Vinylidene chloride, isobutylene

The program will be demonstrated with poly(vinyl alcohol) for tacticity analysis and with copolymer vinylidene chloride isobutylene for monomer sequence analysis. Peak assignments in C-13 spectra were obtained independently by two-dimensional NMR techniques. In some cases, assignments have been extended to longer sequences and confirmed via simulation of the experimental data. Experimental and "best-fit" simulated spectra will be compared. 

Example 2. Vinviidene Chloride Isobutylene Copolymer. The next example is for the carbon-13 spectrum of copolymer vinylidene chloride isobutylene. Figure 5 shows the full spectrum and the peak assignment listing for the non-protonated vinylidene chloride carbon in the 84-92 ppm range. Triad assignments were made (Crowther, M. W., 1987, Syracuse University, unpublished data) using the two-dimensional COLOC (20) experiment. There are ten v-centered pentads representing different environments for the vinylidene chloride carbon. The i represents the non-protonated carbon in the isobutylene polymer unit. 

Figure 5. The C-15 (125.76 Hz) spectrum of approximately 20% w/v copolymer vinylidene chloride Isobutylene In CDCI at 24°C and a peak listing from the Polymer Analysis program.

Figure 6. A porHon of the database for vinylidene chloride isobutylene copolymer. Boxed entries are required input from the user. The peak definition for the first peak is shown.

Use the values determined in Example 7.6 for the vinylidene chloride (M )-isobutylene (M2) systemf to calculate for various values of fi according to the terminal mechanism. Prepare a plot of the results. On the same graph, plot the following experimentally measured values of fi and ... 

Some additional dyad fractions from the research cited in the last problem J are reported at intermediate feedstock concentrations (M = vinylidene chloride M2 = isobutylene) ... 

Poly(hexamethylene adipamide) Poly(vinylidene chloride) 1934 1838 1938 1939 Fibers, thermoplastics Thermoplastics (packing films) Unsaturated polyesters 1930 Poly(isobutylene) Stvrene-butadiene 1926 1936 1937 1937 Thermosets Elastomers Elastomers (letter Bunas)... 

For disubstituted ethylenes, the presence and type of tacticity depends on the positions of substitution and the identity of the substituents. In the polymerization of a 1,1-disubstituted ethylene, CH2=CRR, stereoisomerism does not exist if the R and R groups are the same (e.g., isobutylene and vinylidene chloride). When R and R are different (e.g., —CH3 and —COOCH3 in methyl methacrylate), stereoisomerism occurs exactly as in the case of a monosubstituted ethylene. The methyl groups can be located all above or all below the plane of the polymer chain (isotactic), alternately above and below (syndiotactic), or randomly (atactic). The presence of the second substituent has no effect on the situation since steric placement of the first substituent automatically fixes that of the second. The second substituent is isotactic if the first is isotactic, syndiotactic if the first substituent is syndiotactic, and atactic if the first is atactic. 

For the manufacture of non-crosslinked ionomer polymer mixtures ethylene, butene-1, isobutylene, vinyl chloride, vinylidene chloride, aliphatic carboxylic acids of vinyl esters (C2-C18), aliphatic unsaturated mono and di carboxylic organic acid esters (C3-C8) with mono aliphatic saturated alcohols (C2-C12) and unsaturated aliphatic mono and di carboxylic organic acids (C3-C8) can be used as raw materials. 

Fig. 15-4. Q-e map for a number of important monomers the full horizontal line indi-catea the present choice for the scale of the polarities e the band between the two broken lines represents the location of a more rational e scale (a) chlorotrifiuoroethylene, (b) acrylonitrile, (c) allyl chloride, (d) ct-chloroacrylate, (e) methacrylonitrile, (/) methyl acrylate, (f) vinylidene chloride, (A) methyl methacrylate, (t) vinyl chloride, (j) chloro-prene, -(fc) vinyl acetate, (i) butadiene, (m) styrene, ( ). isobutylene, (o) p-methoxysty-rene. XAlfrey, Bohrer and Mark, Copolyrmruaiion," p. 82, Intencienee Publishers, Ine., New York, 1952.)...

