Title of Invention	"A PROCESS FOR MANUFACTURING LONGER CHAIN ALKYL SULFATE OR ALKYL ALKOXYLATED SULPHATE SURFACTANT MIXTURE COMPOSITIONS"
Abstract	The present invention relates to a process for manufacturing longer chain alkyl sulfate or alkyl alkoxylated sulphate surfactant mixture compositions, said process comprising the steps of: (a) sulfating with SO3 preferably in a falling film reactor, a long chain aliphatic alcohol mixture or polyoxyalkylene alcohol mixture having an average carbon chain length of at least 14.5 to 17.5, said alcohol mixture comprising at least 10% of a mid-chain branched aliphatic alcohol or polyoxyalkylene alcohol. (b) neutralizing the alkyl sufate or alkyl alkoxylated sulphate acid produced by step (a), preferably utilizing a base.

Title of Invention

"A PROCESS FOR MANUFACTURING LONGER CHAIN ALKYL SULFATE OR ALKYL ALKOXYLATED SULPHATE SURFACTANT MIXTURE COMPOSITIONS"

Abstract

The present invention relates to a process for manufacturing longer chain alkyl sulfate or alkyl alkoxylated sulphate surfactant mixture compositions, said process comprising the steps of: (a) sulfating with SO3 preferably in a falling film reactor, a long chain aliphatic alcohol mixture or polyoxyalkylene alcohol mixture having an average carbon chain length of at least 14.5 to 17.5, said alcohol mixture comprising at least 10% of a mid-chain branched aliphatic alcohol or polyoxyalkylene alcohol. (b) neutralizing the alkyl sufate or alkyl alkoxylated sulphate acid produced by step (a), preferably utilizing a base.

Full Text	Case 6405 INDUSTRIAL SULFAT10N Daniel Sicdman Connor Thomas Anthony Cripe R. Craig Jacobs Mike C. Jansen FIF.T.D OF THE INVENTION The present invention relates to methods for producing longer chain length • alkyl sulfatc and/or alkyl alkoxylated sulfate surfactant compositions. This method utilizes the presence of a significant amount of mid-chain branched alcohol and/or mid-chain branched polyoxyalkylcne alcohol in the sulfation reaction to significantly reduce the reaction temperature, thereby improving product quality and" saving energy, BACKGROUND OF THE INVENTION Sulfpnution/sulfatkm of nnionie surfactants worldwide is done on a very large scale, on the order of millions of tons each year. Such processes are well defined and are thoroughly characterized in the art. [Sec for example, Everett E. Gilbert, "Sulfation aiul Related Reactions", copyright 1965 by John Willcy and Son, Inc., pages 345-354; and "Sulfonation Technology in the Detergent Industry", by W. Herman dc Ciroot, copyright 1991 by Kluwer Academic Publishers, especially pages 213-215.] The art recognizes that for lower chain length alcohols, such as lauryl alcohol, the feed temperature for the reaction can be kept low, in the 25-3Q°C range. However, longer chain length alcohols, like the C]6-18 tallow alcohol, require feed temperatures in the 55-60° jnnpc. At such higher temperatures, in addition to the added energy needed to run in the process, there is a need to carefully control the reaction conditions, (e.g., to control the flow rates and reactor temperature dissipation) to avoid producing products with poor physical chnrncteristics, such ns off-odor and/or color. [See for example, pages 213-214 of "Sulfonation Technology in the Detergent Industry", ibid] More specifically, side reactions that may occur, at least In part owing to conventional temperatures and the vigor of the sulfating agent include: dehydration of alkyl sulfatc to form olefin; elimination of water between two molecules to form an ether; oxidation to the aldehyde followed by further oxidation to the acid; and esterification of the acid with fatly alcohol [see: David D. Whyte, J.A.O.C.S., Vol. 32, pp313-316, (1955)]. Thus, milder conditions for such longer chain alcohols is highly sought after in the industry. It has been discovered by the present invention that inclusion of at least 10% of a mid-chain branched, longer chain alcohol mixture into the longer chain length (at least about C]^ 5 average) alcohol mixture to be sulfatcd permits avoidance of high peak instantaneous reaction temperatures of the sulfation reaction, sufficiently Objects of the present invention therefore include one or more of the following: better economy by virtue of lower energy input in preparing tlv? alcohol