Synthesis and Characterisation of Terminal Carbohydrate Modified Poly(dimethylsiloxane)s

Abstract

Summary: In the 1990's, carbohydrate modified silicones were developed as a novel class of hydrophilic modified silicones which are now ready for marketing and industrially available, mainly as ingredients of cosmetic formulations. This report focuses on the synthesis of α,ω‐carbohydrate modified linear poly(dimethylsiloxane)s by hydrosilylation reactions. Thus, a series of carbohydrate derivatives was synthesised and reacted with a hydrodimethylsilyl‐terminated poly(dimethylsiloxane) applying Speier's catalyst. The resulting oils were characterised by MALDI TOF MS and NMR spectroscopy. Deprotection gave a series of novel amphiphilic modified silicones, which were more viscous than their protected analogues, due to hydrogen bonding.

Production and applications of carbohydrate-derived sugar acids as generic biobased chemicals

“…Aldonic acids Metal carriers in biomedical applications (Escandar & Sala, 1992;Junicke et al, 2000) Metal complexing in removal of heavy metals from soil or waste streams Fischer & Bipp, 2002;Fischer et al, 1998) Sequestering agents in detergent builders (Abbadi et al, 1999) Concrete corrosion inhibition (Miksic et al, 1997) Water reducers in concrete (Chun et al, 2006) Antimicrobial agents in hygiene articles (Nemeth et al, 2010) pH Regulation in food industry (McIntyre, 1990;Buytendorp & Zenger, 1988) Oxidation reduction in food industry (Weiss & Todd, 1992) Carcinogen reduction in cooked of food (Tomoda et al, 2004) Silicone surfactants (Henkensmeier et al, 2004b) Uronic acids Metal carriers in biomedical applications (Escandar & Sala, 1992 (Henkensmeier et al, 2004a(Henkensmeier et al, , 2005 Polyesters (PBT-replacement) (Lavilla et al, 2011(Lavilla et al, , 2012) Crosslinkers in hydrogels (Andrews et al, 2011;Pohjanlehto et al, 2011) Production of adipic acid (Boussie et al, 2010) Production of FDCA (terephthalic acid replacement) (Haworth et al, 1945;Taguchi et al, 2008) Metal carriers in biomedical applications (Dornyei et al, 2004) Metal complexing in removal of heavy metals from soil or waste streams Fischer & Bipp, 2002;Fischer et al, 1998) Sequestering agents in detergent builders (Abbadi et al, 1999) Antimicrobial agents in hygiene articles (Nemeth et al, 2010) Corrosion inhibition in deicing liquids (Koefod, 2007) investigations a few decades later by Ogata et al (1980). More recently, Kiely et al have investigated polyamides of various unprotected aldarate esters and ammonium salts (Kiely et al, , 2009.…”

“…Trimethylsilyl protected aldaric acids and D-gluconic acid, have been used to increase hydrophilicity and biodegradability of polydimethylsiloxanes (Henkensmeier et al, 2004a(Henkensmeier et al, ,b, 2005. These types of silicone surfactants are used in the textile, fibre, paint and cosmetic industries.…”

“…Methyl etherification has been commonly used to protect secondary hydroxyls of sugar acids and has also been utilized in the synthesis of polyamides containing aldonic acid moieties (Bueno et al, 1997;Zamora et al, 2000). Oacetyl protection has been utilized in synthesis of mesogalactaric and D-glucaric acid-based polyamides (Bachmann & Thiem, 1992;Henkensmeier et al, 2004a). Various application areas have been proposed for sugar acid-based polyamides, for example slow-release nitrogen fertilizer for plant nutrition (Jahns & Kiely, 2006), adhesive applications (Morton & Kiely, 2000) and membrane materials for chiral separation (Wu et al, 2010).…”

Synthesis, Surface and Spreading Properties of Lactobionamide-Grafted Amphiphilic Glycopolysiloxanes

“…A few glycopolysiloxanes have been reported and they were prepared by hydrosilylation reaction between the allyl-modified carbohydrate and polysiloxane bearing Si-H groups. [13][14][15][16][17] But it involves the time and material consuming steps of protecting and deprotecting the hydroxyl groups of the carbohydrate in order to avoid side reactions in these processes. To overcome the problem, another simpler method has been developed by our group and others [18][19][20][21][22][23] : glycopolysiloxane can be synthesized by forming amide bonds of amino functional polysiloxane with lactones (or acids).…”

Synthesis of New Cellobiose‐Based Glycopolysiloxanes and their Use as Polymer Stabilizers in Miniemulsion Polymerisation

“…The modification of the oligosaccharide in this way is thus a problem since the glycosidic bonds are cleaved. The use of a more‐sophisticated approach such as the reaction of the allyl propargyl with peracetylated derivatives in the presence of boron trifluoride etherate has been described 8. Cellobiose (two glucose units) modified by allylamine previously described14–17could be an alternative for preparing new carbohydrate‐modified PDMSs copolymer with an acetamido linkage instead of ether or thioether groups, as already described.…”