Polyethylene functionalized

Functional polyethylene waxes provide both the physical properties obtained by the high molecular weight polyethylene wax and the chemical properties of an oxidised product, or one derived from a fatty alcohol or acid. The functional groups improve adhesion to polar substrates, compatibHity with polar materials, and dispersibHity into water. Uses include additives for inks and coatings, pigment dispersions, plastics, cosmetics, toners, and adhesives. 

RAFT polymerization has been used to prepare poly(ethylene oxide)-/ /wA-PS from commercially available hydroxy end-functional polyethylene oxide).4 5 449 Other block copolymers that have been prepared using similar strategies include poly(ethylene-co-butylene)-6/oci-poly(S-eo-MAH), jl poly(ethylene oxide)-block-poly(MMA),440 polyethylene oxide)-Moe -poly(N-vinyl formamide),651 poly(ethylene oxide)-Wot A-poly(NlPAM),651 polyfethylene ox de)-b ock-polyfl,1,2,2-tetrahydroperfluorodecyl acrylate),653 poly(lactic acid)-block-poly(MMA)440 and poly( actic acid)-6focA-poly(NIPAM),4 8-<>54... 

Functionalized polyethylene would be of great industrial importance, and if synthetic methods to control the microstructure of functionalized polymers using transition-metal-based catalysis are developed, it would significantly broaden the utility and range of properties of this class of polymers. Recent progress in the field of late transition metal chemistry, such as Brookliart s use of nickel-based diimine catalysts, has enabled the copolymerization of ethylene with functional a-olefins.29 However, these systems incorporate functionalized olefins randomly and with limited quantity (mol percent) into the polymer backbone. 

If mono-hydroxyl functionalized polyethylene glycol), HO-PEG, is added to Ca(NTMS2)2.THF2, then addition of LA affords the diblock PEG-b-PLA (Mn= 15,500, Mn calc = 15,500, Mw/Mn = 1.03).832 Using a similar strategy the reaction of CaFI2 with telechelic diol HO-(PEG)-OH, followed by polymerization of L-LA results in a triblock structure, PLA-b-PEG-b-PLA of narrow polydispersity (1.02-1.08).835 836 Triblock copolymers of morpholine-2,5-diones with PEO have also been prepared in this manner.837... 

Functionalization, silicone network preparation via, 22 568 Functionalized initiators, 14 255 Functional methacrylates, 16 240-242 Functional monomers methacrylate, 16 241-242 polymer colloid, 20 379-380 Functional perfume products, 18 354 Functional polyethylene waxes, 26 220 Functional properties, of wax, 26 215 Functional unit, in life cycle assessment, 14 809... 

PEG has been converted into a solid support by grafting functionalized polyethylene glycol chains onto polystyrene to form constructs such as TentaGel ... 

Alvarez S, Manolache S, Denes F (2003) Synthesis of polyaniline using horseradish peroxidase immobilized on plasma-functionalized polyethylene surfaces as initiator. J Appl Polym Sci 88(2) 369-379... 

Ni phosphorus-ylide complexes were reported by Ittel and co-workers to be active for the co-polymerization of ethylene and non-vinyl-functionalized monomers, yielding functionalized polyethylenes (PEs). These results demonstrate the high potential of late transition metal complexes for the production of co-polymers from hydrocarbon and polar monomers. 

A very efficient catalytic system has been developed by He and coworkers using, under solvent-free conditions, quaternary ammonium bromide-functionalized polyethylene glycol (0.25 mol% 373 K, 8MPa, 5-20min) [68d]. The catalyst worked well for a variety of l-alkyl-2-aryl-substituted aziridines, and could be easily recovered by centrifugation and reused, without any significant loss of catalytic activity and selectivity. 

Miao C-X, He L-N, Wang J-Q et al (2009) Biomimetic oxidation of alcohols catalyzed by TEMPO-functionalized polyethylene glycol and copper chloride in compressed carbon dioxide. Synlett 20 3291-3294... 