for the sulfation process and the ability to avoid having to melt out and control the feed alcohol temperature; faster reaction times; the ability to provide a more mass-effective product, by avoiding the need to include diluents and viscosity reducers; better color compared with high-temperature processing, such as required for tallow alcohols, and thereby avoiding the need for a subsequent bleaching operation; lower viscosity of the "acid mix" (the term used to describe the product of sulfation prior to being neutralized), which in turn impiovcs the case and quality of the neutralization step; lower viscosity of the finished surfactant paste at identical temperature compared to the process required for the tallow alcohol analog, which thereby permits the manufacture of more concentrated paste for use in so called "compact" or "ultra" determent products, the ability to reduce or eliminate alcohol or similar1 materials which are frequently used to thin the final paste; the ability to manufacture new alkyl sulfate products which are completely linear alkyl benzene sulfonatc- free (typical current practice is to co-react tallow alcohol nnd linear alky) benzene to make a mixed tallow alcohol sulfate and linear alkyl benzene sulfonatc product); (lie ability to more easily pump and handle all materials in the sulfation process from starting material to final product; the ability to avoid or eliminate hot storage steps, and the associated costs and potential discoloration of product that may thereby be produced; the ability to use relatively low-cost sulfonation plants which under normal circumstances would be intoleranl of, or could not handle, neat C16-18 alcohols; and the ability to limit side-reactions during sulfation, thereby giving a cleaner product. These and other objects of the present invention will he apparent from the detailed description hereinafter. BACKGROUND ART Sec: Kirk dinner, Kncyclopedht of Chemical Technology, 3/d. Ed., Wiley, 1983, Vol. 22, pp 28-45, article entitled "Sulfonation and Sulfation"; W.H. De Orooi. "siilphonniion Trdmolnpy in Ihr* Dcicrgont Industry", Kluwcr Academic Publishers, Boston, 1991; ISBN 0-7923-1202-3; and "Detergent Manufacturing Including Zeolite Builders arid Other New Materials,", Chemical Technology Review No. 128, Noyes Data Corp., Park Ridge, New Jersey, 1979, pp. 273-310, SUMMARY OF THE INVENTION The present invention relates to a method for manufacturing longer chain alkyl sulfalc surfactant mixture compositions, said method comprising the steps of: (a) sulfating with 863 (preferably in a falling film reactor) a long chain aliphatic alcohol mixture having an average carbon chain length of at least )4.5 lo about J7.5, said alcohol mixture comprising at least about 1 0 % (preferably at least about 25%, more preferably at least about 50%, still more preferably at least about 7$%, and most preferably at least nbout 95%) of a mid-chain branched aliphatic alcohol having the formula: (Formula Removed) wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, R, and R^ branching) is from 14 to 20, and wherein further for this alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14,5 to about 17.5 (preferably greater than about 15 to about 17); R, Rl, and R?- arc each independently selected from hydrop.cn and C]-C3 alkyl (preferably methyl), provided R, R' , and R2 are not all hydrogen and, when z is 1 , nt least R or RJ is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 1 3 ; z is an integer of at least 1 ; and w + x + y •»• z is from 8 to 1 4; and (b) neutralizing the nlkyl .sulfate acid produced by step (a). Preferred processes further utilize an ulcoho' teed temperature for a step (a) of less than about 50°C, preferably within the range T" from about 10°C to about 50°C, more preferably within the range of from aboi ..: 15°C to about 45°C, and most preferably from about 20°C to about 35°C. Typical conditions also include: a mole ratio of SO_3 to alcohol slightly greater than about 1:1; 803 concentrations in the range of 4-5%, volume/volume, in air or nitrogen (although no-air processes can also be used); cooling jacket water temperatures in the range of from about 20C to about 30°C; neulrnli'/ntion temperatures within the range of from about 25°C to t about 35°C; acid feed temperature