Viscometry, on-line

GPC proved to be a method extraordinarily well suited to the analysis and purification of 9-phenylcarbazole monodendrons, naturally branched polymers.12 Monodendrons up to generation four, molecular weight 16.6 kDa, were separated by GPC. Branching, introduced into bacterially produced poly(hydroxy butyrate) by co-polymerization with hydroxyvaleric acid, was analyzed by GPC in chloroform with on-line viscometry.13... 

The use of MM-sensitive detectms has been extensively reported. Crubisic-Gallot et al. [37] applied SEC with on-line viscometry, using a discrete visccxneter (Ubbelohde type), to homopolymers and copolymers. They also used the technique to obtain a relation between viscosity and MM. The disadvantage of this method is that it cannot monitor the eluent continuously. 

SEC-viscometry has also been applied to natural polymers with more complex molecular weight distributions. Timpa (61) used universal calibration and on-line viscometry to measure the MWD of cotton fibers to evaluate different... 

Aqueous SEC of PVA Using On-Line Viscometry Fully Hydrolyzed PVA... 

Monomer conversion can be adjusted by manipulating the feed rate of initiator or catalyst. If on-line M WD is available, initiator flow rate or reactor temperature can be used to adjust MW [38]. In emulsion polymerization, initiator feed rate can be used to control monomer conversion, while bypassing part of the water and monomer around the first reactor in a train can be used to control PSD [39,40]. Direct control of surfactant feed rate, based on surface tension measurements also can be used. Polymer quality and end-use property control are hampered, as in batch polymerization, by infrequent, off-line measurements. In addition, on-line measurements may be severely delayed due to the constraints of the process flowsheet. For example, even if on-line viscometry (via melt index) is available every 1 to 5 minutes, the viscometer may be situated at the outlet of an extruder downstream of the polymerization reactor. The transportation delay between the reactor where the MW develops, and the viscometer where the MW is measured (or inferred) may be several hours. Thus, even with frequent sampling, the data is old. There are two approaches possible in this case. One is to do open-loop, steady-state control. In this approach, the measurement is compared to the desired output when the system is believed to be at steady state. A manual correction to the process is then made, based on the error. The corrected inputs are maintained until the process reaches a new steady state, at which time the process is repeated. This approach is especially valid if the dominant dynamics of the process are substantially faster than the sampling interval. Another approach is to connect the output to the appropriate process input(s) in a closed-loop scheme. In this case, the loop must be substantially detuned to compensate for the large measurement delay. The addition of a dead time compensator can... 

All these factors mean that the study of on-line viscometry is a subject apart, with its own rules and regulations. This is especially true since most liquids of interest are temperature sensitive and non-Newtonian (and possibly viscoelastic) in nature. 

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... 

The experimental techniques for the study of conformational branched properties in solution are the same as used for linear chains. These are, in particular, static and dynamic light scattering, small angle X-ray (SAXS) and small angle neutron (SANS) scattering methods, and common capillary viscometry. These methods are supported by osmotic pressure measurements and, nowadays extensively applied, size exclusion chromatography (SEC) in on-line combination with several detectors. These measurements result in a list of molecular parameters which are given in Table 1. 

Due to the problems encountered with SEC-LALLS and SEC-viscometry, a triple-detector SEC technology has been developed, where three on-line detectors are used together in a single SEC system. In addition to the concentration detector, an on-line viscometer and a LALLS instrument are coupled to the SEC... 

SEC with On-Line Triple Detection Light Scattering, Viscometry, and R( Susan V. Greene... 

The opportunity to measure the dilute polymer solution viscosity in GPC came with the continuous capillary-type viscometers (single capillary or differential multicapillary detectors) coupled to the traditional chromatographic system before or after a concentration detector in series (see the entry Viscometric Detection in GPC-SEC). Because liquid continuously flows through the capillary tube, the detected pressure drop across the capillary provides the measure for the fluid viscosity according to the Poiseuille s equation for laminar flow of incompressible liquids [1], Most commercial on-line viscometers provide either relative or specific viscosities measured continuously across the entire polymer peak. These measurements produce a viscometry elution profile (chromatogram). Combined with a concentration-detector chromatogram (the concentration versus retention volume elution curve), this profile allows one to calculate the instantaneous intrinsic viscosity [17] of a polymer solution at each data point i (time slice) of a polymer distribution. Thus, if the differential refractometer is used as a concentration detector, then for each sample slice i. 

A new development is the use of in-line viscometry (e.g. refs. 38-40), whidi makes it possible to determine in-line and caitinuously the MM of polymers for which neither standards nor a good viscority-MM relation are available. SEC-viscometty can also provide infcHmation on branched polymers (see Section 11.2.4.4). In principle, it can also give the intrinsic viscosity of the polymer and the Maik-Houwink parameters from a siitgle expmment [32,41]. 

It is possible to add a second, molecular weight-sensitive detector to an SEC system to provide a direct means of absolute molecular weight calibration without the need to resort to external standards. These detectors represent refinements in classic techniques, such as light-scattering photometry, capillary viscometry (for intrinsic viscosity), and membrane osmometry for on-line molecular weight determination. Yau recently published a review of this subject with comparisons of the properties and benefits of the principal detectors currently in use (22). The present discussion is restricted to lightscattering and viscometry detectors because Yau s osmometry detector is not yet commercially available. The reader is referred to Chapter 4 for a comprehensive discussion of molecular weight-sensitive detectors. 

SEC-viscometry and universal calibration has been widely used to determine the MWD of synthetic polymers, and selected applications are listed in Table 1. On-line viscometers have been successfully used at high temperatures Pang and Rudin (50) measured the MWD of polyolefins dissolved in 1,2,4-trichlorobenzene at 145°C, and Stacy (17) measured the MWD of polyphenyl sulfide in 1-chloronaphthalene at 220 °C. 

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