Addition polymers olefin copolymers

The use of TAG as a curing agent continues to grow for polyolefins and olefin copolymer plastics and mbbers. Examples include polyethylene (109), chlorosulfonated polyethylene (110), polypropylene (111), ethylene—vinyl acetate (112), ethylene—propylene copolymer (113), acrylonitrile copolymers (114), and methylstyrene polymers (115). In ethylene—propylene copolymer mbber compositions. TAG has been used for injection molding of fenders (116). Unsaturated elastomers, such as EPDM, cross link with TAG by hydrogen abstraction and addition to double bonds in the presence of peroxyketal catalysts (117) (see Elastol rs, synthetic). 

The monomers used to make an addition polymer need not be identical. When two or more different monomers are polymerized into the same chain, the product is a copolymer. For instance, we routinely copolymerize ethylene with small percentages of other monomers such as a-olefins (e.g., 1-butene and 1-hexene) and vinyl acetate. We call the products of these reactions linear low density polyethylenes and ethylene-vinyl acetate copolymer, respectively. We encounter these copolymers in such diverse applications as cling film, food storage containers, natural gas distribution pipes, and shoe insoles. 

Cyclic olefin copolymers (COC)s are engineering thermoplastics derived from norbornene. An addition polymer of norbornene was originally described in 1955 (1). 

It has been proposed to improve the heat sealability of TPX by the addition of a propylene-a-olefin copolymer. Satisfactory results have been achieved by melt mixing a TPX polymer with an 1-butene polymer and a propylene polymer (23). 

In more recent work on hydrogenation of butadiene polymers and copolymers, the attempt was made to explain the dependence on hydrogen pressure with sole rate control by olefin addition to H2RhClPh2 (X3) and quasi-equilibrium rhodium distribution over the complexes with and without hydrogen [59] instead of kinetic significance of the step Xq + H2 — X3. This gives a rate equation for double-bond disappearance of the form... 

Not only polyethylene can be synthesized, but also many kinds of copolymers and elastomers, new structures of polypropylenes, polymers and copolymers of cyclic olefins. In addition, polymerization can be performed in the presence of fillers and oligomerization to optically active hydrocarbons is possible. For recent reviews and books see [17-20]. 

The addition copolymerization of norbornene-type monomers with a-olefins [21] forms the basis of EPDM (ethylene propylene diene monomer) technology. Incorporation of smaU amounts of DCPD or ethylidene norbornene (ENB) in olefinic vinyl addition polymers provides latent crosslink sites in EPDM elastomers. It is weU known in the hterature that incorporation of higher amounts of rigid, bulky multicychc olefins results in materials with higher TgS [22]. In fact, more recent work has concentrated on increasing the Tg of norbornene-type monomer/a-olefin copolymers [23]. The use of late transition metal catalysts to prepare such copolymers is reviewed in Section 4.3. 

Metallocene catalysis is an alternative to the traditional Ziegler-Natta vanadium-based catalysis for commercial polyolefin production, e.g. the use of metallocene-catalyzed ethylene alpha-olefin copolymers as viscosity index modifiers for lubricating oil compositions [23]. The catalyst is an activated metallocene transition metal, usually Ti, Zr or Hf, attached to one or two cyclopentadienyl rings and typically activated by methylaluminoxane. Metallocene catalysis achieves more stereo-regularity and also enables incorporation of higher alpha-olefins and/or other monomers into the polymer backbone. In addition, the low catalyst concentration does not require a cleanup step to remove ash. 

In addition to the above-mentioned fields of application, functionahzation of blends of olefin polymers and copolymers has been widely employed in the manufacture of thermoplastic dynamic vulcanizates (71,72). 

All vinyl polymers are addition polymers. To differentiate the, the homopolymers have been classified by the substituents attached to one carbon atom of the double bone. If the substituent is hydrogen, alkyl or aryl, the homopolymers are listed under polyolefins. Olefin homopolymers with other substituents are described under polyvinyl compounds, except where the substituent is a nitrile, a carboxylic acid, or a carboxylic acid ester or amide. The monomers in the latter cases being derivatives of acrylic acid, the derived polymers are listed under acrylics. Under olefin copolymers are listed products which are produced by copolymerization of two or more monomers. 

Polymers prepared from alkenes (olefins), regardless of whether they are homopolymers or copolymers, are known as polyolefins and are the most familiar addition polymers. 

After Kaminsky, Brintzinger, and Ewen discovered homogeneous metallocene/ methylaluminoxane (MAO) catalysts for stereospecific a-olefin polymerizatiOTi (for reviews on olefin polymerization, see [13-21]), the first report [22, 23] rai addition cycloolefin polymerization without ROMP appeared. This stimulated a great interest in these polymers and in catalysts for cycloolefin polymerization (Fig. 1). Cycloolefins such as cyclopentene, cyclooctene, and norbomene can be polymerized via addition (Fig. 2). Polycycloolefins by metallocenes are difficult to process due to their high melting points and their low solubility in common organic solvents. However, metallocenes allow the synthesis of cyclic olefin copolymers (COC), especially of cyclopentene and norbomene with ethene or propene, which represent a new class of thermoplastic amorphous materials (Scheme 1) [24, 25]. 

As one very striking example of the capabilities of the high-temperature gradient HPLC system, the separation of random ethyleneA inyl acetate copolymers is presented in Fig. 23. On silica gel as the stationary phase and using decaline-cyclo-hexanone as the eluent, full separation of copolymers of different compositions was achieved. In addition, the homopolymers PE and PVAc were well separated from the copolymers. This was the first time that a chromatographic system was available that separates olefin copolymers irrespective of crystallinity and solubiUty over the entire range of compositions. Namely, the mobile phase components used are solvents for both PE and PVAc. The non-polar solvent, decalin, supports adsorption of PVAc on the silica gel, while the polar solvent, cyclohexanone, enables desorption and elution of the adsorbed polymer sample firom the column [155]. 

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... 

The numerous industrial and consumer products made from olefins include many polymers and copolymers, synthetic rubbers [10, 11], plasticizers, surfactants, lube oil additives, synthetic lubricants, chemicals for oil field and fiber industry appUeations,... 

Metallocene based polyolefins and polyolefin elastomeric compositions (POE) are often noted in supplier product literature to exhibit useful (and commercially viable) properties in blends with other polyolefins. Metallocene based polyethylene has also been noted to have the potential to replace the LLDPE/LDPE blends that are employed in a myriad of film applications [32 ]. PP/metaUocene ethylene-a-olefin copolymer blends for car interior applications have been noted [33 ]. MetaUocene-LLDPE blends with HDPE have been proposed for heavy-duty industrial grade bags as well as food packaging films [34]. Exxon-Mobil product literature notes the utility and ease of blending the metallocene LLDPE Exceed with other polyolefins. PP/POE blends showed similar mechanical properties and lower viscosity than the more conventional PP/EPDM blends [35]. Polyolefin plastomers (POP) imder the tradename Affinity GA were introduced by Dow as a polymer blend additive to improve the flow without loss of... 

EFFECT ON POLYMER AND/OR OTHER ADDITIVES All-purpose liquid detergents have become widely accepted for cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc. A grease release agent, which is an ethoxylated maleic anhydride/a-olefin copolymer, having a comb-like structure with both hydrophobic and hydrophilic chains, is used in the formulation. ... 

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