into the neutralize!' within ihc range of from about 35°C to nbout 45°C. It is also preferred that the final alkyl sulfate paste concentration be greater than about 20%, preferably greater than about 50%, and most preferably greater than about 60%. Preferably, the aliphatic alcohol used in the above process comprises at least about 10% (preferably at least about 25%, more preferably at least about 50%, still wore preferably at least about 75%, and most preferably at least about 95%) by weight ofa mixture of two or more mid-chain branched alcohols having the formula: (Formula Removed) or mixtures thereof; wherein a, b, d, and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further when a -f b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b ~ 11, a is an integer from 2 to 10 and b is an integer from 3 to 9; when a -»- b ~ 12, a Is an integer from 2 to 11 and b is an integer from 1 to 10; when a -f b = 13, a is an integer from 2 to 12 find b is an integer from 1 to 11; when a •»- b - 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b - 15, u is an integer from 2 to H and b is an integer from 1 to 33; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to H; when d + c = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d f• e = 9, d is tin integer from 2 to 8 and e is an integer from 1 to 7; when d + c = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d -t- e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d +• c = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d •• e ~ 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d -i e - 14, d is an integer from 2 to 13 and c is fln integer from 1 to 12; wherein for this alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5. Optionally, the present invention process may include a first alkoxylation . step whereby a long chain mid-chain branched polyoxyalkylcnc alcohol compound is produced, which thereafter is sulfatcd to produce alkyl alkoxylated sulfates according to the present invention. Such processes comprise the steps of: (a) alkoxylatiny s\ long chum mid-chain branched aliphatic alcohol mixture having an average carbon chain length of at least 14.5 to about 17.5, said alcohol mixture ccmipiisinj', nt least about 10% (preferably at Jcnst about 25%, more preferably at least about 50%, still more preferably at least about 75%, and most preferably at least about 95%) of a mid-chain branched aliphatic alcohol having the formula: (Formula Removed) wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, R' , and R^ branching) is from 14 to 20, and wherein further for this alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to about 17.5 (preferably greater than about 15 to abouU?); R, R, and R^ are each independently selected from hydrogen and Cj'C} alky) (preferably methyl), provided R, R1, and R^ are not all hydrogen and, when z is 1, at least R or R! is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; 7. is an integer of at least 1; and w + x + y + 7. is from 8 to 14; (b) sulfating the polyoxyalkylene alcohol produced by step (a) with 803; and (c) ncutriili/inp. the alkyl alkoxylate r.ulfntc ncid produced by step (b). The present invention therefore also may produce alkyl alkoxylatcd sulfatcs directly starting from a polyoxyalkylene alcohol. Such method comprises the steps of: (a) sulfating with 803 a long chain aliphatic polyoxyalkylene alcohol mixture having an average aliphatic alcohol carbon chain length of at least 14.5 to about 17.5, said polyoxyalkylcnc nlcohol mixture comprising at least about 10% (preferably at least about 25%, more preferably at least about 50%, still more preferably at least about 75%, and most preferably at least about 95%) of a inid-chain branched aliphatic polyoxyalkylene alcohol having the formula: (Formula Removed) wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, Rl, and R^ branching, but not including the carbon atoms in the EO/PO alkoxy moiety) is from 14 to 20, and wherein further for this polyoxyalkylene alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14,5 to about 17.5 (preferably from about 15 to about .17); R, Rl, and \0- arc each independently selected from hydrogen and Cj-C^ alkyl (preferably methyl), provided R, Rl, and R2 are not all hydrogen and, when z is 1, at least R or l\l is not hydrogen; \v is nn