Radical polymerisation butadiene

First step radical polymerisation of butadiene in the presence of a chain transfer agent to control its molecular mass. 

This technique is extensively used for the free radical polymerisation of vinyl monomers containing water soluble initiators. The monomers like vinyl chloride, butadiene, chloroprene, vinyl acetate, acrylates and methacrylates are polymerised by this technique. 

Although butadiene/styrene copolymers (manufactured by free radical polymerisation processes) are elastomers of great technical importance, rather little... 

One of the issues that concern liquid feedstock cracking operations is a higher rate of fouling. This is not only a consequence of heavier coke forming precursors, but also as a consequence of long lived free radicals which act as agents for the formation of a polymer (often referred to as pop-corn polymer) in the primary fractionator and downstream units. For instance, free radicals based on styrene or indene have sufficiently long half-lives to pass from the pyrolysis section into the primary fractionator. These can concentrate in this unit and produce polymer (free radical polymerisation) when sufficient amounts of suitable olefins are present, in particular styrene itself and di-olefins such as cyclo-pentadiene or butadiene. 

The radical containing an hydroxyethyl group which is formed (9.5), initiates the formation of polymeric chains which, by recombination, give hydroxy-telechelic polymers (reactions 9.6 and 9.7). Based on the principles mentioned various hydroxy-telechelic polymers were obtained by radical polymerisation of styrene [9], acrylonitrile [10], butyl acrylate or butadiene [10-14]. Of course, the oligo-polyols derived from styrene and acrylonitrile are solid and difficult to use in PU, but butyl acrylate and butadiene lead to liquid polymers with terminal hydroxyl groups, which are useful in polyurethane manufacture. 

Synthesis of Polybutadiene Polyols by Radical Polymerisation of Butadiene [2, 3, 5-7, 9-15]... 

The most important oligo-polyol obtained by radical mechanism is hydroxyl terminated poly butadiene. Dienes (butadiene, isoprene), in conditions of radical polymerisation are special monomers because during radical polymerisation, which is a nonstereospecific polymerisation, several types of microstructures are generated in the same chain. Thus, in the particular case of butadiene the following types of microstructures are generated ... 

Thus, the hydroxyl terminated polybutadiene, obtained by the radical polymerisation of butadiene initiated with hydrogen peroxide, has the following general structure [9-10, 15] ... 

The fabrication process of hydroxyl terminated polybutadiene is based on the free radical polymerisation of butadiene, initiated by hydrogen peroxide at 100-150 °C, in the presence of a solvent such as methanol [12], isopropanol [12], or in the presence of tricresyl phosphate [14]. The polymerisation in alcohols is used industrially. 

Iron-arene complexes are known to exhibit extremely high photoactivity as initiators. Quantum efficiencies have been found to be greater than I in the photopolymerisation of dicyanate esters. Phenylglycine derivatives have been found to be excellent co-synergists for the iron-arene complexes when used in conjunction with dyes and amines. Complexes of various types have also been proposed. Maleic anhydride-THF complexes have been used for the photopolymerisation of oligourethane acrylates while metal-ion complexes of spiropyran copolymers undergo reversible polymer precipitation. Azo and polyazo initiators have been used to make butadiene-isoprene block copolymers while charge-transfer complexes of morpholine-chlorine induce the radical polymerisation of methyl methacrylate. The presence of zinc chloride enhances the... 

The earliest rubber to be manufactured synthetically was not poly-isoprene but the copolymer of butadiene and styrene (SBR) by random free radical polymerisation. Modern SBR contains styrene and butadiene units in the ratio 1 3. 

Esterifled phosphonate groups can be added to natural rubber by the action of dialkyl phospho-nates (12.196). Butadiene rubber will undergo free radical polymerisation in the presence of an organic peroxide in a reaction of type (12.197). Cross-linking can be induced by the action of P4S10, or R = allyl in the case of (12.198). 

In addition to polymer stereochemistry, the spectra are sensitive to other types of defects, such as branching, isomerism, head-to-head and tail-to-tail additions, and to chain ends. The sensitivity of the C-NMR spectra to the defects and isomers is illustrated in the spectrum of free-radical polymerised polybutadiene shown in Figure 3.9 [2]. The many resonances are observed because of the statistical incorporation of cis- and 1,4-butadiene, and the random stereochemistry for the addition of 1,2-butadiene. The inset to Figure 3.9 shows a simulation of the olefinic region calculated from a random distribution of cis- and trans-1,4 units and 1,2 units. When quantitative spectra are acquired, the molecular weights can be determined from the ratio of the end groups to main-chain resonances. 

Styrene-Butadiene Copolymers Emulsion Process via Free Radical Polymerisation SBR is a... 

Organic peroxides are used in the polymer industry as thermal sources of free radicals. They are used primarily to initiate the polymerisation and copolymerisation of vinyl and diene monomers, eg, ethylene, vinyl chloride, styrene, acryUc acid and esters, methacrylic acid and esters, vinyl acetate, acrylonitrile, and butadiene (see Initiators). They ate also used to cute or cross-link resins, eg, unsaturated polyester—styrene blends, thermoplastics such as polyethylene, elastomers such as ethylene—propylene copolymers and terpolymers and ethylene—vinyl acetate copolymer, and mbbets such as siUcone mbbet and styrene-butadiene mbbet. 

