Grafted Terpene

To poly(caprolactone) (PCL), in the side chains, rosin esters have been grafted by a combination of a ring-opening polymerization and click chemistry (2). The rosin moieties can be effectively grafted to each repeat unit of the caprolactone. This S5mthesis does not require a sophisticated purification of the raw renewable biomass. 

The bulky hydrophenanthrene group of the rosin increases the glass transition temperature of the modified PCL by greater than lOOX (2). 

Further, the hydrocarbon nature of rosin structures imparts an excellent hydrophobicity to the PCL with a contact angle closely to that of poly(styrene) thus effecting a very low water absorption. The graft copolymers maintain the full degradability and a good biocompatibiUty. 

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Another class of terpene-based polymer bioconjugates includes (co)polymers with pendent terpene moieties. Generally, there are two ways to synthesize these structures (1) graft terpene molecules onto the polymer backbones, and (2) polymerize terpene molecules decorated with polymerizable moieties. This second method is different from the polymerization reactions described in Sect. 2, since... 

Ti/silica catalysts have been prepared by grafting Cp2TiCl2 on hydrophilic amorphous silica with different Ti contents under mild conditions, active for the epoxidation of cyclohexene.1937 Titanium catalysts prepared by grafting Cp2TiCl2 on Si02 are active for the diastereoselective epoxidation of hydroxy-containing unsaturated terpenes.1938... 

Maleic anhydride grafting (cont.) poly(styrene-co-divinylbenzene), 694 poly(styrene-co-isobutylene), 675, 689 poly(styrene-co-nfialeic anhydride), 676, 679 poly(vinyl acetate), 676, 694 poly(vinyl acetate-co-vinyl fluoride), 678 poly(vinyl alkyl ethers), 675, 679, 692, 701 poly(vinyl chloride), 683, 692, 693, 695, 702 poly(vinylidene chloride), 691 poly(vinyl toluene-co-butadiene), 689 radical—initiated, 459-462, 464-466, 471, 475, 476 radiation—initiated, 459, 461, 466, 471, 474 redox-initiated, 476 rubber, 678, 686, 687, 691, 694 to saturated polymers, 459-466, 475, 476 solvents used 460-463, 465, 466, 469, 474-476 styrene block copolymers, 679 tall oil pitch, 678, 697 terpene polymers, 679, 700 thermally-initiated, 462, 464-467, 469, 476 to unsaturated polymers, 459, 466-474 vapor-phase techniques, 464, 474, 475 to wool fibers, 476 Maleic anhydride monomer acceptor for complex formation, 207-210 acetal copolymerization, 316 acetone CTC thermodynamic constants, 211 acetone photo-adduct pyrolysis, 195, 196 acetylacetone reaction, 235 acetylenic photochemical reactions, 193-196 acrylamide eutectic mixtures, 285 acylation of aromatic acids, 97 acylation of aromatics, 91, 92 acylation of fused aromatics, 92, 95, 97, 98 acylation of olefins, 99 acylation of phenols, 94-96 acylic diene Diels-Alder reactions, 104-111, 139 addition polymer condensations, 503-505 adduct with 2-cyclohexylimino-cyclopentanedi-thiocarboxylic acid, 51 adducts for epoxy resins curing, 507-510 adduct with 2-iminocyclopentanedithiocarboxylic acid, 51... 

Hydrosilylation has been used to attach Choi or menthol moieties to polysiloxanes [162-168]. In most cases, double bonds are introduced to the terpenes at the OH position with a spacer (Fig. 7), and then the modified monomers are grafted onto polysiloxanes with Si-H moieties, i.e., polymethylhydrosiloxane. Hexachloroplatinate hydrate has been used as catalyst with usually a little excess of the olefin. The degree of hydrosilylation varies from ca. 50 to 100%, depending on monomers and their combinations. Thermal, optical, and mechanical properties, with emphasis on the LC phase transition, of the terpene-modified polysiloxanes have been studied and modulated with different alkyl spacers, comonomers... 

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