Influence of Different Initiators Against the Mechanical Properties of Poly(e-caprolactone) used for Biodegradable Bone Implants

2008 ◽  
Vol 59 (11) ◽  
Author(s):  
Adriana Lungu ◽  
Teodora Zecheru ◽  
Stanca Comsa ◽  
Horia Iovu

The ability of a strict control for the advanced macromolecular structures synthesis has been an important objective in our research. The development of polymers with defined structures and properties, aimed at biomedical applications, leads to complex and advanced architecture and diversity of the biodegradable polymers. Ring-opening polymerization is one of the most common methods for the synthesis of polymers with improved characteristics. Poly e-(caprolactone) (PCL) is prepared by ring-opening polymerization of the monomer e-caprolactone. The main factors which influence the ring-opening polymerization are the reaction conditions, such as the nature of the initiator, type and concentration of catalyst, reaction temperature and time. Stannous (II) 2-ethylhexanoate is used to catalyze the polymerization and alcohols are used as initiators. The initiators are also used to control the polymers molecular weight. Despite the long use of this catalyst in both industrial use and polymer research, several questions about the properties of the final product still remain. Our study describes the polymerization of e-caprolactone performed in the presence of catalyst (stannous (II) 2-ethylhexanoate) and initiator (1, 6 hexandiol or trimethylol propane) at moderate temperature (110�C). The polymerization of e-caprolactone was also performed in the presence of catalyst alone in order to evaluate the effect of the initiator against the polymers molecular weight. The obtained polymers were characterized by FTIR, GPC and TGA with respect to their mechanical properties. It is crucial to control the molecular weight of PCL for biomedical and pharmaceutical applications, because its molecular weight determines the hydrolysis rate. Several ratios among monomer, catalyst and initiator were studied, and we chose an optimum composition, in order to control the mechanical properties, degradation profiles respectively, and to avoid the cytotoxicity given by the reagents used.

RSC Advances ◽  
2015 ◽  
Vol 5 (40) ◽  
pp. 31554-31557 ◽  
Author(s):  
Ning Zhu ◽  
Zilong Zhang ◽  
Weiyang Feng ◽  
Yuqiang Zeng ◽  
Zhongyue Li ◽  
...  

A simple PTFE tubular microreactor based platform was successfully developed to conduct Sn(OTf)2 catalyzed ε-caprolactone polymerization with better control of reaction conditions, faster polymerizations and narrower molecular weight distributions.


Author(s):  
Sourav Singha Roy ◽  
Sriparna Sarkar ◽  
Debashis Chakraborty

AbstractIn the twenty-first century, one of the central focus of polymer research in academia and industries is directed towards the design of environmentally-benign materials produced from reagents that have minimal deleterious effects on our environment. The aliphatic polyester PLA is one such example. Due to its biodegradable, biorenewable and biocompatible nature, PLA finds diverse applications, especially in the biomedical field. PLA is exclusively synthesized by the ring-opening polymerization of lactide (cyclic dimer of lactic acid) in the presence of a catalyst. The macrocycles and macrocyclic metal moieties can act as effective catalysts for the polymerization resulting in the formation of PLA with controlled tacticity and predetermined molecular weight. This review reports metal-based catalytic systems supported by porphyrin, calixarene and bispyrrolidine- salan as ancillary ligand and metal-free organocatalyst sparteine for the ROP of LA. The variation in catalytic activity, tacticity of PLA, and PLA's molecular weight distribution by substitutional changes in the catalyst framework have been discussed in detail. Graphic abstract


2011 ◽  
Vol 44 (11) ◽  
pp. 4301-4305 ◽  
Author(s):  
Inge van der Meulen ◽  
Erik Gubbels ◽  
Saskia Huijser ◽  
Rafaël Sablong ◽  
Cor E. Koning ◽  
...  

1995 ◽  
Vol 73 (11) ◽  
pp. 2069-2078 ◽  
Author(s):  
Timothy J. Peckham ◽  
Daniel A. Foucher ◽  
Alan J. Lough ◽  
Ian Manners

The silicon-bridged [1]ferrocenophane Fe(η-C5H3SiMe3)2(SiMe2) (5) was synthesized via the reaction of Li2[Fe(η-C5H3SiMe3)2]•tmeda (tmeda = tetramethylethylenediamine) with Me2SiCl2 in hexanes. The disilane-bridged [2]ferrocenophane Fe(η-C5H3SiMe3)2(Si2Me4) (7) was prepared using a similar route from the disilane ClMe2SiSiMe2Cl. Despite the presence of sterically demanding SiMe3 substituents on the cyclopentadienyl rings, compound 5 was found to undergo thermal ring-opening polymerization at 170 °C to produce very soluble, high molecular weight poly(ferrocenylsilane) 6 with Mw = 1.4 × 105, Mn = 8.4 × 104. However, the [2]ferrocenophane 7 was found to be resistant to thermal ring-opening polymerization even at 350 °C and decomposed above 380 °C. A single-crystal X-ray diffraction study of 7 revealed that the steric interactions between the bulky SiMe3 groups are relieved by a significant twisting of the disilane bridge with respect to the plane defined by the centroids of the cyclopentadienyl ligands and the metal atom. The angle between the planes of the cyclopentadienyl rings in 7 was found to be 5.4(6)°, slightly greater than that in the non-silylated analogue Fe(η-C5H4)2(Si2Me4) (4a) (4.19(2)°), and dramatically less than the corresponding tilt angle of the strained, polymerizable, silicon-bridged [1]ferrocenophane Fe(η-C5H4)2(SiMe2) (1) (20.8(5)°). The length of the Si—Si bond in 7 (2.342(3) Å) was found to be close to the sum of the covalent radii (2.34 Å). Crystals of 7 are monoclinic, space group C2/c, with a = 23.689(3) Å, b = 11.174(1) Å, c = 31.027(3) Å, β = 109.16(1)°, V = 7758(2) Å3, and Z = 12. Keywords: ring-opening polymerization, ferrocenophane, organometallic polymers.


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