US2142980A - High molecular weight polar compounds and process of making the same - Google Patents

Description

' PIII'POSBS.

Patented Jan. 3, 1939 UNITED STATES PATENT OFFICE men MOLECULAR wmon'r 'romn com- POUNDS AND rnocnss or MAKING 'rnn SAME No Drawing.

Application February 2'], 1937, Se-

iig lsNo. 128,278. In the Netherlands March 24,

23 Claims.

This invention relates to valuable high-molecular weight organic compounds. of polar character possessing in their structure long carbon-to-carbon chains and having high boiling temperatures, and it also relates to a process for the manufacture oi such valuable compounds which comprises reacting an unsaturated hydrocarbon possessing one double bond with an unsaturated hydrocarbon possessing a plurality of double bonds at a temperature below about 0 C., and reacting the resulting long chain, polyolefinic hydrocarbon product with a reagent capable of reacting therewith by addition to a double bond, whereby a high-boiling, high-molecular weight polar compound adapted to many commercial uses is obtained.

The invention provides a practical and economical process for the production of highmolecular weight polar compounds of controlled and improved character from petroleum hydrocarbons or hydrocarbons derived from petroleum or petroleum products. The products, which are readily obtained in practical yields from such raw materials, are suitable for a wide variety of They are particularly suitable as agents which when added in effective amount to hydrocarbon mixtures, such as lubricating oils, greases, and the like, improve certain characteristics of such mixtures and make them more suitable tor particular as well as general purposes. For example, the viscosity index of lubricating oils may be materially increased by adding thereto a small amount of one or a mixture of such polar compounds. In general, oils comprising relatively small amounts of the agents to which the invention relates, have better lubricating properties, the agents serving to increase their oiliness. The addition of high-boiling polar compounds to lubricating oils also increases their stability, rendering them useful as extreme pressure lubricating compositions. -In many cases, the compounds described act as anti-oxidants; hydrocarbon compositions to which they are added are less subject to auto-oxidation. Other uses for the high molecular weight polar compounds will be apparent to those skilled in the art.

In carrying out this invention, various unsaturated hydrocarbons containing one double bond may be used. The term oleflne is used herein and in the appended claims to designate such hydrocarbons which possess one olefinic linkage, said linkage being between two aliphatic carbon atoms. The following are representative olefines, which may be applied severally or in admixture: ethylene, propylene, the secondary and tertiary base butylenes, as l-butene, 2sbutene and tertiary butylene, the secondary and tertiary base amylenes, hexylenes, heptylenes, octylenes, nonylenes and their higher homologues. It is seen that the olefine co-polymers as dipropylene, di-beta-butylene, diisobutylene, triisobutylene, the diand tri-amylenes, hexylenes, and the lie, as well as the oleflne inter-polymerization products resulting from the polymerization of an olefine with an oleflne of another species, are comprehended as embraced by the term olefine.

The invention may be executed employing various hydrocarbons which are characterized by the possession in their structure of a plurality of olefinic linkages. Diolefines are especially suitable, particularly the conjugated double bond dioleflnes. The term conjugated double bond dioletlne is used herein and in the appended claims to designate those unsaturated hydrocarbons of open chain or cyclic character which possess two oleflnic linkages embraced in the characteristic group C==CC=C. Representative suitable diolefines are butadiene, isoprene, 2,3-dimethyl butadiene-(1,3), 2-ethyl butadiene-(1,3) 1,3- dimethyl butadiene-(1,3) pentadiene- (1,3) pentadiene-(1,4), S-methyl pentadiene-(2,4), 3,-i-dimethyl pentadiene-(2,4), the straight chain, branched chain and cyclic hexadienes, heptadienes, etc., and their homologues, analogues and hydrocarbon substitution products. The diolefines may be used severally, or mixtures comprising more than one species of dioleflne may be applied. Diolefines as diallyl, diisobutenyl, diisoamyl and the like, wherein the two double bonds are not conjugated, also come into consideration as useful diolefines.

In executing the invention, olefines and dioleflnes, or mixtures of the same, from any convenient source may be used. Relatively pure unsaturated hydrocarbon compounds, such as the straight chain, branched chain, and cyclic olefines, may be reacted with relatively pure straight chain, branched chain, and cyclic diolefines, or mixtures of these may be reacted together in controlled proportions to produce the valuable high-molecular weight polar compounds to which the invention relates.

