The present invention generally relates to the field of polymer characterization.  In particular, the invention relates to liquid chromatography and related flow-injection analysis techniques for rapidly characterizing polymer solutions, emulsions and dispersions, and to devices for implementing such techniques.  In preferred embodiments, the characterization of a polymer sample or of components thereof is effected with optical detectors.  The methods and devices disclosed herein are applicable, inter alia, to the rapid characterization of libraries of polymers prepared by combinatorial materials science techniques. 
Currently, there is substantial research activity directed toward the discovery and optimization of polymeric materials for a wide range of applications.  Although the chemistry of many polymers and polymerization reactions has been extensively studied, it is, nonetheless, rarely possible to predict a priori the physical or chemical properties a particular polymeric material will possess or the precise composition and architecture that will result from any particular synthesis scheme.  Thus, characterization techniques to determine such properties are an essential part of the discovery process. 
Combinatorial chemistry refers generally to methods for synthesizing a collection of chemically diverse materials and to methods for rapidly testing or screening this collection of materials for desirable performance characteristics and properties.  Combinatorial chemistry approaches have greatly improved the efficiency of discovery of useful materials.  For example, material scientists have developed and applied combinatorial chemistry approaches to discover a variety of novel materials, including for example, high temperature superconductors, magnetoresistors, phosphors and catalysts.  See, for example, U.S. Pat.  No.  5,776,359 to Schultz et al.  In comparison to traditional materials science research, combinatorial materials research can effectively evaluate much larger numbers of diverse compounds in a much shorter period of time.  Although such high-throughput synthesis and screening methodologies are conceptually promising, substantial technical challenges exist for application thereof to specific research and commercial goals. 
Methods have been developed for the combinatorial (e.g., rapid-serial or parallel) synthesis and screening of libraries of small molecules of pharmaceutical interest, and of biological polymers such as polypeptides, proteins, oligonucleotides and deoxyribonucleic acid (DNA) polymers.  However, there have been few reports of the application of combinatorial techniques to the field of polymer science for the discovery of new polymeric materials or polymerization catalysts or new synthesis or processing conditions.  Brocchini et al.  describe the preparation of a polymer library for selecting biomedical implant materials.  See S. Brocchini et al.,  A Combinatorial Approach for Polymer Design, J. Am.  Chem.  Soc.  119, 4553-4554 (1997).  However, Brocchini et al.  reported that each synthesized candidate material was individually precipitated, purified, and then characterized according to xe2x80x9croutine analysisxe2x80x9d that included gel permeation chromatography to measure molecular weight and polydispersities.  As such, Brocchini et al.  did not address the need for efficient and rapid characterization of polymers. 
Liquid chromatography is well known in the art for characterizing a polymer sample.  Liquid chromatographic techniques employ separation of one or more components of a polymer sample from other components thereof by flow through a chromatographic column, followed by detection of the separated components with a flow-through detector.  Approaches for liquid chromatography can vary, however, with respect to the basis of separation and with respect to the basis of detection.  Gel permeation chromatography (GPC), a well-known form of size exclusion chromatography (SEC), is a frequently-employed chromatographic technique for polymer size determination.  In GPC, the polymer sample is separated into components according to the hydrodynamic volume occupied by each component in solution.  More specifically, a polymer sample is injected into a mobile phase of a liquid chromatography system and is passed through one or more chromatographic columns packed with porous beads.  Molecules with relatively small hydrodynamic volumes diffuse into the pores of the beads and remain therein for longer periods, and therefore exit the column after molecules with relatively larger hydrodynamic volume.  Hence, GPC can characterize one or more separated components of the polymer sample with respect to its effective hydrodynamic radius (Rh).  Another chromatographic separation approach is illustrated by U.S. Pat.  No.  5,334,310 to Frechet et al.  and involves the use of a porous monolithic stationary-phase as a separation medium within the chromatographic column, combined with a mobile-phase composition gradient. ( See also, Petro et al, Molded Monolithic Rod of Macroporous Poly(styrene-co-divinylbenzene) as a Separation Medium for HPLC Synthetic Polymers: xe2x80x9cOn-Columnxe2x80x9d Precipitation-Redissolution Chromatography as an Alternative to Size Exclusion Chromatography of Styrene Oligomers and Polymers, Anal.  