IL23015A - Preparation of alkyl aryl sulfonates - Google Patents

Description

C O H E N Z E D E S P I S B A C H E G N T AT TO R N EYS LEVONTIN 1169 T E L A V I V P A T E N T S D E S I G S O R D I N A N C E SPECIFICATION This invention relates to an improved method for paring detergents and precursors and more ly relates to a method of preparing aryl the sulfonic acids and salts The method of this invention relates particularly to the production of chlorides which are used to alkylate an aryl compound to form aryl the latter which sulfonated form aryl sulfonic acids which when neutralized with an such as caustic produce well known types of biodegradable wetting and namely sodium aryl Early production of sodium aryl sulfonates utilized an hydrocarbon fraction derived from a petroleum hydrocarbon distillate having a boiling range within the sene This hydrocarbon fraction was chlorinated and the resultant alkyl chloride condensed with xylene or the like in the presence of a such as anhydrous aluminum When such alkyl fraction is and the chloride condensed with the resulting alkyl aryl hydrocarbon compounds have come known as benzene and propylene tetramer have been used as starting materials in the preparation of benzene which is subsequently processed to form dodecylbenzene While it is known that the alkyl benzene sulfonates or and therefore accumulate in ground This problem is particularly pronounced when the a ky group is as in the sodium te rapropylene benzene turned its to the facture of straight chain benzene sulfonates which can be sented by the formulas wherein is alkali nitrogen typically nd m and n are integers such m n A known method for preparing these benzene sulfonates to isolate normal paraffins from a kerosene distillate fraction of crude to chlorinate these mixed paraffins and to treat the resulting chloride mixture with benzene in the presence of a as aluminum of the resulting and neutralization gives the desired The that is used has from 9 to carbon atoms per and more from 11 to 14 carbon atoms with the major 13 carbon that tridecahev Such ca be chlorinated free chlorine a variety are obtained in good yield if only partial chlorination is from 5 to of the theoretical chlorine monochlorina is with 10 to being commercially is that several o can arise from each For can yield one primary secondary isomeric In the it has not possible to analyse for the of detergents this did seem portant since the of the chloride did not seem to effect the composition the desired This is no since the alkyl chlorides are known to during thus appeared that the ture of alkyl from a given did not vary in composition regardless of the chlorinating or alkylatin that is the distribution of the alkyl in two it effects the and the of the derived It is known that the sulfonates most biodegradable those with the phenyl group positioned near the end of chain HoweverJ such materials are poor sulfonate almost wholly may be soluble by mixing it with other alkyl bensene sulfonates have the phenyl group positioned along the alkyl the most efficient detergents have the group positioned near the middle of the alkyl Manufacturers of synthetic in an optimum comromise roduct conse uentl su ested h than of the have the group substituted on the atom substituted the and With reference the a re having not only different of but different of n gives desirable suitable distribution of of hereinbefore the with the group end of are readily while the isomers the nearest the kiddie of the chain result in detergents having the washing It is evident that every m there is an distribution of In the past it has been found that known conditions been too In the content of has been too accordance the present invention there is provided a for forming sulfonates having an increased concentration of sulfonates halogenating an to form halides at a temperature below ambient temperature and above the temperature at which fifty per cent of the resulting reaction is a alkylating an aryl compound with the chlorides in the presence of a catalyst at a temperature between and to aryl sulfonating the aryl hydrocarbons to form aryl sulfonic and neutralizing the benzene sulfonic acids to form aryl In accordance the present invention there is provided a method comprising effecting the halogenation of an hydrocarbon to form halides at a temperature below ambient temperature and above the temperature at which fifty per cent of the reaction mass is preferably at a temperature near the incipient crystallization temperature of the In accordance with the present there is also provided a method of alkylating an aryl compound with the halides to increase center substitution on the alkane comprising alkylating at a temperature between and The hydrocarbon is preferably a mixture of derived from a petroleum distillable fraction boil ing within the kerosene range with the having from 9 to 16 carbon atoms per of such a mix hereinafter wherein b and are such that a b is equal to c and c is an integer from 7 to The resulting chlorides are then used to alkylate an aryl such as as illustrated in Equation wherein a and b are such that a b m Xn accordance with the it has been found that by effecting the halogenation of a hydrocarbon at temperatures below ambient temperature and above that temperature at which of the reaction mass is preferably at a temperature near the incipient