ink-pcr from 0 to 11; x is on integer from 0 to 13; y is nn integer from 0 to 13; z is an integer of at Icnst 1; w + x H- y -I- z is from B to 14; and F.O/PO arc alkoxy moieties including lor cx.'implc cthoxy, propoxy, butoxy, etc. preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is ai least about 0.01, preferably within the ranp.c of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 lo nboul 5 fit i.1; to be re.eoj'.m'/ed that the (HO/PO),,, moiety may bc-friiher n distribution with average degree oi'ulkoxylation concsponding to in, or It may be a single specific chain with alkoxylation (e.g., ethoxylation and/or propoxylation) of exactly the number of units corresponding to m); ami (b) neutralizing the alkyl alkoxylated sulfate acid produced by step (a). ,.-, Preferably, the aliphatic polyoxyalkylene alcohol used in step (a) of this process comprises at least about 10% (preferably at least about 25%, more preferably at least about 50%, still more preferably at least about 75%, and most preferably at least about 95%) by weight of a mixture of two or more mid-chain branched aliphatic polyoxyalkylene alcohols having the formula: (Formula Removed) or mixtures thereof; wherein a, b, d, and e are integers, a+b is from 10 to 16, d+e is from 8 to 1 4 and wherein further when alb1 )(), a is an integer from 2 to 9 and b is an integer from 1 to 8; when a -t • b - 1 1 , a is an integer from 2 to 1 0 and b is an integer from 1 to 9; when a I b - 12, a is an integer from 2 to 1 1 and b is an integer from 1 to 10; when a + b = 1 3, a is an integer from 2 to 1 2 and b is ai\ integer from 1 to 1 1 ; when a + b = 14, a is an integer from 2 to 13 and b is an integer fronvl to 12; when a + b - 1 5, a is an integer from 2 to 14 and b is an integer from 1 lo 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and c is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + c = 1 0, d is an integer from 2 to 9 and e is an integer from 1 to 8; i. when d -I 0 " 1 1, d is an integer from ? to 10 and e is an integer from 1 to 9; when d + e = 1 2, d is an integer from 2 to 1 1 and e is an integer from 1 to 1 0; when d + e = 1 3, d is an integer from ?. lo 12 and e is an integer from 1 to 1 1 ; when d i e ": H, d is an inle^u1 from '). to 13 and c is an integer from 1 to 12; wherein for this polyoxyalkylcne alcohol mixture the average total number of carbon atoms in the branched primai-y alkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5; and wherein EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and niixed cthoxy/propoxy groups, wherein m is at least about 0.01, preferably within the range of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5, All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless.pthcnvise specified. All documents cited arc in relevant part, incorporated herein by reference. PETAILEP DESCRIPTION OF THEJNVBNT10N The present invention sulfation process may start with alcohols arid/or polyoxyalkylenc alcohols essentially comprising at least about 10% (preferably at least about 25%, more preferably at least about 50%, still more preferably at least about 75%, and most preferably at least about 95%) by weight of the following mid-chain branched materials, (a) .Mid-chain branchedhiliphntic alcohols: Mid-chain branched aliphatic alcohols useful in the present invention .';iilf;ition process hnve the formula: (Formula Removed) The alcohol mixtures useful in the present invention comprise molecules having a linear primary alkyl chain backbone (i.e., the longest linear carbon chain which includes the hydroxylated carbon atom). These alkyl chain backbones comprise from 12 to 19 carbon atoms; and further the molecules comprise a branched primary alkyl moiety having at least a total of 14, but not more than 20, carbon atoms. In addition, the alcohol mixture has an average total number of carbon atoms for the branched primary alkyl moieties within the range of from greater than M.5 to about 17.5. Thus, the present invention mixtures comprise at least one branched primary alkyl alcohol compound having a longest linear carbon chain of not less than 12 carbon moms or more than J9 carbon atoms, and the total k number of carbon atoms including branching must be al least 14, and further the avciagc total number of carbon atoms for the