Non-hydrocarbon monomers

Copolymerization of ethylene with non-hydrocarbon monomers such as vinyl acetate, methyl acrylate and ajS-dicarboxylic acids, the latter providing an opportunity for ionic cross-linking via metal cations. 

As already mentioned in previous sections ethylene may also be copolymerised with several non-hydrocarbon polymers. Some of these copolymers are elastomeric and they also have a measure of oil resistance. Two monomers used commercially are vinyl acetate and, the structurally very similar, methyl acrylate ... 

Coordination polymerisation via re complexes comprises polymerisation and copolymerisation processes with transition metal-based catalysts of unsaturated hydrocarbon monomers such as olefins [11-19], vinylaromatic monomers such as styrene [13, 20, 21], conjugated dienes [22-29], cycloolefins [30-39] and alkynes [39-45]. The coordination polymerisation of olefins concerns mostly ethylene, propylene and higher a-olefins [46], although polymerisation of cumulated diolefins (allenes) [47, 48], isomerisation 2, co-polymerisation of a-olefins [49], isomerisation 1,2-polymerisation of /i-olcfins [50, 51] and cyclopolymerisation of non-conjugated a, eo-diolefins [52, 53] are also included among coordination polymerisations involving re complex formation. 

Step growth reactions involving the homo- and heteropolycondensation of various bifunctional unsaturated monomers in the presence of transition metal-based coordination catalysts have appeared to be a very useful synthetic tool for the preparation of low and high molecular weight polymers with an unsaturation in the polymer backbone. These reactions lead to unsaturated hydrocarbon and non-hydrocarbon polymers where polymeric chains are formed by carbon-carbon and carbon-heteroatom coupling respectively. 

Polymerisation of Non-hydrocarbon (Heterocyclic and Heterounsatu rated) Monomers... 

Important copolymerizations with Ziegler-Natta catalysts are between hydrocarbon monomers. An example is the reaction of ethylene, propylene, and a non-conjugated diene, such as 5-ethylidene-2-norbornene, to produce the so-called EPDM (ethylene-propylene-diene monomer) elastomers. These products have... 

It follows from this discussion that all solvents and monomers used must be carefully purified. Hydrocarbons should be stirred over sulphuric acid for many days and ethers refluxed over sodium—potassium alloy or sodium fluorenone before fractionation. Traces of unsaturated materials in aliphatic hydrocarbons can be removed by silica gel. After fractionation, a preliminary drying over calcium hydride can be followed by storage over sodium—potassium alloy for ethers, or a treatment with butyllithium or similar non-volatile reactive organometallic reagent for hydrocarbons. Monomers cannot be treated quite so drastically, but fractionation followed by a pre-polymerization in vacuum over butyl-... 

Although Saran is a generic name for VDC copolymers in the United States, it is a Dow trademark in most foreign countries. Other trade names include Daran (Hampshire Chemical Corporation) and Serfene (Morton Chemical) in the United States, and Haloflex (Zeneca Resins), Diofan (BASE), Ixan (Solvay SA), and Polyidene (Scott-Bader) in Europe. The monomer is of particular economic interest because it is only 27 wt % hydrocarbon. In addition, B. E. Goodrich Chemicals (GEON) supply non-barrier VDC copolymers. 

The reaction is considerably modified if the so-called emulsion polymerisation technique is used. In this process the reaction mixture contains about 5% soap and a water-soluble initiator system. The monomer, water, initiator, soap and other ingredients are stirred in the reaction vessel. The monomer forms into droplets which are emulsified by some of the soap molecules. Excess soap aggregates into micelles, of about 100 molecules, in which the polar ends of the soap molecules are turned outwards towards the water whilst the non-polar hydrocarbon ends are turned inwards (Figure 2.17). 

In addition to the species Pn+ and Pn+ M, one must consider the complexes formed by the carbenium ions with other n- or n-donors in the system, in particular the polymers formed from monomers containing aromatic groups or hetero-atoms. This means that the polymers formed from non-aromatic hydrocarbons, e.g., isobutene, form a distinct class of noncomplexing polymers we will call these the Class A polymers. It is likely that the internal double-bonds in, for example, poly-(cyclopentadiene) are such poor complexors for steric reasons, that polymers containing them can be placed into the same class. 

Using a recent equation of state of the van der Waals type developed to describe non-polar components, a model is presented which considers water as a mixture of monomers and a limited number of polymers formed by association. The parameters of the model are determined so as to describe the pure-component properties (vapour pressure, saturated volumes of both phases) of water and the phase equilibria (vapour-liquid and/or liquid-liquid) for binary systems with water including selected hydrocarbons and inorganic gases. The results obtained are satisfactory for a considerable variety of different types of system over a wide range of pressure and temperature. 

In many cases both Kolbe and non-Kolbe products are isolated from a reaction. Carboxylic acids with an a-alkyl substituent show a pronounced dual behaviour. In these cases, an increase in the acid concentration improves the yield of the Kolbe product. An example of the effect of increased substrate concentration is given in Kolbe s classical paper [47] where 2-methylbutyric acid in high concentration affords mostly a dimethylbexane whereas more recent workers [64], using more dilute solutions, obtained both this hydrocarbon and butan-2-ol. Some quantitative data is available (Table 9.2) for the products from oxidation of cyclohexanecar-boxylic acids to show the extent of Kolbe versus non-Kolbe reactions. The range of products is here increased through hydrogen atom abstraction by radical intermediates in the Kolbe reaction, which leads to some of the monomer hydrocarbon... 

The same type of addition—as shown by X-ray analysis—occurs in the cationic polymerization of alkenyl ethers R—CH=CH—OR and of 8-chlorovinyl ethers (395). However, NMR analysis showed the presence of some configurational disorder (396). The stereochemistry of acrylate polymerization, determined by the use of deuterated monomers, was found to be strongly dependent on the reaction environment and, in particular, on the solvation of the growing-chain-catalyst system at both the a and jS carbon atoms (390, 397-399). Non-solvated contact ion pairs such as those existing in the presence of lithium catalysts in toluene at low temperature, are responsible for the formation of threo isotactic sequences from cis monomers and, therefore, involve a trans addition in contrast, solvent separated ion pairs (fluorenyllithium in THF) give rise to a predominantly syndiotactic polymer. Finally, in mixed ether-hydrocarbon solvents where there are probably peripherally solvated ion pairs, a predominantly isotactic polymer with nonconstant stereochemistry in the jS position is obtained. It seems evident fiom this complexity of situations that the micro-tacticity of anionic poly(methyl methacrylate) cannot be interpreted by a simple Bernoulli distribution, as has already been discussed in Sect. III-A. 

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