Indeterminate mixtures comprising dioleflnes and olefines, or particular fractions of such mixtures may be advantageously treated in accordance with the process of the invention. Such hydrocarbon mixtures are obtainable by the pyrogenesis or cracking of petroleum oils, shale oils, petroleum products, etc., and by the destructive distillation of coal, peat, pitches, waxes, asphalts, animal oils, vegetable oil and the like carbonaceous material. Cracked petroleum distillates or special fractions of'such distillates are useful starting materials. Certain fractions of such distiliates may be used per se when they contain the desired proportions of oleilnes and dioleflnes, or different fractions may be mixed depending upon their composition and the desired composition of the mixture to be treated, or varying proportions of relatively pure oleflnes and/or dioleflnes may be mixed with certain hydrocarbon fractions to provide starting materials of the desired composition.

In a preferred mode of executing the process of the invention, a substantial molecular excess of an oleilne is condensed with a diolefine at a temperature not greater than C. and in the presence of a suitable polymerization or condensation agent or catalyst. Catalysts of the class known as condensation catalysts have been found to be useful for our purpose. A suitable subgroup of catalysts embrace the acid-acting halides of the elements aluminum, boron, iron, tin, antimony, arsenic, bismuth, molybdenum, tungsten, vanadium, zinc, titanium, thorium, cerium, zirconium, indium, thalium and the like. Boron fluoride, aluminum chloride, aluminum bromide, zinc chloride, ferric chloride and ferric bromide are particularly suitable catalysts of this subgroup. Another valuable subgroup of catalysts comprises the above-described and the like acidacting halides in combination to form a complex catalyst with an inorganic or organic compound possessing a dipole moment. Such a complex catalyst may comprise an acid-acting metal halide or boron halide in combination with an inorganic acid-acting halide of another species, with a hydrogen halide, or with an inorganic neutral-acting metal halide such as the alkali metal halides, the alkaline earth metal halides, the halides of metals as nickel, silver, cobalt, and the like. On the other hand such a complex catalyst may comprise an acid-acting metal halide or boron halide in combination as a complex with an organic oxycompound possessing a dipole moment such as the organic nitro-compounds of which the nitroparafllns, the nitro-aralkyl compounds, and the nitro-isocyclic compounds as nitro-benezene, nitro-cyclohexane and the like and their homologues and substitution products are representative; such as the ketones of aliphatic, aralkyl, aromatic or mixed character of which acetone, methyl ethyl retone, methyl propyl ketone, acetophenone, ethyl phenyl ketone, benzophenone and the like and their homologues and substitution products are representative; such as the aliphatic, aralkyl or aromatic carboxylic acid halides, particularly the aromatic carboxylic acid halides as benzoyl chloride, benzoyl bromide, etc., and their homologues and suitable substitution products; such as the organic sulphones, particularly the aryl and aralkyl sulphones as diphenyl sulphone, benzyl sulphone, and their homologues and suitable substitution products; and other organic compounds possessing a dipole moment and capable of combining with a boron halide or acidacting metal halide to form a complex.

Condensation catalysts comprising an aluminum halide such as AlCl3, AlBrs, AlCla-NaCl, AlCl:BaClz, AlBr:KCl, AlCl3--AgCl, A1F3 NaCl, AlBr3AgBr, AlBn-BaBn, AlClanitromethane, AlCl:nitrobenzene, AlCh-nitrobenzene-NaCl, AlCls-acetone, ACla-acetophenone, AlCla-benzophenone, AlCla-benzoyl chloride,

AlCla-diphenyl sulphone, AlCh-dibenzyl sulphone and the like may be advantageously employed. Another preferred subgroup of condensation catalysts embraces those comprising a boron halide such as BF: BCla, BF:HF, BF:- NaCl, BCla-NaCl, BFa-AgF, BF:-BaClz, BIB- nitromethane, BFE|nitrobenzene and the like.

