Fumarate-based polymers

A.S. Mistry, Q.P. Pham, C. Schouten, T. Yeh, E.M. Christenson, A.G. Mikos, J.A. Jansen, In vivo bone biocompatibiUty and degradation of porous fumarate-based polymer/alumoxane nanocomposites for bone tissue engineering. J. Biomed. Mater. Res. A 92 (2)... 

The following polyesters are based on fumaric acid, a naturally occurring substance found in the Krebs cycle [8]. Three types of fumarate-based polymers are discussed poly(propylene fumarate) (PPF), poly(propylene fumarate-co-ethylene glycol) (P(PF-co-EG)), and oligo(poly(ethylene glycol) fumarate) (OPF). 

Demonstrated feasibility of fabricating degradable nanocomposite scaffolds for bone tissue engineering by photo-crosslinking fumarate-based polymers, alumoxane nanoparticles... 

Haesslein, A., H. Ueda, M. C. Hacker, S. Jo, D. M. Ammon, R. N. Borazjani, J. F. Kunzler, J. C. Salamone, and A. G. Mikos. 2006. Long-term release of fluocinolone acetonide using biodegradable fumarate-based polymers. / Control Release 114(2) 251-60. 

Mistry, A. S., S. El. Cheng, T. Yeh, E. Christenson, J. A. Jansen, and A. G. Mikos. 2009. Fabrication and in vitro degradation of porous fumarate-based polymer/alumoxane nanocomposite scaffolds for bone tissue engineering. J Biomed Mater Res A 89(1) 68-79. 

Reactive (unsaturated) epoxy resins (qv) are reaction products of multiple glycidyl ethers of phenoHc base polymer substrates with methacrylic, acryhc, or fumaric acids. Reactive (unsaturated) polyester resins are reaction products of glycols and diacids (aromatic, aUphatic, unsaturated) esterified with acryhc or methacrylic acids (see POLYESTERS,unsaturated). Reactive polyether resins are typically poly(ethylene glycol (600) dimethacrylate) or poly(ethylene glycol (400) diacrylate) (see PoLYETPiERs). 

Timmer, M. D., Jo, S. B., Wang, C. Y., Ambrose, C. G. Mikos, A. G. (2002) Characterization of the cross-linked structure of fumarate-based degradable polymer networks. Macromolecules, 35, 4373-4379. 

Kharas, G. B., Kamenetsky, M., Simantirakis, J., Beinlich, K., C, Rizzo, A.-M., T., Caywood, G., A. Watson, K. 1997. Synthesis and characterization of fumarate-based polyesters for use in bioresorbable bone cement composites. Journal of Applied Polymer Science, 66, 15. 

The development of fumarate-based polyesters for biomedical applications started around 20 years ago. Fumaric acid is a natural metabolite involved in Krebs cycle, and is comprised of a reactive double bond available for chemically crosslinking reactions. These characteristics make fumaric acid a candidate building block for crosslinkable polymers. The first and most comprehensively investigated fumarate-based copolymer is the biodegradable copolyester poly(propylene fumarate) (PPF) (Fig. 6.8). ... 

Low molecular weight oligo(lactide)s end capped with fumarate groups have been used for in situ cross-linkable scaffolds for tissue engineering [74]. Side chain functionalized diastereomeric lactides were synthesized from commercially available amino acids and their subsequent polymerization or copolymerization [75]. This approach allows the incorporation of any protected amino acid for the preparation of functionalized cyclic monomers. The quantitative deprotection of amino acids leads to the formation of new functionalized PLA-based polymers. 

Databook - Section D3 Bisphenol - A, Epoxide, Vinyl Cyanate Esters Fumaric Based Jotun Polymer AS - continued ... 

In our laboratory, we have studied the effects of various surface-modified alumoxane nanoparticles on the mechanical properties of a biodegradable polymer for load-bearing bone tissue applications [4j. Alumoxane nanoparticles with three different surface modifications were tested — activated alumoxanes possessing two reactive double bonds available for interaction with the cross-link network of the polymer surfactant alumoxanes modified with long fatty acid chains to aid in dispersion within the hydrophobic polymer and hybrid alumoxanes modified with a surfactant chain and a reactive double bond within the same substituent (Figure 40.2). These nanoparticles were incorporated into a biodegradable poly(propylene fumarate)-based (PPF) system and the nanocomposites were tested for flexural and compressive mechanical properties. 

Some polymers like PE and NR get cross-linked on exposure to radiation while others like those based on vinylidene polymers, e.g., polymethylmethacrylate (PMMA), polyisobutylene, degrade. Certain other types of polymer stmctures (high aromatic content or thermoset) resist degradation by high-energy radiation. Coating polymers usually contain acrylic, methacryUc, or fumaric vinyl unsaturation along or attached to the backbone. 

Polyanhydrides based on unsaturated and fatty acid-derived monomers are shown in Table III. Poly(fumaric acid) (PFA) was fist synthesized by Domb et al. (1991) by both melt polycondensation and solution polymerization. The copolymer of fumaric acid and sebacic acid (P(FA-SA)) has been synthesized and characterized (Domb et al., 1991 Mathiowitz et al., 1990b). The mucoadhesive properties of this polymer... 

The unperturbed dimensions of various condensation polymers obtained by the present method are listed in Table 10. A polyelectrolyte chain, sodium polyphosphate, has been included because theta-solvent results are available. The freely-rotating chain dimension (Lzyof of poly(dimethylsiloxane) in the table is due to Flory and his coworkers (705), that for the polyphosphate chains is taken directly from the paper of Strauss and Wineman 241 ), while most of the others have been calculated in the standard manner with the convenient and only negligibly incorrect assumption that all the aliphatic bond angles are tetrahedral. The free-rotation values for the maleate and fumarate polyesters are based on parameters consistent with those of Table 6 for diene polymers. 

The first useful photolocking system (68) was based on the addition of ethyl-2-(l-naphthyl)acrylate to reactive fumarate groups attached to the methacrylate polymer shown in Fig. 21. 

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