Isobutyl vinyl ether polymerization

In the cationic-initiated polymerization of alkyl vinyl ethers it is possible to exercise fairly rigorous control of the configuration of the product by appropriate choice of the monomer and conditions. For example, isobutyl vinyl ether polymerized by BF3 etherate at 195 K in toluene can give isotactic polymer [15]. In this low polarity solvent, close association of the gegen ion with the cationic propagating center helps to block one mode of entry of fresh monomer (Eq. 22.45). 

The observation in 1949 (4) that isobutyl vinyl ether (IBVE) can be polymerized with stereoregularity ushered in the stereochemical study of polymers, eventually leading to the development of stereoregular polypropylene. In fact, vinyl ethers were key monomers in the early polymer Hterature. Eor example, ethyl vinyl ether (EVE) was first polymerized in the presence of iodine in 1878 and the overall polymerization was systematically studied during the 1920s (5). There has been much academic interest in living cationic polymerization of vinyl ethers and in the unusual compatibiUty of poly(MVE) with polystyrene. 

At -50°C Mn s remained unchanged (Mn % 3 x 10, [p-DCC]Q = 0.50 mM) with increasing Wjgyg and Mw/Mn % 2.0. The polymerization is no longer quasiliving but follows a conventional chain-transfer-dominated course. Nonpolar media are evidently unsuitable for quasiliving polymerization of isobutyl vinyl ethers. 

A number of publications purport to give values for the absolute propagation rate constant kp for the polymerization of isobutyl vinyl ether (Table 2). The values of Okamura et ah, are derived by techniques and arguments which are of doubtful validity [54a] and they seem much too small. Eley s value, derived from an analysis of non-stationary kinetics, is four orders of magnitude smaller than the kp deduced from studies of radiation... 

Table 5-1 shows the various kinetic parameters, including k+ and kp, in the polymerization of styrene initiated by triflic acid in 1,2-dichloroethane at 20°C. Data for the polymerization of isobutyl vinyl ether initiated by trityl hexachloroantimonate in methylene chloride at 0°C are shown in Table 5-2. Table 5-3 shows values for several polymerizations initiated... 

TABLE 5-2 Kinetic Parameters in (t)3C+SbCl6 Polymerization of Isobutyl Vinyl Ether in CH2CI2 at 0°C ... 

Stronger Lewis acids such as SnCLi, TiCLt, and CH3AICI2 yield fast but uncontrolled polymerization with broad PDI. LCP of vinyl ethers can be achieved if the other components and reaction parameters are appropriately adjusted by various combinations of lower reaction temperature, added nucleophile, added common salt, and solvent prolarity. For example, polymerization of isobutyl vinyl ether using HC1 as the initiator (or one can use the preformed adduct of monomer and HC1) with SnCLt or TiCLj in CH2CI2 is non-LCP... 

Fig. 5-2 Dependence of M and MwfMn on conversion for the polymerization of isobutyl vinyl ether by HI/I2 in CH2C12 at - 15°C. [M] = 0.38 M at beginning of each batch [HI] = 0.01 M [I2] = 0.02 M (A), 0.001 M ( ), 0.005 M (o). After Sawamoto and Higashimura [1986] (by permission of Huthig and Wepf Verlag, Basel and Wiley-VCH, Weinheim).

The first reported instance of stereoselective polymerization was probably the cationic polymerization of isobutyl vinyl ether in 1947 [Schildknecht et al., 1947]. A semicrystalline polymer was obtained when the reaction was carried out at —80 to —60°C using boron tri-fluoride etherate as the initiator with propane as the solvent. The full significance of the polymerization was not realized at the time as the crystallinity was attributed to a syndiotactic structure. X-Ray diffraction in 1956 indicated that the polymer was isotactic [Natta et al., 1956a,b], (NMR would have easily detected the isotactic structure, but NMR was not a routine tool in 1947.)... 

Cationic Polymerization of Isobutyl Vinyl Ether with BFj-Etherate at Low Temperatures... 

Radical polymerization of AN is monotonously retarded by the addition of isobutyl vinyl ether (IBVE) when initiated by azobisiso-butyronitrile in the dark. The rate of initiation would be kept constant at varying concentrations of IBVE and the change of rate of polymerization must be caused by a reduced rate of propagation or an enhanced... 

Apart from some experiments with methyl and /i-chloroethyl vinyl ethers the initiator concentrations employed were such that the initiating cations, and presumably the propagating species, were essentially dissociated from the corresponding counterion. Once again therefore this data is a measure of the reactivity of the free polymeric cations derived from the various monomers. Isobutyl vinyl ether is the monomer most widely studied, and as would be anticipated for free cationic reactivities, the data varies little with the counterion employed (SbClg or BF4), or indeed with the carbocation used as initiator (C7H7 or Ph3C+) under similar experimental conditions. 

