Comonomers ethylene

Keywords Acrylate comonomers, Ethylene, Mechanism, Palladium catalysts, Polar groups, Polymerization catalysis, Random copolymers... 

Active sites present in palladium-based catalysts, which promote the alternating insertion of coordinating comonomers, ethylene to the acyl Pd-C(O) bond and carbon monoxide to the alkyl Pd-CH2 bond, appear to be cationic Pd(II) species with a square planar, formally d° 8-electron structure, [L2(M)Pd(II)—P ]+, accompanied with weakly coordinating counter-anions [478 180,484],... 

The copolymerization between trioxane and suitable comonomers (ethylene oxide, 1,3-dioxolane, diethylene glycol formal, 1,4-butane diol formal in amounts of 2-5% by weight) is performed using cationic initiators. The cationic initiators could be Lewis acids, such as BF3 or its etherate BF3Bu20 which was used, for example by Celanese (the mechanism of this reaction was studied in detail [163,164]) or protic acids such as perchloric acid, perfluoroalkane sulfonic acids and their esters and anhydrides. Heteropoly acids were used and also a series of carbenium, oxocarbenium salts, onium compounds, and metal chelates. To regulate the molecular weight chain-transfer agents, such as methylal and butylal, are added. 

Branching may be produced deliberately by copolymerizing the principal monomer with a suitable comonomer. Ethylene and 1-butene can be copolymerized with a diethylaluminum chloride/iitanium chloride (Section 9.5) and other catalysts to produce a polyethylene with ethyl branches ... 

The incorporation of a-olefins is usually considered to be first order in olefin, as is also true of ethylene. Therefore, it is the ratio of comonomer/ ethylene concentrations in the reactor that determines the degree of branching. The lower reactivity of a-olefins relative to ethylene implies that relatively high concentrations of comonomer are needed to achieve the desired incorporation [32], For example, to obtain only 2-3 mol% of monomer units from 1-hexene in the polymer, ethylene and 1-hexene concentrations in a molar ratio near 1 1 are needed in the reactor. This incorporation efficiency can be critical in determining whether a polymer can be produced commercially. 

The first experiment was carried out with Cr(VI) catalyst, to which 1-hexene was added from an external source in the normal way. This catalyst required a molar comonomer/ethylene ratio of 0.094 in the reactor to achieve an incorporation molar ratio (branches/ethylene) of 0.0093 in the polymer. Dividing one number by the other gives an overall incorporation efficiency of about 10%. 

Ethylene-vinyl acetate copolymers can be thought of as modified high pressure polyethylenes. Because of the free-radical polymerization process they have structural characteristics such as short-chain and long-chain branching in addition to the effects due to the incorporation of the vinyl acetate comonomer. Ethylene and vinyl acetate have a reactivity ratio which is close to 1 and as a result EVA copolymers contain vinyl acetate which is homogeneously distributed among the polymer chains. The major effect of the VA on polymer properties is to reduce... 

Vinyl Bromide. Vinyl bromide [593-60-2] is prepared by the base-promoted dehydrobromination of ethylene dibromide [106-93 ]. It is used as a comonomer in the production of acrylic fibers. 

Copolymerization is effected by suspension or emulsion techniques under such conditions that tetrafluoroethylene, but not ethylene, may homopolymerize. Bulk polymerization is not commercially feasible, because of heat-transfer limitations and explosion hazard of the comonomer mixture. Polymerizations typically take place below 100°C and 5 MPa (50 atm). Initiators include peroxides, redox systems (10), free-radical sources (11), and ionizing radiation (12). 

Most commercial processes involve copolymerization of ethylene with the acid comonomer followed by partial neutralization, using appropriate metal compounds. The copolymerization step is best carried out in a weU-stirred autoclave with continuous feeds of all ingredients and the free-radical initiator, under substantially constant environment conditions (22—24). Owing to the relatively high reactivity of the acid comonomer, it is desirable to provide rapid end-over-end mixing, and the comonomer content of the feed is much lower than that of the copolymer product. Temperatures of 150—280°C and pressures well in excess of 100 MPa (1000 atm) are maintained. Modifications on the basic process described above have been described (25,26). When specific properties such as increased stiffness are required, nonrandom copolymers may be preferred. An additional comonomer, however, may be introduced to decrease crystallinity (10,27). 

Itaconic acid is a specialty monomer that affords performance advantages to certain polymeric coatings (qv) (see Polyesters, unsaturated). Emulsion stabihty, flow properties of the formulated coating, and adhesion to substrates are improved by the acid. Acrylonitrile fibers with low levels of the acid comonomer exhibit improved dye receptivity which allows mote efficient dyeing to deeper shades (see Acrylonitrile polymers Fibers, acrylic) (10,11). Itaconic acid has also been incorporated in PAN precursors of carbon and graphite fibers (qv) and into ethylene ionomers (qv) (12). 

The compositional distribution of ethylene copolymers represents relative contributions of macromolecules with different comonomer contents to a given resin. Compositional distributions of PE resins, however, are measured either by temperature-rising elution fractionation (tref) or, semiquantitatively, by differential scanning calorimetry (dsc). Table 2 shows some correlations between the commercially used PE characterization parameters and the stmctural properties of ethylene polymers used in polymer chemistry. 

Density. The density (crystallinity) of catalyticaHy produced PE is primarily determined by the amount of comonomer ( a-olefin) in ethylene copolymer. This amount is easily controlled by varying the relative amounts of ethylene and the comonomer in a polymerization reactor. In contrast, the density of PE produced in free-radical processes is usually controlled by temperature. 

Although the reaction rate of ethylene and various copolymers differs substantially, the reaction constants can be estabUshed by using an arbitrary value of 1 for ethylene (5). Thus, a value of 0.1 would indicate that the comonomer reacts at 10 times the rate of ethylene. However, the wide range of reaction rates can present problems not only in determining the comonomer content of the final product but also in producing a homogeneous product (4,6). 

Phillips Petroleum Company developed an efficient slurry process used for the production of both HDPE and LLDPE (Eig. 6). The reactor is built as a large folder loop containing long mns of pipe from 0.5 to 1 m ia diameter coimected by short horizontal stretches of pipe. The reactor is filled with a light solvent (usually isobutane) which circulates through the loop at high speed. A mixed stream containing ethylene and comonomers (1-butene,... 

Random insertion of ethylene as comonomer and, in some cases, butene as termonomer, enhances clarity and depresses the polymer melting point and stiffness. Propylene—butene copolymers are also available (47). Consequendy, these polymers are used in apphcations where clarity is essential and as a sealant layer in polypropylene films. The impact resistance of these polymers is sligbdy superior to propylene homopolymers, especially at refrigeration temperatures, but still vastiy inferior to that of heterophasic copolymers. Properties of these polymers are shown in Table 4. 

IFP Process for 1-Butene from Ethylene. 1-Butene is widely used as a comonomer in the production of polyethylene, accounting for over 107,000 t in 1992 and 40% of the total comonomer used. About 60% of the 1-butene produced comes from steam cracking and fluid catalytic cracker effluents (10). This 1-butene is typically produced from by-product raffinate from methyl tert-huty ether production. The recovery of 1-butene from these streams is typically expensive and requires the use of large plants to be economical. Institut Francais du Petrole (IFP) has developed and patented the Alphabutol process which produces 1-butene by selectively dimerizing ethylene. 

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