mechanical strength compared with amorphous polycarbonate PPC. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1734–1741

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

One-pot synthesis of terpolymers with long l -lactide rich sequence derived from propylene oxide, CO₂ , and l -lactide catalyzed by zinc adipate

Tang

Luo

Xiao

et al. 2015

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

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“…Thus, for the selective and efficient synthesis of polycarbonates (PCs) from the copolymerization of CO 2 and epoxides, many Lewis acid catalysts such as organometallic complexes usually used in combination with a nucleophile have been developed. In particular, the important characteristics of metal-based catalysts (zinc [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37], aluminum [38,39], chromium [40][41][42][43], cobalt [44][45][46][47], magnesium [48,49], iron [19,[50][51][52][53][54], titanium [55,56], copper [57], ytterbium [58], . .…”

Section: Introductionmentioning

confidence: 99%

A Rational Investigation of the Lewis Acid-Promoted Coupling of Carbon Dioxide with Cyclohexene Oxide: Towards CO2-Sourced Polycyclohexene Carbonate under Solvent- and Cocatalyst-Free Conditions

Grondin

Aupetit

Tassaing

2019

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We report a rational investigation of the selective synthesis of poly(cyclohexene carbonate) from CO 2 and cyclohexene oxide by using commercially available Lewis acids with nontoxic metal centers. After a preliminary screening, we focused on the use of zinc salts, and the effect of the pressure, the temperature, the catalyst loading, and the presence of cocatalyst or a solvent on the reaction yields, selectivity, and molar masses was evaluated for selected catalytic platforms. Thus, we found that ZnTosylate in catalytic amounts under solvent-and cocatalyst-free conditions enables the selective synthesis of poly(cyclohexene carbonate) with a molecular weight of about 62.1 kg/mol with about 70% yields at 343 K and 4 MPa. To the best of our knowledge, this is a rare example of high molar mass polycyclohexene carbonates that are moreover obtained under solvent-and cocatalyst-free conditions. The high selectivity of ZnTos towards the formation of poly(cyclohexene carbonate) was interpreted, thanks to in situ FTIR spectroscopy and DFT calculations, as resulting from its ability to coactivate CO 2 . Abstract:We report a rational investigation of the selective synthesis of poly(cyclohexene carbonate) from CO2 and cyclohexene oxide by using commercially available Lewis acids with nontoxic metal centers. After a preliminary screening, we focused on the use of zinc salts, and the effect of the pressure, the temperature, the catalyst loading, and the presence of cocatalyst or a solvent on the reaction yields, selectivity, and molar masses was evaluated for selected catalytic platforms. Thus, we found that ZnTosylate in catalytic amounts under solvent-and cocatalyst-free conditions enables the selective synthesis of poly(cyclohexene carbonate) with a molecular weight of about 62.1 kg/mol with about 70% yields at 343 K and 4 MPa. To the best of our knowledge, this is a rare example of high molar mass polycyclohexene carbonates that are moreover obtained under solvent-and cocatalyst-free conditions. The high selectivity of ZnTos towards the formation of poly(cyclohexene carbonate) was interpreted, thanks to in situ FTIR spectroscopy and DFT calculations, as resulting from its ability to coactivate CO2.

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“…However, it has been difficult to find wide commercial application for polycarbonates obtained according to this process due to their low glass transition temperature and relatively poor mechanical properties. Recently, new catalysts such as cobalt complexes [4,5], zinc adipate [6,7] or a double metal cyanide complex [8] were investigated to improve the efficiency of copolymerization CO 2 with oxiranes. The main advantage of aliphatic polycarbonates similarly to aliphatic polyesters is theirs biodegradability.…”

Section: Introductionmentioning

confidence: 99%

Aliphatic-aromatic poly(ester-carbonate)s obtained from simple carbonate esters, α,ω-aliphatic diols and dimethyl terephthalate

et al. 2015

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Two reaction pathways for synthesis of high molar mass (M w above 50 000 g/mol) aliphatic-aromatic poly(estercarbonate)s were elaborated. Simple organic carbonates such as dimethyl carbonate or propylene carbonate were used as carbonate linkage sources and dimethyl terephthalate as the precursor of ester linkages. 1,4-Butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,10-decanediol were used as diol monomers. To adjust the carbonate units content in the copolymer, solid alkylene bis(methylcarbonate) was used as a semiproduct instead of volatile dimethyl carbonate. In case of usage propylene carbonate as a starting material the process can be carried out in one pot without the need for isolation of the semiproduct. The obtained copolymers based on 1,4-butanediol, containing ca. 50 mol.% of carbonate units exhibited better mechanical strength (37 MPa) than commercially available aliphatic-aromatic copolyester Ecoflex ® keeping the thermal properties at the same level.

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Zinc adipate/tertiary amine catalytic system: efficient synthesis of high molecular weight poly(propylene carbonate)

Cited by 24 publications

References 29 publications

One-pot synthesis of terpolymers with long l -lactide rich sequence derived from propylene oxide, CO₂ , and l -lactide catalyzed by zinc adipate

One-pot synthesis of terpolymers with long l -lactide rich sequence derived from propylene oxide, CO₂ , and l -lactide catalyzed by zinc adipate

A Rational Investigation of the Lewis Acid-Promoted Coupling of Carbon Dioxide with Cyclohexene Oxide: Towards CO2-Sourced Polycyclohexene Carbonate under Solvent- and Cocatalyst-Free Conditions

Aliphatic-aromatic poly(ester-carbonate)s obtained from simple carbonate esters, α,ω-aliphatic diols and dimethyl terephthalate

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Zinc adipate/tertiary amine catalytic system: efficient synthesis of high molecular weight poly(propylene carbonate)

Cited by 24 publications

References 29 publications

One-pot synthesis of terpolymers with long l -lactide rich sequence derived from propylene oxide, CO2 , and l -lactide catalyzed by zinc adipate

One-pot synthesis of terpolymers with long l -lactide rich sequence derived from propylene oxide, CO2 , and l -lactide catalyzed by zinc adipate

A Rational Investigation of the Lewis Acid-Promoted Coupling of Carbon Dioxide with Cyclohexene Oxide: Towards CO2-Sourced Polycyclohexene Carbonate under Solvent- and Cocatalyst-Free Conditions

Aliphatic-aromatic poly(ester-carbonate)s obtained from simple carbonate esters, α,ω-aliphatic diols and dimethyl terephthalate

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One-pot synthesis of terpolymers with long l -lactide rich sequence derived from propylene oxide, CO₂ , and l -lactide catalyzed by zinc adipate

One-pot synthesis of terpolymers with long l -lactide rich sequence derived from propylene oxide, CO₂ , and l -lactide catalyzed by zinc adipate