Molecular weight dependency of refractive index increment of polystyrene determined by uniform oligomers

Itakura, Masanao; Sato, Keisuke; Lusenkova, Marina A.; Matsuyama, Shigetomo; Shimada, Kayori; Saito, Tetsuya; Kinugasa, Shinichi

doi:10.1002/app.21006

Cited by 27 publications

(19 citation statements)

References 10 publications

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“…The molecular weight of a given polymer, as determined by light scattering, depends on the square of dn/dc; even a slight variation in dn/dc therefore results in a large error in the value of M n . 26 However, when the polymer is examined in solid-state-film form, the intermolecular interactions and packing efficiency become important. As the molecular weight of the polymers decreases, the intermolecular interactions and packing efficiency may lead to an increased packing density of the chains in a given area, as is described by the Lorenz-Lorentz relationship.…”

Section: Resultsmentioning

confidence: 99%

The preparation of well-controlled poly(N-cyclohexyl-exo-norbornene-5,6-dicarboximide) polymers

Spring

Qiu

et al. 2014

Polym J

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We have studied the ring-opening metathesis polymerization of N-cyclohexyl-exo-norbornene-5,6-dicarboximide using the following 4 initiators: Grubbs 1, Grubbs 2, Hoveyda-Grubbs 1 (HG1) and Hoveyda-Grubbs 2 (HG2). Only the Grubbs 1 initiator was able to precisely control the polymer molecular weight. Polymerizations initiated by the HG1, Grubbs 2 and HG2 initiators could not be controlled well. Both the Grubbs 1 and HG1 yielded polymers with a high trans % (85-98%), whereas Grubbs 2 and HG2 yielded polymers with a lower trans % (50-52%). The level of molecular weight control for the four initiators decreased in the order Grubbs 14HG14HG24Grubbs 2. We also demonstrated that, in the case of polymers produced using Grubbs 1, the refractive indices (RIs) of the polymers decreased in a linear and controllable fashion from 1.539 to 1.534 at 633 nm, as the molecular weight was increased from 6700 to 26 400. This change represented a decrease in the RI of 0.005. INTRODUCTIONThe academic interest in poly(N-exo-norbornene-5,6-dicarboximide) (poly(NDI)) polymers has recently increased substantially, and its applications span physics, 1 chemistry 2 and biology. 3 A small selection of these interesting applications include cell adhesion materials, membranes, insulating materials and various optics applications. [4][5][6][7][8][9] This breadth of applications can be attributed to the fact that, as a polymer class, poly(NDI)s have been demonstrated to exhibit favorable thermal and mechanical properties, which greatly extend their range of practical applications. 10-14 Furthermore, ring-opening metathesis polymerization allows the preparation of well-defined random, block and alternating copolymers that extend the utility of poly(NDI)s as a system to prepare reactive and functional polymers. 15,16 Therefore, a systematic study of the influence of the Grubbs initiator on the precise controllability of the molecular weight and stereochemistry of a standard NDI monomer is of practical utility. Monomer preparation for poly(NDI)s is simple and easy. 17 Tlenkopatchev and coworkers have studied poly(NDI)s in detail using the Grubbs 1 (G1) and Grubbs 2 (G2) initiators. 13,14,18,19 Such initiators are known to impart trans-cis conformations into the polymer backbone. In this study, we focused on the monomer N-cyclohexyl-exo-norbornene-5,6-dicarboximide (CyNDI (4)) (Scheme 1). This monomer and polymer are soluble in common organic solvents such as chloroform and tetrahydrofuran. Furthermore, the monomer CyNDI (4) is easy to prepare in large quantities. Currently, the four different initiators G1, G2, Hoveyda-Grubbs 1

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Section: Resultsmentioning

confidence: 99%

The preparation of well-controlled poly(N-cyclohexyl-exo-norbornene-5,6-dicarboximide) polymers

Spring

Qiu

et al. 2014

Polym J

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“…For an oligomeric sample, however, it is well known that (Ѩn/Ѩc) depends on molecular mass. 13 Therefore, a common analysis using a Zimm plot for oligomer gives an apparent mass-average molecular mass M w(app) , which is defined as follows: where…”

Section: Correction Of Density Scatteringmentioning

confidence: 99%

A convenient method to determine the Rayleigh ratio with uniform polystyrene oligomers

Itakura

Shimada

Matsuyama

et al. 2005

J of Applied Polymer Sci

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ABSTRACT:The Rayleigh ratio of toluene at 25°C for a wavelength of 632.8 nm was determined by static light scattering measurement of a certified polystyrene reference material PS 2400 with exactly evaluated or certified mass-average molecular mass (M w ). At first, static light scattering measurements were carried out for PS 2400 in toluene with a literature value of the Rayleigh ratio of toluene. Then, corrections of degree of depolarization, density fluctuations, and molecular mass dependence of refractive index increment were applied to the observed M w of PS 2400 to obtain apparent M w . Finally, from the ratio between the apparent M w and the certified M w , the Rayleigh ratio of toluene was reevaluated.

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“…with ( dn/dc ) = ‐0.1 mL/g (constant literature value, ‐0.1 for PE) yielded k RI values clearly dependent on molar mass. In this work, a dependence of dn/dc with molar mass was assumed according to a previously published equation:

{(\frac{d n}{d c})}_{M} = {(\frac{d n}{d c})}_{0} true(1 - \frac{d}{M_{normalw}} true)

where ( dn/dc ) 0 is the constant literature value (−0.1 for PE), d is a fitting parameter and M w is the weight average molar mass.…”

Section: Resultsmentioning

confidence: 99%

“…As expected a stable response from the IR was found, while a high variation was observed in the case of DRI. A procedure to correct this undesired effect of DRI response is described and was successfully applied …”

Section: Introductionmentioning

confidence: 99%

Direct Comparison of IR and DRI Detector for HT‐GPC of Polyolefins

Honghong

Guo

Dong

et al. 2015

Macromolecular Symposia

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Molar mass Ortdistribution (MMD) of polyolefins is routinely analyzed by gel permeation chromatography (GPC), also known as size exclusion chromatography (SEC), practiced in different methods and detector systems. The filter-based infrared detector (IR) has become a preferred alternative to the traditional use of differential refractive index detector (DRI) for high temperature GPC (HT-GPC) when applied to polyolefins. The main reason is that a modern multiple band filter-based IR detector can be used to determine the distribution of co-monomer along the molar mass distribution in a copolymer, in a single HT-GPC analysis directly without the need of additional analytical procedures. In addition to that, the performance of the modern IR detector when used as primary concentration detector in the HT-GPC instrument, in either the single or the multiple detection schemes, proves to be superior to that of DRI detector. This is due to the high signal-to-noise ratio achievable by the modern IR detector and its excellent baseline stability. Such high detection quality can be attributed to the inherent robustness of IR spectroscopy against external factors such as GPC temperature and flow rate variations. The impact of that higher detection performance on the final processed analytical results of polymer MMD and molar mass averages among others, is the focus of this current investigation. Different application scenarios of industrial interest have been selected to show a direct comparison of both the IR and DRI detectors installed on a same GPC instrument.

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Molecular weight dependency of refractive index increment of polystyrene determined by uniform oligomers

Cited by 27 publications

References 10 publications

The preparation of well-controlled poly(N-cyclohexyl-exo-norbornene-5,6-dicarboximide) polymers

The preparation of well-controlled poly(N-cyclohexyl-exo-norbornene-5,6-dicarboximide) polymers

A convenient method to determine the Rayleigh ratio with uniform polystyrene oligomers

Direct Comparison of IR and DRI Detector for HT‐GPC of Polyolefins

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