Solid-State 13C-NMR Analysis of Hypercrosslinked Polystyrene

ROYCHEN JOSEPH, 1 WARREN T. FORD, 1 SHANMIN ZHANG, 1 M. P. TSYURUPA, 2 A. V. PASTUKHOV, 2 V. A. DAVANKOV 2

1

Department of Chemistry, Oklahoma State University, Stillwater, Oklahoma 74078

2 Nesmeyanov Institute of Organo-Element Compounds, Russian Academy of Sciences, Vavilov Street 28, Moscow 117813, Russian Federation

Received 28 March 1996; accepted 29 July 1996

ABSTRACT: Hypercrosslinked polystyrenes, synthesized by reaction of linear or lightly

crosslinked polystyrene with chloromethyl methyl ether (CME) and a Lewis acid in a good solvent, swell even in nonsolvents for polystyrene. Structures and dynamics of hypercrosslinked polystyrenes in both dry solid and solvent-swollen gel states have been determined by 13C-NMR spectroscopy. Deconvolution of 13C solid-state CP/MAS spectra gave the relative numbers of quaternary carbon atoms in monosubstituted and disubstituted benzenes. A typical sample, crosslinked by reaction of a mixture containing 0.5 mol of CME per mol of repeat units, contains 35% of unreacted and 65% of crosslinked aromatic rings, and no residual chloromethyl groups. Gels swollen in CDCl3 and in CH3OH have residual static dipolar interactions enabling crosspolarization and require magic angle spinning (MAS) and high power 1H decoupling to reduce chemical shift anisotropy from 10 4 Hz to 10 3 Hz. A single proton spin-lattice relaxation time in the rotating frame measured from all peaks in the 13C spectra of dry samples indicates homogeneity on a nanometer scale. Proton NMR line widths indicate no substantial molecular motions in a dry hypercrosslinked polystyrene up to at least 200 C. 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 695701, 1997 Keywords: hypercrosslinked polystyrene; solids NMR; structure; relaxation measurements

INTRODUCTION
The structure and properties of hypercrosslinked polystyrene networks differ from the networks obtained by radical copolymerization with divinylbenzene.1 In the conventional network polymer, the crosslinks are distributed nonuniformly due to unequal comonomer reactivity.2 The hypercrosslinked polymers are prepared by crosslinking linear polystyrene in solution or lightly crosslinked

Correspondence to: Warren T. Ford Contract grant sponsor: National Science Foundation; contract grant numbers: DMR 9503626, DMR 9202755 1997 John Wiley & Sons, Inc. CCC 0887-624X/97/040695-07

poly(styrene-co-divinylbenzene) in a highly swollen gel state using bifunctional alkylating agents such as p-xylylene dichloride or chloromethyl methyl ether (CME) via a FriedelCrafts reaction.3 7 They can also be made by FriedelCrafts crosslinking of polymers of chloromethylstyrene.8 These hypercrosslinked networks swell not only in thermodynamically good solvents such as toluene, but also in nonsolvents such as aliphatic alcohols and water.3 8 Hypercrosslinked polystyrenes have been used as sorbents in applications such as removal of organic acids, dyes, and phenols from waste waters, removal of lipids from protein solutions, microbial production of amino acids, and concentration of hydrocarbon pollutants from
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