Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
2001-06-07
2002-11-12
Acquah, Samuel A. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S301000, C528S302000, C528S306000, C528S308000, C528S308600, C524S765000, C435S183000
Reexamination Certificate
active
06479618
ABSTRACT:
BACKGROUND OF THE INVENTION
Chemically, the esterification of dicarboxylic acids with polyhydric alcohols is very difficult to control and gives highly crosslinked polyesters at very high temperatures, i.e. beyond the melting points of the dicarboxylic acids. By contrast, the lipase-catalyzed transesterification of dicarboxylic acid esters leads to the formation of linear polyesters under mild reaction conditions. By contrast, the esterification of the free dicarboxylic acids depends on the use of a solvent because the optimal reaction temperatures of the lipase are below the melting temperatures of the dicarboxylic acids.
Since the free dicarboxylic acids are more readily accessible on an industrial scale than their esters, the problem addressed by the present invention was to provide a new process which would enable linear polyesters to be obtained in quantitative yields and favorable reaction times from dicarboxylic acids and polyols under mild conditions without the use of solvents.
BRIEF SUMMARY OF THE INVENTION
The present invention relates, in general, to processes for the production of linear polyesters from aliphatic, substituted aliphatic, aromatic and/or substituted aromatic dicarvoxylic acids and polyols in the presence of small quantities of a low-boiling primary alcohol and lipase as catalyst but without the addition of solvent. The linear polyesters can be used as thickeners and softeners in cosmetic preparations.
The present invention also relates to the use of linear polyesters obtained by reaction of aliphatic, substituted aliphatic, aromatic and/or substituted aromatic dicarboxylic acids containing 2 to 10 carbon atoms and polyols containing 2 to 15 carbon atoms and at least two primary hydroxyl groups in the presence of small quantities of a low-boiling primary alcohol and lipase as catalyst without the addition of solvents as thickeners and softeners in cosmetic preparations.
It has surprisingly been found that linear polyesters can be obtained from dicarboxylic acids and polyols for the first time without the addition of solvents providing the reaction is carried out in the presence of a low-boiling primary alcohol and lipase as catalyst. The esterification is distinguished by mild reaction conditions, favorable reaction times and quantitative yields. The invention includes the observation that advantageously water-soluble linear polyesters are also obtained where dicarboxylic acid mixtures containing hydroxydicarboxylic acids are used.
DETAILED DESCRIPTION OF THE INVENTION
Dicarboxylic Acids
Aliphatic, substituted aliphatic, aromatic and/or substituted aromatic dicarboxylic acids containing 2 to 10, preferably 3 to 9 and more preferably 4 to 6 carbon atoms are used for the production of polyesters. The aliphatic dicarboxylic acids used include, for example, oxalic acid, malonic acid, succinic acid and adipic acid, azelaic acid, dodecanedioic acid and brassylic acid while the aromatic dicarboxylic acids used include phthalic acid, isopththalic acid and terephthalic acid. The substituted dicarboxylic acids used include the aminodiacids, preferably glutamic acid, and hydroxydicarboxylic acids containing at least two primary hydroxyl groups, preferably maleic acid, citric acid, glutaconic acid and glutaric acid and, more particularly, tartaric acid. Aliphatic unbranched dicarboxylic acids and hydroxydicarboxylic acids are preferably used.
In addition, mixtures of dicarboxylic acids may be used, in which case at least one dicarboxylic acid is a hydroxydicarboxylic acid containing at least two primary hydroxyl groups, preferably malic acid, citric acid, glutaconic acid and glutaric acid and, more particularly, tartaric acid. The molar ratio of dicarboxylic acid to hydroxydicarboxylic acid is 1:10 to 10:1, preferably 1:5 to 5:1 and more preferably 1:2 to 1:1.
Polyols
Polyols suitable for the purposes of the invention preferably contain 2 to 15, more preferably 3 to 7 and more particularly 4 to 6 carbon atoms and at least 2, preferably at most 6 and more particularly 3 hydroxyl groups. The polyols may contain other functional groups, more particularly amino groups, or may be modified with nitrogen. Typical examples are
glycerol;
alkylene glycols such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1000 dalton;
technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as, for example, technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
methylol compounds such as, in particular, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol and dipentaerythritol;
lower alkyl glucosides, particularly those containing 1 to 8 carbon atoms in the alkyl group, for example methyl and butyl glucoside;
sugar alcohols containing 5 to 12 carbon atoms, for example sorbitol or mannitol,
sugars containing 5 to 12 carbon atoms, for example glucose or sucrose;
amino sugars, for example glucamine;
dialcoholamines, such as diethanolamine or 2-aminopropane-1,3-diol.
Preferred alkylene glycols are propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 dalton. Particularly suitable polyols are glycerol, sorbitol, sorbitan, trimethylol propane, pentaerythritol and 2-aminopropane-1,3-diol. Oligomers thereof, for example dimers, trimers, tetramers, pentamers and/or hexamers, may also be used.
Low-boiling Primary Alcohols
Low-boiling primary alcohols suitable for the purposes of the invention are alcohols with a boiling point below 100° C. Methanol, isopropanol and propanol and particularly ethanol are preferably used.
Lipases
Lipases derived from
Candida cylindracea, Candida lipolytica, Candida rugosa, Candida antarctica
B,
Candida utilis, Chromobacterium viscosum, Geotrichum viscosum, Geotrichum candidum, Mucor javanicus, Mucor miehei, porcine pancreas
, Pseudomonas species,
Pseudomonas fluorescens, Pseudomonas sepacia, Rhizomucor meihei, Rhizopus arrhizus, Rhizopus delemar, Rhizopus delemar, Rhizopus niveus, Rhizopus oryzae, Aspergillus niger, Penicillium roquefortii, Penicillum cambertii, Pseudomonas fluorescens
or from an esterase of Bacillus sp.,
Bacillus thermoglucosidasius, Mucor miehei
, horse liver,
Saccharomyces cerevisiae
, pig liver are used as catalyst for the production of the linear polyols according to the invention. The lipases may be used individually or in combination with one another. The lipases are used in quantities which effect adequate catalysis of the polyesterification according to the invention and lead to a desired molecular weight of the linear polyesters. Lipases derived from Mucor miehei and Aspergillus niger are preferably used. In particular, Novozym® 388 L (
Rhizomucor miehei
lipase, free), Lipozym® IM (
Rhizomucor miehei
lipase, immobilized), Novozym® 735 L (
Candida antarctica
B lipase, free), Novozym® 525 L (
Candida antarctica
B lipase, free) and/or Novozym® 435 (
Candida antarctica
B lipase, immobilized), which are all products of Nono Nordisk, Denmark, are used. The lipases are preferably used in quantities of 0.01 to 15% by weight and more particularly in quantities of 1 to 10% by weight, based on the dicarboxylic acid.
Production Process
According to the invention, the linear polyols are obtained by reaction of mixtures of dicarboxylic acids containing a hydroxydicarboxylic acid with polyols in the presence of small quantities of a low-boiling primary alcohol and lipase as catalyst without the addition of solvents. The low-boiling alcohol released is preferably removed from the reaction mixture. The reaction is carried out at temperatures of preferably 50 to 90° C. and more particularly 70° C. and under pressures of generally 0 to 1013, preferably 0.01 to 500 and more preferably 10 to 250 mbar. The reaction time is 8 hours to 4 days and preferably 24 to 48 hours. To produce the polyesters according to the invention, the dicarboxylic acids and polyols are used in a molar ra
Acquah Samuel A.
Cognis Deutschland GmbH
Ettelman Aaron R.
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