crystallization temperature of the the isomeric distribution of the resulting as the is altered by there is a decrease in concentration of Fo if tridecane whose freezing point is is chlorinated with free chlorine below the resulting mixture will contain less tridecane if chlorination is as is usually the case at or above Xn accordance with a preferred embodiment of the a mixture of is chlorinated with free chlorine at a temperature below ambient temperature and above that at which of the reaction mass is solid to chloridess preferably at a temperature above the incipient crystallization temperature of the The mixture of is derived from a petroleum tillate fraction boiling the kerosene range and having from 6 to carbon preferably 11 to 14 carbon It is desirable to only chlorinate the so as to minimize the formation of polychlo Soft ultraviolet light may used to accelerate the reaction but this is not The resultin chlorides in admixture with ins then introduced into an alkylation reaction arid an as such as aluminum chloride is added to and the mixture is maintained at a temperature of for from 5 to the mixture is raised to a temperature of from for to 40 minutes to further improve the isomeric The aromatic hydrocarbons formed a smaller concentration of and aryl than other order to effect the yl pound with chlorides trithin such a temperature it is necessary that there exist a minimal ratio of aryl pounds to the For when ing benzene point of from to and The yields alkyl benzenes increase as the of benzene to chlorides is increased an mum ratio is B chlorinating the to low per cent conversions a larger concentration of unreacted hydrocarbons are present which higher ratios of benzene to chlorides after addition of the benzene but which or lower concentration of benzene in the resulting The effected in batch or in tinuous It been found that staged counterflow operation is particularly The compound is preferably or The distribution of the benzene is not solely by the isomeric distribution of the chloride the isomeric istribution pf the benzenes under normal alkylation is apparently insensitive to the isomeric tion of the chlorides so even starting with a single alkyl an mixture of benzenes and it is similar to the isomeric obtained from chlorinated isomeric distributio of the benzene obtained by effecting the alk of benzene with a halide at normal conditions is not altered by changing the varying the concentration of the alkyl chloride relative to the ar l com ound or var in catal st Α solvent may be used to assist in achieving the low temperatures necessary for liquid phase Such solvents include carbon pentane and liquid sulfur particularly effective where keryl chlorides are the alkylating The product in the alkylation zone is thereafter isolated and sulfonated such as by the benzenes with oleum to form benzene sulfonic which then with an aqueous hydroxide to form preferably effected at peratures from about to The invention is illustrated by 1 The value the made by low temperature and the resulting benzenes made by low can be ing embodiment of this normal paraffi r having he composition shown in was by chlorine at was used accelerate the reactio but is not Chlorine additio can be continued ntil the ture gains of from 2 to in chlorination was continued there was a increase in To the resulting of monochlp des and fihs are added mole of benzene and part of aluminum Of from to 3 of zene can be with mole being Alkylation allowed to completio at The resulting alkylate found by chromatography to contain only of the nyl no detectable and a total When the process was carried out identically in all details that chlorination at the esulting contained isomers about somers and such as branched iaateriais know to be deleterious to gency are reduced abou by chlorinatin near the incipient crystallizatio temperatures of the reaction EXAMPLE II A paraffin as in Table chlorinated at and at until there was a increase in weight of Table 3 sets forth the data taken on the resulting Table 3 of that is 1 carbon 5 B 10 As determined by nuclear magnetic resonance spectrometer EXAMPLE III The alkyl mixtures of Example IX were mixed with and aluminum chloride under the conditions in Table 4 OF OF AICI3 A 23 164 g 3 32 227 g 3 analyses of the alkyl are set forth in TOTAL A 125 30 EXAMPLE A normal paraffin having a composition as shown in chlorinated on a steam bath it had gained in Table 6 Mixture The resulting mixture was mixed with benzene and aluminum chloride with efficient agitation under reaction conditions set forth completion the as distilled and analyzed the analyses set forth in Table ble 7 Kerosene Time g g A 80 220 600 6 150 80 220 6 Table 8 A B ΐ 20 27 23 30 18 18 16 16 17 19 1 23 branched 100 The only differences in the conditions between periments A and were temperature and and the quantity of benzene added to the alkyl chlorides prior to initiation of there is a in the uantit of the hen h drocarbons with an increase of there is a reduction in branched chain kylates which are not as biodegradable straight chain Alky ation of the aryl is fected in the presence of aluminum other catalysts are useful are Crafts catalysts a metallic halide wherein metallic halide includes aluminum boron and ferric The invention has been described with regard to the chlorination of a bromination of such is insufficientOCRQuality

