Polymerization of 1,3-Butadiene and Isoprene

Si02-supported neodymium-based catalyst mixtures Nd(naph)3/Al2Et3Cl3/ A1( Bu)3 (54) and Al( Bu)2H (DIBAH), instead of Al( Bu)3, were also tested as initiators for the gas-phase polymerization of 1,3-butadiene by varying the polymerization temperature, nature and feed of co-catalyst and polymerization time (Table 12.8). High ds-1,4-contents (97.8-98.9%) and activities between 400 and 2300 kg-PBD molNd h bar were observed, but the polymers displayed broad molecular weight distributions of 2 M /M 8 [158-160]. 

Supported precatalyst Activator (ratio) Time (h) Activity Selectivity (%) 10 M PDI (polydispersity index) Reference 

Supported precatalyst Activator Time (h) Activity Selectivity 10 M PDI Reference 

TIBA = tris-iso-butylaluminium DIBAH = di-iso-butylaluminium hydride BEM = n-butylethylmagnesium. xs = excess (3mmol L ). 

Measured by infrared spectroscopy according to the method of Silas et al. [182]. 

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Ionic Polymerization. Ionic polymerizations, especially cationic polymerizations, are not as well understood as radical polymerizations because of experimental difficulties involved in their study. The nature of the reaction media is not always clear since heterogeneous initiators are often involved. Further, it is much more difficult to obtain reproducible data because ionic polymerizations proceed at very fast rates and are highly sensitive to small concentrations of impurities and adventitious materials. Butyl rubber, a polymer of isobutene and isoprene, is produced commercially by cationic polymerization. Anionic polymerization is used for various polymerizations of 1,3-butadiene and isoprene. 

Anionic polymerization can be initiated by a variety of anionic sources such as metal alkoxides, aryls, and alkyls. Alkyllithium initiators are among the most useful, being employed commercially in the polymerization of 1,3-butadiene and isoprene, due to their solubility in hydrocarbon solvents. Initiation involves addition of alkyl anion to monomer... 

Alkyllithium compounds are probably the most useful of these initiators, employed com-merically in the polymerizations of 1,3-butadiene and isoprene. Initiation proceeds by addition of the metal alkyl to monomer... 

The first results of anionic polymerization (the polymerization of 1,3-butadiene and isoprene induced by sodium and potassium) appeared in the literature in the early twentieth century.168,169 It was not until the pioneering work of Ziegler170 and Szwarc,171 however, that the real nature of the reaction was understood. Styrene derivatives and conjugated dienes are the most suitable unsaturated hydrocarbons for anionic polymerization. They are sufficiently electrophilic toward carbanionic centers and able to form stable carbanions on initiation. Simple alkenes (ethylene, propylene) do not undergo anionic polymerization and form only oligomers. Initiation is achieved by nucleophilic addition of organometallic compounds or via electron transfer reactions. Hydrocarbons (cylohexane, benzene) and ethers (diethyl ether, THF) are usually applied as the solvent in anionic polymerizations. 

Lithium and alkyllithiums in aliphatic hydrocarbon solvents are also used to initiate anionic polymerization of 1,3-butadiene and isoprene.120,183-187 As 1,3-butadiene has conjugated double bonds, homopolymerization of this compound can lead to several polymer structures. 1,4 Addition can produce cis-1,4- or tram-1,4-polybutadiene (19, 20). 1,2 Addition results in a polymer backbone with vinyl groups attached to chiral carbon atoms (21). All three spatial arrangements (isotactic, syndiotactic, atactic) discussed for polypropylene (see Section 13.2.4) are possible when polymerization to 1,2-polybutadiene takes place. Besides producing these structures, isoprene can react via 3,4 addition (22) to yield polymers with the three possible tacticites ... 

The living anionic polymerization of 1,3-butadiene and isoprene is industrially important for the production of various synthetic elastomers, thermoplastic elastomers, and styrene-butadiene rubbers (SBRs). In addition, numerous alkyl- and aryl-substituted 1,3-diene monomers have been subjected to anionic polymerization to develop new elastomers. Unfortunately, the anionic polymerization of functional... 

