US3405187A - Alkyl substituted bicyclic monoolefins - Google Patents

Description

United States Patent 3,405,187 ALKYL SUBSTITUTED BICYCLIC MONOOLEFINS Herman S. Bloch, Skokie, Ill., assignor to Universal Oil Products Company, Des Plaines, 11]., a corporation of Delaware No Drawing. Original application Oct. 28, 1964, Ser. No. 407,232. Divided and this application June 28, 1967, Ser. No. 649,459

4 Claims. (Cl. 260-666) ABSTRACT OF THE DISCLOSURE A monoolefin having from about 9 to about 20 carbon atoms is condensed with a conjugated cyclodiolefin to produce an alkyl substituted bicyclic monoolefin suitable for use in the manufacture of detergents.

This application is a division of my copending application Ser. No. 407,232, filed Oct. 28, 1964, now U.S. Patent 3,370,080, issued Feb. 20, 1968.

This invention relates to a novel biodegradable detergent and to a process for making the same. More specifically, this invention relates to a novel detergent whose composition is:

wherein R is an alkyl group of substantially normal character having from 1 to about 17 carbon atoms, R is selected from the group consisting of hydrogen and an alkyl group of substantially normal character having from 1 to about 17 carbon atoms such that the sum of carbon atoms in R plus R does not exceed 18, R" is (Ch2) where z is 1 or 2 and X is a hydrophilic group. Further, this invention relates to a process for the production of the above described novel detergent which comprises condensing a monoolefin having from about 9 to about 20 carbon atoms with a conjugated cyclodiolefin and introducing a hydrophilic group into the condensed product. The resulting product which contains both a hydrophilic and a hydrophobic group is a detergent material subject to bacterial attack and degradation in a subsequent sewage treatment process after the detergent has been used in a laundering or other cleaning operation and discharged into such sewage treatment facilities.

One of the major problems prevalent in centers of population throughout the world is the disposal of sewage and the inactivation of detergents dissolved in the sewage in even small quantities. Such disposal problem is especially vexatious in the case of those detergents having an alkylaryl structure at the nuclear portion of the detergent molecule. These detergents produce stable foams in hard or soft waters in such large quantities that the foam clogs sewage treatment facilities and often appears in sufiicient concentration in such facilities to destroy the bacterial necessary for suflicient biological action for proper sewage treatment. One of the principal offenders of this type of detergent is the alkylaryl sulfonates, which, unlike the fatty acid soaps, do not precipitate when mixed with hard water containing calcium or magnesium ions in solution. Since these compounds are only partly biodegradable, the detergent persists in solution and is carried through the sewage treatment plant in substantially unchanged or still active form. Because of the abiding tendency of such detergents to form, especially when mixed 'with aerating devices and stirrers, large quantities of foam are discharged from the sewage digestion plant into rivers and streams where the continuing presence of the detergent is marked by large billows of foam on the surface. Other offenders of this type of detergent are the polyoxyalkylated alkylphenols and the polyoxyalkylated alkylanilines. These same synthetic detergents also interfere with the anaerobic process of degradation of other materials such as grease, and thus compound further the pollution caused by sewage plant efiluents containing such detergents. These dilute detergent solutions often enter subsurface water currents which feed into underground water strata from which many cities draw their water supplies and these detergents find their way into the water supplies drawn from water taps in homes, factories, hospitals and schools. Occasionally these detergents turn up in suflicient quantities in tap water to make drinking water foam as it pours from the tap.

It is an object of this invention to produce a detergent capable of biological degradation during the treatment of sewage containing such detergents. It is another object of this invention to provide a process for making the biodegradable detergent.

It is a more specific object of this invention to produce a detergent of the composition:

III

wherein R, R, R" and X are as described hereinbefore.

It is another more specific object of this invention to produce the biodegradable detergent by condensing a monolefin with a conjugated cyclodiolefin and introducing a hydrophilic group into the condensed product.