In XXXV the polymer chain is drawn in the plane of the text with the H and Y substituents placed above and below the plane of the text. The dotted and triangular lines indicate substituents below and above this plane, respectively. Such interactions are referred to as 1,3-interactions and are responsible for the decreased A/f values in monomers such as isobutylene, a-methylstyrene, methyl methacrylate, and vinylidene chloride. The effect in a-methylstyrene is especially significant. The Al value of —35 kJ mol is essentially the smallest heat of polymerization of any monomer. 

Polymerizations in thiourea canal complexes yields high melting crystaUine trans-l,A polybutadiene, 2,3-dimethylbutadiene, 2,3-dichlorobutadiene, and 1,3-cyclohexadiene. Cyclohexadiene monoxide, vinyl chloride, and acrylonitrile also form stereoregular polymers. On the other hand, polymerizations of isobutylene and of vinylidene chloride fail to yield stereospecific polymers. 

Poly(vinylidene chloride) 1838 1939 Thermoplastics (packing films) Poly( isobutylene) — 1937 Elastomers... 

Isobutane Isobutyric acid Isoamyl acetate Isoamyl alcohol tert-Amy alcohol Acetoacetic acid Vinylidene chloride Vinylidene fluoride Ethylene dichloride Dichloroethylene ortho-Xylcne Ethylene oxide Propylene oxide meta-Xylenc Ethylene carbonate Propylene carbonate para-XylQTiQ Caprolactone Ricinoleic acid Bisphenol A Pentaerythritol Dimethylol propionic acid Neopentane Isobutylene... 

Several procedures for 93, based on the simple chemicals chloral, isobutylene, CCI4, CHCI3, isobutene, isopentene, vinylidene chloride and so on, were worked out to render the diazoester method an attractive option, as shown in Reaction scheme 55 based on chloral. 

The interpretation of the NMR spectrum of a copolymer in terms of its structure is easiest when its monomer units differ considerably in electronegativity, when no asymmetric atoms are present and when the resonance of the nuclei studied is not complicated by spin-spin interactions. When these conditions are met, sharp, intense, easily resolved signals are obtained and the spectrum is easily studied. Copolymers of isobutylene with vinylidene chloride meet all these requirements and the methylene resonance (Fig. 1) of such copolymers consists of a series of well resolved lines that afford information about diad and tetrad distri-... 

Maleic anhydride grafting (cont.) poly(styrene-co-divinylbenzene), 694 poly(styrene-co-isobutylene), 675, 689 poly(styrene-co-nfialeic anhydride), 676, 679 poly(vinyl acetate), 676, 694 poly(vinyl acetate-co-vinyl fluoride), 678 poly(vinyl alkyl ethers), 675, 679, 692, 701 poly(vinyl chloride), 683, 692, 693, 695, 702 poly(vinylidene chloride), 691 poly(vinyl toluene-co-butadiene), 689 radical—initiated, 459-462, 464-466, 471, 475, 476 radiation—initiated, 459, 461, 466, 471, 474 redox-initiated, 476 rubber, 678, 686, 687, 691, 694 to saturated polymers, 459-466, 475, 476 solvents used 460-463, 465, 466, 469, 474-476 styrene block copolymers, 679 tall oil pitch, 678, 697 terpene polymers, 679, 700 thermally-initiated, 462, 464-467, 469, 476 to unsaturated polymers, 459, 466-474 vapor-phase techniques, 464, 474, 475 to wool fibers, 476 Maleic anhydride monomer acceptor for complex formation, 207-210 acetal copolymerization, 316 acetone CTC thermodynamic constants, 211 acetone photo-adduct pyrolysis, 195, 196 acetylacetone reaction, 235 acetylenic photochemical reactions, 193-196 acrylamide eutectic mixtures, 285 acylation of aromatic acids, 97 acylation of aromatics, 91, 92 acylation of fused aromatics, 92, 95, 97, 98 acylation of olefins, 99 acylation of phenols, 94-96 acylic diene Diels-Alder reactions, 104-111, 139 addition polymer condensations, 503-505 adduct with 2-cyclohexylimino-cyclopentanedi-thiocarboxylic acid, 51 adducts for epoxy resins curing, 507-510 adduct with 2-iminocyclopentanedithiocarboxylic acid, 51... 

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