Anionic polymerization alkali metal initiation

The use of alkali 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. Independendy and simultaneously, the use of sodium metal to polymerize butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene was described (17). Interest in alkali 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 t /s- 1,4-polyisoprene, similar in structure and properties to Hevea natural rubber (see Elastomers, synthetic-polyisoprene Rubber, natural). 

HI. Mechanism of Anionic Polymerizations A. Alkali-Metal Initiated Polymerizations... 

Anionic polymerization of 1,3-butadiene allows for a wide range of heterotactic vinyl enchainment levels. The structures obtained in hydrocarbon solvents with alkali metal initiators are shown in Table 9. Lithium polybutadiene maintains the lowest vinyl, highest 1,4 content possible via anionic polsrmerization. The microstructure produced via a free-radical emulsion polymerization is provided as a reference. 

A wide variety of typical anionic initiators is described for the polymerization of PMVK. Grignard reagents are used as well as complexes formed of alkylaluminum or alkylzinc compounds with alkali metal alkyls (so called -ate complexes ). Alkali metal initiators and alkoxides are also described. Some examples are given in Table 5. 

All of them have been studied in the anionic polymerization of CL, initiated with alkali metal lactam salts, and have found a more suitable application in the potymerization of 2-pyrrolidone at 30-50 °C, initiated by potassium 2-oxopyrro-lidin-l-ide. °... 

Alkali metals initiate anionic polymerization indirectly by an electron transfer process ... 

Some of the results of bulk polymerization of 61 by using different anionic catalysts are summarized in Table 858 It was easily polymerized in the presence of alkali metal compounds above 60 °C. The polymerization at 150 °C was too fast to be controlled. The yield and the viscosity number, i gp/c, of the resulting polyamide increased with the reaction time. The initial rate of the polymerization became higher with the size of the countercation, in analogy to the case of anionic polymerization of e-caprolactam59. The rate increased also with raising temperature as shown in Fig. 658. ... 

Anionic polymerization of 1,3-disilacyclobutanes also is possible. Solid KOH and alkali metal silanolates were mentioned as being effective by Russian authors [18, 19. 20]. However, alkyllithiums, which can initiate polymerization of silacyclobutanes (eq. 8) [21], do not initiate polymerization of 1,3-disilacyclobutanes [18, 22]. The problem is one of steric hindrance. 

Another differential reaction is copolymerization. An equi-molar mixture of styrene and methyl methacrylate gives copolymers of different composition depending on the initiator. The radical chains started by benzoyl peroxide are 51 % polystyrene, the cationic chains from stannic chloride or boron trifluoride etherate are 100% polystyrene, and the anionic chains from sodium or potassium are more than 99 % polymethyl methacrylate.444 The radicals attack either monomer indiscriminately, the carbanions prefer methyl methacrylate and the carbonium ions prefer styrene. As can be seen from the data of Table XIV, the reactivity of a radical varies considerably with its structure, and it is worth considering whether this variability would be enough to make a radical derived from sodium or potassium give 99 % polymethyl methacrylate.446 If so, the alkali metal intitiated polymerization would not need to be a carbanionic chain reaction. However, the polymer initiated by triphenylmethyl sodium is also about 99% polymethyl methacrylate, whereas tert-butyl peroxide and >-chlorobenzoyl peroxide give 49 to 51 % styrene in the initial polymer.445... 

Block copolymers of (R,S)-(3-butyrolactone and eCL have been synthesized by combining the anionic ROP of the first monomer with the coordinative ROP of the second one (Scheme 15) [71]. The first step consisted of the synthesis of hydroxy-terminated atactic P(3BL by anionic polymerization initiated by the alkali-metal salt of a hydroxycarboxylic acid complexed with a crown ether. The hydroxyl end group of P(3BL could then be reacted with AlEt3 to form a macroinitiator for the eCL ROP. 

