Copolymers identifying

U.se SpartanView to compare chain-growth polymers A-E. Identify the monomers found in each, and tell whether each is a homopolymer or a copolymer. If a copolymer, identify it as either random, alternating, or block. 

The theoretical formulations of the cmc of symmetric diblock copolymers identify the important parameter as where x is the interaction parameter... 

The spectrum shown in Fig. 7.5 shows the appropriate portion of the spectrum for a copolymer prepared from a feedstock for which fj = 0.153 It turns out that each polyene produces a set of three bands The dyad is identified with the peaks at X = 298, 312, and 327 nm the triad, with X = 347 367, and 388 nm and the tetrad with X = 412 and 437 nm. Apparently one of the tetrad bands overlaps that of the triad and is not resolved. Likewise only one band (at 473 nm) is observed for the pentad. The identification ol these features can be confirmed with model compounds and the location and relative intensities of the peaks has been shown to be independent of copolymer composition. 

Combination techniques such as microscopy—ftir and pyrolysis—ir have helped solve some particularly difficult separations and complex identifications. Microscopy—ftir has been used to determine the composition of copolymer fibers (22) polyacrylonitrile, methyl acrylate, and a dye-receptive organic sulfonate trimer have been identified in acryHc fiber. Both normal and grazing angle modes can be used to identify components (23). Pyrolysis—ir has been used to study polymer decomposition (24) and to determine the degree of cross-linking of sulfonated divinylbenzene—styrene copolymer (25) and ethylene or propylene levels and ratios in ethylene—propylene copolymers (26). 

A number of high melting poiat semiaromatic nylons, iatroduced ia the 1990s, have lower moisture absorption and iacreased stiffness and strength. Apart from nylon-6 /6,T (copolymer of 6 and 6,T), the exact stmcture of these is usually proprietary and they are identified by trade names. Examples iaclude Zytel HTN (Du Pont) Amodel, referred to as polyphthalamide or PPA (Amoco) and Aden (Mitsui Petrochemical). Properties for polyphthalamide are given ia Table 2. A polyphthalamide has been defined by ASTM as "a polyamide ia which the residues of terephthaUc acid or isophthahc acid or a combination of the two comprise at least 60 molar percent of the dicarboxyhc acid portion of the repeating stmctural units ia the polymer chain" (18). 

The polyamide copolymer of dodecanoic acid with methylenedi(cyclohexylamine) (MDCHA, PACM) was sold as continuous filament yam fiber under the tradename QIANA. As late as 1981, over 145,000 t was produced using high percentages, typically 80%, of trans, trans MDCHA isomer. The low melting raffinate coproduct left after t,t isomer separation by fractional crystallisation was phosgenated to produce a Hquid aUphatic diisocyanate marketed by Du Pont as Hylene W. Upon terrnination of their QIANA commitment, Du Pont sold the urethane intermediate product rights to Mobay, who now markets the 20% trans, trans—50% cis, trans—30% cis, cis diisocyanate isomer mixture as Desmodur W. In addition to its use in polyamides and as an isocyanate precursor, methylenedi (cyclohexyl amine) is used directiy as an epoxy curative. The Hquid diamine mixture identified historically as PACM-20 is marketed as AMICURE PACM by Anchor Chemical for performance epoxies. 

Polymerization Processes. Vinyl acetate has been polymerized industrially by bulk, solution, suspension, and emulsion processes (34). Perhaps 90% of the material identified as poly(vinyl acetate) or copolymers that are predominantly vinyl acetate are made by emulsion techniques. Detailed information is in patent and scientific Hterature and in procedures available in the brochures from monomer producing companies (15,34). 

Another phase which has attracted recent interest is the gyroid phase, a bicontinuous ordered phase with cubic symmetry (space group Ia3d, cf. Fig. 2 (d) [10]). It consists of two interwoven but unconnected bicontinuous networks. The amphiphile sheets have a mean curvature which is close to constant and intermediate between that of the usually neighboring lamellar and hexagonal phases. The gyroid phase was first identified in lipid/ water mixtures [11], and has been found in many related systems since then, among other, in copolymer blends [12]. 

Figure 12.4 Cliromatograms of a styrene-isoprene-styrene tiiblock copolymer sample (a) microcolumn SEC trace (b) capillary GC ti ace of the inti oduced section x . Peak identification is as follows 1, ionol 2, not identified 3, Iiganox 565. Reprinted with pennission from Ref. (12).

The structure of PP-g-polystyrene was studied by wide and narrow angle x-ray diffractometry. The polystyrene component formed discrete amorphous structures, which were identified after chloromethylation [143]. Structure of Rayon-Styrene graft copolymer was characterized by IR, wide angle x-ray, and SEM, grafting occurred mainly in the amorphous regions of rayon [1441. 