Du Y, Wu Y, Liu A-H et al (2008) Quaternary ammonium bromide functionalized polyethylene glycol a highly efficient and recyclable catalyst for selective synthesis of 5-aryl-2-oxazolidinones from carbon dioxide and aziridines under solvent-free conditions. J Org Chem 73(12) 4709-4712... 

Wang X, Yang H, Feng B et al (2009) Functionalized polyethylene glycol)-stabilized palladium nanoparticles as an efficient catalyst for aerobic oxidation of alcohols in supercritical carbon dioxide/poly(ethylene glycol) biphasic solvent system. Catal Lett 132 34-40... 

Tian J-S, Miao C-X, Wang J-Q et al (2007) Efficient synthesis of dimethyl carbonate from methanol, propylene oxide and C02 catalyzed by recyclable inorganic base/phosphonium halide-functionalized polyethylene glycol. Green Chem 9(6) 566—571... 

End-functionalized polyethylene (PE) [8, 9], polypropylene (PP) [10], and polyisobutylene (PIB) [11] have been transformed to their corresponding macromonomers carrying (meth)acrylate, oxazoline, and methacrylate end groups, 1, 2, and 3, respectively. Polybutadienyl lithium was terminated with chlo-rodimethylsilane, followed by hydrogenation to saturated polyolefin (PHBd) [12]. Hydrosilylation of the end silane with allyl glycidyl ether afforded an epox-... 

A similar procedure was used for the preparation of functionalized polyethylenes such as that including ester groups as the internal function regularly placed in the chain [79] (Scheme 34). Thus, the ester with two terminal alkene bonds was successively submitted to homogeneous ADMET to give the unsaturated polymer. Then, after addition of silica gel, the product was submitted to hydrogenation. A highly crystalline polymer (Tm = 97 °C) [- C02(CH2)i8 - n was produced (Scheme 34). 

In a subsequent investigation by the author [2] bi-functional polyethylene glycol derivatives, (II), were prepared. 

Functionalized Polyethylene via ADMET Model Copolymers of Ethylene and Vinyl Monomers... 

A hybrid between combinatorial synthesis on solid phase and in solution phase is the liquid-phase method characterized by the application of carrier polymers completely soluble in one solvent and insoluble in another solvent, for example functionalized polyethylene glycol [32,33]. 

Furthermore, the group of Deimede [338-340] performed the synthesis of a-dicarboxy end-functionalized PS macromonomers by using ATRP (Scheme 72). Further polycondensation with dihydroxy end functionalized polyethylene oxide) led to alternating branched PS/poly(ethylene oxide) poly(macromonomers) (Scheme 72). These novel amphiphilic compounds afforded the formation of stable micelles, especially in THF or dioxane. 

Table 21.1 Chemical and Physical Properties of Low Molecular Weight Functionalized Polyethylene. ...

Figure 21.1 Chemical structure of functionalized polyethylenes. (From Reference 46 with permission from Wiley Interscience.)...

Table 21.8 Viscoelastic Properties of Epoxy Resin Modified with Functionalized Polyethylene.

The polymer-bound species, a catalyst, a product, or a by-product, can be separated from the reaction mixture. Macroscopic solids and gels can usually be separated from liquids by filtration. Soluble polymers and colloids can be separated from low molecular weight compounds by ultrafiltration. Colloids can be coagulated and filtered. The functionalized polyethylenes described by Bergbreiter in chapter 2 are soluble hot and insoluble cold so that they can be filter. ... 

We have also carried out some unpublished studies on the temperature dependence of hydrophobic recovery of plasma treated PDMS. The activation energy of this thermal restructuring process is 44 kJ/mol. This is more than the activation energy of viscous flow of PDMS (15 kJ/mol) 2 but much less than the only similar measurement of which we are aware for a carboxylic acid functionalized polyethylene surface (210 kJ/mol). ... 

---