Block Copolymers of γ-Methacryloxypropyltrimethoxysilane and Methyl Methacrylate by RAFT Polymerization. A New Class of Polymeric Precursors for the Sol−Gel Process

Mellon, Véronique; Rinaldi, David; Bourgeat‐Lami, Élodie; D’Agosto, Franck

doi:10.1021/ma048143j

Cited by 56 publications

(62 citation statements)

References 40 publications

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“…Figure 1-b shows that TMSPMA polymerised successfully without any signs of hydrolysis of its alkoxy-silane moiety, which would translate to a decrease of the relative integration of the methoxy groups (δ ≈ 3.58 ppm) to the first protons on the propyl chain (δ ≈ 3.90 ppm) after polymerisation. 45,46 After purification and redispersion in ethanol, pTMSPMA was added to a solution of hydrolysed tetraethyl orthosilicate (TEOS) at different concentrations to aim at inorganic to organic ratios of 29 % (only the polymer), 50 % and 75 %, later called I29, I50, I75 respectively (Schematic of the reaction in Figure 2-a). A control, I100, consisting of a pure silica gel, was also synthesised under the same experimental conditions (pH, water content, ethanol content).…”

Section: Polymers and Hybrids Synthesismentioning

confidence: 99%

Ductile silica/methacrylate hybrids for bone regeneration

Maçon

Chung

et al. 2016

J. Mater. Chem. B

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BioglassR was the first synthetic material capable of bonding with bone without fibrous encapsulation, and fulfils some of the criteria of an ideal synthetic bone graft. However, it is brittle and toughness is required. Here, we investigated hybrids consisting of co-networks of high crosslinking density polymethacrylate and silica (class II hybrid) as a potential new generation of scaffold materials. Poly(3-(methoxysilyl)propyl methacrylate) (pTMSPMA) and tetraethyl orthosilicate (TEOS) were used as sol-gel precursors and hybrids were synthesised with different inorganic to organic ratios (I h ). The hybrids were nanoporous, with a modal pore diameter of 1 nm. At I h = 50 %, the release of silica was controlled by varying the molecular weight of pTMSPMA while retaining a specific surface area above 100 m 2 g −1 . Strain to failure increased to 14.2 %, for I h = 50 % using a polymer of 30 kDa, compared to 4.5 % for pure glass. The modulus of toughness (U T ) increased from 0.73 (pure glass) to 2.64 GPa. Although, the hybrid synthesised in this report did not contain calcium, pTMSPMA/SiO 2 hybrid was found to nucleate bone-like mineral on its surface after 1 week of immersion in simulated body fluid (SBF), whereas pure silica sol-gel glass did not. This increase in apatite forming ability was due to the ion-dipole complexation of calcium with the ester moieties of the polymer that were exposed after release of soluble silica from TEOS. No adverse cytotoxicity for MC3T3-E1 osteoblast-like cells was detected and improved cell attachment was observed, compared to a pure silica gel. pTMSPMA/SiO 2 hybrids have potential for the regeneration of hard tissue as they overcome the major drawbacks of pure inorganic substrates while retaining cell attachment.Bone is the second most transplanted tissue after blood and musculoskeletal pathology treatments represent £10 billion per year in the U.K. alone. 1,2 Effective alternatives must be found to the current methods of skeletal defect treatments to avoid postoperation infection or revision, which can cost up to £70,000 per patient. 3 One attractive approach is to design biodegradable implants that could actively promote the bone growth and tissue remodelling by stimulating cellular activities whilst providing a mechanical support to the tissue. 4 Bioglass R (BG), a biodegradable bioactive silicate glass (46.1 mol % SiO 2 , 26.9 mol % CaO, 24.2 mol % Na 2 O, 2.6 mol % P 2 O 5 ), was the first material capable of bonding with bone by the formation of an apatite layer that forms on its surface after grafting. 5 A second mode of action is its dissolution products (in particular silica), which enhance osteoblast activities, whilst promoting extra- * Corresponding author, E-mail: julian.r.jones@imperial.ac cellular matrix (ECM) production and cells differentiation. 6-8 3D scaffolds have been produced from bioactive glasses, with interconnected pore networks in the form of foams 9,10 or 3-D printed structures 11 , which can take load in compression, up to 150 MPa when 3D printed. 12 ...

