Chloroform oligomers

FIGURE 13.25 Using chloroform as the solvent, a mixture of polystyrene standards were nicely separated on the 3-m set of columns. Run times here were 160 min. Plate count for toluene was calculated at 240,000 plates. The 500 MW Standard is separated nicely into its oligomers. 

Monomer-oligomer equilibria. [Ni(Me-sal)2], mentioned above as a typical planar complex, is a much studied compound. In pyridine it is converted to the octahedral bispyridine adduct (/zsoo = 3.1 BM), while in chloroform or benzene the value of is intermediate but increases with concentration. This is ascribed to an equilibrium between the diamagnetic monomer and a paramagnetic dimer, which must involve a coordination number of the nickel of at least 5 a similar explanation is acceptable also for the paramagnetism of the solid when heated above 180°C. The trimerization of Ni(acac)2 to attain octahedral coordination has already been referred to but it may also be noted that it is reported to be monomeric and planar in dilute chloroform solutions. 

Starting from the assumption that the geometry relaxation after excitation is of primary importance with respect to the luminescence response, we decided to employ a solid polymer matrix to suppress conformational changes of the oligomers. For the measurements, dilute blends with polysulfone as the transparent host matrix were prepared. In Figure 16-13, the PL decay curves for the two cyano compounds in both chloroform and polysulfone are presented, as are the PL spectra of Ooct-OPV5-CN in chloroform and polysulfone [69J. 

The cyclic dimer, tetramer, and hexamer can be crystallized in acetonitrile, and also in chloroform (the former two oligomers). X-ray analysis of the crystals of the cyclic dimer47 disclosed that it consisted of a pair of different enantiomers of 53 and that all of the four substituents attached to the two tetrahydropyran rings occupied the axial position as illustrated in Fig. 54s). Such a conformation is in... 

Synthesis of siloxane-urethane copolymers from various hydroxyalkyl-terminated PDMS oligomers and aliphatic diisocyanates, such as tetramethylene- and hexame-thylene diisocyanate and HMDI was reported 333,334). Reactions were conducted either in chloroform or 1,4-dioxane and usually low molecular weight, oily products were obtained. No data were available on the molecular weights or the thermal and mechanical properties of the copolymers obtained. These products were later cross-linked by a peroxide. Resulting materials were characterized by IR spectroscopy and water contact angle measurements for possible use as contact lenses. 

Cyclizations can also be carried out with an esterified oligomer of phosphoric acid called polyphosphate ester, which is chloroform soluble.55 Another reagent of this type is trimethylsilyl polyphosphate (Scheme 11.4, Entry 13).56 Neat methanesul-fonic acid is also an effective reagent for intramolecular Friedel-Crafts acylation (Scheme 11.4, Entry 14).57... 

Mori, S., Elution behavior of oligomers on a polyvinyl alccohol gel column with chloroform, methanol, and their mixtures, ]. Liq. Chromatogr., 11, 1205, 1988. 

Applications The determination and quantification of oligomers from PET has been carried out using various techniques Soxhlet extraction followed by gravimetric analysis with identification by HPLC-DAD, selective precipitation of the polymer (from a trifluoroacetic acid solution), and chloroform extraction under pressure in a sealed Parr bomb [112]. Heating of a 1 g sample in 20 mL chloroform at 100 °C for 2h allows a precision of 5 %. 

Reflux extraction of additives and wax from polyolefins was reported [116]. Subsequently, the additives were adsorbed onto an adsorbent (Florisil) and the wax was removed from the extract before chromatography. Boiling extractions of SBR are described in ASTM D 1416-89 1 g of rubber is extracted by boiling in two 100 mL portions of 75/25 vol% isopropyl alcohol/toluene. Reflux heating with strong solvents, such as THF, dichloromethane or chloroform has been reported [117]. Reflux extraction has also been used for the 3 h extraction of caprolactam and oligomers from PA6 in boiling methanol. 