Other condensation and/or polymerization catalysts of acid, basic or neutral character, may be advantageously used. For example, the contact condensation catalysts as the heavy metal oxides, benzoyl peroxide and the like, the siliceous materials as fuller's earth, diatomaceous earth, Florida earth, kieselguhr, silica gel, porcelain chips, etc., charcoal and the like may be used to advantage. The catalysts may be prepared in any suitable manner and used singly or in admixture. If desired, the metal halide and boron halide catalysts may be used in admixture with or deposited on the siliceous materials as clay, silica gel, etc.

As an example of a suitable method of executing the process of the invention, the following procedure may be followed: An oleiine, or a mixture of oleflnes, and a diolefine, or a mixture of diolefines, or an appropriate mixture comprising oleilnes and diolefines is charged to any suitable reaction vessel. A suitable reaction vessel comprises a kettle of the desired capacity equipped with mechanical stirring means, suitable means for cooling and heating its contents, and suitable inlet and outlet means. Suitable refrigerating means employing liquid ammonia, sulphur dioxide, propane, butane, etc. may be used to maintain the contents of the reaction vessel at the desired low temperature during the condensation reaction. The reaction is preferably effected in the liquid phase; however, one or more of the reactants may be in the vapor phase. For example, gaseous ethylene or propylene may be passed into a liquid mixture of one or more diolefines and the condensation catalyst. The reactants in the desired proportions may be mixed before, during or after their introduction into the reaction vessel.

The proportions of the olefine to the dioleflne in the mixture condensed may vary considerably depending upon the nature of the high-molecular weight polar compound desired. Preferably we employ a considerable molecular excess of the oleilne over the diolefine. By regulating the ratio of the reactants, stable polyolefinic hydrocarbon products of the desired high-molecular weight are obtained. Polyoleflnic hydrocarbon materials having molecular weights as high as 10,000 and higher may be obtained by the condensation reaction. For example, if 90 molecules of isobutene are condensed with 10 molecules of butadiene, the condensation product may contain 10 double bonds and have a molecular weight as high as about 5600 (an equivalent molecular weight of about 560 per olefinic linkage).

The condensation may or may not be effected in the presence of a solvent or diluent. When hydrocarbon fractions containing olefines and diolefines are treated, the inert hydrocarbons may act as solvents or diluent which may be subsequently separated from the products. When pure olefines and diolefines are recated, suitable inert solvents or diluents may be added. It is desirable to employ a solvent or diluent which is inert under the conditions of the condensation reaction.

The condensation catalyst may be added to the reaction mixture as a solid, as a liquid in some auaoeo cases, or suspended or dissolved in a suitable medium or solvent therefor. The desired amount of the catalyst may be added to the reaction mixture in the reaction vessel all at once, but it is preferably added to the agitated reaction mixture slowly in a continuous or intermittent manner until the required amount has been added. An effective amount of the catalyst is added. The relative amount oi the catalyst used in each particular case will depend upon the particular catalyst or mixture of catalysts employed, upon the particular reactants condensed, and upon the nature of the particular end-product desired. By a suitable regulation of the rate of addition of the catalyst, the temperature of the reaction mixture may be more eflectively maintained within the desired temperature range.

The condensation reaction is eflected at a temperature not greater than about 0 C. Temperatures in the range of from -l00 C. to 0 C. are in general suitable but lower temperatures may be employed if desired. The low reaction temperature is maintained by suitable cooling of the reaction vessel. The reaction is advantageously eilected at atmospheric pressure. Subatmospheric or superatmospheric pressures may be used if desired.

The condensation reaction is preferably effected while stirring the reaction mixture to eflect more intimate contact of the reactants with each other and the catalyst. When the condensation reaction has proceeded to substantial completion or to the desired extent, the polyoleflnic hydrocarbon product of high molecular weight is caused to react with a reagent capable of reacting therewith by addition to one or more of the oleflnic linkages, whereby the hydrocarbon condensation product is converted to a high-molecular weight, high-boiling polar compound particularly useful as a component of lubricating oils and greases.