branched primary alky] chains is williin the ninye of j'.ieatrr than H.5 (o about 17.5. For example, a C16 total carbon primary alkyl alcohol having 13 carbon atoms in the backbone must have ) , 2, or 3 branching units (i.e., R, R1 and/or R3) whereby total number of carbon atom?; in the molecule is ot least 16. In this example, the C16 total carbon requirement may be satisfied equally by having, for example, one propyl branching unit or three methyl branching units. R, R1, and R^ arc each independently selected from hydrogen and C)-C3 alkyl (preferably hydrogen or Cj-C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R' , and R^ are not all hydrogen. Further, when is 1 , at least R or R' is not hydiogen, Although for the purposes of the present invention alcohol compositions having the above formula do not include molecules wherein the units R, R1 , and R^ are all hydrogen (i.e., linear non-branched primary alkyl sulfates), it is to be recognized that the present invention compositions may still further comprise some amount of linear, non-brtmched primary alkyl nlcohol. Further, this linear non-branched primary alkyl alcohol surfactant may be present as the result of the process used to manufacture the alcohol mixture having the requisite one or more mid-chain branched primary alkyl sulfates according to the present invention, or for purposes of formulating detergent compositions some amount of linear non-branched primary alkyl alcohol may be admixed into the alcohol mixture. Further regarding the above formula, vv is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at hast 1 ; and w I x •! y i '/. is an integer from 8 to I A. Certain points of branching (i.e., the location along the chain of the R, Rl, and/or R^ moieties it) the above foimulu) arc preferred over other points of branching along the backbone of the alcohol. The formula below illustrates the mid-chain branching range (i.e., where points of branching occur), preferred mid-chain branching range, and more preferred mid-chain branching range for mono-methyl substituted linear alkyl alcohols (the same applies to the polyoxyalkylenc alcohols described in detail herein after) of the present invention. I more preferred range preferred range. — — mid-ehiiin blanching rtinyc It should be noted that for the mono-methyl substituted alcohols these ranges i-xcluiif the (wo tciniinnl imrlxui atom-; i>Hhc chain mul the two carbon rUom.'i immediately adjacent to the- hydroxyl (or polyoxyalkylenc moieties) group. For alcohol mixtures comprising two or more of R, R1, or R^, alkyl branching at the 2-carbon atom is within the scope of the present invention. Alcohols having chains longer than ethyl (i.e. €3 alky) substitutents) on the 2-carbon atom, however, are less preferred, The formula below illustrates the mid-chuin branching range, prcfcncd mid-chain branching range, and more preferred mid-chain branching range for di-methyl substituted linear alkyl alcohols (the same applies to the polyoxyalkylene alcohols described in detail herein after) of the present invention, A e more preferred rang preferred range mid-chain branching range- When di-alkyl substituted primary nlkyl alcohol;; ore combined with mono-substituted mid-chain branched primary alky] alcohols, the di-alkyl substituted primary alkyl alcohols having one methyl substitution on the 2-carboo position and another methyl substitution in the preferred range as indicated above, are within the present invention. MIC preferred alcohol mixtures of the present invention have nt Icfi.si 0.001%, more preferably at least 5%, most preferably at least 20% by weight, of the mixture one or more branched primary alkyl sul fates having the formula (Formula Removed) wherein the total number of carbon atoms, including branching, is from 15 to 18, and wherein further for this alcohol mixture the average total number of carbon atoms in the branched primary alkyi moieties havimi the above formula is within the range of greater than 14,5 to about 17.5; R^ and R2 are each independently hydrogen or C j -C.