Thermal and Photoinduced Polymerization of Thin Diacetylene Films. 1. Phthalimido-Substituted Diacetylenes

• Published in: Macromolecules Vol. 33; no. 3; pp. 766 - 774
• Main Authors: Barentsen, Helma M, van Dijk, Marinus, Zuilhof, Han, Sudhölter, Ernst J. R
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 08.02.2000
• Subjects: Applied sciences; Exact sciences and technology; Laboratorium voor Organische chemie; Laboratory for Organic Chemistry; Organic Chemistry; Organische Chemie; Physicochemistry of polymers; Polymerization; Polymers and radiations; Substituent effect; Bulk polymerization; Asymmetric molecule; Diacetylene polymer; Experimental study; Functional polymer; Alcohol polymer; Imide; Conjugated polymer; Photopolymerization; Thermal polymerization; Polyacid; Property structure relationship; Monomer; Chemical reactivity
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma990471+

A series of phthalimido-substituted (Pht) diacetylenes with the structure Pht−(CH2) n −C⋮C−C⋮C−(CH2) m −R was synthesized. The influence of the length of the alkyl spacer n between the phthalimido group and the diacetylene group, the length of the alkyl spacer m and an additional polar group R on the thermal and UV-induced polymerization was investigated by systematic variation of n, m, and R (for R = H and m = 8, n = 1, 3, 4, 5, 8, 9; for n = 9 and m = 3, R = H, CH2OH, COOH). All synthesized compounds underwent thermal polymerization. The polymerization temperature increased with longer n spacer or shorter m spacer, and no effect was observed on variation of R. For UV-induced polymerization, a spacer length n of more than four carbon atoms was necessary. Introduction of a hydrogen-bond-forming hydroxyl or carboxyl group at the other side of the diacetylene yielded polymers with a significantly higher degree of conjugation and also improved film formation on quartz enormously.