The first synthesis of star polymers with a microgel core was reported by Sa-wamoto et al. for poly(isobutyl vinyl ether) (poly(IBVE)) [3,4]. In the first step, living cationic polymerization of IBVE was carried out with the HI/ZnI2 initiating system in toluene at -40 °C. Subsequent coupling of the living ends was performed with the various divinyl ethers 1-4. 

Tanabe el al. studied in detail the catalytic action and properties of metal sulfates most of the sulfates showed the maximum acidity and activity by calcination at temperatures below 500°C, with respect to the surface acidity and the acid-catalyzed reaction (118, 119). Other acid-catalyzed reactions were studied with the FeS04 catalyst together with measurement of the surface acidity of the catalyst the substance calcined at 700°C showed the maximum acidity at Ho s 1.5 and proved to be the most active for the polymerization of isobutyl vinyl ether, the isomerization of d-limonene oxide, and the dehydration of 2-propanol (120-122). It is of interest that the catalyst calcined at a slightly higher temperature, 750°C, was completely inactive and zero in acidity in spite of the remarkable activity and acidity when heat treated at 700°C. 

Similarly, zwitterionic tetramethylenes as initiators of anionic polymerization were also observed. For example, methyl a-cyanoacrylate polymerizes via an anionic mechanism in the presence of n-butyl vinyl ether [90]. A Diels-Alder adduct is also formed. In another example, the reaction of isobutyl vinyl ether and nitroethylene leads to an unstable adduct [91], which is capable of initiating the anionic polymerization of excess nitroethylene, and also the cationic polymerization of added VCZ. 

The evidence in the case of styrene, where both modes of radiation-induced polymerization can be conveniently studied, is quite convincing that reduction of the concentration of water changes the predominating mode of propagation from purely free radical to essentially ionic. Evidence for an ionic propagation initiated by radiation has also been obtained in pure a-methylstyrene (3, 24), isobutylene (12, 32), cyclopenta-diene (5), / -pinene (2), 1,2-cyclohexene oxide (II), isobutyl vinyl ether (6), and nitroethylene (38), although the radical process in these monomers is extremely difficult, if not impossible, to study. 

Ueno et al. (35) have reported similar behavior for styrene. In their work, at 30°C. and a dose rate of 2.42 X 1014 e.v. cc. 1 sec. 1, there was an approximate inverse linear relationship between the rate of polymerization of styrene and the concentration of triethylamine, between 10 6 and 10 4M amine. Ammonia and amines have also been observed to inhibit the polymerization of isobutyl vinyl ether (6) and a-methvl-styrene (17). 

Use of triphenylmethyl and cycloheptatrienyl cations as initiators for cationic polymerization provides a convenient method for estimating the absolute reactivity of free ions and ion pairs as propagating intermediates. Mechanisms for the polymerization of vinyl alkyl ethers, N-vinylcarbazole, and tetrahydrofuran, initiated by these reagents, are discussed in detail. Free ions are shown to be much more reactive than ion pairs in most cases, but for hydride abstraction from THF, triphenylmethyl cation is less reactive than its ion pair with hexachlorantimonate ion. Propagation rate coefficients (kP/) for free ion polymerization of isobutyl vinyl ether and N-vinylcarbazole have been determined in CH2Cl2, and for the latter monomer the value of kp is 10s times greater than that for the corresponding free radical polymerization. 

Radiation-induced polymerization of isobutyl vinyl ether in bulk leads to an estimate (42) for kp of 10+5M 1 sec.-1 at 30 °C. with Ea = 6 kcal./mole. This value, extrapolated to the temperatures used in the present work, yields an estimate of kp within one order of magnitude of that now reported. Considering the experimental problems in these vastly different techniques, and the fact that different solvents are involved, such agreement is remarkable and provides support for the assumptions made to evaluate kp. 

Initiation with Tropylium Ion. Tropylium hexachlorantimonate reacts with vinyl alkyl ethers in a manner very similar to the reactions of triphenylmethyl salts. Again, rapid initiation is followed by propagation without apparent termination. Termination can be demonstrated to be absent from experiments in which fresh samples of monomer are added to completed polymerizations, whereupon the measured reaction rates parallel those previously recorded (Table II). Molecular weights of the polymers from isobutyl vinyl ether are very similar to those obtained with triphenylmethyl salts as initiators and again give clear evidence for excessive monomer transfer. Gas chromatographic analysis of the reaction mixtures showed that cycloheptatriene (product of hydride abstraction) was not present which indicates clearly that initiation must arise via addition of the tropylium ion to the vinyl ether—i.e.,... 

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