Poly , tactic structures

PSSA may also be prepared by sulfonation of polyst5rrene or by hydrolysis of poly(re-propyl p-vinylbenzenesulfonate). The latter cases allow preparation of tactic structures. Copol5uners can also be prepared by free-radical copolymerization of appropriate monomers or post-reaction. Poljuners are purified by precipitation of aqueous solutions with methanol, alkaline methanol, or other alcohols. Controlled structure PSSA homopolymers and block copolymers may also be prepared directly in aqueous media via RAFT using 4-cyanopentanoic acid dithiobenzoate as the CTA and V-501 as the radical source (48). NMP has been successfully... 

To this date, poly((C02Me)2NBD) prepared with the catalyst system MoCl5/Me4Sn/dioxane stands out as a rare example of an isotactic, all-cis polymer obtained with a conventional transition metal halide catalyst. This microstructure contrasts with the atactic and moderately syndio-tactic structures of poly(NB) and poly(5,5-Me2NB), respectively, that are obtained with the MoCl5/Me4Sn/dioxane system. 

Iso tactic poly(methyl methacrylate) (it-PMMA) can form a stereocomplex with st-PMMA. Recent X-ray studies 179) of this material indicate that the two polymer chains probably interact to form a double helical structure. The it-PMMA chain forms the inner helix and is surrounded by the st-PMMA helical chain which winds around it. If subsequent work confirms this model, this material would constitute a most unusual inclusion compound involving only one monomeric substance. 

The tacticity or distribution of asymmetric units in a polymer chain can be directly determined using NMR spectroscopy and infrared (IR) spectroscopy and has been studied for a variety of polymers. Figure 5(a) and 5(b) show the proton NMR spectra [26,27] and IR spectra [28,29], respectively, for the two stereoisomers of poly(methyl methacrylate) (PMMA), syndiotactic and isotactic PMMA. These two structures in a polymer like PMMA give rise to different signatures in both the techniques. In the case of the NMR spectra [26,27], the... 

Further confirmation of the structure and tacticity of poly/5-methyl-l,4-hexadiene)was obtained from X-ray diffraction and u-NMR data of its hydrogenated polymer (Scheme 2). The hydrogenated polymer sample showed a highly crystalline pattern (Figure 7), with diffraction spots that were well defined. This pattern was identical to that of isotactic poly(5-methyl-l-hexene) as reported in the literature (26) (measured identity period, 6.2 A lit., 6.33 A). 

The measurement of polymer configuration was difficult and sometimes speculative until the early 1960 s when it was shown that proton NMR could be used, in several instances, to define clearly polymer stereochemical configuration. Bovey was able to identify the configurational structure of poly(methylmethacrylate) in terms of the configurational triads, mm, mr and rr, in a classic example (3). In the case of polypropylene, configurational information appeared available but was not unambiguously accessible because severe overlap complicated the identification of resonances from the mm, mr and rr triads (4). Several papers appeared on the subject of polypropylene tacticity but none totally resolved the problem (5). 

Note Structure-based names of tactic polymers are formed before the application of adjectives designating tacticity thus, syndiotactic poly(methylmethylene) is preferred to syndiotactic poly(l,2-dimethylethane-l,2-diyl) because a shorter repeating unit is identified, in conformity with the rules in Ref. 3. 

Seki and Tirrell [436] studied the pH-dependent complexation of poly(acrylic acid) derivatives with phospholipid vesicle membranes. These authors found that polyfacrylic acid), poly(methacrylic arid) and poly(ethacrylic acid) modify the properties of a phospholipid vesicle membrane. At or below a critical pH the polymers complex with the membrane, resulting in broadening of the melting transition. The value of the critical pH depends on the chemical structure and tacticity of the polymer and increases with polymer hydro-phobicity from approximately 4.6 for poly(acrylic acid) to approximately 8 for poly(ethacrylic acid). Subsequent photophysical and calorimetric experiments [437] and kinetic studies [398] support the hypothesis that these transitions are caused by pH dependent adsorption of hydrophobic polymeric carboxylic acids... 

Kennedy and Thomas (1) first reported the synthesis of a crystalline poly(3-methyl- 1-butene) by cationic polymerization at —130°C. Preliminary HNMR studies indicated that the polymer was not simply a tactic modification of the conventional 1,2-polymer but, in fact, possessed a repeat structure which resulted... 

