Polycaprolactones caprolactone

Polycaprolactone. Polycaprolactone is synthesized from epsilon-caprolactone as shown below ... 

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. 

Controlled block copolymerization of olefins with polar monomers was performed with a lanthanide complex by the successive polymerization of hexene (or pentene) and methylmethacrylate (or caprolactone). Polyhexene-block-poly(methyl methacrylate), polyhcxcnc-fo/ock-polycaprolactone, poly-pentene-fc/ock-poly(methyl methacrylate), and polypentene-Wock-polycapro-lactone were synthesized using a lanthanide complex as initiator [140-143]. 

While PHB and PHV are not considered true plastics, another biodegradable polymer polycaprolactone (PCL) is a plastic material because its monomer e-caprolactone is obtained on an industrial scale from petrochemical products (cyclohexanone and peroxyacetic acid). This synthetic plastic with its low melting point is easily extrudable and applications in the packaging area are envisioned. 

Liquefaction of untreated wood can also be achieved at a lower temperature of 150°C and at atmospheric pressure in the presence of a catalyst [12]. Phenolsulfonic acid, sulfuric acid, hydrochloric acid, and phosphoric acid were used as catalysts. In this acid catalyst method, phenols and polyhydric alcohols can also be used for the coexisting organic solvents. Phenol, cresol, bisphenol A and F, and so forth are successfully adoptable as the phenols. Polyethylene glycols, polyether polyols (epoxide additionally reacted polyether polyol, polyethylene terephthalate polyol) have been found to liquify wood resulting in polyol solutions [13]. Liquefaction of wood in the presence of -caprolactone, glycerin, and sulfuric acid has also been accomplished. It was confirmed in this case that liquefaction and polymerization, the latter of which produces polycaprolactone, take place in the reaction system at the same time [14]. Besides the wood material, it has become apparent that trunk and coconut parts of palm, barks, bagasse, coffee bean wastes, and used OA papers can also be liquified [15]. 

A similar approach uses the co-polymerization of ethylene with 5-ethylidene-2-norbornene, followed by hydroboration/oxidation of the unreacted vinyl group. The hydroxylic functions in the co-polymer are then converted into -OAlEt2 groups and used as catalysts for -caprolactone polymerization, thus leading to poly(ethylene-fo-ENB)-graft-polycaprolactone co-polymers.600... 

The divalent samarium complex 159 was studied as an initiator in the polymerization of -caprolactone (Scheme 8) [98]. The catalytic reactions at room temperature within 1 h afforded the corresponding polycaprolactones in high yields (92-95%). A strong dependence of the polymer molecular weights on the concentration of... 

Li WJ et al (2003) Biological response of chondrocytes cultured in three-dimensional nanofibrous poly(epsilon-caprolactone) scaffolds. J Biomed Mater Res 67A(4) 1105-1114 Venugopal J et al (2005) In vitro study of smooth muscle cells on polycaprolactone and collagen nanofibrous matrices. Cell Biol Int 29(10) 861-867... 

Hakkarainen [19,36] Poly(vinyl chloride)/ polycaprolactone-carbonate blend Thermo-oxidation, hydrolysis 6-Hydroxyhexanoic acid, caprolactone PDMS-DVB... 

ZrPA = Zirconium phosphate amorphous, TiPA = Titanium phosphate amorphous, SnPC = Tin phosphate crystaiiine, ZrWP = Zirconium/tungsto. phosphate, MeCN = Acetonitrile, AcOH = Acetic acid, CX = Cyclohexanone, CP = Cyclopentanone, PIN = Pinacolone, AP = Acetophenone, 6-HCA = 6-Hydroxycaproic acid, e-Cap. = e-Caprolactone, Polymer = Polycaprolactone of unknown molecular weight, DVL = S-Valerolactone, t-BA = t-Butylacetate, PhA = Phenyl acetate, PhOH = Phenol,... 

Immobilized CALB has frequently been applied in the literature as a catalyst for polymerization of aliphatic polyesters, polycarbonates, polyurethanes and their copolymers. In the present work on CALB catalyzed polymerization, the ring opening of e-caprolactone to polycaprolactone was selected as the model polymerization reaction (Figure 3.3). This model reaction has been well established in the literature [24-27] as an example of a polymerization reaction that can be successfully catalyzed by immobilized lipases (see also Chapter 4). Polymer synthesis and characterization was performed in four steps (i) polymerization (ii) separation (iii) purification and (iv) characterization. 

Figure 3.3 Ring opening polymerization of e-caprolactone to polycaprolactone (PCL).

M = molecular weight of polycaprolactone polyol n = number of mols of caprolactone reacted 114 = molecular weight of caprolactone x = % conversion ROH = mols of starter... 

Liu L, Wang YS et al (2005) Preparation of chitosan-g-polycaprolactone copolymers through ring-opening polymerization of epsilon-caprolactone onto phthaloyl-protected chitosan. Biopolymers 78 163-170... 

In order to achieve lower gelation doses for saturated linear aliphatic polyesters such as polycaprolactone, certain functional groups including unsaturation can be incorporated. In this regard, and as will be discussed here, e-caprolactone has been copolymerized with a relatively small amount of allyl glycidyl ether. Therefore, the randomly distributed allyl glycidyl ether units(2-6 mole percent) in the synthesized caprolactone-allyl... 

Besides melt intercalation, described above, in situ intercalative polymerization of E-caprolactone (e-CL) has also been used [231] to prepare polycaprolactone (PCL)-based nanocomposites. The in situ intercalative polymerization, or monomer exfoliation, method was pioneered by Toyota Motor Company to create nylon-6/clay nanocomposites. The method involves in-reactor processing of e-CL and MMT, which has been ion-exchanged with the hydrochloride salt of aminolauric acid (12-aminodecanoic acid). Nanocomposite materials from polymers such as polystyrene, polyacrylates or methacrylates, styrene-butadiene rubber, polyester, polyurethane, and epoxy are amenable to the monomer approach. 

Polycaprolactone (PCL) is obtained by ring-opening polymerization of the six-membered lactone, e-caprolactone (Figure 30.4f), which yields a semicrystalline polymer with a melting point of 59°C-64°C and a glass transition temperature of 60°C with great organic solvent solubility. Anionic, cationic, coordination, or radical polymerization routes are all applicable for synthesis. " " " ... 

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