Anionic polymerization copolymerization

Despite numerous efforts, there is no generally accepted theory explaining the causes of stereoregulation in acryflc and methacryflc anionic polymerizations. Complex formation with the cation of the initiator (146) and enoflzation of the active chain end are among the more popular hypotheses (147). Unlike free-radical polymerizations, copolymerizations between acrylates and methacrylates are not observed in anionic polymerizations however, good copolymerizations within each class are reported (148). 

Unlike ftee-tadical polymerizations, copolymerizations between acrylates and methacrylates ate not observed in anionic polymerizations however, good copolymerizations within each class ate reported (99). 

Bamford, Eastmond and coworkers have employed metal complexpolymeric halide redox systems to initiate block and graft copolymerization. The polymeric halides can be synthesized by a variety of techniques, including radical polymerization,281 anionic polymerization (Scheme 7.28),"so... 

The arm-first synthesis of star microgels by initiating polymerization or copolymerization of a divinyl monomer such as diviny lbenzene or a bis-maleimide with a polystyryl alkoxyamine was pioneered by Solomon and coworkers.692 693 The general approach had previously been used in anionic polymerization. The method has now been exploited in conjunction with NMP,692 6 ATRP69 700 and RAFT.449 701 702 The product contains dormant functionality in the core. This can be used as a core for subsequent polymerization of a monoene monomer to yield a mikto-arm star (NMP ATRP704). 

Anionic polymerization of pivalolactone with the polystyrene anion produced only homopolymer mixtures, but the polystyrene carboxylate anion was able to give a block copolymer336. The block efficiency depends on catalyst ratio and conversion because the initiation step is slow compared with propagation337. Tough and elastic films were obtained by graft copolymerization or block copolymerization of pivalolactone onto elastomers containing tetrabutylammonium carboxylate groups338,339. ... 

Anionic Polymerization of Other Methacrylates and Their Copolymerization... 

Another important consequence of the limitations concerning cross-addition is that anionic polymerization is not suited for the synthesis of random copolymers. If a mixture of two anionically polymerizable monomers is reacted with an initiator, the most electrophilic monomer will polymerize while the other is left almost untouched 30). In other words, a general feature of anionic binary copolymerization is that one of the reactivity ratios is extremely high while the other is close to zero. 

The role of reactive centers is performed here by free radicals or ions whose reaction with double bonds in monomer molecules leads to the growth of a polymer chain. The time of its formation may be either essentially less than that of monomer consumption or comparable with it. The first case takes place in the processes of free-radical polymerization whereas the second one is peculiar to the processes of living anionic polymerization. The distinction between these two cases is the most greatly pronounced under copolymerization of two and more monomers when the change in their concentrations over the course of the synthesis induces chemical inhomogeneity of the products formed not only for size but for composition as well. 

Anionic polymerization in suitable systems allows the preparation of polymers with controlled molecular weight, narrow molecular weight distributions and functional termination. The functional termination of a living anionic polymerization with a polymerizable group has been used frequently in the preparation of macromonomers (4). Our research has encompassed the anionic homo and block copolymerizations of D- or hexamethyl cyclotrisiloxane with organolithiums to prepare well defined polymers. As early as 1962 PSX macromonomers were reported in the literature by Greber (5) but the copolymerization of these macromonomers did not become accepted technique until their value was demonstrated by Milkovich and... 

Cyclosilazanes are found to be reluctant to polymerize by the ring-opening process, probably for thermodynamic reasons. On the other hand, six- and eight-membered silazoxane rings are able to undergo anionic polymerization under similar conditions to those which have been widely used for cyclosiloxane polymerization provided there is no more than two silazane units in the cyclic monomer. They can also copolymerize with cyclosiloxanes however, the chain length of the linear polymer formed is substantially decreased with increasing proportion of silazane units. 

Anionic polymerization of polystyrene takes place very rapidly- much faster than free radical polymerization. When practiced on a large scale, this gives rise to heat transfer problems and limits its commercial practice to special cases, such as block copolymerization by living reactions. We employ anionic polymerization to make tri-block copolymer rubbers such as polystyrene-polybutadiene-polystyrene. This type of synthetic rubber is widely used in the handles of power tools, the soft grips of pens, and the elastic side panels of disposable diapers. 

