Atactic copolymer

From the NMR spectrum of copolymers produced from cyclohexene oxide and carbon dioxide it is difficult to assess low levels of asymmetric induction, i.e., low degrees of desymmetrization in the epoxide ring-opening step. In order to determine the extent of asymmetric induction it is necessary to hydrolyze the copolymer leading to the tra s-cyclohexane-l,2,-diol and examine the enantiomeric excess (4) [22]. Figure 4 shows the NMR spectrum in the carbonate region of atactic copolymer produced from cyclohexene oxide and CO2 using an achiral (salen)CrX catalyst. 

Using an Ising model for rotational isomeric states the unperturbed dimensions, 0 / nl2, are evaluated for copolymers of propylene and pentene-1. Chemical composition, tacticity, and sequence length distribution are varied. It is found that only for atactic copolymers 0 I n 2 depends linear on the chemical composition. Deviations from linearity cannot be attributed... 

The difference in behavior of fhe two diastereomeric ligands 84 and 85 (Scheme 8.16) was remarkable whereas ligand 84 produced a completely regioregular but atactic copolymer wifh very high catalytic activity, 85 gave a completely regular isotactic copolymer wifh very low catalytic activity. 

In the absence of R, when the two substiments at C4 are equal to (R = R = H or CH3) or when they are both different from hydrogen, essentially atactic copolymers are produced. However, the systan containing a chiral ligand (R = CH3, R = C6H5CH2, R = H) also gave the atactic copolymer. luCTeasing steric hindrance at C4 caused decreased catalytic activity. 

When a bulky P N ligand was used, the electronically favored 2,1-insertion and the sterically favored 1,2-insertion compete with each other, providing a regioirregular styrene/CO copolymer. Regiocontrolled but atactic copolymers were obtained using pyridine-imidazole or diimine ligands. 

The successive repeat units in strucutres [VI]-[VIII] are of two different kinds. If they were labeled Mj and M2, we would find that, as far as microstructure is concerned, isotactic polymers are formally the same as homopolymers, syndiotactic polymers are formally the same as alternating copolymers, and atactic polymers are formally the same as random copolymers. The analog of block copolymers, stereoblock polymers, also exist. Instead of using Mj and M2 to differentiate between the two kinds of repeat units, we shall use the letters D and L as we did in Chap. I. 

Unlike most crystalline polymers, PVDF exhibits thermodynamic compatibiUty with other polymers (133). Blends of PVDF and poly(methyl methacrylate) (PMMA) are compatible over a wide range of blend composition (134,135). SoHd-state nmr studies showed that isotactic PMMA is more miscible with PVDF than atactic and syndiotactic PMMA (136). MiscibiUty of PVDF and poly(alkyl acrylates) depends on a specific interaction between PVDF and oxygen within the acrylate and the effect of this interaction is diminished as the hydrocarbon content of the ester is increased (137). Strong dipolar interactions are important to achieve miscibility with poly(vinyhdene fluoride) (138). PVDF blends are the object of many papers and patents specific blends of PVDF and acryflc copolymers have seen large commercial use. 

The nmr spectmm of PVAc iu carbon tetrachloride solution at 110°C shows absorptions at 4.86 5 (pentad) of the methine proton 1.78 5 (triad) of the methylene group and 1.98 5, 1.96 5, and 1.94 5, which are the resonances of the acetate methyls iu isotactic, heterotactic, and syndiotactic triads, respectively. Poly(vinyl acetate) produced by normal free-radical polymerization is completely atactic and noncrystalline. The nmr spectra of ethylene vinyl acetate copolymers have also been obtained (33). The ir spectra of the copolymers of vinyl acetate differ from that of the homopolymer depending on the identity of the comonomers and their proportion. 

Epichlorohydrin Elastomers without AGE. ECH homopolymer, polyepichlorohydrin [24969-06-0] (1), and ECH—EO copolymer, poly(epichlorohydrin- (9-ethylene oxide) [24969-10-6] (2), are linear and amorphous. Because it is unsymmetrical, ECH monomer can polymerize in the head-to-head, tail-to-tail, or head-to-tail fashion. The commercial polymer is 97—99% head-to-tail, and has been shown to be stereorandom and atactic (15—17). Only low degrees of crystallinity are present in commercial ECH homopolymers the amorphous product is preferred. 

The properties of styrenic block copolymers are dependent on many factors besides the polymerization process. The styrene end block is typically atactic. Atactic polystyrene has a molecular weight between entanglements (Me) of about 18,000 g/mol. The typical end block molecular weight of styrenic block copolymers is less than Mg. Thus the softening point of these polymers is less than that of pure polystyrene. In fact many of the raw materials in hot melts are in the oligomeric region, where properties still depend on molecular weight (see Fig. 1). 

The observation of the spectrum for styrene polymerized on the surface of silane-treated silica and of the difference spectrum of polystyrene adsorbed on the surface of silica have revealed that there are absorption bands of atactic polystyrene at 1602, 1493, 1453, 756, and 698 cm. The absorption bands at 1411 and 1010 cm are related to vinyl trimethoxy silane, and C of the difference spectrum is below the base line. This indicates that the vinyl groups of silane react with styrene to form a copolymer. 

Samples of the poly(dialkylphosphazenes) 1 and 2 displayed X-ray powder diffraction patterns characteristic of crystalline regions in the materials. The peaks in the diffraction pattern of 1 were of lower amplitude and greater angular breadth than those of 2. These data indicate that poly(diethylphosphazene) (2) is highly crystalline while poly(dimethyl-phosphazene) (1) is more amorphous with smaller crystalline zones. This high degree of crystallinity is probably responsible for the insolubility of 2 as noted above. All of the phenyl substituted polymers 3-6 were found to be quite amorphous in the X-ray diffraction studies, a result that is further evidence for an atactic structure of the poly(alkylphenylphosphazenes) 3 and 4 and for a random substitution pattern in the copolymers 5 and 6. 

Atactic poly(methyl methacrylate/methacrylic acid), the copolymer of methyl methacrylate (MMA) and methacrylic acid (MAA), was synthesized "directly" as a prepolymer to be esterified with bis(tri-n-butyltin) oxide (TBTO). Two formulations of poly (MMA/MAA) were synthesized, a 1 1 and a 2 1 MMA and MAA copolymer whose syntheses differ only in the proportion of monomer reacted. 

Polystyrene is unusual among commodity polymers in that we can prepare it in a variety of forms by a diversity of polymerization methods in several types of reaction vessel. j Polystyrene may be atactic, isotactic, or syndiotactic. Polymerization methods include free radical, cationic, anionic, and coordination catalysis. Manufacturing processes include bulk, solution, suspension, and emulsion polymerization. We manufacture random copolymers ... 

---