Poly hexadiene

The terminal double bond is active with respect to polymerisation, whereas the internal unsaturation remains in the resulting terpolymer as a pendent location for sulfur vulcanisation. The polymer is poly(ethylene- (9-prop5iene- (9-l,4-hexadiene) [25038-37-3]. 

Similar divergences are found for lithium poly-2,4-hexadiene solution (1 10-3 M in living polymers) for which a sixfold decrease of viscosity upon protonation corresponding to a degree of association of 1.7 was reported 113), whereas only a threefold decrease, i.e. a degree of association of 1.4 was indicated earlier 1,8). The difference between the 1.7 and 1.4 values was tentatively attributed to a slow decomposition of the active ends over a period of two weeks U8) notwithstanding their reported good... 

Hydrogenation. Hydrogenation of poly(5-methyl-l,4-hexadiene) was carried out with p-toluenesulfonyl hydrazide (20) in refluxing xylene (2il molar ratio of the hydrazide to the polymer repeat unit). 

Compression molded (150°C for 3 minutes press chilled with cold water immediately thereafter) samples of poly(trans-l,4-hexadiene) (14) and poly(5-methyl-l,4-hexadiene) were examined with a General Electric (XRD-3) X-ray unit. Transmission Laue X-ray photographs were taken using nickel filtered copper X-radiation. Samples were stretched to four times of their original lengths to obtain oriented fibers. The fiber patterns were obtained in a flat plate film holder with the specimen to film distance standardized at 5 centimeters. X-ray diffraction patterns were similarly obtained for the hydrogenated sample of poly(5-methyl-l,4-hexadiene). 

We have examined poly(5-methyl-1,4-hexadiene) by IR spectroscopy and by 300 MHz Ml- and spectroscopy. The IR... 

The 1,2-polymerization of 5-methyl-l,4-hexadiene was further confirmed by ozonolysis of the polymer. The resulting solution, after triphenylphosphine treatment, contained only acetone and no detectable formaldehyde by GLC. As shown below in Scheme 1, the volatile products expected by the above chemical treatment of poly(5-methyl-l,4-hexadiene) are acetone and formaldehyde if the polymer was formed by 1,2- and 4,5-polymerization, respectively. 

Figure 2. IR spectrum of poly(5-methyl-l,4-hexadiene) prepared with a EttAlCl/ h-TiCl3 catalyst at 0°C in pentane solvent. Reproduced, with permission from Ref. 13. Copyright 1979, American Institute of Physics.

To clarify the tacticity problem, trans-l,4-hexadiene and 5-methyl-l,4-hexadiene polymers were examined by X-ray diffraction. Fiber diagrams were obtained from samples stretched to four times their original lengths. Eight reflections from the poly(trans-1,4-hexadiene) fiber pattern may be interpreted on the0basis of a pseudo-orthorhombic unit cell with a = 20.81 + 0.05 A b =... 

MILLER INDICES AND BRAGG DISTANCES FOR POLY (TRANS-1, 4 -HEXADIENE )... 

The poly(5-fnethyl-l, 4-hexadiene) fiber pattern (Figure 6) gave an identity period of 6.3 A, indicating a 3 isotactic helix structure. The X-ray diffraction pattern was not very sharp, which may be due to the difficulty of the side chain with a double bond to fit in a crystalline lattice. The crystallinity was determined to be 15% using the Hermans and Weidinger method (27). A Chloroform-soluble fraction free from catalyst residues showed no improvement in the sharpness of the X-ray diffraction pattern. These data show that the configuration of the 1,2-polymerization units in the homopolymer of 5-methyl-1,4-hexadiene is isotactic. 

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). 

Figure 7. X-ray fiber diagram of hydrogenated poly(5-methyl-l, 4-hexadiene). Solvent cast film strip cold drawn to four times its original length. Reproduced, with permission, from Ref. 19. Copyright 1976, John Wiley Sons, Inc.

The polymers of 1,4-hexadienes have unusually wide molecular weight distributions. This is illustrated by the gel permeation chromatogram of the methanol-insoluble fraction of poly(5-methyl-1,4-hexadiene) in tetrahydrofuran (Figure 9). The polymer was obtained in 82% conversion and had an inherent viscosity of 2.1 dl./g. in toluene at 25°C. 