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Section: Polymers and Hybrids Synthesismentioning

confidence: 99%

Ductile silica/methacrylate hybrids for bone regeneration

Maçon

Chung

et al. 2016

J. Mater. Chem. B

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“…Although, few references exist on homopolymerization of TMSPMA [20][21][22] and copolymerization [22][23] with others acrylate and methacrylate comonomers. Koh et al [23] have synthesized amphiphilic block copolymers by atom-transfer radical polymerization (ATRP) with TMSPMA, methyl methacrylate and poly(ethylene oxide) methyl ether methacrylate in order to form organic/inorganic hybrid nanocapsules used in the encapsulation of substances into confined spaces.…”

Section: Introductionmentioning

confidence: 99%

“…[24] D'Agosto et al also synthesized amphiphilic block copolymers by RAFT technique which can self-assemble into a variety of nano-objects and can be used as colloid stabilizers, nanoreactors, or templates for making inorganic solids. [20] The aim of the work was firstly, the determination of the transfer constant (C T ) of TMSPMA in the presence of 2-mercaptoethanol by telomerization and the check of non-attendance of the side reactions between trimethylsilyl groups and the functional telogen. Secondly, the free-radical cotelomerization of TMSPMA with PFDA in the presence of 2-mercaptoethanol was studied in order to prepare α-hydroxy terminated statistical oligomer-type backbone which may be further used to obtain graft copolymers.…”

Section: Introductionmentioning

confidence: 99%

Kinetics of cotelomerization of 3-(trimethoxysilyl)propyl methacrylate and perfluorodecylacrylate

Pardal

Lapinte

Robin

2009

European Polymer Journal

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“…PMPS homopolymer and P(MMA-b-MPS) block copolymers were successfully synthesized with MWs up to 40 000 g·mol −1 and a low polydispersity (PDI < 1.3) [225].…”

Section: Silane-based Polymer Chainsmentioning

confidence: 99%

Toward New Materials Prepared via the RAFT Process: From Drug Delivery to Optoelectronics?

Favier

Lambert

Charreyre

2008

Handbook of RAFT Polymerization

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IntroductionThe development of controlled/living ionic and radical polymerization techniques during the last decades represents a major breakthrough in polymer chemistry and polymer science. Since these techniques lead to the synthesis of a wide range of tailor-made macromolecular architectures, significant improvements are expected in the current or future application fields of polymers. The industrial impact will however depend on the versatility and applicability of each technique, and of course on the extra cost for the final product.In this context, controlled radical polymerizations (CRP) and especially the reversible addition-fragmentation chain transfer (RAFT) process [1-3] have attracted a lot of attention since they combine the advantages of conventional radical polymerization and living ionic polymerizations. Conventional radical polymerizations are cost-effective techniques, easy to process with a low sensitivity to water and oxygen and applicable to a wide range of monomers. In addition, CRP techniques result in a very efficient control over molecular weight (MW), molecular-weight distribution (MWD), microstructure, chain-end functionality and macromolecular architecture.As shown in the previous chapters of this handbook, the RAFT process appears as one of the most interesting CRP techniques. First, RAFT polymerization is very similar to conventional radical polymerization since it only requires the addition of a chain-transfer agent (CTA) in the medium. Second, RAFT is a very versatile process able to control the (co)polymerization of a large variety of monomers leading to a virtually unlimited macromolecular design library.As a consequence, RAFT polymerization is a well-suited and promising technique to prepare high-performance polymers for a wide range of applications. Indeed, an efficient control at the macromolecular level is a very important step to control and improve the macroscopic properties of the final materials ( Fig. 13.1).

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Block Copolymers of γ-Methacryloxypropyltrimethoxysilane and Methyl Methacrylate by RAFT Polymerization. A New Class of Polymeric Precursors for the Sol−Gel Process

Cited by 56 publications

References 40 publications

Ductile silica/methacrylate hybrids for bone regeneration

Ductile silica/methacrylate hybrids for bone regeneration

Kinetics of cotelomerization of 3-(trimethoxysilyl)propyl methacrylate and perfluorodecylacrylate

Toward New Materials Prepared via the RAFT Process: From Drug Delivery to Optoelectronics?

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