Chem.,  68, 315-321 (1996); and Petro et al, Immobilization of Trypsin onto xe2x80x9cMoldedxe2x80x9d Macroporous Poly(Glycidyl Methacrylate-co-Ethylene Dimethacrylate) Rods and Use of the Conjugates as Bioreactors and for Affinity Chromatography, Biotechnology and Bioengineering, Vol.  49, pp.  355-363 (1996)).  Chromatography involving the porous monolith is reportedly based on a precipitation/redissolution phenomenon that separates the polymer according to sizexe2x80x94with the precipitated polymer molecules selectively redissolving as the solvent composition is varied.  The monolith provides the surface area and permeation properties needed for proper separation.  Other separation approaches are also known in the art, including for example, normal-phase adsorption chromatography (with separation of polymer components being based on preferential adsorption between interactive functionalities of repeating units and an adsorbing stationary-phase) and reverse-phase chromatography (with separation of polymer components being based on hydrophobic interactions between a polymer and a non-polar stationary-phase).  After separation, a detector can measure a property of the polymer or of a polymer componentxe2x80x94from which one or more characterizing properties, such as molecular weight can be determined as a function of time.  Specifically, a number of molecular-weight related parameters can be determined, including for example: the weight-average molecular weight (Mw), the number-average molecular weight (Mn), the molecular-weight distribution shape, and an index of the breadth of the molecular-weight distribution (Mw/Mn), known as the polydispersity index (PDI).  Other characterizing properties, such as mass, particle size, composition or conversion can likewise be determined. 
Flow-injection analysis techniques have been applied for characterizing small molecules, such as pigments.  Typically, such techniques include the detection of a sample with a continuous-flow detectorxe2x80x94without chromatographic separation prior to detection.  However, such approaches have not, heretofore, been applied in the art of polymer characterization.  Moreover, no effort has been put forth to optimize such approaches with respect to sample-throughput. 
A variety of continuous-flow detectors have been used for measurements in liquid chromatography systems.  Common flow-through detectors include optical detectors such as a differential refractive index detector (RI), an ultraviolet-visible absorbance detector (UV-VIS), or an evaporative mass detector (EMD)xe2x80x94sometimes referred to as an evaporative light scattering detector (ELSD).  Additional detection instruments, such as a static-light-scattering detector (SLS), a dynamic-light-scattering detector (DLS), and/or a capillary-viscometric detector (C/V) are likewise known for measurement of properties of interest.  Light-scattering methods, both static and dynamic, are established in several areas of polymer analysis.  Static light scattering (SLS) can be used to measure Mw and the radii of gyration (Rg) of a polymer in a dilute solution of known concentration.  Dynamic light scattering (DLS) measures the fluctuations in the scattering signal as a function of time to determine the diffusion constant of dissolved polymer chains or other scattering species in dilute solution or of polymer particles comprising many chains in a heterogeneous system such as dilute emulsion or latex dispersion.  The hydrodynamic radius, Rh, of the chains or particles can then be calculated based on well-established models. 
Presently known liquid chromatography systems and flow-injection analysis systems are not suitable for efficiently screening larger numbers of polymer samples.  Known chromatographic techniques can typically take up to an hour for each sample to ensure a high degree of separation over the wide range of possible molecular weights (i.e., hydrodynamic volumes) for a sample.  The known chromatographic techniques can be even longer if the sample is difficult to dissolve or if other problems arise.  Additionally, polymer samples are typically prepared for characterization manually and individually, and some characterization systems require specially-designed sample containers and/or substantial delay-times.  For example, optical methods such as light-scattering protocols typically employ detector-specific cuvettes which are manually placed in a proper location in the light-scattering instrument.  Such optical protocols can also require a sample to thermally equilibrate for several minutes before measurement.  Moreover, because of the nature of many commercial polymers and/or polymer samplesxe2x80x94such as their non-polarity and insolubility in water and/or alcohols, their heterogeneous nature, their lack of sequence specificity, among other aspects, the methods, systems and devices developed in connection with the biotechnological, pharmaceutical and clinical-diagnostic arts are generally not instructive for characterizing polymers.  Hence, known approaches are not well suited to the rapid characterization of polymers. 