Claims (18)

HAVING WOW particularly described and ascertained . the nature of our said invention and in what manner the same is to be performed, we declare that whaV we claim is : ΤVιHΤΤS¾ΤIΑtΊaΓp* ¾ TfT)* ^ Γj^Τip AgTwMgP-gTy¾ ^U TSSCP,?>„5

1. The method of forming n-alkyl ary sulfonates having an increased concentration of center-substituted sulfonates wherein (a) an n-alkane is halogenated to form n-alkyl halides, (b) an aryl compound is alkylated with the n-alkyl halides in the presence of a Friedel-Crafts catalyst to form n-alkyl aryl hydrocarbons, (c) the n-alkyl aryl hydrocarbons are sulfonated to form n-alkyl aryl sulfonic acids, and (d) the n-alkyl benzene sulfonic acids are neutralized to form n-alkyl aryl sulfonates, comprising (a) halogenating at a temperature below ambient temperature and above the temperature at which fifty per cent of the resulting reaction mass is a solid, and alkylating (b) at a temperature between -25°C. and 10"G.

2. The method according to Claim 1 wherein the halogen is chlorine.

3. The method of either of Claim 1 or 2 wherein halo-genation is continued until there is an increase in weight of 2-10 per cent.

4. The method of any of Claims 1-3 wherein the n- alkane has from 9 to 16 carbon atoms per molecule.

5. The method of any of Claims 1-3 wherein the n-al- kane has from 11 to 14 carbon atoms per molecule.

6. The method of any of Claims 1*3 wherein the n-al- kane comprises & petroleum distillate fraction boiling in the kerosene range.

' 7. The method of any of Claims 1-6 wherein 1 to 25 moles of the aryl compound are used for each mole of n-alkyl halides in (b).

8. The method of any of Claims 1-7 wherein the aryl compound is benzene, toluene or xylene.

9. The method of any of Claims 1-8 wherein the al- kylation (b) is effected in the presence of a solvent.

10. The method of Claim 9 wherein the solvent is sulfur dioxide.

11. The method of Claim 9 wherein the solvent is un- chlorinated para fin.

12. The method of halogenating an n-alkane with halogen comprising halogenating the n-alkane at a temperature below ambient temperature and above the temperature at which 50 per cent of the reaction mass is solid.

13. The method according to Claim 12 wherein the halogen is chlorine. 14. The method according to either Claim 12 or 13 wherein halogenation is continued until there is an increase in weight of 2-10 per cent. P.A.23015 Pile 12972

14. III.68

15. The method according to any of Claims 12-14 wherein the n-alkane has from 9 to 16 and particularly 11 to 141 carbon atoms per molecule.

16» The method according to Claim 15 wherein the n-alkane comprises a petroleum distillat fraction boiling within the kerosene range.

17. The method of halogenating an n-alkane substantially as described by Examples 1A and II.

18. The method of alkylating an aryl compound with an n-alkyl halide to increase center substitution on the n-alkane substantiall as described by Examples IA, IIIB and IVB. COHEN ZEDEK AND 3PISBACH P.O. Box 1169» Tel Aviv Attorneys for Applicants