Characterization Intrinsic Viscosity

Following the procedure described in the last problem, Taylorf fractionated nylon-6,6 into a series of cuts which he characterized by viscosity. These cuts were then refractionated. The following is a list of the intrinsic viscosi-... 

Experiments based on the Poiseuille equation make intrinsic viscosity an easily measured parameter to characterize a polymer. In the next section we consider how this property can be related to the molecular weight of a polymer. 

Since viscometer drainage times are typically on the order of a few hundred seconds, intrinsic viscosity experiments provide a rapid method for evaluating the molecular weight of a polymer. A limitation of the method is that the Mark-Houwink coefficients must be established for the particular system under consideration by calibration with samples of known molecular weight. The speed with which intrinsic viscosity determinations can be made offsets the need for prior calibration, especially when a particular polymer is going to be characterized routinely by this method. 

Solution Polymers. Acryflc solution polymers are usually characterized by their composition, solids content, viscosity, molecular weight, glass-transition temperature, and solvent. The compositions of acryflc polymers are most readily determined by physicochemical methods such as spectroscopy, pyrolytic gas—liquid chromatography, and refractive index measurements (97,158). The solids content of acryflc polymers is determined by dilution followed by solvent evaporation to constant weight. Viscosities are most conveniently determined with a Brookfield viscometer, molecular weight by intrinsic viscosity (158), and glass-transition temperature by calorimetry. 

Analytical and test methods for the characterization of polyethylene and PP are also used for PB, PMP, and polymers of other higher a-olefins. The C-nmr method as well as k and Raman spectroscopic methods are all used to study the chemical stmcture and stereoregularity of polyolefin resins. In industry, polyolefin stereoregularity is usually estimated by the solvent—extraction method similar to that used for isotactic PP. Intrinsic viscosity measurements of dilute solutions in decahn and tetraHn at elevated temperatures can provide the basis for the molecular weight estimation of PB and PMP with the Mark-Houwiok equation, [rj] = KM. The constants K and d for several polyolefins are given in Table 8. 

Intrinsic viscosity is often used to characterize tetrahydrofuran polymers. Intrinsic viscosities in a variety of solvents and Mark-Houwink constants for the equation [rj] = Khave been deterrnined for a wide variety of solvents (39—45),where [Tj] is the intrinsic viscosity, M is molecular weight, and K and a are constants many of the constants have been summarized and tabulated (6). 

Dilute Polymer Solutions. The measurement of dilute solution viscosities of polymers is widely used for polymer characterization. Very low concentrations reduce intermolecular interactions and allow measurement of polymer—solvent interactions. These measurements ate usually made in capillary viscometers, some of which have provisions for direct dilution of the polymer solution. The key viscosity parameter for polymer characterization is the limiting viscosity number or intrinsic viscosity, [Tj]. It is calculated by extrapolation of the viscosity number (reduced viscosity) or the logarithmic viscosity number (inherent viscosity) to zero concentration. 

Synthetic, nonionic polymers generally elute with little or no adsorption on TSK-PW columns. Characterization of these polymers has been demonstrated successfully using four types of on-line detectors. These include differential refractive index (DRI), differential viscometry (DV), FALLS, and MALLS detection (4-8). Absolute molecular weight, root mean square (RMS) radius of gyration, conformational coefficients, and intrinsic viscosity distributions have... 

In SEC, universal calibration is often utilized to characterize a molecular weight distribution. For a universal calibration curve, one must determine the product of log(intrinsic viscosity molecular weight), or log([7j] M). The universal calibration method originally described by Benoit et al. (9) employs the hydro-dynamic radius or volume, the product of [tj] M as the separation parameter. The calibration curves for a variety of polymers will converge toward a single curve when plotted as log([7j] M) versus elution volume (VJ, rather than plotted the conventional way as log(M) versus V, (5). Universal calibration behavior is highly dependent on the absence of any secondary separation effects. Most failures of universal calibration are normally due to the absence of a pure size exclusion mechanism. 

The most widely used molecular weight characterization method has been GPC, which separates compounds based on hydrodynamic volume. State-of-the-art GPC instruments are equipped with a concentration detector (e.g., differential refractometer, UV, and/or IR) in combination with viscosity or light scattering. A viscosity detector provides in-line solution viscosity data at each elution volume, which in combination with a concentration measurement can be converted to specific viscosity. Since the polymer concentration at each elution volume is quite dilute, the specific viscosity is considered a reasonable approximation for the dilute solution s intrinsic viscosity. The plot of log[r]]M versus elution volume (where [) ] is the intrinsic viscosity) provides a universal calibration curve from which absolute molecular weights of a variety of polymers can be obtained. Unfortunately, many reported analyses for phenolic oligomers and resins are simply based on polystyrene standards and only provide relative molecular weights instead of absolute numbers. 

