Epoxy ether polyamides

Issued April 15, 1965\

Date drawing March 17, 1965.

Copyright reserved.

PATENT BOARD

<img file="NL110976C_D0001.tif" />

THE NETHERLANDS

PATENT No. 110976.

CLASS 124 q 2 q 2 x (124 q 2 q 2; 124 q 2 q 2 a; 124 q 2 q 2 f).

IPO C 08 g.

SWIFT &amp; COMPANY of Chicago, Illinois, Ver. St. v. Am.

Process for preparing polyether polymers, as well as articles consisting of or coated with these polymers.

Application No. 220398 Ned., filed Aug. 31, 1957, 11 hrs 23 mins;

made public

Avg.:

German Patent Application H.20.190, which led to Patent Specification 969,930, describes a process for preparing high molecular weight compounds, according to which epoxidized fats, fatty acids, fatty acid derivatives or fatty alcohols containing more than one epoxy group per molecule are prepared at normal temperature. with a catalytic amount of a Friedel-Crafts catalyst. such as SnCl₄, FeCl₃, SbCl₅, ZnCl₂ or BF₃.

When the polymerization is carried through as far as possible, three-dimensionally crosslinked polymers are formed.

Acting in the presence of a solvent, e.g., water, and an emulsifier, low impact rubbery polymers are produced which are insoluble in most solvents but still swell in benzene and the like, Examples 10 and 11.

Furthermore, the said patent application on page 2, lines 31-40 and 61-66 states that by diluting the catalyst solution, the polymerization can be retarded, so that after the reaction has ended, highly viscous products are formed which still dissolve in solvents. These are apparently not linked.

When using an undiluted catalyst, i.e. a catalyst without a solvent, the problem arises that if the catalyst is added to the epoxidized fats, fatty acids, etc., a solid polymer locally forms which forms a coating around the catalyst particles, which causes decreased activity. The invention now provides for a rapid polymerization of said starting materials, avoiding the entrapment of the catalyst by the polymer and increasing the effective utilization of the catalyst.

BACKGROUND OF THE INVENTION This invention relates to a process for preparing polyether polymers from epoxidized fats, fatty acids, fatty acid derivatives or fatty alcohols containing more than one epoxy group per molecule, by contacting them with a catalytic amount of boron trifluoride, stannic chloride, zinc chloride or a similar catalyst, which process is characterized in that the catalyst is used in combination with an alcohol, wherein the amount of alcohol is at least 1 µmol per µmol catalyst, but not more than 1 µmol alcohol per µmol oxirane oxygen.

November 1964, precedence from April 10, 1957 onwards, Ver. St. v. Am., No. 651822.

ir. AF Arnold cs in The Hague.

In this way, both linear and crosslinked polyether polymers can be prepared without difficulty.

In carrying out the method according to the invention, any epoxidized fat or fatty product can be started from, provided it contains more than one epoxy group per fatty acid molecule. This includes epoxidized animal, vegetable or marine triglycerides, fatty acids and fatty acid esters, amides, alcohols, aldehydes and ketones, as well as mixtures thereof. 10 Examples of epoxidized glycerides with more than one epoxy group are: epoxidized soybean oil, linseed oil, rapeseed oil and fish oil, as well as epoxidized sperm oil and lard oil. Examples of epoxy fatty acids having more than 1 epoxy group are di- and tri-epoxystearic acid.

Preferably a BF . is used as a catalyst₃-ether complex modified with alcohol. However, other catalysts, which can be regarded as strong Lewis acids, such as stannic chloride, zinc chloride, aluminum chloride as well as sulfuric acid and perchloric acid, can also be used in modified form.

The amount of catalyst required to effect polymerization depends on the type of epoxidized grease or the like to be polymerized and also on the reactivity of the catalyst.

The amount of alcohol required to modify the catalyst may be relatively small and generally should not exceed 1 µmole per epoxy group in the epoxidized fat, fatty acid, etc., otherwise polymer formation is inhibited. Moreover, it is now possible to predetermine by controlling the amount of alcohol whether a linearly polymerized or a three-dimensionally crosslinked end product will be obtained. For linear soluble polymers, the molecular ratio of alcohol to oxirane oxygen should be less n-1 than unity, but greater than—when n is the number of epoxy groups per molecule of the epoxidized fat, etc. Conversely, if an amount of n-1 alcohol not greater than ---- is used, crosslinking will occur. n polymers that are too insoluble are formed.

Suitable alcohols are, for example, methanol, isopropanol and 2-methoxyethanol.

Available at the Industrial Property Office in The Hague — Price per copy ƒ 1,50

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The reaction between the epoxidized fats, fats of linear polymers are made. Acidification etc and the catalyst is exothermic and does not require acidification of the saponified product requires polyether warming. polymers of oxy-fatty acids.

The following examples illustrate the preparation of cross-linked polymers. 5 Example V.

Example I The cross-linked product from Example I was saponified by refluxing with

To 100 g of epoxidized soybean oil (6.2% 0.5 N alcoholic KOH for 1 hour. Epoxy oxygen acidification) was added with stirring 10 ml of methyl-10 of the reaction mixture resulting in the separation of cellosolve (2-methoxyethanol) containing 1 ml of a viscous oil layer which was isolated and contained a boron trifluoride-ether complex. Dried after 19. The oil was a polyether polymer of steaseconds, the whole solidified with the temperaric acid, wherein C₁₈chains of interconnected ture had risen to about 120°C. The product was washed by oxygen atoms in positions 9,10,12 or a light yellow trap transparent solid with a large 13.

elasticity. It could be finely ground into a powder. In this manner, soluble polymers with a high absorption capacity are also available. soaps prepared from epoxidized lard oil, epoxidized olive oil, epoxidized linseed oil and Example H. epoxidized safflower oil.