Obtaining aliphatic branched polycarbonates via simple copolymerization of trimethylene carbonate with cyclic carbonate containing pendant ester groups

Pastusiak, Małgorzata; Jaworska, Joanna; Kawalec, Michał; Kasperczyk, Janusz; Dobrzyński, P.

doi:10.1002/pola.28431

Cited by 6 publications

(7 citation statements)

References 35 publications

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“…The same conclusions were noted in the case of our previous study relating to the copolymerization of TMC with MTC‐Et …”

Section: Resultssupporting

confidence: 87%

“…This was an expected effect since our previous studies showed low susceptibility of the carbonate groups to the transesterification reactions. Mechanism of this type of reaction has already been presented in detail in our previous article describing a model copolymerization of TMC with MTC‐Et . It occurs as a result of the attack of the active end of the growing chain onto the ester group located in the other molecule's side chain.…”

Section: Resultsmentioning

confidence: 96%

“…Copolymerization of the MTC–Bz with TMC was carried out in bulk, using coordination initiators. Those initiators were selected on the basis of their usefulness in our previous, similar reactions, in copolymerization of MTC‐Et (methyl 5‐methyl‐2‐oxo‐1,3‐dioxane‐5‐carboxylate) with TMC, in which zinc and lanthanum acetylacetonates played a role of a single component initiator. Copolymers that differed in unit content were obtained by changing the composition of the initial mixture as well as the reaction time.…”

Section: Resultsmentioning

confidence: 99%

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Biodegradable polycarbonates containing side carboxyl groups—synthesis, properties, and degradation study

Jaworska

Kawalec

Pastusiak

et al. 2017

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

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The main objective of the presented research was to synthesise biodegradable aliphatic polycarbonates containing reactive carboxyl pendant groups and to examine the influence of the copolymer chain microstructure and composition on the process of their hydrolytic degradation and cytocompatibility. The work describes copolymerization of cyclic trimethylene carbonate derivative containing benzyl-ester pendant group (benzyl 5-methyl-2-oxo-1,3-dioxane-5-carboxylate) with trimethylene carbonate. The copolymerization was conducted with the use of zinc (II) and lanthanum (III) acetylacetonates as ring-opening polymerization coordination initiators. Detailed NMR analysis allowed to define the microstructure of the obtained copolymers, which depended on the composition and type of used initiator. The final tapered chain microstructure of the obtained copolymers was related to huge differences in comonomers reactivity and evidenced low level of transesterification of the main copolymer backbone. Chosen copolymers, with unprotected carbonyl groups, were subjected to in vitro degradation test and cytocompatibility studies. It was found that high concentration of carboxyl groups resulted in copolymers which formed hydrogels and were very prone to hydrolytic degradation; they were also cytotoxic toward osteoblastlike MG 63 cells. Copolymers with lower content of carboxyl groups were found less susceptible to degradation and cytocompatible with studied cells.

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“…The same conclusions were noted in the case of our previous study relating to the copolymerization of TMC with MTC‐Et …”

Section: Resultssupporting

confidence: 87%

Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Biodegradable polycarbonates containing side carboxyl groups—synthesis, properties, and degradation study

Jaworska

Kawalec

Pastusiak

et al. 2017

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

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“…In addition, an analogous phenomenon was already observed during the copolymerization of ethyl 5-methyl-2-oxo-1,3-dioxane-5-carboxylate (MTC-Et) with trimethylene carbonate (TMC) initiated with Zn[(acac) 2 H 2 O]. This process was much more intensive than that described in this work, as evidenced by the final dispersion of the molecular mass reaching a Ð value of more than 100 [21]. The growth of the amount of carbonate units in the obtained copolymers caused a decrease in their glass transition (T g ); however, this decrease was significantly slower than expected based on the calculation using the Fox equation (Table 1).…”

