E-Caprolactone s

Balas, A., Palka, G., Foks, J., and Janik, H., Properties of cast urethane elastomers prepared from poly( e-caprolactone)s,... 

Yan J, Zhang Y, Xiao Y, Zhang Y, Lang MD (2010) Novel poly(e-caprolactone)s bearing amino groups Synthesis, characterization and biotinylation. React Funct Polym 70 400-407... 

Li H, Riva R, Kricheldorf FIR, Jerome R, Lecomte P (2008) Synthesis of eight and starshaped poly(e-caprolactone)s and their amphiphilic derivatives. Chem Eur J 14 358-368... 

TABLE 1. Molecular Weights and Physical Properties of Crosslinkable Poly(propylene-fumarate)-block-e-caprolactone)s of the Current Invention... 

Recently, our laboratory immobilized CALB on a series of methyl methacrylate resins with identical average pore diameter (250 A) and surface area (500 mVg) but varied particle size (35 to 560-710 pm). CALB adsorbed more rapidly onto smaller beads. Infrared microspectroscopy revealed CALB forms protein loading fronts for resins with particle sizes 560-710 and 120 pm. In contrast, CALB appeared evenly distributed throughout 35 pm resins. Titration with /j-nitrophenyl n-hexylphosphate (MNPHP) showed the fraction of active CALB molecules a orbed onto resins was <50 %. By increasing loading of CALB from 0.9 to 5.7 % (w/w) onto 35 pm methyl methacrylate beads, an increase in the fraction of active CALB molecules from 30 to 43% was observed. Furthermore, by decreasing the immobilization support diameter, a regular increase in e-caprolactone (s-CL) conversion to polyester resulted. Similar trends were observed for condensation polymerizations between 1,8-octanediol and adipic acid. 

Naka3rama, A., Yamano, N., Kawasaki, N., Nakayama, Y. Synthesis and biodegradation of poly(2-pyrrolidone-co-e-caprolactone)s. 

W. Yuan, et al.. Asymmetric penta-armed poly(e-caprolactone)s with short-chain phosphazene core synthesis, characterization, and in vitro degradation, Polym. Int. 54 (9) (2005) 1262-1267. 

Linear poly(L-lactide-co-e-caprolactone)s (PLACLs) were produced by Lu s team [27]. The lactide/lactone ratio was varied between 90/10 and 60/40 which was associated with a large change in the (reduction from 54 to 14°C). For shaping, = T + 1Z°C, whereas for shape fixing, T=T — 15°C were... 

Nagata, M. and Yamamoto, Y. (2009) Synthesis and characterization of pho-tocrosslinked poly(e-caprolactone)s showing shape-memory properties. J. Polym. Sci., Part A Polym. Chem., 47 (9), 2422 -2433. 

T.T. Reddy, A. Kano, A. Maruyama, A. Takahara, Synthesis, characterization and drug release of biocompatible/biodegradable non-toxic poly(urethane urea)s based on poly(E-caprolactone)s and lysine-based diisocyanate, J. Biomater. Sci. Polym. Ed. 21 (2010) 1483-1502. 

Kwak,S. Y. Choi, J. Song, H. J. (2005) Viscoelastic Relaxation and Molecular Mobility of Hyperbranched Poly(E-caprolactone)s in Their Melt State, Chem. Mater. Vol.l7, 1148-1156. 

However, side reactions, such as formation of ether groups or cychzation, were not investigated. Turner et al. [11] reported on the Bu2Sn(OAc)2-catalyzed polycondensation of 5-(2 -hydroxyethoxy) isophthalic acid in bulk at 190 °C. Dimethyl isophthalate served as core monomer in several experiments. Polycondensation promoted by bis(cyclohexyl)carbodiimide (DCC) were reported for the aromatic monomer (f), Formula 11.1 [35]. The mild reaction conditions prevented transesterification, but only low molar mass polyesters (Mw < 17 kDa) were obtained. Similar molar masses were achieved by Voit et al. [36] for carbodiimide promoted polycondensations of the triazene monomers (b) and (c), Formula 11.4. Somewhat more successful were DCC-activated polycondensations of trifunctional oligo(e-caprolactone)s such as (d), Formula 11.4, reported by Hedrick et al. [37, 38]. Syntheses of LC polyesters from monomers (e), Formula 11.4, and isomers were achieved by means of thionyl chloride and pyridine [39]. 

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... 

Goma K and Gogolewski S. Biodegradable polyurethane implants U in vitro degradadon and calcification of materials from poly (e-caprolactone)-polyethylene) diols and various chain extenders. J Biomater Res, 2002, 60, 592-606. 