A radical initiator based on the oxidation adduct of an alkyl-9-BBN (47) has been utilized to produce poly(methylmethacrylate) (48) (Fig. 31) from methylmethacrylate monomer by a living anionic polymerization route that does not require the mediation of a metal catalyst. The relatively broad molecular weight distribution (PDI = (MJM ) 2.5) compared with those in living anionic polymerization cases was attributed to the slow initiation of the polymerization.69 A similar radical polymerization route aided by 47 was utilized in the synthesis of functionalized syndiotactic polystyrene (PS) polymers by the copolymerization of styrene.70 The borane groups in the functionalized syndiotactic polystyrenes were transformed into free-radical initiators for the in situ free-radical graft polymerization to prepare s-PS-g-PMMA graft copolymers. 

Applying these methodologies monomers such as isobutylene, vinyl ethers, styrene and styrenic derivatives, oxazolines, N-vinyl carbazole, etc. can be efficiently polymerized leading to well-defined structures. Compared to anionic polymerization cationic polymerization requires less demanding experimental conditions and can be applied at room temperature or higher in many cases, and a wide variety of monomers with pendant functional groups can be used. Despite the recent developments in cationic polymerization the method cannot be used with the same success for the synthesis of well-defined complex copolymeric architectures. 

The synthesis and properties of heat-resistant polyazomethines containing 2,5-disubstituted oxadiazole fragments, being insulators convertible into semiconductors by doping with iodine, have been described. The radical copolymerization of alkenes with the fluorescent co-monomer 2-/-butyl-5-(4 -vinyl-4-biphenylyl)-l,3,4-oxadiazole has resulted in useful macromolecular scintillators. Anionic polymerization of 2-phenyl-l,3,4-oxadiazolin-5-one has produced a nylon-type product <1996CHEC-II(4)268>. 

Fig. 56. Dependence of Mwof the microgels on the polymer yield in the anionic polymerization of EDMA in toluene by n-BuLi [254] (see Figure 53 caption for the reaction conditions). Reduced viscosity vs concentration of microgels a) Composition (mol %) N,N -methyl-enebisacrylamide (55%), methacrylamide (33%), methacrylic acid (2%), methacrylamido acetaldehyd-dimethylacetal (10%),measured at 20 °C in water, b) Composition (mol %) 1,4-DVB (35%), propenic acid amide-2-methyl-N-(4-methyl-2-butyl-l,3-dioxolane prepared by emulsion copolymerization and measured in dimethylformamide.

Siloxane containing block or segmented copolymers can be synthesized either by living anionic polymerization of the cyclic organosiloxane trimers with appropriate vinyl monomer(, 4 ) or by step-growth or condensation copolymerization of preformed a,w-difunctional siloxane oligomers with conventional difunctional... 

Over 5.5 billion pounds of synthetic rubber is produced annually in the United States. The principle elastomer is the copolymer of butadiene (75%) and styrene (25) (SBR) produced at an annual rate of over 1 million tons by the emulsion polymerization of butadiene and styrene. The copolymer of butadiene and acrylonitrile (Buna-H, NBR) is also produced by the emulsion process at an annual rate of about 200 million pounds. Likewise, neoprene is produced by the emulsion polymerization of chloroprene at an annual rate of over 125,000 t. Butyl rubber is produced by the low-temperature cationic copolymerization of isobutylene (90%) and isoprene (10%) at an annual rate of about 150,000 t. Polybutadiene, polyisoprene, and EPDM are produced by the anionic polymerization of about 600,000, 100,000, and 350,000 t, respectively. Many other elastomers are also produced. 

Szwarc, M. and J. Smid, The Kinetics of Propagation of Anionic Polymerization and Copolymerization, Chap. 5 in Progress in Reaction Kinetics, Vol. 2, G. Porter, ed., Pergamon Press, Oxford, 1964. 

The reactivity of monomers with electron-releasing substituents in anionic copolymerization is nil. Correlation of reactivity in copolymerization with structure has been achieved in some studies [Favier et al., 1977 Shima et al., 1962]. The reactivities of various substituted styrenes and methacrylates in anionic polymerization, as well as the reactivities of various vinyl... 

