Polycaprolactone copolymers

Selection of a tissue engineering substrate includes a choice between absorbable and nonabsorbable material, as well as a choice between synthetic and naturally derived materials. The most common synthetic polymers used for fibrous meshes and porous scaffolds include polyesters such as polylactide and polyglycolide and their copolymers, polycaprolactone, and polyethylene glycol. Synthetic polymers have advantages over natural polymers in select instances, such as the following i... 

Tribloc copolymer (polycaprolactone-polydimethylsiloxane-polycaprolactone) integrated into plastic (reduced cellular and protein adhesion)... 

Copolymers of S-caprolactone and L-lactide are elastomeric when prepared from 25% S-caprolactone and 75% L-lactide, and rigid when prepared from 10% S-caprolactone and 90% L-lactide (47). Blends of poly-DL-lactide and polycaprolactone polymers are another way to achieve unique elastomeric properties. Copolymers of S-caprolactone and glycoHde have been evaluated in fiber form as potential absorbable sutures. Strong, flexible monofilaments have been produced which maintain 11—37% of initial tensile strength after two weeks in vivo (48). 

See also PBT degradation structure and properties of, 44-46 synthesis of, 106, 191 Polycaprolactam (PCA), 530, 541 Poly(e-caprolactone) (CAPA, PCL), 28, 42, 86. See also PCL degradation OH-terminated, 98-99 Polycaprolactones, 213 Poly(carbo[dimethyl]silane)s, 450, 451 Polycarbonate glycols, 207 Polycarbonate-polysulfone block copolymer, 360 Polycarbonates, 213 chemical structure of, 5 Polycarbosilanes, 450-456 Poly(chlorocarbosilanes), 454 Polycondensations, 57, 100 Poly(l,4-cyclohexylenedimethylene terephthalate) (PCT), 25 Polydimethyl siloxanes, 4 Poly(dioxanone) (PDO), 27 Poly (4,4 -dipheny lpheny lpho sphine oxide) (PAPO), 347 Polydispersity, 57 Polydispersity index, 444 Poly(D-lactic acid) (PDLA), 41 Poly(DL-lactic acid) (PDLLA), 42 Polyester amides, 18 Polyester-based networks, 58-60 Polyester carbonates, 18 Polyester-ether block copolymers, 20 Polyester-ethers, 26... 

Preparation and characteristics of ABA type polycaprolactone-b-polydimethyl-siloxane block copolymers have been recently reported 289). In this study, ring-opening polymerization of e-caprolactone was achieved in melt, using a hydroxybutyl terminated PSX as the initiator and a catalytic amount of stannous octoate. Reactions were completed in two steps as shown in Reaction Scheme XIX. 

Aliphatic polyesters based on monomers other than a-hydroxyalkanoic acids have also been developed and evaluated as drug delivery matrices. These include the polyhydroxybutyrate and polyhydroxy valerate homo- and copolymers developed by Imperial Chemical Industries (ICI) from a fermentation process and the polycaprolactones extensively studied by Pitt and Schindler (14,15). The homopolymers in these series of aliphatic polyesters are hydrophobic and crystalline in structure. Because of these properties, these polyesters normally have long degradation times in vivo of 1-2 years. However, the use of copolymers and in the case of polycaprolactone even polymer blends have led to materials with useful degradation times as a result of changes in the crystallinity and hydrophobicity of these polymers. An even larger family of polymers based upon hydroxyaliphatic acids has recently been prepared by bacteria fermentation processes, and it is anticipated that some of these materials may be evaluated for drug delivery as soon as they become commercially available. 

Figure 6.6 Reactive extrusion block copolymer of poly(ethylene terephthalate) and polycaprolactone...

Abstract. This paper reviews the degradation behavior of aliphatic polyesters of current interest, including polylactide, polycaprolactone, poly(3-hydroxybutyrate) and their copolymers. Special focus is given to degradation products formed in different abiotic and biotic environments. The influence of processing and processing additives on the properties and degradation behavior is also briefly discussed. 

Chemically-Controlled Systems. In these systems, the polymer matrix contains chemically-labile bonds. On exposure to water or enzymes the bonds hydrolyze, erode the three dimensional structure of the polymer and release the incorporated reagent into the surrounding medium. Depending on the polymer used, the erosion products may act as interferences, such as by altering the pH of the solution. Examples of these systems are polyglycolic acid (PGA) and a polyglycolic acid - polylactic acid (PGA/PLA) copolymer. PGA hydrolyzes to hydroxyacetic acid, and PGA/PLA hydrolyzes to lactic acid and hydroxyacetic acid. Other chemically-controlled systems are based on polyorthoesters, polycaprolactones, polyaminoacids, and polyanhydrides. 

As pointed out by Heller (2), polymer erosion can be controlled by the following three types of mechanisms (1) water-soluble polymers insolubilized by hydrolytically unstable cross-links (2) water-insoluble polymers solubilized by hydrolysis, ionization, or protonation of pendant groups (3) hydrophobic polymers solubilized by backbone cleavage to small water soluble molecules. These mechanisms represent extreme cases the actual erosion may occur by a combination of mechanisms. In addition to poly (lactic acid), poly (glycolic acid), and lactic/glycolic acid copolymers, other commonly used bioerodible/biodegradable polymers include polyorthoesters, polycaprolactone, polyaminoacids, polyanhydrides, and half esters of methyl vinyl ether-maleic anhydride copolymers (3). 

Allen, C. Han, J. Yu, Y. Maysinger, D. Eisenberg, A. Polycaprolactone-b-poly(ethylene oxide) copolymer micelles as a delivery vehicle for dihydrotestosterone. J. Controlled Rel. 2000, 63, 275-286. 

Low profile plastics are added to reduce shrinkage during cure. They are normally thermoplastics that include polyvinyl acetates, polymethyl methacrylate, and copolymers with other acrylate, vinyl chloride-vinyl acetate copolymers, polyurethane, polystyrene, polycaprolactone, cellulose acetate butyrate, saturated polyester, and styrene butadiene copolymers. More details about the low profile additive (LPA) mechanism are published in the literature. ... 

The hydrophobic core of nanoparticles is mostly made of solid glassy polymers such as polycaprolactone, polylactide, and their random copolymers. Drags are physically trapped and dispersed in the core. Except for the initial burst release period, the drug release from the solid nanoparticle cores tends to be a slow diffusion-controlled process [126]. Thus, nanoparticles responding to the acidic environments of tumor intercellular fluid or intracellular acidic compartments have been developed for fast drug release. 

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