Self-Test 19.5A Use Fig. 19.14 to identify the type of copolymer formed by monomers A and B —AAAABBBBB—. 

Identify the type of copolymer formed by monomers A and B —BBBBAA—. 

Recently, Teymour and coworkers developed an interesting computational technique called the digital encoding for copolymerization compositional modeling [20,21], Their method uses symbolic binary arithmetic to represent the architecture of a copolymer chain. Here, each binary number describes the exact monomer sequence on a specific polymer chain, and its decimal equivalent is a unique identifier for this chain. Teymour et al. claim that the... 

The simplest, from the viewpoint of topological structure, are the linear polymers. Depending on the number m of the types of monomeric units they differentiate homopolymers (m=1) and copolymers (m>2). In the most trivial case molecules in a homopolymer are merely identified by the number l of monomeric units involved, whereas the composition of a copolymer macromolecule is defined by vector 1 with components equal to the numbers of mono-... 

On-line SFE-pSFC-FTIR was used to identify extractable components (additives and monomers) from a variety of nylons [392]. SFE-SFC-FID with 100% C02 and methanol-modified scC02 were used to quantitate the amount of residual caprolactam in a PA6/PA6.6 copolymer. Similarly, the more permeable PS showed various additives (Irganox 1076, phosphite AO, stearic acid - ex Zn-stearate - and mineral oil as a melt flow controller) and low-MW linear and cyclic oligomers in relatively mild SCF extraction conditions [392]. Also, antioxidants in PE have been analysed by means of coupling of SFE-SFC with IR detection [121]. Yang [393] has described SFE-SFC-FTIR for the analysis of polar compounds deposited on polymeric matrices, whereas Ikushima et al. [394] monitored the extraction of higher fatty acid esters. Despite the expectations, SFE-SFC-FTIR hyphenation in on-line additive analysis of polymers has not found widespread industrial use. While applications of SFC-FTIR and SFC-MS to the analysis of additives in polymeric matrices are not abundant, these techniques find wide application in the analysis of food and natural product components [395]. 

Spectroscopic analyses are widely used to identify the components of copolymers. Infrared (IR) spectroscopy is often sufficient to identify the comonomers present and their general concentration. Nuclear magnetic resonance (NMR) spectrometry is a much more sensitive tool for analysis of copolymers that can be used to accurately quantify copolymer compositions and provide some information regarding monomer placement. 

Many characteristic molecular vibrations occur at frequencies in the infrared portion of the electromagnetic spectrum. We routinely analyze polymers by measuring the infrared frequencies that are absorbed by these molecular vibrations. Given a suitable calibration method we can obtain both qualitative and quantitative information regarding copolymer composition from an infrared spectrum. We can often identify unknown polymers by comparing their infrared spectra with electronic libraries containing spectra of known materials. 

We use carbon-13 NMR spectrometry to identify the monomer units present in copolymers, their absolute concentrations, the probability that two or more monomer units occur in proximity, and long chain branching concentrations. For instance, in the case of polyethylene, we can not only distinguish and quantify ethyl, butyl, and hexyl branches, but we can also determine whether branches are present on carbon backbone atoms separated by up to four bonds. We can compare the observed adjacency of branches to a theoretical value calculated for random comonomer incorporation. By this method, we can determine whether comonomers are incorporated at random, as blocks, or in some intermediate fashion. 

Identification of individual film layers was performed using ATR-FTIR. The outside layer labeled "1" was optically clear and was identified as an aromatic polyester most likely polyfethylene terephthalate) (PET) or an ethylene terephthalate/isophthalate copolymer. 

The polyethylene layer shows a series of fault lines that run perpendicular to the direction of applied stress. The fracture surface of the polyethylene is sharp and jagged, and shows no signs of elongation or ductility. Beneath the polyethylene layer "2" was a thin layer ("3") that was identified as ethylene/vinyl acetate copolymer (EVA). The EVA layer did show evidence of ductile failure in the SEM images. 

Figure 69 shows the ATR-FTIR spectra of the inside heat seal layer of the white film from both the "good" and "bad" packages. A library spectrum of an EVA copolymer is also shown for comparison. The heat seal layer is identified as EVA, based on the position of peaks in the sample spectra compared to the library EVA spectrum. The heat seal layer appears to have a lower vinyl acetate content compared to the library spectrum, which was acquired from a 14% vinyl acetate copolymer. There were no significant spectral differences between the spectra of the "good" and "bad" samples. 

---