Synthesis of Carbohydrate-Segmented Polydimethylsiloxanes by Hydrosilylation DIRK HENKENSMEIER, 1 BORS CAJUS ABELE, 2 ANTON CANDUSSIO, 2 JOACHIM THIEM 1 1 Institut fu ¨ r Organische Chemie, Martin-Luther-King-Platz 6, 20146 Hamburg, Germany 2 Wacker-Chemie GmbH, Johannes-Hess-Straße 24, 84489 Burghausen, Germany Received 27 August 2004; accepted 28 March 2005 DOI: 10.1002/pola.20852 Published online in Wiley InterScience (www.interscience.wiley.com). ABSTRACT: Carbohydrate-modified polysiloxanes have been presented several times within the last decade. In this work, a new route to carbohydrate-segmented poly- siloxanes is presented. A series of allyl-group-containing bifunctional carbohydrate derivatives was synthesized and reacted with hydrodimethylsilyl-terminated poly- siloxane in hydrosilylation reactions with Speier’s catalyst. The carbohydrate mono- mers and the resulting materials were fully characterized with 1 H and 13 C NMR spectroscopy. V V C 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3814–3822, 2005 Keywords: carbohydrates; hydrosilylation; polysiloxanes; silicones; synthesis INTRODUCTION Since the 1990s, carbohydrate-modified polysi- loxanes have been presented several times. The three main pathways are the reactions between amino-functionalized silicones and sugar lac- tones, epoxy-functionalized silicones, or sugar amines and the hydrosilylation of allyl modified carbohydrates. In most of the latter cases, poly- (dimethyl-co-hydromethyl)siloxanes have been used, giving access to comb structures. 1–9 Only in two cases have chain-end-modified polysilox- anes been synthesized. 10,11 In no cases have bifunctional carbohydrates been hydrosilylated by  ,!-functionalized polydimethylsiloxanes, leading to carbohydrate-segmented polydime- thylsiloxane block copolymers. Recently, the syn- thesis of these materials has been published, with the application of aldaric acid lactones or esters and aminoalkyl-terminated polysilox- anes. 12,13 In this work, we focused on synthesiz- ing such compounds by the hydrosilylation approach, which is not restricted to aldaric acid derivatives but can be applied to any bisallyl- substituted carbohydrate derivatives. EXPERIMENTAL Materials and Methods NMR spectra were recorded on a Bruker AMX- 400 spectrometer at 400 ( 1 H) or 100 MHZ ( 13 C), and IR spectra were recorded on a PerkinElmer 1720x Fourier transform infrared spectrometer. Optical rotation values were acquired with a PerkinElmer PE 341 polarimeter. Gel permea- tion chromatograms were acquired with a sys- tem consisting of a Spectra System P1000 pump, a precolumn, and four analytical columns from MZ Analysentechnik; the pore sizes were 10 5 , 10 3 , 500, and 100 A ˚ . The signals were recorded with a UV detector (Spectra Series UV 150) at 260 nm. The eluent was chloroform at a flow rate of 1 mL/min. Calibration was performed Correspondence to: J. Thiem (E-mail: thiem@chemie. uni-hamburg.de) Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 3814–3822 (2005) V V C 2005 Wiley Periodicals, Inc. 3814