Figure 8. 13C-NMR spectra of (A) hydrogenated poly(5-methyl-l,4-hexadiene) and (B) poly(5-methyl-l-hexene).

Recent advances in the development of well-defined homogeneous metallocene-type catalysts have facilitated mechanistic studies of the processes involved in initiation, propagation, and chain transfer reactions occurring in olefins coordi-native polyaddition. As a result, end-functional polyolefin chains have been made available [103].For instance, Waymouth et al.have reported about the formation of hydroxy-terminated poly(methylene-l,3-cyclopentane) (PMCP-OH) via selective chain transfer to the aluminum atoms of methylaluminoxane (MAO) in the cyclopolymerization of 1,5-hexadiene catalyzed by di(pentameth-ylcyclopentadienyl) zirconium dichloride (Scheme 37). Subsequent equimolar reaction of the hydroxyl extremity with AlEt3 afforded an aluminum alkoxide macroinitiator for the coordinative ROP of sCL and consecutively a novel po-ly(MCP-b-CL) block copolymer [104]. The diblock structure of the copolymer... 

The (co)polymerization of dienes can be a good method for the preparation of polymers with reactive vinyl groups, a method that enables the preparation of polymers possessing plural vinyl groups per polymer chain. A fluorinated bis(phenoxy-imine) Ti complex was shown by Coates and co-workers to convert 1,5-hexadiene to poly(methylene-l,3-cyclopentane-fti-3-vinyl tetramethylene), which contained multiple vinyl groups. As already discussed, Saito et al. and others revealed that bis(phenoxy-imine) Ti complexes favored secondary insertion. " This is probably responsible for the formation of 3-vinyl tetramethylene units. Likewise, the same catalyst system can form sPP-/ -poly(methylene-l,3-cyclopentane-z -3-vinyl tetramethylene) from propylene and 1,5-hexadiene. Very recently. 

Andere 1-substituierte Butadiene, die ebenfalls in ditaktische Poly-mere iiberfiihrt wurden, sind 1,3-Hexadien (III), 1,3-Heptadien (IV), 1,3-Octadicn. (V), 5-Methyl-l,3-hexadicn (VI) und 6-Methyl-l,3-hepta-dien (VII) (73). 

These requirements have met using a mixed catalystic system consisting of an iron catalyst complex that can oligomerize ethylene and a zirconium transition metal complex that can copolymerize ethylene and the nonconjugated monomer 5-ethylidene-2-norbomene. Using this catalytic pair nonbrancy poly(ethylene-co5-ethylidene-2-norbomene) and poly (ethylene-col,4-hexadiene) were prepared. 

The curable copolymer, poly(ethylene-co-l,4-hexadiene), was also prepared as illustrated below. 

Scheme 68 illustrates cyclopolymerization of 1,5-hexadiene catalyzed by a homogeneous chiral zirconocene complex to form optically active poly(methylenecyclopentane), whose chirality derives from configurational main-chain stereochemistry (757). This polymer is predominantly isotactic and contains predominantly trans cyclopentane rings. 

Marvel et al. 2471 attempted synthesis of poly(p-phenylene) from poly(l,3-cyclo-hexadiene), produced by Ziegler initiation ... 

Cyclopolymerisation leading to polymers with monocyclic units in the main chain proceeds in two steps the first step involves a 1,2-insertion of the coordinated a, ffl-diolefin via one olefinic bond, and the second step, which is a ringclosing reaction, involves an intramolecular insertion of the other olefinic bond undergoing coordination scheme (89) presents both steps for 1,5-hexadiene cyclopolymerisation leading to a cycloaliphatic polymer with poly(methylene-1,3-cyclopentane) structural units [30,450,497] ... 

In the case of the formation of a cycloaliphatic polymer with bicyclic units in the main chain, such as the polymer with poly[methylene-l,3-(2,5-methanocy-clohexane)] structural units obtained in the cyclopolymerisation of 3-vinyl-1,5-hexadiene, the intramolecular insertion, analogous to that presented in scheme (89), is followed by another intramolecular insertion involving a vinyl substituting group ... 

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