How can one explain the occurrence of steric defects in tactic poly(ot-olefin)s Explain why high-resolution nuclear magnetic resonance is the most convenient method for determining the chain micro structure in poly(a-olefin)s. Consider how 3H and 13C NMR spectroscopy can provide stereochemical information concerning a-olefin polymer chains on the diad level (m, r) and the triad level (mm, rr, mr). Explain why /1-olefins, which do not homopolymerise (without isomerisation) in the presence of Ziegler-Natta catalysts, undergo copolymerisation with ethylene in the presence of these catalysts. 

Several reviews of early work on topotactic polymerizations and isomeriza-tions are available, and the reader is referred to the summaries of Morawetz [88] and Gougoutas [8] for a more complete account. The earliest study of a topotactic reaction appears to have been the observation, in 1932, of the polymerization of trioxane to poly-oxy-methylene [89]. Similar polymerizations of tetraoxane [90] and of trithiane [91 ] have also been reported to show retention of crystallographic axes from the monomer lattice. Other examples are discussed below. The topo-tacticity of a reaction can be determined solely by x-ray crystallographic analysis at the reactant and product endpoints. Thus a simple classification of a reaction as topotactic tells very little about how the structure of the crystal lattice changed in the course of reaction. 

NMR spectroscopy can be also used in investigations of polymer aggregates in solution, gels etc, i.e. in systems which are between liquids and solids. As an example, studies of the formation and structure of a stereo-complex of poly(methyl methacrylate) (PMMA) by Spevacek and Schneider (1974, 1975) can be mentioned. The formation of ordered associated structures of the stereo-complex upon mixing solutions of isotactic and syndio-tactic PMMA manifests itself by the broadening of all polymer lines and results in disappearance of HR-NMR signals wide-lines then can be detected. 

The C-NMR spectrum of poly(4-(ethoxycarbonyl)-4-(lS,2R,5S)-(+)-men-thoxycarbonyl-1,6-heptadiyne) indicates a polymer containing almost solely five-membered rings (Fig. 10). In addition, only one single set for each type of carbon was observed, indicative of a highly tactic base. Keeping the symmetry restrictions described above in mind, either a cis or trans-st structure can be assigned. 

The chemical structure of a polymer determines whether it will be crystalline or amorphous in the solid state. Both tacticity (i.e., syndio-tactic or isotactic) and geometric isomerism (i.e., trans configuration) favor crystallinity. In general, tactic polymers with their more stereoregular chain structure are more likely to be crystalline than their atactic counterparts. For example, isotactic polypropylene is crystalline, whereas commercial-grade atactic polypropylene is amorphous. Also, cis-pol3nsoprene is amorphous, whereas the more easily packed rans-poly-isoprene is crystalline. In addition to symmetrical chain structures that allow close packing of polymer molecules into crystalline lamellae, specific interactions between chains that favor molecular orientation, favor crystallinity. For example, crystallinity in nylon is enhanced because of... 

Iwamura, H., Inoue, K. and Kaga, N. (1998). Tacticity versus dimension of the extended structures in the crystals of heterospin magnets made of transition-metal complexes with the poly(aminoxyl) radical. New J. Chem. 201-210... 

Nuclear Magnetic Resonance. The successful study of polymers in solution by high resolution NMR spectroscopy started with the pioneering work on the sequence structure of poly methyl methacrylate in 1960. Since then, an ever-increasing number of investigations have been carried out ranging from the elucidation of the statistics of homopolymer and copolymer structure to the study of conformation, relaxation and adsorption properties of polymers. The aspects of sequence length determination and tacticity have received considerable attention (Klesper 84, for example, reports more than 500 entries). Therefore, a detailed review will not be attempted. (For a detailed description of the NMR Theory and statistics of polymer structure, see Bovey 59, Randall 23, and Klesper 84). 

The polymer composed of 2-cyclohexenyl-l,4 units can exhibit high Tg (176 °C) when the tacticity is controlled well [62]. Recently, [( -allyl)NiBr]2, in conjunction with MAO, was found to initiate stereo- and regiospecific polymerization of 1,3-cyclohexadiene [63]. Although the polymer has too poor solubility in organic solvents to be analyzed by NMR spectroscopy, the copolymers of 1,3-cyclohexadiene with 1,3-butadiene and norbornene prepared by the Ni catalyst show NMR spectra that indicate the presence of the 2-cyclohexene- 1,4-diyl unit formed via 1,4-polymerization of 1,3-cyclohexadiene (Eq. 11). X-ray diffraction analysis of the crystalline poly( 1,3-cyclohexadiene) as well as studies by molecular dynamics confirmed the cis-syndiotactic structure of the polymer [64]. 

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