Copolymerization with polar monomers

Mention has been made of the fact that the polar character of polymer surfaces is strongly affected by the ionic polymer end groups that are residues of initiator-derived ion radicals, when persulfates are used in emulsion polymerizations. Variation of the initiator type between those that yield ionic and nonionic end groups is an effective way to control particle stability and avoid complications due to migration of surfactant from one polymer surface to another [25]. This method can also be supplemented by copolymerization with polar monomers to affect surface hydrophilicity. 

Ethylene can also be copolymerized with polar monomers in order to widely modify the characteristics of the corresponding materials. The comonomers are most often (meth)acrylic monomers or vinyl acetate, with the latter being the most used for the production of EVA copolymers (ethylene/vinyl acetate). EVAs generally contain about 20% mass of comonomer and are very interesting due to their adhesive properties. 

Acrylamide copolymerizes with many vinyl comonomers readily. The copolymerization parameters ia the Alfrey-Price scheme are Q = 0.23 and e = 0.54 (74). The effect of temperature on reactivity ratios is small (75). Solvents can produce apparent reactivity ratio differences ia copolymerizations of acrylamide with polar monomers (76). Copolymers obtained from acrylamide and weak acids such as acryUc acid have compositions that are sensitive to polymerization pH. Reactivity ratios for acrylamide and many comonomers can be found ia reference 77. Reactivity ratios of acrylamide with commercially important cationic monomers are given ia Table 3. 

Block Copolymerization of Ethylene with Polar Monomers. 96... 

Table 14. Block copolymerization of ethylene with polar monomers...

In contrast, commercial processes for the copolymerization of ethylene with polar monomers such as acrylate and vinyl acetate still exclusively employ free radical processes [13]. The use of free radical initiators across the entire acrylic polymer... 

However, the practical, direct synthesis of functionalized linear polyolefins via coordination copolymerization olefins with polar monomers (CH2 = CHX) remains a challenging and industrially important goal. In the mid-1990s Brookhart et al. [25, 27] reported that cationic (a-diimine)palladium complexes with weakly coordinating anions catalyze the copolymerization of ethylene with alkylacrylates to afford hyperbranched copolymers with the acrylate functions located almost exclusively at the chain ends, via a chain-walking mechanism that has been meticulously studied and elucidated by Brookhart and his collaborators at DuPont [25, 27], Indeed, this seminal work demonstrated for the first time that the insertion of acrylate monomers into certain late transition metal alkyl species is a surprisingly facile process. It spawned almost a decade of intense research by several groups to understand and advance this new science and to attempt to exploit it commercially [30-33, 61]. 

These catalysts represent the current state-of-the-art in ethylene copolymerization with polar olefinic monomers, being able to copolymerize a wide variety of polar monomers containing both O and N heteroatoms to generate completely linear, high molecular weight, random copolymers. There are leads to enhance the modest activity of these catalysts, and it will be interesting to watch further developments over the next few years. 

There have also been several papers [61-63] on the importance of carefully establishing the reaction mechanism when attempting the copolymerization of olefins with polar monomers since many transition metal complexes can spawn active free radical species, especially in the presence of traces of moisture. The minimum controls that need to be carried out are to run the copolymerization in the presence of various radical traps (but this is not always sufficient) to attempt to exclude free radical pathways, and secondly to apply solvent extraction techniques to the polymer formed to determine if it is truly a copolymer or a blend of different polymers and copolymers. Indeed, even in the Drent paper [48], buried in the supplementary material, is described how the true transition metal-catalyzed random copolymer had to be freed of acrylate homopolymer (free radical-derived) by solvent extraction prior to analysis. 

For example, a proline-based chiral ligand was attached to a vinyl-substituted monomer (Fig. 42.15) by reacting vinylbenzoyl chloride with the amine functionality of the ligand [106]. As mentioned previously, the apolar Merrifield resin as a support is not swollen in polar solvents. Hence, in order to match the polarity of the resin with that of the typically used substrates in enantioselective hydrogenation, the functionalized monomer was copolymerized with polar units of methacrylic acid 2-hydroxyethyl ester. 

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. 