Aspects of polymer characterization, such as sample preparation and polymer separation, have been individually and separately investigated.  For example, Pochxc3xa9 et al.  report a system and approach for automated high-temperature dissolution of polymer samples.  See Pochxc3xa9 et al.,  Use of Laboratory Robotics for Gel Permeation Chromatography Sample Preparation: Automation of High-Temperature Polymer Dissolution, J. Appl.  Polym.  Sci.,  64(8), 1613-1623 (1997).  Stationary-phase media that reduce chromatographic separation times of individual polymer samples have also been reported.  See, for example, Petro et al.,  Molded continuous poly(styrene-co-divinylbenzene) rod as a separation medium for the very fast separation of polymers; Comparison of the chromatographic properties of the monolithic rod with columns packed with porous and no-porous beads in high-performance liquid chromatography, Journal of Chromatography A, 752, 59-66 (1996); and Petro et al.,  Monodisperse Hydrolyzed Poly(glcidyl methacrylate-co-ethylene dimethacrylate) Beads as a Stationary Phase for Normal-Phase HPLC, Anal.  Chem.,  69, 3131 (1997).  However, such approaches have not contemplated nor been incorporated into protocols and systems suitable for large-scale, or even moderate-scale, combinatorial chemistry research, and particularly, for combinatorial material science research directed to the characterization of polymers. 
With the development of combinatorial techniques that allow for the parallel synthesis of arrays comprising a vast number of diverse industrially relevant polymeric materials, there is a need for methods and devices and systems to rapidly characterize the properties of the polymer samples that are synthesized
It is therefore an object of the present invention to provide systems and protocols for characterizing combinatorial libraries of polymer samples, and particularly, libraries of or derived from polymerization product mixtures, to facilitate the discovery of commercially important polymeric materials, catalysts, polymerization conditions and/or post-synthesis processing conditions.  It is also an object of the invention to provide polymer characterization systems and protocols that can be employed in near-real-time industrial process control. 
Briefly, therefore, this invention provides methods and apparatus for the rapid characterization or screening of polymers by chromatographic techniques and related flow-injection analysis techniques, and particularly, those employing optical detection methods.  This invention provides a number of embodiments for such rapid characterization or screening of polymers and those embodiments can be employed individually or combined together.  More specifically, polymer characterization approaches and devices are presented involving flow characterization and non-flow characterization, and with respect to both of the same, involving rapid-serial, parallel, serial-parallel and hybrid parallel-serial approaches.  Some preferred approaches and embodiments are directed to rapid-serial flow characterization of polymer samples. 
Among the several significant aspects of the rapid-serial flow characterization techniques are protocols and systems related to automated sampling, chromatographic separation (where applicable) and/or detectionxe2x80x94which individually and collectively improve the sample-throughput when applied to characterize a plurality of polymer samples.  The automated polymer sampling can be effected at faster sampling rates, with equipment optimized for such purposes, and in sequences that benefit overall throughput and/or minimize extraneous steps.  A number of chromatographic separation techniques can be employed to efficiently and effectively separate one or more of the various components of a heterogeneous polymer sample from one or more other components thereof.  Generally, such techniques relate to column geometry, separation medium and mobile-phase medium.  Certain approaches and systems disclosed herein involve improved aspects of detection.  In addition, rapid, indirect calibration standards and methods impact overall system speed.  Moreover, several important aspects of the invention have direct implications for high-temperature characterization efforts (typically ranging from about 75xc2x0 C. to about 225xc2x0 C.). 
Many of such aspects of the invention can be directly translated for use with parallel or serial-parallel protocols, in addition to rapid-serial protocols.  In a preferred embodiment, for example, a parallel or serial-parallel dynamic light-scattering system and protocols can be used for polymer characterization with very high sample throughput. 
Hence the methods, systems and devices of the-present invention are particularly suited for screening of arrays of polymerization product mixtures prepared in the course of combinatorial materials discoveryxe2x80x94thereby providing a means for effectively and efficiently characterizing large numbers of different polymeric materials.  While such methods, systems and devices have commercial application in combinatorial materials science research programs, they can likewise be applied in industrial process applications for near-real-time process monitoring or process control. 
Other features, objects and advantages of the present invention will be in part apparent to those skilled in art and in part pointed out hereinafter.  All references cited in the instant specification are incorporated by reference for all purposes.  Moreover, as the patent and non-patent literature relating to the subject matter disclosed and/or claimed herein is substantial, many relevant references are available to a skilled artisan that will provide further instruction with respect to such subject matter.