Suitable reagents capable ofreacting with the double bonds of the hydrocarbon condensation products by addition thereto without disrupting the hydrocarbon chain of the condensation prodnot are the halogens, as chlorine and bromine, the carboxylic acids, the substituted carboxylic acids, the carboxylic acid anhydrides, the mineral acids as hydrogen sulphide, the boric acids, hydrogen cyanide, the phosphoric acids, sulphuric acid, etc., the acid anhydrides as sulphur dioxide, the nitrogen oxides, the phosphorus oxides, etc., the polyhydric alcohols, particularly those containing three or more carbinol groups as glycerol, alphamethyl glycerol, beta-methyl glycerol, alphaethyl glycerol, beta-ethyl glycerol and the like and their homologues and analogues.

A particularly suitable subgroup oi reagents which may be reacted with the polyoleflnic hydrocarbon materials resulting from the condensation embraces those which are of acid character, that is, which are themselves acids or which are capable of forming acids on reaction with water. Included in this subgroup are the mineral acids, the mineral-acting acids, the carboxylic acids, the substituted carboxylic acids, other organic acids, the mineral acid anhydrides, the carboxylic acid anhydrides and the like which are capable of reacting with an olefinic hydrocarbon by addition to the double bond thereof. Hydrogen sulphide is a representative mineral acid of 'this subgroup; acetic acid is a representative monocarboxylic acid; maleic acid is a representative polycarboxylic acid; thioglycolic acid is a representative substituted carboxylic acid; sulphur dioxide is a representative mineral acid anhydride; acetic anhydride is a representative monocarboxylic acid anhydride; and maleic acid anhydride is a representative polycarboxylic acid anhydride. 0i this preferred subgroup, the polycarboxylic acid anhydrides, especially maleic acid anhydride and its homologues, analogues and substitution products, are particularly suitable.

The reaction whereby a reagent is added to a double bond of the polyoleflnic condensation product may be efl'ected in the same reaction vessel in which the condensation was eii'ected, or it may be eifected in another vessel better adapted to the particular additive reaction. In general, the same reaction vessel, it it is adapted to use at high as well as low temperatures, may be used throughout. The relative amount of the particular reagent to be reacted with the polyoleflnic hydrocarbon material depends upon the nature of the product, that is, upon whether it is desired to saturate all, several or only one 01' the oleflnic linkages oi. a molecule of the hydrocarbon. The conditions of temperature, pressure, etc., at which the addition reaction is effected will depend upon the nature of the particular addition reaction involved. For example, some of the addition reactions are best effected at room temperature or lower temperatures, while other are best eflected at elevated temperatures. When it is desired to add a halogen, such as chlorine, to the double bonds of the polyoleflnic hydrocarbon, the chlorination may be eflected with the chlorine in the liquid or gaseous phase, and in the presence or absense of a catalyst. The chlorination may be eilected at about room temperature, temperatures below room temperatures, or at moderately elevated temperatures. Suitable chlorination catalysts are, e. g., the metal halides as ferric chloride, nickel chloride, calcium chloride and the like.

The carboxylic acids and carboxylic acid anhydrides are preferably reacted with the poyoleflnic hydrocarbon material at elevated temperatures. For example, the carboxyic acid anhydrides, such as maleic acid anhydride, are conveniently reacted with one or more double bonds of the polyoleflnic material at temperatures of from about 100 C. to about 300 C. or higher. When maleic acid anhydride is the reagent added, it is, in general, desirable to employ it in excess and eflect the reaction at a temperature of about 200 C. After a carboxylic acid anhydride is reacted with the hydrocarbon material, the resulting product may be hydrolyzed by heating it with water at an elevated temperature of about 100 C. or higher, whereby a high-molecular weight, high-boiling polycarboxylic acid is obtained.

The following specific example illustrates a suitable mode of executing the process of the invention to obtain an oil-soluble organic polar compound of high-molecular weight and highboiling temperature which is a valuable agent to add to lubricating oils to increase their viscosity index, their oiliness, their extreme pressure lubrieating qualities and other characteristics. It is to be understood that the invention is not to be regarded as limited to the specific reactants, catalyst, or mode of operation disclosed in the example.