One of the starting materials in the process of this invention is a monoolefin preferably of substantially normal character having about 9 to 20 carbon atoms per molecule. This material may be prepared by any well known method such as wax cracking or it may be prepared from substantially normal paraffins. In this latter source, the normal paraffins are separated from hydrocarbon mixture by molecular sieve extraction. The substantially normal paraflin may be reacted with a halogen selected from the group consisting of chlorine and bromine to form the alkyl halide. The alkyl halide is then dehydrohalogenated to' form the substantially normal monoolefin. The monoolefin has the generic formula RCH=CHR' where R is an alkyl group of substantially normal character having from 1 to about 17 carbon atoms and R is selected from the group consisting of hydrogen and an alkyl group of substantially normal character having from 1 to about 17 carbon atoms such that the sum of R plus R does not exceed 18.

Another of the starting materials in the process of this invention is a conjugated cyclodiolefin having the generic formula:

the conjugated cyclodiolefin at temperatures of from about 100 C. to about 250 C. and at pressure of atmospheric or moderately superatmospheric. The thermally condensed product which is a substituted bicyclic monoolefin is separated and is thereupon converted to a water soluble, surface active detergent by introducing a hydrophilic group into it. The thermal condensation reaction is further illustrated below with a generic chemical reaction equation:

The resulting substituted bicyclic monoolefin may be treated in a number of conventional ways to introduce a hydrophilic group into its structure thereby forming a detergent. For example, the hydrophilic group may be a sulfate group, a sulfonate group or a hydroxypolyoxyalkylene group.

The sulfate group may be introduced by reacting the substituted bicyclic monolefin with concentrated sulfuric acid at temperatures below 50 C. and preferably about C. The resulting sulfate is then neutralized with a basic material, preferably a metal hydroxide or ammonia to form the finished surface active product. The alkali metals are preferable cations for said metal hydroxide, sodium and potassium being especially preferable.

The sulfonate group may be introduced into the substituted bicyclic monoolefin by hydrohalogenating said bicyclic monoolefin and reacting the resulting halide with a metal sulfite salt thereby forming the sulfonate. The halogen is preferably selected from the group consisting of chlorine and bromine while the metal sufite is preferably selected f-rom the group consisting of sodium sufite and potassium sulfite. Alternatively the sulfonate may be for-med by reacting the bicyclic monoolefin with a metal bisulfite at temperatures of about 100 to 125 C. The metal 'bisulfite is preferably selected from the group consisting of sodium bisulfite and potassium bisulfite.

Another procedure for introducing hydrophilic groups into the substituted bicyclic monoolefin is to hydrate the monoolefin with dilute acid such as sulfuric or hydrofiuoric acid thereby forming the corresponding alcohol. The alcohol may thereupon be sulfated or oxyethylated to render it water soluble and surface active. This latter step is accomplished by reacting the alcohol with ethylene oxide in the presence of a trace amount of a basic material such as sodium acetate, sodium carbonate or sodium hydroxide at temperatures of about 80 C. to form the 'hydrophilic w-hydroxy polyoxyalkylene group.

These and other well known methods and hydrophilic groups may be employed to form a water soluble, surface active detergent from the substituted bicyclic monoolefin. The resulting detergent has the following generic composition:

wherein R is an alkyl group of substantially normal character having from about 1 to about 17 carbon atoms, R is selected from the group consisting of hydrogen and an alkyl group of substantially normal character having from 1 to about 17 carbon atoms such that the sum of carbon atoms in R plus R does not exceed 18, R" is an alkylene group whose formula is (CH and z is 1 or 2 and X is a hydrophilic group preferably selected from the group consisting of a sulfate (X is OSO M where M is hydrogen, amine ion or an equivalent of a metal), a sulfonate (X is SO M where M is as defined above), and w-hydroxy polyoxyalkylene [X is -O(C H O) H where n is 2 or 3 and y is a number from S to 30] and a sulfate of an w-hydroxy polyoxyalkylene where n, y and M are as defined above].