Koleske, J. V., Blends containing poly( e-caprolactone) and related polymers, in Polymer Blends. Vol. 2 (D. R. Paul and S. Newman, eds.). Academic Press, New York, 1978, pp. 369-389. 

Endo, M., Aida, T., and Inoue, S., Immortal polymerization of e-caprolactone initiated by aluminum porphyrin in the presence of alcohol. Macromolecules, 20, 2982-2988, 1987. 

Rhee, S.H. (2004) Bone-like apatiteforming ability and mechanical properties of poly(e-caprolactone)/silica hybrid as a function of poly (e-caprolactone) content Biomaterials, 25, 1167-1175. 

Rhee, S.H. (2003) Effect of calcium salt content in the poly(e-caprolactone)/ silica nanocomposite on the nudeation and growth behavior of apatite layer. Journal of Biomedical Materials Research, 67A,1131-1138. 

It should be mentioned that when a hexa(hydroxyl) initiator is used for the lipase catalyzed polymerization of s-CL, only one hydroxy function is active [100]. This leaves five remaining OH groups for polymerization of new or another monomers. Comb poly(e-CL)s have also been prepared [101, 102] starting from a copolymer of e-CL and 5-ethylene ketal-e-caprolactone as shown below ... 

J. Singh, S. Pandit, V. W. Bramwell, and H. O. Alpar. Diphtheria toxoid loaded poly-(e-caprolactone) nanoparticles as mucosal vaccine delivery systems. Methods 38 96-105 (2006). 

Materials. PCL and polypropiolactone (PPL) were prepared by ring opening polymerization of e -caprolactone ( ) and S -propiolactone respectively in benzene in a nitrogen atmosphere at 60 C with a di-... 

Ekin A, Webster DC (2006) Library synthesis and characterization of 3-aminopropyl-terminated poly(dimethylsiloxane)s and poly(e-caprolactone)-b-poly(dimethylsiloxane)s. J Polym Sci Part A Polym Chem 44 4880-4894... 

Interestingly, enzymes are chiral catalysts and their potential for enantio-selective polymerization has been investigated [93]. Several examples are reported where a racemic mixture of lactones is polymerized by enzymatic polymerization to afford the corresponding optically active polyester [93]. For instance, lipase CA (Novozym 435) catalyses the ROP of racemic 4-methyl-s-caprolactone and 4-ethyl-s-caprolactone in bulk at 45 °C and 60 °C to afford (S )-eiuiched poly(4-methyl-e-caprolactone) and poly(4-ethyl- -caprolactone) with an enantiomeric purity higher than 95% [153]. 

Bailey WJ, Ni Z, Wu S-R (1982) Synthesis of poly-e-caprolactone via a free radical mechanism. Free radical ring opening polymerization of 2-methylene-l,3-dioxepane. J Polym Sci A Polym Chem 20 3021-3030... 

Duda A, Penczek S (1991) Anionic and pseudoanionic polymerization of e-caprolactone. Makromol Chem, Macromol Symp 42/43 135-143... 

Kricheldorf HR, Eggerstedt S (1998) Macrocycles 2. Living macrocyclic polynnerization of e-caprolactone with 2,2-dibutyl-2-stanna-l,3-dioxepane as initiator. Macromol Chem Phys 199 283-290... 

Kowalski A, Duda A, Penczek S (1998) Kinetics and mechanism of cyclic esters polymerization initiated with tin(II) octoate, 1 Polymerization of e-caprolactone. Macromol Rapid Commun 19 567-572... 

Kowalski A, Libiszowski J, Majerska K, Duda A, Penczek S (2007) Kinetics and mechanism of E-caprolactone and LJ--lactide polymerization coinitiated with zinc octoate or aluminum acetylacetonate The next proofs for the general alkoxide mechanism and synthetic applications. Polymer 48 3952-3960... 

Shueh ML, Wang Y-S, Fluang B-H, Kuo C-Y, Lin C-C (2004) Reactions of 2,2 -methylenebis(4-chloro-6-isopropyl-3-methylphenol) and 2,2 -ethylenebis(4,6-di-tert-butylphenol)with Mg"Bt2 efficient catalysts for the ring-opening polymerization of e-caprolactone and L-lactide. Macromolecules 37 5155-5162... 

Gazeau-Bureau S, Delcroix D, Martin-Vaca B, Bourissou D, Navarro C, Magnet S (2008) Organo-catalyzed ROP of e-caprolactone methanesulfonic acid competes with trifluoro-methanesulfonic acid. Macromolecules 41 3782-3784... 

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