Example About 5 kilograms of butadiene and about kilograms oi. isobutene were introduced into a suitable reaction vessel equipped with heating and cooling means and means for mechanically stirring its contents. The mixture was stirred and cooled to about 80 C. while BF: was added in an amount sufllcient to effect the condensation. The condensation reaction was efiected at a temperature of about 80 C. and at about atmospheric pressure. When the condensation reaction was substantially complete, an excess of maleic acid anhydride was added to the polyoleflnic hydrocarbon material, which was in the form of a viscous oil having a molecular weight of about 4000, and the resulting mixture stirred and heated at a temperature of about 200 C. for about 24 hours. During this period, maleic acid anhydride was added from time to time to maintain it in substantial excess in the reaction vessel. At the end of the heating period, an excess of water was added to the contents of the reaction vessel and the mixture stirred and heated at about 100 C. until the hydrolysis was substantially complete. The product of the hydrolysis reaction was a high-boiling polycarboxylic acid having a weight equivalent of about 2000.

While we have described our invention in a detailed manner and illustrated suitable means of executing the same, it is to be understood that modifications may be made and that no limitations other than those imposed by the scope of the appended claims are intended.

We claim as our invention:

1. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing an oleflne with a polyoleflne at a temperature not greater than about C., and reacting the resulting high-molecular weight polyolefinic hydrocarbon product with a reagent capable of reacting therewith by addition to an olefinic linkage whereby a high-boiling polar compound is obtained.

2. A process for the production of organic polar compounds or high molecular weight and boiling temperature which comprises condensing an oleflne with a diolefine in the presence of a condensation catalyst at a temperature not greater than about 0 C., and reacting the resulting high-molecular weight polyolefinic hydrocarbon product with a reagent capable of reacting therewith by addition to an olefinic linkage whereby a high-boiling polar compound is obtained.

3. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing a substantial molecular excess of an olefine with a dioleflne in the presence of a condensation catalyst at a temperature not greater than about 0 C., and reacting the resulting high-molecular weight polyolefinic hydrocarbon product with a reagent capable of reacting therewith by addition to an olefinic linkage whereby a high-boiling polar compound is obtained.

4. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing an olefine with a diolerlne in the presence of a condensation catalyst comprising an acid-acting halide of the class consisting of the acid-acting metal halides and the boron halides at a temperature not greater than about 0 C., and reacting the resulting high-molecular weight polyoleflnic hydrocarbon product with a reagent capable of reacting therewith by addition to an oleflnic linkage whereby a high-boiling polar compound is obtained.

5. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing an ole= fine with a dioleflne in the presence or a condensation catalyst comprising an acid-acting metal halide at a temperature not greater than about 0 C., and reacting the resulting high-molecular weight polyoleflnic hydrocarbon product with a reagent capable of reacting therewith by addition to an olefinic linkage whereby a high-boiling polar compound is obtained.

6. A process for the production or organic polar compounds of high molecular weight and boiling temperature which comprises condensing an olefine with a dioleflne in the presence of a condensation catalyst comprising an aluminum halide at a temperature below about 0 C., and reacting the resulting high-molecular weight polyolefinic hydrocarban product with a reagent capable of reacting therewith by addition to an oleflnic linkage whereby a high-boiling polar compound is obtained.

7. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing an oleline with a diolefine in the presence of a condensation catalyst at a temperature not greater than about 0 C., and reacting the resulting highmolecular weight polyolefinic hydrocarbon product with a reagent of acid character capable of reacting therewith by addition to an olefinic linkage whereby a high-boiling polar compound is obtained.

8. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing an oleflne with a dioleilne in the presence of a condensation catalyst at a temperature not greater than about 0 C., and reacting the resulting highmolecular weight polyoleflnic hydrocarbon product with a reagent of the class consisting of carboxylic acids and carboxylic acid anhydrides which is capable of reacting therewith by addition to an olefinic linkage whereby a high-boiling polar oxy-compound is obtained.

9. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing an olefine with a diolefine in the presence of a condensation catalyst at a temperature not greater than about 0 C., and reacting the resulting highmolecular weight polyoleflnic hydrocarbon product with a carboxylic acid anhydride, the acid anhydride adding to an oleflnic linkage of the unsaturated hydrocarbon product whereby a highboiling oxy-compound of high-molecular weight is obtained.

10. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing an olefine'with a diolefine in the presence of a condensation catalyst at a temperature not greater than about 0 C., and reacting the resulting high-molecular weight polyoleflnic hydrocarbon product with maleic acid anhydride whereby a high-boiling oxy-compound of high-molecular weight is obtained.

11. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing an olefine with a dioleflne in the presence of a condensation catalyst comprising boron fluoride at a temperature not greater than about 0 C.,

and reacting the resulting high-molecular weight polyolefinic hydrocarbon product with a reagent presence of a condensation catalyst comprising capable of reacting therewith by addition whereby a high-boiling polar compound is obtained.

12. A processior. the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing a substantial molecular excess of an olefine with a diolefine in the presence of boron fluoride at a temperature not greater than about 0., and reacting the resulting high-molecular weight polyolefinic hydrocarbon product with a carboxylic acid anhydride, whereby a high-boiling polar compound is obtained.

13. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing a substantial molecular excess ofan olefine with a conjugated double bond diolefine in the presence. of boron fluoride at a temperature not greater than about 0 0., and reacting the resulting high-molecular weight polyoleflnic hydrocarbon product with maleic acid anhydride at a temperature greater than about 100 0., whereby a high-boiling polar compound is obtained.

14. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing about nine parts by weight of isobutene with about one part by weight of butadiene in the presence of boron fluoride at a temperature of about 80 0., reacting the resulting high-molecular weight polyolefinic hydrocarbon product with an excess of maleic acid anhydride at a temperature of about 200 0., and heating the reaction mixture with water at a temperature of about 100 0., whereby a high-boiling polycarboiwlic acid having a weight equivalent of about 2000 is obtained.

15. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing an olefine with a diolefine in the presence of a condensation catalyst comprising aluminum chloride at a temperature not greater than about 0' 0., and halogenating the resulting high-molecular weight polyoleflnic hydrocarbon product whereby a high-boiling polyhalogenated organic compound is obtained.

16. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing a substantial molecular excess of an olefine with 18. In a process for the production of organic polar compounds of high molecular weight and boiling temperature, the step which comprises condensing an olefine with a dioleflne in the an acid-acting halide of the class consisting of the acid-acting metal halides and the boron halides at a temperature not greater than about 0 0. to obtain a high molecular weight poly- .olefinic product.

19. As a composition of matter: the organic polar compounds of high molecular weight and boiling temperature obtained by condensing an olefine with a diolefine in the presence of a condensation catalyst at a temperature not greater than about 0 0. and reacting the resulting polyoleflnic hydrocarbon product with an agent capable of reacting therewith by addition to an olefinic linkage.

20. As a composition of matter: the organic polar compounds of high molecular weightand boiling temperature obtained by condensing a substantial molecular excess of an olefine with a dioleiine in the presence of a condensation catalyst comprising an acid-acting halide of the class consisting of the acid-acting metal halides and the boron halides at a temperature not greater than about 0 C. and reacting the resulting polyolefinic hydrocarbon product with maleic acid anhydride.

21. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing a substantial molecular excess of a tertiary olefine with a diolefine in the presence of a condensation catalyst at a temperature not greater than about 0 0., reacting the resulting highmolecular weight polyolefinic' hydrocarbon product with an excess of a carboxylicacid anhydride at a temperature of about 200 0., and heating the resulting reaction mixture with water at a temperature of about 100 0., whereby a high-boiling polycarboxylic acid having a high weight equivalent is obtained.

22. A composition of matter: the organic polar compounds of high molecular weight and boiling temperature obtained by condensing a substantial molecular excess of an olefine with a diolefine in the presence of a condensation catalyst comprising an acid-acting halide of the class consisting of the acid-acting metal halides and the boron halides at a temperature not greater than about 0 0. and reacting the resulting polyolefinic hydrocarbon product with carboxylic acid anhydrode.

23. A process for the production of organic polar compounds of high molecular weight and boiling temperature which comprises condensing an olefine with a dioleflne in the mol ratio of about 9 to 1 in the presence of a condensation catalyst comprising an acid-acting halide of the class consisting of the acid-acting metal halides and the boron halides at a temperature not greater than about 0 0., and reacting the resulting high-molecular weight polyoleflnic hydrocarbon product with a reagent capable of reacting therewith by addition to an oleflnic linkage whereby a high-boiling polar compound is obtained.

HEITDRIK WILLEM HUIJSER. CHRISTIAAN NICOLAAS JACOBUS DI: NOOIJER.