UV Laser-Induced Gas-Phase Copolymerization of Carbon Disulfide and Ethene Radmila Tomovska, 1 Marke´ta Urbanova´, 1 Radek Fajgar, 1 Zdeneˇk Bastl, 2 Jan S ˇ ubrt, 3 Josef Pola* 1 1 Laser Chemistry Group, Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic, 16502 Prague, Czech Republic Fax: (þ42) 02 20920661; E-mail: pola@icpf.cas.cz 2 J. Heyrovsky´ Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, 18223, Prague, Czech Republic 3 Institute of Inorganic Chemistry, Academy of Sciences of the Czech Republic, 25068 R ˇ ezˇ near Prague, Czech Republic Received: August 8, 2003; Revised: December 16, 2003; Accepted: December 16, 2003; DOI: 10.1002/marc.200300081 Keywords: copolymerization; laser-induced polymers; photopolymerization; thin films Introduction The gas-phase photo-polymerization of carbon disulfide has been paid much recent attention because of the potential to prepare novel conjugated sulfur-containing polymers. Irradiations resonant with the 280 – 390 nm band provide conditions for the formation and polymerization of excited CS 2 molecule, such as CS, S 2 , and CS species which are allowed to obtain a polymeric material [1–7] similar to Bridgman’s carbon disulfide. [8] Laser irradiations resonant with the 230–190 nm band induce photolytic dissociation of CS 2 into CS and S (e.g., references [9,10]) and allow the gas-phase polymerization of CS and the chemical vapour deposition of a (CS) x polymer. [11] This laser-induced gas-phase polymerization of CS is a unique process, since the gas-phase generated CS has been previously known to polymerize only through wall reactions. [12,13] The proposed mechanism involved a two- photon-controlled depletion of CS 2 and an intermediacy of aC 2 S 2 species. [11] Summary: The laser irradiation at 193 nm of a gaseous mix- ture of carbon disulfide and ethene induces the copolymer- ization of both compounds and affords the chemical vapour deposition of a C/S/H polymer, the composition of which indicates the reaction between two to three CS 2 molecules and one C 2 H 4 molecule. Polymer structure is interpreted on the basis of X-ray photoelectron and FT-IR spectra as consisting of >C S, >C C<, –CH 2 –CH 2 –, (C C)S n C 4  n , –C–(C S)–S–, –S–(C S)–S–, and C–S–S–C configurations. The gas-phase copolymerization of carbon disulfide and ethene represents the first example of such a reaction between carbon disulfide and a common monomer. Scheme showing the expected reaction of excited CS 2 molecules with other CS 2 molecules to form dimers, which then react with another CS 2 molecule or add to ethene. Macromol. Rapid Commun. 2004, 25, 587–591 DOI: 10.1002/marc.200300081 ß 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Communication 587