% alkyl; x is from 0 to 1 1 ; y is from 0 to 11; 7, is at least 2; and x + y + / is from 9 to 13; provided R^ and R^ are not both hydrogen. More preferred are compositions having at least 5% of the mixture comprising one or more mid-chain branched primary alkyl sul fates wherein x •» y is equal to 9 and z is at least 2. Preferably, the mixtures of alcohols comprise at least 5% of a mid chain branched primary alkyl alcohol having R! and R^ independently hydrogen, methyl, provided R 1 and R^ are not both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2. More preferably the mixtures of alcohol comprise at least 20% of a rnid chain branched primary alkyl alcohol having lO and R2 independently hydrogen, methyl, provided R1 and R2 arc not botli hydrogen; x + y is equal to 8,9, or 10 and z is at least 2. Preferred alcohol mixtures according to the present invention comprise from about 0.001% to about 99% of a mixture of mid-chain branched primary alkyl alcohols, said mixture comprising at least about 5 % by weight of two or more mid- chain branched alkyl alcohols having the formula: (Formula Removed) or mixtures thereof; wheieina, b, d, ajid e are integers, a+b is from 10 to 16, d+c is from 8 to 14 and wherein further when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 1 1 , a is an integer from 2 lo 1 0 and b is an integer from 1 to 9; when a + b - 12, a is an integer from 2 to 1 1 and b is an integer from 1 to 1 0; when a -f b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b - 14, a is an integer from 2 to 1 3 and b is an integer from 1 to 12; when a •• b - ] 5, a is an integer from ?. to 14 and b is nn integer from 1 to 13; when a + b - 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + c = 8, d is an integer from 2 to 7 and c is an integer from 1 to 6; \vhcn d H r •-' V, d is tin intern liom '}. to K mid c is nn integer from 1 lo 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + c = 1 1 , d is an integer from 2 to 1 0 and e is an integer from 1 to 9; when d + e = 12, d is an integer from' 2 to 1 1 and c is an integer from 1 to 10; when d + e = 1 3, d is an integer from 2 to 1 2 and e is an integer from 1 to 1 1 ; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein further for this surfactant mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5. Preferred mono-methyl branched primary alkyl alcohols useful in the present process are selected from the group consisting of: 3-mclhyl pcntadecanol , 4-mcthyl peiitaclecanol , 5-methyl pcntadecanol , 6-methyl pcntadecanol , 7-mcthyl pentadecatiol , 8-methyl pcntadecanol , 9-methyl pcntadecanol , 10-methyl pc-madeeano) , 1 1 -methyl pcnladociuiol , 12-mHhyl prntadccanol , 13-methyl pcntadecanol » 3-methyl hexadecaiiol , 4-mcthyl hcxadecanol , 5-methyl hexadecanol, 6-methyl hexadecanol, 7-methyl hcxadecanol, 8-methyl hexadecanol , 9-rnelhyl hexadecanol , 10-methyl liexadecanol, 11-methyl hexadecanol, 12-mcthyl hexadecanol, 13-methyl hexadecanol, 14-methyl hexadecanol. and mixtures thereof. Preferred di-methyl branched primary nlkyl alcohols arc selected from the group consisting of: 2,3-mcthy) tctradecanol, 2,4-methyl tetradccanol , 2,5-methyl tctradccnnol, 2,6-niethyl ictradccanol , 2,7-meihyl tctradecanol, 2,8-mcthyJ tetradccanol, 2,9-mcthyI tetradecanol, 2,10-rncthyl tetradecanol, 2,11-methyl tetradecanol, 2,12-methyI tetradecanol, 2,3-methyl pentadecanol, 2,4-methyl pcnladecanol, 2,5-mcthyl pentadecanol, 2,6-mcthyl pcnUidccanol, 2,7-mcthyl pentadecanol, 2,8-methyl pentadecanol, 2,9-methyI pentadecanol»2,10-methyl pentadecanol, 2,11-methyl pentadecanol, 2,12-mcthyl pentadecanol, 2,13-methyl pentadecanol, and mixtures thereof. (b) Mid-chain branched aliphatic polyoxvalkvlene alcohols: Mid-chain branched aliphatic polyoxyalkylcnc alcohols useful in the present invention sulfation process have the formula: (Formula Removed) These alcohol mixtures of the present invention comprise molecules having a linear primary polyoxyalkylene chain backbone (i.e., the longest linear carbon chain which includes the ulkoxylated carbon atom). These alkyl chain backbones comprise from 12 to 19 carbon atoms; and further the molecules comprise a branched primary alkyl moiety having at least a total of 14, but not more than 20, carbon atoms. In addition, the alcohol mixture has an average total number of carbon atoms for the branched primary alkyl moieties within the range of from greater than 14.5 to about 17.5. Thus, the present invention mixtures comprise at least one polyoxyalkylene compound having a longest linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl chains is within the range of greater than H..