The ionic strength dependence of intrinsic viscosity is function of molecular structure and protein folding, ft is well known that the conformational and rheological properties of charged biopolymer solutions are dependent not only upon electrostatic interactions between macromolecules but also upon interactions between biopolymer chains and mobile ions. Due electrostatic interactions the specific viscosity of extremely dilute solutions seems to increase infinitely with decreasing ionic concentration. Variations of the intrinsic viscosity of a charged polyampholite with ionic strength have problems of characterization. 

Low-molecular weight chains do not experience enough shear force to induce scission. Watson et al." demonstrated (by the intrinsic viscosity characterization of masticated NR) that the limiting molecular weight for the shear-induced degradation is in the order of 0.7-1.0 X 10 Frenkel independently speculated that shear-induced cleavage occurs near the midpoint of the polymer chain. 

Hydroformylation and subsequent hydrogenation of C=C and -CHO groups of PBD appear to be an appropriate means whereby a pendent hydroxy group can be introduced onto the polymer backbone. A variety of partially hydroformyl ated (2-20%) and hydroxymethy-lated polymers have been synthesized by a two-step catalytic reaction and characterized by I.R. and 1H N.M.R. spectroscopy. As expected, the hydrophilic group, OH, in the polymer resulted in a greater decrease in the intrinsic viscosity as compared to the HPBD. 

CHARACTERIZATION. The intrinsic viscosity of the soluble fractions was determined in toluene at 30 C. The MAH content of the soluble fractions was determined by heating a 0.5-1.0g portion in refluxing water-saturated xylene for 1 hr and titrating the hot solution with 0.05N ethanolic KOH using 1% thymol blue in DMF as indicator. 

Anionic polymerization techniques were also critical for the synthesis of a model cyclic triblock terpolymer [cyclic(S-fo-I-fr-MMA)] [196]. The linear cctw-amino acid precursor S-fr-I-fr-MMA was synthesized by the sequential anionic polymerization of St, I and MMA with 2,2,5,5-tetramethyl-l-(3-lithiopropyl)-l-aza-2,5-disilacyclopentane as the initiator and amine generator, and 4-bromo-l,l,l-trimethoxybutane as a terminator and carboxylic acid generator. Characterization studies of the intermediate materials as well as of the final cyclic terpolymer revealed high molecular and compositional homogeneity. Additional proof for the formation of the cyclic structure was provided by the lower intrinsic viscosity found for the cyclic terpolymer compared to that of the precursor. 

It is now recognized that a continuum of architecture and properties, which begins with the classical branched polymers, resides between these two classes. Typical branched structures such as starch or high pressures polyethylene are characterized by more than two terminal groups per molecule, possessing substantially smaller hydrodynamic volumes and different intrinsic viscosities compared to linear polymers, yet they often exhibit unexpected segmental expansion near the theta state . 

Figure 5.14 Hot crystallization rate as a function of intrinsic viscosity during SSP T, 220 °C [26]. From Wick, G., Characterization of PET polymer for bottle manufacturing, presentation given at the Society of Plastics Engineers Benelux Seminar, 20-21 May, 1980, Amsterdam, and reproduced with permission of KoSa GmbH Co. KG...

Table 13.1 Intrinsic viscosity and molecular weight data for the three characterized polymers (cf. Figure 13.2) [13]. From Some effects of the rheological properties of PET on spinning line profile and structure developed in high-speed spinning , Perez, G., in High-Speed Fiber Spinning, Ziabicki, A. and Kawai, H. (Eds), 1985, pp. 333-362, copyright (1985 John Wiley Sons, Inc.). Reprinted by permission of John Wiley Sons, Inc.

The numerical efficiency of the viscosity lower bound method has allowed calculations on considerably longer chains. The long chain Hmit results for 12-arm stars without intramolecular interactions and with EV (up to 325 beads) and in the theta region (up to 145 beads) [164] are close to the previous estimates with shorter chains (the extrapolated ratio g obtained in this study is also included in Table 4). The lower bound method has also served to characterize globule-coil transitions of 12-arm star chains from intrinsic viscosity calculations [143], though finite size effects are considerably more important than in the characterization of this transition from the radius of gyration data (see Fig. 17). This is due to the noticeable increase in the solvent permeabiHty associated with the chain expansion in better solvent conditions. However, the permeability effects are smaller in the more compact star chains than in their linear counterparts. 

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