Tenside, Polymerbausteine und Polymere aus nachwachsenden Rohstoffen durch Epoxidringöffnungen mit Aminen und enzymatische Polykondensationen

This work describes new syntheses of surfactants and polymers based on renewable raw materials, mainly oleochemical epoxides and polyolamines based on carbohydrates using. Polyolamines, which are available by reductive amination of reducing carbohydrates, were reacted with different epoxides to synthesize carbohydrate-based surfactants. Selective conversion in methanol / water -mixtures at 70°C conversion led to quantitative yields. Epoxides used were alpha-epoxides, omega-epoxy fatty acid methyl esters, glycidyl ethers of fatty alcohols, glycidol, mono- and diepoxides of alpha,omega-diolefins as well as glycidyl ethers of diols or glycerol. First the epoxides were reacted with glucamine and N-alkyl glucamines. Depending on combination, surfactants having different structures were obtained (linear surfactants, symmetric and asymmetric Y-type structures). The use of diepoxides of alpha,omega-diolefins or glycidyl ethers of diols or glycerol led to Bola- or Gemini-surfactants or, reacted with glucamine, to polymers. The products of the last-mentioned polyaddition were water-soluble polymers (Mw up to 22500 g/mol). Also cyclization was observed and this was forced by the dilution principle. The low molecular weight products and the polymers could be separated by fractionation or ultra-filtration. Especially, the products based on long-chain N-alkyl glucamines and glycidol as well as the Gemini-surfactants showed high surface activity. Many of the further products were rather poor surfactants, which was caused mostly by their low solubility in water. The surface active properties of these derivatives could be increased by conversion to the corresponding hydrobromides (acidification with HBr). After this, instead of the above glucamines further polyolamines were used. Galactamines, polyolamines based on disaccharides, ' fructamines ' and 2-glucamin, which was obtained from glucosamine hydrochloride (product from hydrolysis of chitin), as well as glucamines from reductive amination with hydrophilic amines (ethanolamine or glucamine) or diamines were reacted with epoxides. More hydrophilic amines led to water-soluble products and the use of diamines to a further group of Gemini-surfactants. Both groups of carbohydrate-based surfactants showed good surface active properties. Further Gemini-surfactants could be obtained by reaction of 1:2,7:8-diepoxy octane with an excess of glucamine followed by addition of long-chain epoxides. Enzymatic hydrolysis or alkaline saponification of the products based on omega-epoxy fatty acid esters led to amphoteric surfactants. Measurement of surface active properties showed high surface activity and the amphoteric character of the surfactants obtained. The products based on omega-epoxy fatty acid methyl esters are surfactants as well as potential polymer building blocks. Similar derivatives were synthesized by reaction of omega-epoxy fatty acid esters with piperazine, dimethyl piperazine or Kryptofix 22. Enzyme-catalysed polycondensation of the sugar-based building blocks led to oligomers, the analogous reaction of diamine derivatives yielded products having polymerisation degrees up to 20. Novozym®435, a lipase from Candida antarctica immobilized on polyacryl, was used as biocatalyst.

Grantor dc:publisher

Publikationsserver der RWTH Aachen University

Year dc:date

2003

Author dc:creator

• Brüse, Falk

Contributors dc:contributor

• Warwel, Siegfried

• info:eu-repo/classification/ddc/660
• Technische Chemie
• Kohlenhydrat-Tenside
• Epoxide
• Nachwachsende Rohstoffe

Statement dc:rights

• info:eu-repo/semantics/openAccess

Language dc:language

ger

Identifier

https://publications.rwth-aachen.de/search?p=id:%22RWTH-CONV-120552%22

OAI identifier oai:identifier

oai:publications.rwth-aachen.de:58703