Ethylene, mechanism

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

Dzabiev, T. S., and Karfova, N. D., Oligomerization of ethylene. Mechanism and kinetical aspects, Kinet. Kataliz, 15, 67, 1974 (Russian). 

Studies to determine the nature of intermediate species have been made on a variety of transition metals, and especially on Pt, with emphasis on the Pt(lll) surface. Techniques such as TPD (temperature-programmed desorption), SIMS, NEXAFS (see Table VIII-1) and RAIRS (reflection absorption infrared spectroscopy) have been used, as well as all kinds of isotopic labeling (see Refs. 286 and 289). On Pt(III) the surface is covered with C2H3, ethylidyne, tightly bound to a three-fold hollow site, see Fig. XVIII-25, and Ref. 290. A current mechanism is that of the figure, in which ethylidyne acts as a kind of surface catalyst, allowing surface H atoms to add to a second, perhaps physically adsorbed layer of ethylene this is, in effect, a kind of Eley-Rideal mechanism. 

Finally, it should also be clear that ER reactions do not necessarily yield a gas-phase product. The new molecule may be trapped on the surface. There is evidence for an ER mechanism in the addition of incident Ft atoms to ethylene and benzene on Cii(l 11) [91], and in the abstraction of Ft atoms from cyclohexane by incident D atoms [92], and the direct addition of Ft atoms to CO on Rii(OOl) [93]. 

Many of the features of the generally accepted mechanism for the addition of halogens to alkenes can be introduced by referring to the reaction of ethylene with bromine... 

Neither bromine nor ethylene is a polar molecule but both are polarizable and an induced dipole/mduced dipole force causes them to be mutually attracted to each other This induced dipole/mduced dipole attraction sets the stage for Br2 to act as an electrophile Electrons flow from the tt system of ethylene to Br2 causing the weak bromine-bromine bond to break By analogy to the customary mechanisms for electrophilic addition we might represent this as the formation of a carbocation m a bimolecular elementary step... 

Thus the mechanism for electrophilic addition of Bi2 to ethylene as presented m Figure 6 12 IS characterized by the direct formation of a cyclic bromonium ion as its... 

FIGURE 6 12 Mechanism of electrophilic addition of bromine to ethylene... 

FIGURE 6 17 Mechanism of peroxide initiated free radical polymerization of ethylene... 

The mechanism of free radical polymerization of ethylene is outlined m Figure 6 17 Dissociation of a peroxide initiates the process m step 1 The resulting per oxy radical adds to the carbon-carbon double bond m step 2 giving a new radical which then adds to a second molecule of ethylene m step 3 The carbon-carbon bond forming process m step 3 can be repeated thousands of times to give long carbon chains... 

Figure 10 12 shows the interaction between the HOMO of one ethylene molecule and the LUMO of another In particular notice that two of the carbons that are to become ct bonded to each other m the product experience an antibondmg interaction during the cycloaddition process This raises the activation energy for cycloaddition and leads the reaction to be classified as a symmetry forbidden reaction Reaction were it to occur would take place slowly and by a mechanism m which the two new ct bonds are formed m separate steps rather than by way of a concerted process involving a sm gle transition state... 

Polymerization of styrene is carried out under free radical conditions often with benzoyl peroxide as the initiator Figure 1111 illustrates a step m the growth of a poly styrene chain by a mechanism analogous to that of the polymerization of ethylene (Sec tion 6 21)... 

Figure 14 5 outlines a mechanism for ethylene polymerization m the presence of Cp2ZrCl2 Step 1 describes the purpose of the MAO promoter which is to transfer a methyl group to the metallocene to convert it to its catalytically active form This methyl group will be incorporated into the growing polymer chain—indeed it will be the end from which the rest of the chain grows... 

FIGURE 14 5 Mechanism for the polymerization of ethylene in the presence of a Ziegler-Natta catalyst... 

When applied to the synthesis of ethers the reaction is effective only with primary alcohols Elimination to form alkenes predominates with secondary and tertiary alcohols Diethyl ether is prepared on an industrial scale by heating ethanol with sulfuric acid at 140°C At higher temperatures elimination predominates and ethylene is the major product A mechanism for the formation of diethyl ether is outlined m Figure 15 3 The individual steps of this mechanism are analogous to those seen earlier Nucleophilic attack on a protonated alcohol was encountered m the reaction of primary alcohols with hydrogen halides (Section 4 12) and the nucleophilic properties of alcohols were dis cussed m the context of solvolysis reactions (Section 8 7) Both the first and the last steps are proton transfer reactions between oxygens... 

Most of the polymer s characteristics stem from its molecular stmcture, which like POE, promotes solubiUty in a variety of solvents in addition to water. It exhibits Newtonian rheology and is mechanically stable relative to other thermoplastics. It also forms miscible blends with a variety of other polymers. The water solubiUty and hot meltable characteristics promote adhesion in a number of appHcations. PEOX has been observed to promote adhesion comparable with PVP and PVA on aluminum foil, cellophane, nylon, poly(methyl methacrylate), and poly(ethylene terephthalate), and in composite systems improved tensile strength and Izod impact properties have been noted. 

In poly(ethylene terephthalate) (14—16) and poly(methyl methacrylate) (17—19), the mechanism of action of phosphoms flame retardants is at least partly attributable to a decrease in the amount of combustible volatiles and a corresponding increase in nonvolatile residue (char). In poly(methyl methacrylate), the phosphoms flame retardant appears to cause an initial cross-linking through anhydride linkages (19). 

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