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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MDPI AG
2023-07-01
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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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