Polyethylene functionalization

Recently, our group has found that functionalized ethylene oligomers can be used as ligands to prepare recoverable, reusable homogeneous catalysts from both transition metals like rhodium and nickel and from lanthanide salts. In complimentary studies of polyethylene functionalization, we have found that ethylene oligomers of My > 1200 are quantitatively entrapped in polyethylene precipitates when a solution of polyethylene and a functionalized ethylene oligomer is cooled to room temperature or when polyethylene and the functionalized oligomer are co-precipitated by addition of a second solvent such as methanol Suitably... 

I. Novak, A. Popelka, I. Krupa, 1. Chodak, I. Janigova, T. Nedelcev, M. Spirkova, A. Kleinova, High-density polyethylene functionalized by cold plasma and silanes. Vacuum 86,... 

PE-g-AM is a linear polyethylene functionalized with maleic anhydride. Melt index is 2.6 and the MA content is about 1.8%. 

Kim H, Kobayashi S, AbdurRahim MA, Zhang MJ, Khusainova A, Hillmyer MA, Abdala AA, Macosko CW (2011) Graphene/polyethylene nanocomposites effect of polyethylene functionalization and blending methods. Polymer 52 1837-1846... 

Opper, K.L., Fassbender, B., Brunklaus, G. etal. (2009) Polyethylene functionalized with precisely spaced phosphonic acid groups. Macromolecules, 42,4407-4409. 

Figure Cl.5.8. Spectral jumping of a single molecule of terrylene in polyethylene at 1.5 K. The upper trace displays fluorescence excitation spectra of tire same single molecule taken over two different 20 s time intervals, showing tire same molecule absorbing at two distinctly different frequencies. The lower panel plots tire peak frequency in tire fluorescence excitation spectmm as a function of time over a 40 min trajectory. The molecule undergoes discrete jumps among four (briefly five) different resonant frequencies during tliis time period. Arrows represent scans during which tire molecule had jumped entirely outside tire 10 GHz scan window. Adapted from...

Secondly, the ultimate properties of polymers are of continuous interest. Ultimate properties are the properties of ideal, defect free, structures. So far, for polymer crystals the ultimate elastic modulus and the ultimate tensile strength have not been calculated at an appropriate level. In particular, convergence as a function of basis set size has not been demonstrated, and most calculations have been applied to a single isolated chain rather than a three-dimensional polymer crystal. Using the Car-Parrinello method, we have been able to achieve basis set convergence for the elastic modulus of a three-dimensional infinite polyethylene crystal. These results will also be fliscussed. 

The properties that make polyethylene so useful come from its alkane like struc ture Except for the ends of the chain which make up only a tiny portion of the mole cule polyethylene has no functional groups so is almost completely inert to most sub stances with which it comes m contact... 

Figure 1.8 Hindered rotation around a carbon-carbon bond, (a) The definition of (p (from 0 = 0) in terms of the ethane molecule, (b) The potential energy as a function of (p. (c) Here (p is shown (from (p = 0) for a carbon-carbon bond along a polyethylene backbone, (d) The potential energy for case (c) shown as a function of (p. [Panels (b) and (d) reprinted with permission from W. J. Taylor, J.Chem.Phys. 16 257 (1948).]...

Figure 4.8 Fraction of amorphous polyethylene as a function of time for crystallizations conducted at indicated temperatures (a) linear time scale and (b) logarithmic scale. Arrows in (b) indicate shifting curves measured at 126 and 130 to 128°C as described in Example 4.4. [Reprinted with permission from R. H. Doremus, B. W. Roberts, and D. Turnbull (Eds.) Growth and Perfection of Crystals, Wiley, New York, 1958.]...

Materials that typify thermoresponsive behavior are polyethylene—poly (ethylene glycol) copolymers that are used to functionalize the surfaces of polyethylene films (smart surfaces) (20). When the copolymer is immersed in water, the poly(ethylene glycol) functionaUties at the surfaces have solvation behavior similar to poly(ethylene glycol) itself. The abiUty to design a smart surface in these cases is based on the observed behavior of inverse temperature-dependent solubiUty of poly(alkene oxide)s in water. The behavior is used to produce surface-modified polymers that reversibly change their hydrophilicity and solvation with changes in temperatures. Similar behaviors have been observed as a function of changes in pH (21—24). 

The spring ensures a soHd closing action and is usually wound from stainless steel wire. The dip tube conducts the product from the container to the valve. It is usually extmded from polyethylene or polypropylene and has an inside diameter of over 2.54 mm, although it can be provided in capillary sizes having diameters down to 0.25 mm. These small tubes are used to reduce flow rate and may function in place of the Hquid metering orifice in the valve housing. 

A large number of polymeric compounds have been investigated, but most modem propellants utilize prepolymers that ate hydroxy-functional polybutadienes (HTPB), carboxy-functional polybutadienes (CTPB), or a family of polyethylene oxides (PEGs) to form urethanes. Typical cure reactions... 

Carbon Cha.in Backbone Polymers. These polymers may be represented by (4) and considered derivatives of polyethylene, where n is the degree of polymeriza tion and R is (an alkyl group or) a functional group hydrogen (polyethylene), methyl (polypropylene), carboxyl (poly(acryhc acid)), chlorine (poly(vinyl chloride)), phenyl (polystyrene) hydroxyl (poly(vinyl alcohol)), ester (poly(vinyl acetate)), nitrile (polyacrylonitrile), vinyl (polybutadiene), etc. The functional groups and the molecular weight of the polymers, control thek properties which vary in hydrophobicity, solubiUty characteristics, glass-transition temperature, and crystallinity. 

Functional derivatives of polyethylene, particularly poly(vinyl alcohol) and poly(acryLic acid) and derivatives, have received attention because of their water-solubility and disposal iato the aqueous environment. Poly(vinyl alcohol) is used ia a wide variety of appHcations, including textiles, paper, plastic films, etc, and poly(acryLic acid) is widely used ia detergents as a builder, a super-absorbent for diapers and feminine hygiene products, for water treatment, ia thickeners, as pigment dispersant, etc (see Vinyl polymers, vinyl alcohol polymers). 

The materials used in a total joint replacement ate designed to enable the joint to function normally. The artificial components ate generally composed of a metal piece that fits closely into bone tissue. The metals ate varied and include stainless steel or alloys of cobalt, chrome, and titanium. The plastic material used in implants is a polyethylene that is extremely durable and wear-resistant. Also, a bone cement, a methacrylate, is often used to anchor the artificial joint materials into the bone. Cementiess joint replacements have mote tecentiy been developed. In these replacements, the prosthesis and the bone ate made to fit together without the need for bone cement. The implants ate press-fit into the bone. 

The material in use as of the mid-1990s in these components is HDPE, a linear polymer which is tough, resiUent, ductile, wear resistant, and has low friction (see Olefin polymers, polyethylene). Polymers are prone to both creep and fatigue (stress) cracking. Moreover, HDPE has a modulus of elasticity that is only one-tenth that of the bone, thus it increases the level of stress transmitted to the cement, thereby increasing the potential for cement mantle failure. When the acetabular HDPE cup is backed by metal, it stiffens the HDPE cup. This results in function similar to that of natural subchondral bone. Metal backing has become standard on acetabular cups. 

Fig. 14. Shear viscosity, Tj, and extensional viscosity, Tj as a function of deformation rate of a low density polyethylene (LDPE) at 150°C (111). To convert...

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. 

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