Dispersant and Protective Roles of Amphiphilic Poly(ethylene phosphate) Block Copolymers in Polyester/Bone Mineral Composites

Composites of synthetic bone mineral substitutes (BMS) and biodegradable polyesters are of particular interest for bone surgery and orthopedics. Manufacturing of composite scaffolds commonly uses mixing of the BMS with polymer melts. Melt processing requires a high homogeneity of the mixing, and is...

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Main Authors: Ilya Nifant’ev, Alexander Tavtorkin, Pavel Komarov, Egor Kretov, Sofia Korchagina, Maria Chinova, Dmitry Gavrilov, Pavel Ivchenko
Format: Article
Language:English
Published: MDPI AG 2023-07-01
Series:International Journal of Molecular Sciences
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Online Access:https://www.mdpi.com/1422-0067/24/13/11175
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author Ilya Nifant’ev
Alexander Tavtorkin
Pavel Komarov
Egor Kretov
Sofia Korchagina
Maria Chinova
Dmitry Gavrilov
Pavel Ivchenko
author_facet Ilya Nifant’ev
Alexander Tavtorkin
Pavel Komarov
Egor Kretov
Sofia Korchagina
Maria Chinova
Dmitry Gavrilov
Pavel Ivchenko
author_sort Ilya Nifant’ev
collection DOAJ
description Composites of synthetic bone mineral substitutes (BMS) and biodegradable polyesters are of particular interest for bone surgery and orthopedics. Manufacturing of composite scaffolds commonly uses mixing of the BMS with polymer melts. Melt processing requires a high homogeneity of the mixing, and is complicated by BMS-promoted thermal degradation of polymers. In our work, poly(<i>L</i>-lactide) (PLLA) and poly(ε-caprolactone) (PCL) composites reinforced by commercial β-tricalcium phosphate (βTCP) or synthesized carbonated hydroxyapatite with hexagonal and plate-like crystallite shapes (hCAp and pCAp, respectively) were fabricated using injection molding. pCAp-based composites showed advanced mechanical and thermal characteristics, and the best set of mechanical characteristics was observed for the PLLA-based composite containing 25 wt% of pCAp. To achieve compatibility of polyesters and pCAp, reactive block copolymers of PLLA or PCL with poly(<i>tert-</i>butyl ethylene phosphate) (C1 and C2, respectively) were introduced to the composite. The formation of a polyester-<i>b</i>-poly(ethylene phosphoric acid) (PEPA) compatibilizer during composite preparation, followed by chemical binding of PEPA with pCAp, have been proved experimentally. The presence of 5 wt% of the compatibilizer provided deeper homogenization of the composite, resulting in a marked increase in strength and moduli as well as a more pronounced nucleation effect during isothermal crystallization. The use of C1 increased the thermal stability of the PLLA-based composite, containing 25 wt% of pCAp. In view of positive impacts of polyester-<i>b</i>-PEPA on composite homogeneity, mechanical characteristics, and thermal stability, polyester-<i>b</i>-PEPA will find application in the further development of composite materials for bone surgery and orthopedics.
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spelling doaj.art-b58a73a39ae44424932ca7785fc682692023-11-18T16:49:08ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672023-07-0124131117510.3390/ijms241311175Dispersant and Protective Roles of Amphiphilic Poly(ethylene phosphate) Block Copolymers in Polyester/Bone Mineral CompositesIlya Nifant’ev0Alexander Tavtorkin1Pavel Komarov2Egor Kretov3Sofia Korchagina4Maria Chinova5Dmitry Gavrilov6Pavel Ivchenko7A.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaA.V. Topchiev Institute of Petrochemical Synthesis RAS, 29 Leninsky Pr., 119991 Moscow, RussiaComposites of synthetic bone mineral substitutes (BMS) and biodegradable polyesters are of particular interest for bone surgery and orthopedics. Manufacturing of composite scaffolds commonly uses mixing of the BMS with polymer melts. Melt processing requires a high homogeneity of the mixing, and is complicated by BMS-promoted thermal degradation of polymers. In our work, poly(<i>L</i>-lactide) (PLLA) and poly(ε-caprolactone) (PCL) composites reinforced by commercial β-tricalcium phosphate (βTCP) or synthesized carbonated hydroxyapatite with hexagonal and plate-like crystallite shapes (hCAp and pCAp, respectively) were fabricated using injection molding. pCAp-based composites showed advanced mechanical and thermal characteristics, and the best set of mechanical characteristics was observed for the PLLA-based composite containing 25 wt% of pCAp. To achieve compatibility of polyesters and pCAp, reactive block copolymers of PLLA or PCL with poly(<i>tert-</i>butyl ethylene phosphate) (C1 and C2, respectively) were introduced to the composite. The formation of a polyester-<i>b</i>-poly(ethylene phosphoric acid) (PEPA) compatibilizer during composite preparation, followed by chemical binding of PEPA with pCAp, have been proved experimentally. The presence of 5 wt% of the compatibilizer provided deeper homogenization of the composite, resulting in a marked increase in strength and moduli as well as a more pronounced nucleation effect during isothermal crystallization. The use of C1 increased the thermal stability of the PLLA-based composite, containing 25 wt% of pCAp. In view of positive impacts of polyester-<i>b</i>-PEPA on composite homogeneity, mechanical characteristics, and thermal stability, polyester-<i>b</i>-PEPA will find application in the further development of composite materials for bone surgery and orthopedics.https://www.mdpi.com/1422-0067/24/13/11175carbonated apatitecompositesmechanical characteristicsthermal degradationpolylactidepoly(ε-caprolactone)
spellingShingle Ilya Nifant’ev
Alexander Tavtorkin
Pavel Komarov
Egor Kretov
Sofia Korchagina
Maria Chinova
Dmitry Gavrilov
Pavel Ivchenko
Dispersant and Protective Roles of Amphiphilic Poly(ethylene phosphate) Block Copolymers in Polyester/Bone Mineral Composites
International Journal of Molecular Sciences
carbonated apatite
composites
mechanical characteristics
thermal degradation
polylactide
poly(ε-caprolactone)
title Dispersant and Protective Roles of Amphiphilic Poly(ethylene phosphate) Block Copolymers in Polyester/Bone Mineral Composites
title_full Dispersant and Protective Roles of Amphiphilic Poly(ethylene phosphate) Block Copolymers in Polyester/Bone Mineral Composites
title_fullStr Dispersant and Protective Roles of Amphiphilic Poly(ethylene phosphate) Block Copolymers in Polyester/Bone Mineral Composites
title_full_unstemmed Dispersant and Protective Roles of Amphiphilic Poly(ethylene phosphate) Block Copolymers in Polyester/Bone Mineral Composites
title_short Dispersant and Protective Roles of Amphiphilic Poly(ethylene phosphate) Block Copolymers in Polyester/Bone Mineral Composites
title_sort dispersant and protective roles of amphiphilic poly ethylene phosphate block copolymers in polyester bone mineral composites
topic carbonated apatite
composites
mechanical characteristics
thermal degradation
polylactide
poly(ε-caprolactone)
url https://www.mdpi.com/1422-0067/24/13/11175
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