Oiganometallic usage is shown in the piepaiation of titanium- oi vanadium-containing catalysts foi the polymerisation of styrene or butadiene by the reaction of dimethyl sulfate with the metal chloride (145). Free-radical activity is proposed for the quaternary product from dimethylaruline and dimethyl sulfate and for the product from l,l,4,4-tetramethyl-2-tetra2ene and dimethyl sulfate (146,147). 

Polybutadiene was first prepared in the early years of the 20th century by such methods as sodium-catalysed polymerisation of butadiene. However, the polymers produced by these methods and also by the later free-radical emulsion polymerisation techniques did not possess the properties which made them desirable rubbers. With the development of the Ziegler-Natta catalyst systems in the 1950s, it was possible to produce polymers with a controlled stereo regularity, some of which had useful properties as elastomers. 

The butadiene-acrylonitrile rubbers were first prepared about 1930 about five years after the initial development of free-radical-initiated emulsion polymerisation. Commercial production commenced in Germany in 1937, with the product being known as Buna N. By the late 1980s there were about 350 grades marketed by some 20 producers and by the early 1990s world production was of the order of 250000 tonnes per annum, thus classifying it as a major special purpose rubber. 

The common feature of these materials was that all contained a high proportion of acrylonitrile or methacrylonitrile. The Vistron product, Barex 210, for example was said to be produced by radical graft copolymerisation of 73-77 parts acrylonitrile and 23-27 parts by weight of methyl acrylate in the presence of a 8-10 parts of a butadiene-acrylonitrile rubber (Nitrile rubber). The Du Pont product NR-16 was prepared by graft polymerisation of styrene and acrylonitrile in the presence of styrene-butadiene copolymer. The Monsanto polymer Lopac was a copolymer of 28-34 parts styrene and 66-72 parts of a second monomer variously reported as acrylonitrile and methacrylonitrile. This polymer contained no rubbery component. 

The thermal reactions of l-oxa-l,3-butadienes such as acroleine 2-78 with alkenes such as 2-79 usually need relatively harsh conditions (150°C-250°C) [120]. As a side reaction polymerisation of the a,/l-unsaturated carbonyl compound can take place addition of radical inhibitors such as hydroquinone or 2,6-di-ferf-butyl-4-methylphenol can be helpful in avoiding this unwanted transformation. In the described hetero Diels-Alder reaction the cycloadduct 2-80 was obtained which was then transformed into racemic-/3-santalene 2-81 (Fig. 2-22). 

First study of co-polymerisation by Wagner-Jauregg Early theories of rubber-elasticity (Mark, Meyer, Guth, Kuhn and others) Carothers famous work proves by means of organic synthesis that polymers are giant, stable molecules. He first proves it by the discovery of neoprene (polychloro-butadiene), then by the condensation polymerisation of amino acids and esters. As a consequence the first fully synthetic textile fibre, nylon, is developed. In Carothers group Flory elucidates the mechanisms of radical and condensation polymerisation... 

Dithienothiophenes give cation polymeric radicals capable of further copolymer addition" while polystryene with a narrow polydispersity has been prepared through the use of an end-capped photoactive anthryl group. ° Large differences in radical termination rates have been found to be responsible for the marked variations in molecular weights of polymer from the UV flash polymerisation of 1,3-butadiene. tra 5-l,2-bis(5-Phenyl-2-oxazolyl)ethene has been found to exhibit low laser conversion efficiency due to preferential dimerisation while thermally activated patterns can be formed on the surface of poly(methyl methacrylate) by coating with photodimerisable 9-anthraldehyde. " ... 

Another variant for the synthesis of hydroxy telechelic polybutadiene is based on the anionic living polymerisation of butadiene, using sodium naphthalene as catalyst [16]. Sodium naphthalene generates, by reaction with butadiene, a radical anion (9.8). If two of these radicals are coupled together, they generate a dianion (9.9), which is an ideal bifunctional initiator for the synthesis of perfectly bifunctional polybutadiene by anionic polymerisation. 

Hybrid (or composite) latexes (169) are essentially a combination of the artificial latex and emulsion polymerisation methods (68, 167). A water-insoluble species (such as polymer) may be dissolved in monomer and dispersed in water in the same marmer as the artificial latexes. However, rather than removing the monomeric solvent, it is polymerised in the droplets by the addition of initiator. The monomer-swollen polymer particles capture radicals and polymerise to form a polymeric blend or structured domains. In this maimer, polystyrene particles with styrene-butadiene mbber (SBR) inclusions have been prepared for impact modification applications. 

Pressures during emulsion polymerisation are typically low (near atmospheric pressure). Since the atmospheric oxygen present in the headspace of a reactor is an excellent free radical scavenger, a nitrogen purge or blanket is introduced into the reactor to flush out the oxygen. Otherwise, an induction period (a period in which the polymerisation is inhibited) or a retardation effect (a reduction in the rate of polymerisation) may be observed. Not all emulsion polymerisations are at low pressure. For example, polymerisations of vinyl acetate-ethylene (88), vinyl chloride, and styrene-butadiene mbber are typically run at high pressure. 

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