Section: Copolymerization Of L-lactide With 5-methyl-2-oxo-13-dioxane-5-carboxylate (Mtc-bz)supporting

confidence: 78%

Synthesis of Polyacids by Copolymerization of l-Lactide with MTC-COOH Using Zn[(acac)(L)H2O] Complex as an Initiator

et al. 2022

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This work presents the results of research on the preparation of bioresorbable functional polyestercarbonates containing side carboxyl groups. These copolymers were synthesized in two ways: the classic two-step process involving the copolymerization of L-lactide and a cyclic carbonate containing a blocked side carboxylate group in the form of a benzyl ester (MTC-Bz) and its subsequent deprotection, and a new way involving the one-step copolymerization of L-lactide with this same carbonate, but containing an unprotected carboxyl group (MTC-COOH). Both reactions were carried out under identical conditions in the melt, using a specially selected zinc chelate complex, with Zn [(acac)(L)H2O] (where: L-N-(pyridin-4-ylmethylene) phenylalaninate ligand) as an initiator. The differences in the kinetics of both reactions and their courses were pictured. The reactivity of the MTC-COOH monomer without a blocking group in the studied co-polymerization was much higher, even slightly higher than L-lactide, which allowed the practically complete conversion of the comonomers in a much shorter time. The basic final properties of the obtained copolymers and the microstructures of their chains were determined. The single-step synthesis of biodegradable polyacids was much simpler. Contrary to the conventional method, this made it possible to obtain copolymers containing all carbonate units with carboxyl groups, without even traces of the heavy metals used in the deprotection of the carboxyl groups, the presence of which is known to be very difficult to completely remove from the copolymers obtained in the two-step process.

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“…Previously we described a very similar and analogical phenomenon, which proceeded during the polymerization of cyclic carbonates containing side ester groups [22]. A mechanism of transesterification in which the attack of active ends is directed to the ester bonds of the main chain is also very probable.…”

Section: Synthesis and Characterization Of L-lactide Copolymers With mentioning

confidence: 76%

Synthesis and Properties of Bioresorbable Block Copolymers of l-Lactide, Glycolide, Butyl Succinate and Butyl Citrate

et al. 2020

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The paper presents the course of synthesis and properties of a series of block copolymers intended for biomedical applications, mainly as a material for forming scaffolds for tissue engineering. These materials were obtained in the polymerization of l-lactide and copolymerization of l-lactide with glycolide carried out using a number of macroinitiators previously obtained in the reaction of polytransesterification of succinic diester, citric triester and 1,4-butanediol. NMR, FTIR and DSC were used to characterize the materials obtained; wettability and surface free energy were assessed too. Moreover, biological tests, i.e., viability and metabolic activity of MG-63 osteoblast-like cells in contact with synthesized polymers were performed. Properties of obtained block copolymers were controlled by the composition of the polymerization mixture and by the composition of the macroinitiator. The copolymers contained active side hydroxyl groups derived from citrate units present in the polymer chain. During the polymerization of l-lactide in the presence of polyesters with butylene citrate units in the chain, obtained products of the reaction held a fraction of highly branched copolymers with ultrahigh molecular weight. The reason for this observed phenomenon was strong intermolecular transesterification directed to lactidyl side chains, formed as a result of chain growth on hydroxyl groups related to the quaternary carbons of the citrate units. Based on the physicochemical properties and results of biological tests it was found that the most promising materials for scaffolds formation were poly(l-lactide–co–glycolide)–block–poly(butylene succinate–co–butylene citrate)s, especially those copolymers containing more than 60 mol % of lactidyl units.

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Obtaining aliphatic branched polycarbonates via simple copolymerization of trimethylene carbonate with cyclic carbonate containing pendant ester groups

Cited by 6 publications

References 35 publications

Biodegradable polycarbonates containing side carboxyl groups—synthesis, properties, and degradation study

Biodegradable polycarbonates containing side carboxyl groups—synthesis, properties, and degradation study

Synthesis of Polyacids by Copolymerization of l-Lactide with MTC-COOH Using Zn[(acac)(L)H2O] Complex as an Initiator

Synthesis and Properties of Bioresorbable Block Copolymers of l-Lactide, Glycolide, Butyl Succinate and Butyl Citrate

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