Controlled block copolymerization of olefins with polar monomers was performed with a lanthanide complex by the successive polymerization of hexene (or pentene) and methylmethacrylate (or caprolactone). Polyhexene-block-poly(methyl methacrylate), polyhcxcnc-fo/ock-polycaprolactone, poly-pentene-fc/ock-poly(methyl methacrylate), and polypentene-Wock-polycapro-lactone were synthesized using a lanthanide complex as initiator [140-143]. 

Boffa LS, Novak BM, Copolymerization of Polar Monomers with Olefins Using Transition-Metal Complexes, Chem Rev, 100, 1479-1494 (2000), and refs therein... 

Michalak A, Ziegler T, DFT Studies on the Copolymerization of a-Olefins with Polar Monomers Comonomer Binding by Nickel- and Palladium-Based Catalysts with Brookhart and Grubbs Ligands, Organometallics, 20, 1521-1532 (2001)... 

T he free radical initiated polymerization of polar monomers containing pendant nitrile and carbonyl groups—e.g., acrylonitrile and methyl methacrylate—in the presence of metal halides such as zinc chloride and aluminum chloride, is characterized by increased rates of polymerization (2, 3, 4, 5,10, 30, 31, 32, 33, 34, 53, 55, 65, 66, 75, 76, 77, 87). Imoto and Otsu (30, 33, 34) have attributed this effect to the formation of a complex between the polar group and the metal halide. The enhanced reactivity of the complexed monomer extends to copolymerization with uncomplexed monomers, such as vinylidene chloride, which are readily responsive to... 

The copolymerization of olefins together with polar monomers is just beginning and has a great potential. 

Post-polymerization fimctionalization has been used to this end, but most research has been directed toward the copolymerization of ethylene with polar monomers. In this manner, inexpensive monomers can be used to create novel polymeric materials with a wide range of applications. The major drawback to this methodology is the inherent difference in reactivity between ethylene and other vinyl monomers during chain polymerization. This phenomenon is known to yield copolymers with low polar monomer incorporation and increased branch content arising from chain transfer events caused by side reactions with polar and/or protic functionaUties [45]. 

Desurmont, G, Tokimitsu, T., and Yasuda, H. (2000) First controlled block copolymerizations of higher 1-olefins with polar monomers using metallocene type single component lanthanide initiators. Macromolecules, 33, 7679. 

The dual function of the precatalysts 4 opened the way to well-controlled block polymerization of ethylene and MMA (eq. (5)) [89, 90]. Homopolymerization of ethylene (Mn = 10000) and subsequent copolymerization with MAA (Mn 20000) yielded the desired linear AB block copolymers. Mono and bis(alkyl/silyl)-substituted flyover metallocene hydride complexes of type 8 gave the first well-controlled block copoymerization of higher a-olefins with polar monomers such as MMA or CL [91]. In contast to the rapid formation of polyethylene [92], the polymerization of 1-pentene and 1-hexene proceeded rather slowly. For example, AB block copolymers featuring poly( 1-pentene) blocks (M 14000, PDI = 1.41) and polar PMMA blocks (M 34000, PDI = 1.77) were obtained. Due to the bis-initiating action of samarocene(II) complexes (Scheme 4), type 13-15 precatalysts are capable of producing ABA block copolymers of type poly(MMA-co-ethylene-co-MMA), poly(CL-co-ethylene-co-CL), and poly(DTC-co-ethylene-co-DTC DTC = 2,2-dimethyltrimethylene carbonate) [90]. 

The chemical modification of SHOP-catalysts was the center of interest of Klabunde and Ittel who intensively focused on the synthesis of high molecular weight products and on the copolymerization of ethene with a-olefms. Therein, the combination of ethene with polar monomers and carbon monoxide depicts the major concern [14]. They realized the importance of the nature of donor ligands coordinating to the nickel center as the primary factor limiting the polymer molecular weight (Fig. 2.3, C). 

Remarkably high activities for the polymerization of ethene similar to those of active Ziegler-Natta systems have been reported and the physical properties of the polyolefins produced can be tailored by the choice of the metal center and the substitution pattern of the hgand backbone [12-14]. Some of these catalytic systems are not only compatible with polar monomers, but also copolymerization of... 

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