Analysis of Macrocyclic Polystyrenes. 1. Liquid Chromatographic Investigations

Pasch, Harald; Deffieux, Alain; Henze, Inka; Schappacher, Michel; Rique‐Lurbet, Laurence

doi:10.1021/ma960915r

Cited by 52 publications

(38 citation statements)

References 11 publications

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“…13,46 In this method, the mobile and stationary phases as well as temperature were selected for optimum LCCC conditions. Chain length effects are absent, and polymers with different MWs are eluted at the same volume, but polymers with different compositions or different architectures are eluted at different volumes.…”

Section: Psmentioning

confidence: 99%

Synthesis and characterization of macrocyclic vinyl aromatic polymers

Hogen‐Esch

2006

J. Polym. Sci. A Polym. Chem.

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The synthesis and characterization by size exclusion chromatography, liquid chromatography, NMR, matrix‐assisted laser desorption/ionization, thermal analysis, and other techniques of well‐defined and narrow molecular weight distribution macrocyclic polystyrene (PS), poly(2‐vinylpyridine), poly(α‐methylstyrene), poly (2‐vinyl‐naphthalene) (P2VN), and poly(9,9‐dimethyl‐2‐vinylfluorene) (PDMVF) containing a single 1,4‐benzylidene, methylidene, or 9,10‐anthracenylidene unit are reviewed. The absorption and emission spectroscopy of PS, P2VN, and PDMVF is also discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2139–2155, 2006

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Section: Psmentioning

confidence: 99%

Synthesis and characterization of macrocyclic vinyl aromatic polymers

Hogen‐Esch

2006

J. Polym. Sci. A Polym. Chem.

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“…20) They have applied the liquid chromatography at the critical condition (LCCC) for the fractionation of ring PSs. LCCC, which has been developed since 1990, 21), 22) can fractionate ring PSs efficiently from many reaction products such as linear PSs and concatenated ring PSs whereas the standard size exclusion chromatography (SEC) cannot remove the impurities completely. 18) Hence, their result is more reliable than previous work by Roovers and Toporowski.…”

Section: Summary and Discussionmentioning

confidence: 99%

General Polygonal Length Dependence of the Linking Probability for Ideal Random Polygons

Hirayama

Tsurusaki

Deguchi

2011

Prog. Theor. Phys. Suppl.

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The linking probability that two closed random walks (i.e., random polygons: RPs) are mutually entangled, P link , is investigated numerically quite accurately. Here, P link is a function of the distance between two RPs, R, and the number of polygonal segments, N . In a previous paper, we numerically estimated P link precisely in the wide region of 0 ≤ ξ ≤ 3.0 where ξ denotes the normalized distance, i.e., the ratio of R to the radius of gyration R g : ξ = R/R g . We have also shown that the N -and R-dependence of P link can be well approximated by a simple function:, where κ 1 , ν 1 , κ 2 , ν 2 and C are fitting parameters which depend on N . In this paper we extract the general N -dependence of P link . We evaluate numerically the five fitting parameters as functions of N , i.e., κ 1 (N ), ν 1 (N ), κ 2 (N ), ν 2 (N ) and C(N ). Considering physical requirements of P link , we impose constraints on these functions. By taking account of both the numerical data from N = 32 to 512 and the constraints, we propose good approximate functions of N for the above fitting parameters. We find that they are valid from N = 32 to 512. We expect that they should also be effective for approximating the linking probability at least in some region of N > 512, although it is not clear how effective it is for large values of N . This result enables us not only to estimate P link for an arbitrary N at least roughly, but also to predict the possible asymptotic behavior of P link at N = ∞. §1. IntroductionRing polymers are fascinating objects in polymer science. By simply connecting both ends of a linear polymer, some statistical properties of the polymer become nontrivial 1)-9) because of the crucial condition, namely the topological condition that the initial topology of the ring polymer never changes when it is moving and fluctuating under thermal noise. The topological condition makes the phase space of a ring polymer decompose into smaller subspaces with different topological states and any ring polymer in the system does not move from the phase subspace of a given initial topology to another subspace with a different topology. The restriction of possible phase spaces leads to a considerable amount of decrease in the entropy; consequently we have the entropic force derived from the topological constraint acting on the ring polymer. Hereafter, we call such an entropic force that is derived from topological conditions as a topological force.The topological force may strongly affect several physical properties of ring polymers in dilute solution 1)-6) and melt. 7)-9) Furthermore, we may regard polymer netDownloaded from https://academic.oup.

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“…On the other hand, Pasch et al [69] have observed that linear PS eluted and cyclic PS eluted independently of molar mass - Fig. 6 -from the same column and at the same eluent composition.…”

Section: Polymer Peaks and Solvent Peaks Under Critical Conditionsmentioning

confidence: 94%

Liquid Chromatography under Critical and Limiting Conditions: A Survey of Experimental Systems for Synthetic Polymers

Macko

Hunkeler

2003

Liquid Chromatography / FTIR Microspectroscopy / Microwave Assisted Synthesis

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At the interface between the entropic size exclusion separation and the enthalpydominated liquid adsorption chromatography it is possible, experimentally, to identify conditions where polymer samples elute independent of their molar mass. These "critical conditions" function according to theory by compensating the entropy and enthalpy of the separation. For a series of common and specialty polymers, the mobile phase compositions and temperature which provide the molar mass independent elution behavior, for a given stationary phase, have been extracted from literature and summarized herein. This collection may help to select, or forecast, suitable LC systems, when an application of liquid chromatography under critical conditions for a polymer is required. Correlations between properties of solvents, sorbents and polymers, such as solubility parameters, eluotropic strength and Mark-Houwink constants have been extracted from the collected data. Specifically, solubity parameters of critical mobile phases corresponding to a pair polymer-sorbent are in a majority of cases very similar. The elution strength of the first component of a critical binary eluent correlates linearly with the volume percent of the second component, especially, when an identical silica gel is applied. However, the critical conditions are independent of the thermodynamic quality of the solvent. Under limiting conditions, the mobile phase may be even a precipitant or a strong adsorption promoting liquid for an injected polymer. Possibilities for increase of the upper molar mass separation limit are outlined and influence of sample solvent on elution behavior is described. Applications of liquid chromatography under conditions of enthalpy-entropy compensation for separation of homo-and copolymers are also, briefly, summarized.

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Analysis of Macrocyclic Polystyrenes. 1. Liquid Chromatographic Investigations

Cited by 52 publications

References 11 publications

Synthesis and characterization of macrocyclic vinyl aromatic polymers

Synthesis and characterization of macrocyclic vinyl aromatic polymers

General Polygonal Length Dependence of the Linking Probability for Ideal Random Polygons

Liquid Chromatography under Critical and Limiting Conditions: A Survey of Experimental Systems for Synthetic Polymers

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