It is to be noted that the relative number of carbon atoms in R and R is determined by the position of the double bond in the starting monoolefin. Thus when the monoolefin is an alpha olefin, then R will be hydrogen and R will contain all the carbon atoms in the original monoolefin except the two which become part of the cyclic structure.

The resulting detergents are readily degraded by treatment in conventional sewage facilities.

The following examples are presented to illustrate the process of this invention but it is not intended to limit the scope of this invention to the feed materials or products of those specifically shown reactions in the examples.

Example I A glass liner containing 189 grams (1.5 mole) of 4-nonene, cc. of hexane and 33.1 grams of cyclopentadiene is sealed into an autoclave. The autoclave and contents are heated to a temperature of about 200 C. and maintained at this temperature for a period of about 8 hours at the end of which time the autoclave and contents thereof are cooled to room temperature and the desired bicyclic monoolefin is separated by ordinary batch fractionation. The substituted bicyclic monoolefin is introduced into a flask which is immersed in a bath maintained at 0 C. Concentrated sulfuric acid at a temperature of 0 C. is introduced into the flask and the contents thereof thoroughly mixed. The resulting product is thereupon neutralized with sodium hydroxide until a pH of 7 is attained. The product is a crystalline cream colored solid which is completely soluble in water and shows excellent wetting properties.

EXAMPLE II A mixture of about 252 grams (1.5 mole) of a methyl- 3-undecene, 100 cc. of hexane and 40.1 grams of cyclohexadiene is sealed into an autoclave. The autoclave and contents are heated to a temperature of about 175 C. and maintained at this temperature for a period of about 12 hours at the end of which time the autoclave and contents thereof are cooled to room temperature and the desired bicyclic monoolefin is separated by ordinary batch fractionation. The substituted bicyclic monoolefin is hydrated with diluted hydrofluoric acid at 40 C., to form the corresponding bicyclic alcohol, which is separated and placed in a glass liner and sealed into an autoclave with 0.5 weight percent of powdered sodium hydroxide. Sufiicient ethylene oxide is pressured in to result in a ratio of 9 moles of ethylene oxide to 1 mole of bicyclic alcohol. The autoclave and contents are heated to C. and maintained at that temperature for a period of 2 hours at the end of which time the autoclave and the contents thereof are cooled to room temperature and the desired polyoxyethylated detergent is removed. It is found to have good foaming and detergent properties.

EXAMPLE III A glass liner containing about 420 grams (1.5 mole) of 5-eicosene, 200 cc. of hexane and 33.1 grams of cyclopentadiene is sealed into an autoclave. The autoclave and contents are heated to a temperature of about C. and maintained at this temperature for a period of about 16 hours at the end of which time the autoclave and contents thereof are cooled to room temperature and the desired bicyclic monoolefin is separated by ordinary batch fractionation. The substituted bicyclic monoolefin is contacted with anhydrous hydrogen chloride to form the corresponding hydrohalide, and the latter is contacted with an excess of sodium sulfite by mixing together in a glass flask. The mixture is maintained at 115 C. for one hour whereupon the desired resulting sulfonate is recovered from the flask. It is a water-soluble, surface-active solid.

I claim:

1. The process for the production of alkyl substituted bicyclic monoolefins suitable for use in the manufacture of detergent by thermally and noncatalytically condensing a monoolefinic acyclic hydrocarbon of from about 9 to about 20 carbon atoms with cyclopentadiene or cyclohexadiene at a temperature of from about 100 C. to about 250 C.

2. The process of claim 1 further characterized in that said monoolefinic hydrocarbon is 4-nonene.

3. The process of claim 1 further characterized in that said monoolefinic hydrocarbon is a methyl-3-un decene.

4. The process of claim 1 further characterized in that said monoolefinic hydrocarbon is S-eicosene.

References Cited UNITED STATES PATENTS DELBERT E. GANTZ, Primary Examiner.

V. OKEEFE, Assistant Examiner.