A PET oligomer isolation method has utilised chloroform extraction in a Parr bomb lined with a Teflon-TFE fluoro-carbon resin [40]. The analytics of fluoropolymer processing aids (combustion analysis, XRF, EUR, 19F NMR, OM) have recently been described [29]. Combustion analysis (Parr Oxygen Bomb Calorimeter) can be used for quantitative analysis... 

Figure 4. Ratios of optical densities at 1730 cm1 (linear oligomers)/1705 cm"1 (cyclic dimers) as a function of mole fraction of acrylic acid in various solvents (1) dioxane (2) methanol (3) acetic acid (4) chloroform (5) toluene (6) CClk (4).

Materials. A series of a,to-bis(hydroxyphenyl)PSU oligomers with different molecular weights were synthesized and characterized as was previously reported (12). Two samples of PPO (one from Aldrich and one from General Electric Co.) were both purified by precipitation from chloroform solution into methanol. A commercial sample (Dow Chemical) of an isomeric mixture of chloromethylstyrenes (C1MS, 40% para, 60% meta) was used as received. 1-Chloromethoxy-4-chlorobu-tane (CMCB) was prepared according to a procedure developed by Olah et al. (14) and modified by Daly et al. (15), i.e., from paraformaldehyde, tetrahydrofuran and anhydrous HC1. 

Xu, R., Leonard J., and Bui, V.T. Vapor pressure for mixtures of methylene ester oligomers with /rdioxane and chloroform, /. 

Table 2 contains the characteristics of the amic ester-aryl ether copolymers including coblock type, composition, and intrinsic viscosity. Three series of copolymers were prepared in which the aryl ether phenylquinoxaline [44], aryl ether benzoxazole [47], or aryl ether ether ketone oligomers [57-59] were co-re-acted with various compositions of ODA and PMDA diethyl ester diacyl chloride samples (2a-k). The aryl ether compositions varied from approximately 20 to 50 wt% (denoted 2a-d) so as to vary the structure of the microphase-separated morphology of the copolymer. The composition of aryl ether coblock in the copolymers, as determined by NMR, was similar to that calculated from the charge of the aryl ether coblock (Table 2). The viscosity measurements, also shown in Table 2, were high and comparable to that of a high molecular weight poly(amic ethyl ester) homopolymer. In some cases, a chloroform solvent rinse was required to remove aryl ether homopolymer contamination. It should also be pointed out that both the powder and solution forms of the poly(amic ethyl ester) copolymers are stable and do not undergo transamidization reactions or viscosity loss with time, unlike their poly(amic acid) analogs.

The presence of a folded state was evaluated by studying the spectroscopic properties of 1-9 in both chloroform and acetonitrile, which are good and bad solvents, respectively [23,25,26]. The molar absorptivity of 1-9 in chloroform increased in a linear fashion with respect to oligomer length (Fig. 2). However, when UV spectra were taken in acetonitrile two linear trends were identified. Oligomers 1-5 displayed a slope similar to that observed in chloroform, while 4-9 displayed a much smaller slope. The decrease in slope is... 

Fig. 2 The molar extinction coefficient e (303 nm) for oligomers 1-9 in chloroform (straight line) and acetonitrile (broken line). The lines are linear fit to the data...

The metathesis reaction of the imine bond was also able to dynamically select for oligomers that form the most stable host-guest complex [88]. It has been shown that rodlike and dumbbell-shaped guests have a higher affinity and specificity for oligomers of 20-22 repeat units [58,61 ]. Imine starter sequences 60,61a, and 61b, which can potentially form 16- (63a), 22- (63b), and 28-mers (63c) as well as smaller molecular weight (MW) materials (62a and 62b), were chosen as starter sequences for an imine ligation experiment (Fig. 37). When equiUbrated in chloroform the product distribution of 63a-c was close to 1 1 1,... 

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