The reaction involves the transfer of an electron from the alkali metal to naphthalene. The radical nature of the anion-radical has been established from electron spin resonance spectroscopy and the carbanion nature by their reaction with carbon dioxide to form the carboxylic acid derivative. The equilibrium in Eq. 5-65 depends on the electron affinity of the hydrocarbon and the donor properties of the solvent. Biphenyl is less useful than naphthalene since its equilibrium is far less toward the anion-radical than for naphthalene. Anthracene is also less useful even though it easily forms the anion-radical. The anthracene anion-radical is too stable to initiate polymerization. Polar solvents are needed to stabilize the anion-radical, primarily via solvation of the cation. Sodium naphthalene is formed quantitatively in tetrahy-drofuran (THF), but dilution with hydrocarbons results in precipitation of sodium and regeneration of naphthalene. For the less electropositive alkaline-earth metals, an even more polar solent than THF [e.g., hexamethylphosphoramide (HMPA)] is needed. 

Electron-transfer initiation from other radical-anions, such as those formed by reaction of sodium with nonenolizable ketones, azomthines, nitriles, azo and azoxy compounds, has also been studied. In addition to radical-anions, initiation by electron transfer has been observed when one uses certain alkali metals in liquid ammonia. Polymerizations initiated by alkali metals in liquid ammonia proceed by two different mechanisms. In some systems, such as the polymerizations of styrene and methacrylonitrile by potassium, the initiation is due to amide ion formed in the system [Overberger et al., I960]. Such polymerizations are analogous to those initiated by alkali amides. Polymerization in other systems cannot be due to amide ion. Thus, polymerization of methacrylonitrile by lithium in liquid ammonia proceeds at a much faster rate than that initiated by lithium amide in liquid ammonia [Overberger et al., 1959]. The mechanism of polymerization is considered to involve the formation of a solvated electron ... 

Electron-transfer initiation also occurs in heterogeneous polymerizations involving dispersions of an alkali metal in monomer. Initiation involves electron transfer from the metal to monomer followed by dimerization of the monomer radical-anion to form the propagating... 

Strong bases such as alkali metals, metal hydrides, metal amides, metal alkoxides, and organometallic compounds initiate the polymerization of a lactam by forming the lactam anion XXXIV [Hashimoto, 2000 Sebenda, 1989 Sekiguchi, 1984], for example, for e-caprolactam with a metal... 

The anionic polymerization of cyclic siloxanes can be initiated by alkali metal hydroxides, alkyls, and alkoxides, silanolates such as potassium trimethylsilanoate, (CH3)3SiOK, and other bases. Both initiation... 

For the anionic polymerization of methacrylonitrile (MAN), many initiators have been developed, which include alkali-metal alkyls such as butyllithium [42], triphenylmethylsodium [43], phenylisopropylpotassium [43], the disodium salt of living a-methylstyrene tetramer [44], alkali-metal amides [45], alkoxides [46], and hydroxide [47], alkali metal in liquid NH3 [48], quaternary ammonium hydroxide [49], and a silyl ketene acetal coupled with nucleophilic or Lewis acidic catalysts [50]. However, only a single example of the synthesis of PMAN with narrow molecular-weight distribution can be cited, and the reported number-average molecular weights were much higher than those calculated from the stoichiometry of the butyllithium initiator [42]. 

One of the most interesting processes in electrically initiated polymerization was an initiation with the solvated electron proposed by Laurin and Parravano (22), who studied electro-anionic polymerization of 4-vinylpyridine in liquid ammonia solution of alkali metal salts in the temperature range — 33 to — 78° C. Rapid and efficient polymerization occurred and conversions of monomer to polymers formed exclusively at the cathode in the form of an orange-red, porous, solid deposit, suggesting the formation of a pile of living polymers. 

In anionic polymerization the reaction is initiated by a strong base, eg, a metal hydride, alkali metal alkoxide, oiganometaUic compounds, or... 

The use of alkali melals for anionic polymerization of diene monomers is primarily of historical interest. The electron-transfer mechanism of the anionic polymerization of styrenes and 1,3-diencs initiated by alkali metals has been described in detail the dimerization of radical anion intermediates is the important step. 

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