Copolymerizations of nonpolar monomers with polar monomers such as methyl methacrylate and acrylonitrile are especially comphcated. The effects of solvent and counterion may be unimportant compared to the side reactions characteristic of anionic polymerization of polar monomers (Sec. 5-3b-4). In addition, copolymerization is often hindered by the very low tendency of one of the cross-propagation reactions. For example, polystyryl anions easily add methyl methacrylate but there is little tendency for poly(methyl methacrylate) anions to add styrene. Many reports of styrene-methyl methacrylate (and similar comonomer pairs) copolymerizations are not copolymerizations in the sense discussed in this chapter. 

Penultimate effects have been observed for many comonomer pairs. Among these are the radical copolymerizations of styrene-fumaronitrile, styrene-diethyl fumarate, ethyl methacrylate-styrene, methyl methacrylate l-vinylpyridine, methyl acrylate-1,3-butadiene, methyl methacrylate-methyl acrylate, styrene-dimethyl itaconate, hexafluoroisobutylene-vinyl acetate, 2,4-dicyano-l-butene-isoprene, and other comonomer pairs [Barb, 1953 Brown and Fujimori, 1987 Buback et al., 2001 Burke et al., 1994a,b, 1995 Cowie et al., 1990 Davis et al., 1990 Fordyce and Ham, 1951 Fukuda et al., 2002 Guyot and Guillot, 1967 Hecht and Ojha, 1969 Hill et al., 1982, 1985 Ma et al., 2001 Motoc et al., 1978 Natansohn et al., 1978 Prementine and Tirrell, 1987 Rounsefell and Pittman, 1979 Van Der Meer et al., 1979 Wu et al., 1990 Yee et al., 2001 Zetterlund et al., 2002]. Although ionic copolymerizations have not been as extensively studied, penultimate effects have been found in some cases. Thus in the anionic polymerization of styrene t-vinylpyri-dine, 4-vinylpyridine adds faster to chains ending in 4-vinylpyridine if the penultimate unit is styrene [Lee et al., 1963]. 

Most polystyrene products are not homopolystyrene since the latter is relatively brittle with low impact and solvent resistance (Secs. 3-14b, 6-la). Various combinations of copolymerization and blending are used to improve the properties of polystyrene [Moore, 1989]. Copolymerization of styrene with 1,3-butadiene imparts sufficient flexibility to yield elastomeric products [styrene-1,3-butadiene rubbers (SBR)]. Most SBR rubbers (trade names Buna, GR-S, Philprene) are about 25% styrene-75% 1,3-butadiene copolymer produced by emulsion polymerization some are produced by anionic polymerization. About 2 billion pounds per year are produced in the United States. SBR is similar to natural rubber in tensile strength, has somewhat better ozone resistance and weatherability but has poorer resilience and greater heat buildup. SBR can be blended with oil (referred to as oil-extended SBR) to lower raw material costs without excessive loss of physical properties. SBR is also blended with other polymers to combine properties. The major use for SBR is in tires. Other uses include belting, hose, molded and extruded goods, flooring, shoe soles, coated fabrics, and electrical insulation. 

Polyoxymethylene, also referred to as acetal resin or POM, is obtained either by anionic polymerization of formaldehyde or cationic ring-opening copolymerization of trioxane with a small amount of a cyclic ether or acetal (e.g., ethylene oxide or 1,3-dioxolane) [Cherdron et al., 1988 Dolce and Grates, 1985 Yamasaki et al., 2001]. The properties and uses of POM have been discussed in Sec. 5-6d. 

Inoue, S. and T. Aida, Anionic Ring-Opening Polymerization Copolymerization, Chap. 37 in Comprehensive Polymer Science, Vol. 3, G. C. Eastmond, A. Ledwith, S. Russo, and P. Sigwalt, eds., Pergamon Press, London, 1989. 

To the first category belong the homo- and copolymerization of macromonomers. For this purpose, macromolecules with only one polymerizable end group are needed. Such macromonomers are made, for example, by anionic polymerization where the reactive chain end is modified with a reactive vinyl monomer. Also methacrylic acid esters of long-chain aliphatic alcohols or monofunctional polyethylene oxides or polytetrahydrofurane belong to the class of macromonomers. 

The low temperature peroxyborane system is very effective for converting thiocarbonyl fluoride to homopolymer. The product is comparable to those formed by anionic polymerization. Since polymerization of thiocarbonyl fluoride is substantially slower than that of the chlorofiuoride, this monomer copolymerizes with exceptional ease with a large number of vinyl compounds to give products that appear to be random copolymers. 

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