The stability of polystyryl carbanions is greatly decreased in polar solvents such as ethers. In addition to hydride elimination, termination in ether solvents proceeds by nucleophilic displacement at the C—O bond of the ether. The decomposition rate of polystyryllithium in THF at 20°C is a few percent per minute, but stability is significantly enhanced by using temperatures below 0°C [Quirk, 2002], Keep in mind that the stability of polymeric carbanions in the presence of monomers is usually sufficient to synthesize block copolymers because propagation rates are high. The living polymers of 1,3-butadiene and isoprene decay faster than do polystyryl carbanions. 

Fe compounds have received much less significant attention than Ni or Co compounds as the diene polymerization catalyst. FeEt2(bpy)2 catalyzes cyclodimerization of 1,3-butadiene [79] and polymerization of vinyl monomers such as acyclic ester [80]. Recently, FeEt2(bpy)2/MAO was found to show high catalytic activity toward 1,2-polymerization of 1,3-butadiene and 3,4-polymerization of isoprene at -40 to +25 °C (Eq. 14) [81]. The crystalline polybutadiene prepared below 0 °C is composed of... 

Conjugated dienes are among the most significant building blocks both in laboratories and in the chemical industry [1], Especially, 1,3-butadiene and isoprene are key feedstocks for the manufacture of polymers and fine chemicals. Since the discovery of the Ziegler-Natta catalyst for the polymerizations of ethylene and propylene, the powerful features of transition metal catalysis has been widely recognized, and studies in this field have been pursued very actively [2-7]. 

The anionic polymerization of 1,3-dienes yields different polymer structures depending on whether the propagating center is free or coordinated to a counterion [Morton, 1983 Quirk, 2002 Senyek, 1987 Tate and Bethea, 1985 Van Beylen et al., 1988 Young et al., 1984] Table 8-9 shows typical data for 1,3-butadiene and isoprene polymerizations. Polymerization of 1,3-butadiene in polar solvents, proceeding via the free anion and/or solvent-separated ion pair, favors 1,2-polymerization over 1,4-polymerization. The anionic center at carbon 2 is not extensively delocalized onto carbon 4 since the double bond is not a strong electron acceptor. The same trend is seen for isoprene, except that 3,4-polymerization occurs instead of 1,2-polymerization. The 3,4-double bond is sterically more accessible and has a lower electron density relative to the 1,2-double bond. Polymerization in nonpolar solvents takes place with an increased tendency toward 1,4-polymerization. The effect is most pronounced with... 

A thermoplastic elastomer similar to the above structures was made by utilizing conjugated 1,3 diolefins that can be polymerized anionically. The work of Halasa and co-workers(2 ) illustrate the point. These workers polymerized 1,3-butadiene and isoprene to produce a diblock copolymer of poly(butadiene)-poly(isoprene)... 

We have not discussed the polymerization of dienes very much so far. Part of the reason for this stems from the added complexity caused by the second double bond. Depending upon the polymerization conditions chosen, polymers with mixtures of repeat units can form. If only one of the double bonds participates in the polymerization, this is referred to as 1,2-polymerization. If both double bonds participate, the polymerization is called 1,4. Common monomers that fall in this category include 1,3-butadiene and isoprene ... 

This section summarizes the copolymerization of conjugated dienes with other monomers catalyzed by transition metal complexes. Some of the reactions here were also mentioned in the previous section. The catalyst CpTiCl3/MAO is active not only for the polymerization of 1,3-butadiene, isoprene, 1,3-pentadiene, and styrene but also for the copolymerization of these individual monomers [82]. 

Conjugated Dienes and Other Monomers. Alkyllithiums such as n-butyllithium—and even the growing polyethylene carbon-lithium bond complexed with chelating diamines such as TMEDA—are effective initiators for the polymerization of conjugated dienes such as 1,3-butadiene and isoprene. A polybutadiene of high 1,2-content can be produced from butadiene in hydrocarbon solvents using these N-chelated organolithium catalysts. 

Let us briefly summarize the state of the art in the polymerization of other monomer groups in the presence of polymer-boxmd metal complexes. Considerable progress has been achieved in polymerization of dienes, namely, butadiene and isoprene, catalyzed by macromolecnlar complexes based on rare earth halides [114], Co-oligomerization of 1,3-butadiene and CO2 with immobilized palladium complexes (phosphynated PS as macromolecnlar ligand) [115] and polymerization of acetylene monomers with immobilized complexes of Mo(V), W(VI), and Pd(II) have been developed though they have not been investigated intensively. 

The preparation of syndiotactic polypropylene is carried out in the 195-230 K range, while the preparation of isotactic polypropylene takes place at 295-365 K if the catalyst is suspended and at 380-425 K in the presence of a homogeneous catalyst. These conditions are very mild compared to those for radical polymerization which is carried out at 295-470 K and 100-300 MPa. Ziegler-Natta catalysts are also utilized in polymerization of 1,3 dienes and cycloalkenes, for example, butadiene, isoprene, cyclobutene, cyclopentene, and dicyclopentadiene. Conjugated dienes may form the... 

The polymerization of 1,3-dienes (e.g., 1,3-butadiene and isoprene) with Ziegler-Natta catalysts began in 1954, soon after the first results obtained in a-olefin polymerization since then many transition metal and lanthanide catalysts have been examined and several stereoregular diene polymers have been obtained [30, 31], 1,3-Dienes can generate several types of polymers having different stmctures trans-1,4 cis-1,4 1,2 and, in the case of asymmetric monomers (e.g., isoprene), 3,4. Stereoregular 1,2- or 3,4-polydienes may also exhibit iso- or syndiotacticity. (Figure 11.1). 

It may also be possible to synthesize various polymers of functional 1,3-butadienes and their block copolymers with 1,3-butadiene and isoprene simply by employing the successful protective strategy developed in the living anionic polymerization of functional styrene monomers, although this has not been realized at the moment. The resulting poly(functional l,3-butadiene)s are important materials as they can provide additional functionalities to the present synthetic elastomers. 

The final type of isomerism we take up in this section involves various possible structures which result from the polymerization of 1,3-dienes. Three important monomers of this type are 1,3-butadiene, 1,3-isoprene, and 1,3-chloroprene, structures [X]-[XII], respectively ... 

The use of alkaU metals for anionic polymerization of diene monomers is primarily of historical interest. A patent disclosure issued in 1911 (16) detailed the use of metallic sodium to polymerize isoprene and other dienes. Independentiy and simultaneously, the use of sodium metal to polymerize butadiene, isoprene, and 2,3-dimethyl-l,3-butadiene was described (17). Interest in alkaU metal-initiated polymerization of 1,3-dienes culminated in the discovery (18) at Firestone Tire and Rubber Co. that polymerization of neat isoprene with lithium dispersion produced high i7j -l,4-polyisoprene, similar in stmcture and properties to Hevea natural mbber (see ELASTOLffiRS,SYNTHETic-POLYisoPRENE Rubber, natural). 

In the free radical polymerization of 1,3-dienes, 1,4 addition dominates 1,2 addition. The proportion of 1,2 (and 3,4 )units decreases in passing from butadiene to its methyl and chlorine substitution products isoprene, 2,3-dimethylbutadiene and chloroprene. The trans configuration of the 1,4 unit from butadiene is formed preferentially, the proportion of trans increasing rapidly with lowering of the polymerization temperature. 

Another large use of normal butenes in the petrochemical industry is in the production of 1,3-butadiene (CH2 = CH = CH = CH2). In the process, a mixture of n-butenes, air, and steam is passed over a catalyst at a temperature of 500°C to 600°C. Butadiene is used extensively to produce synthetic rubbers (see Isoprene) in polymerization reactions. The greatest use of butadiene is for styrene-butadiene rubber, which contains about a 3 1 ratio of butadiene to styrene. Butadiene is also used as a chemical intermediate to produce other synthetic organics such as chloroprene, for adhesives, resins, and a variety of polymers. 

When a mixture of styrene and 1,3-butadiene (or isoprene) undergoes lithium-initiated anionic polymerization in hydrocarbon solution, the diene polymerizes first. It is unexpected, since styrene when polymerized alone, is more reactive than, for example, 1,3-butadiene. The explanation is based on the differences of the rates of the four possible propagation reactions the rate of the reaction of the styryl chain end with butadiene (crossover rate) is much faster than the those of the other three reactions484,485 (styryl with styrene, butadienyl with butadiene or styrene). This means that the styryl chain end reacts preferentially with butadiene. 

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