> to about 17.$. For example, a C16 total carbon (in the alkyl chain) primary polyoxyalkylene alcohol having 15 carbon atoms in the backbone must have a methyl biandiing unil (fitlicr R, R' ot J?2 is mctliyl) whereby ON? toUtl number oT carbon atoms in the molecule is 16. R, R1 „ and R2 are each independently selected from hydrogen and C\-C$ alkyl (preferably hydrogen or Ci-Co alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R' , and R2 are not all hydrogen. Further, when z is ], at least R or R1 is not hydrop.en. Although for tin- purposes of the present invention alcohol compositions the above formula does no! include molecules wherein the units R, lO, and R^ arc all hydrogen (i.e., linear non-branched primary polyoxyulkylenes), it is to be recognized that the present invention compositions may still further comprise some amount of linear, non-branched primary polyoxynlkylenc. Further, this linear non-btanched primary polyoxyalkylcnc alcohol may be present as the result of the piocess used to manufacture the alcohol mixture having the requisite mid-chain branched primary polyoxyalkylenes according to the present invention, or for purposes of formulating deleigcnt compositions some amount of linear non-branched primary polyoxyalkylene may be admixed into the final product formulation. Further it is to be similarly recognized that non-alkoxylutcd mid-chain branched alcohol may comprise some amount of the present invention polyoxyalkylenc-containing compositions. Such materials may be present as the result of incomplete alkoxylation of the alcohol used to prepare the polyoxyalkylene alcohol, or these alcohols may be separately added to the present invention alcohol mixtures along with n mid-chain branched polyoxynlkylenc alcohol iior.ordiny to the present invention. Further regarding the above formula, w is an integer from 0 to 13; x is an integer from 0 to 1 3; y is an integer from 0 lo 13; z is an integer of at least ]; and w •i- x H y + z is an integer from 8 to 14. F.O/PO are alkoxy moieties, preferably selected from cthoxy, propoxy, and mixed elhoxy/propoxy groups, wherein m is at least about 0.01, preferably within the. range of from about 0,1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5. The (E0/P0)ni moiety may be either o distribution with average degree of alkoxylation (e.g., ethoxylation and/or propoxylation) corresponding to in, or it may be a single specific chain with nlkoxyhilion (e.g., elhoxyhtion and/or propoxylation) ol exactly the number of units corresponding to m. The preferred alcohol mixtures of the present invention have at least 0.001%, 4 more preferably at least 5%, most preferably at least 20% by weight, of the mixture one or more mid-chain branched primary alkyl polyoxyalkylencs having the formula (Formula Removed) wherein the total number of carbon atoms, including branching is from 15 to 18, and wherein further for this alcohol mixture the overage total number of carbon atoms in (lu- bi;mduxl piimaiy alkyl moieties having the above formula is within the range of greater (hnn H.5 to about 17.5; R1 and R2 are each independently hydrogen or C]-€3 alkyl; x is from 0 to 11; y is from 0 to 11; z is at least 2; and x + y H z is from 9 to 13; provided R1 and R2 are not both hydrogen; and EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propQjy groups, wherein in is nt least about 0.01, preferably within the range of from about O.I to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5. More preferred are compositions having at least 5% of the mixture comprising one or more mid-chain branched primary polyoxyalkylencs wherein / is at least 2. Preferably, the mixtures of surfactant comprise at least 5%, preferably at least about 20%, of a mid chain branched primary alkyl polyoxyalkylenc having R1 and R^ independently hydrogen or methyl, provided R' and R^ ore not both hydrogen; x -(- y is equal to 8, 9 or 10 and z is at least 2. Preferred alcohol mixtures according to the present invention comprise from about 0.001% to about 99% of a mixture of mid-chain branched primary alkyl polyoxyalkylene alcohols, said mixture comprising at least about 5 % by weight of one or more mid-chain branched alkyl polyoxyalkylencs having the formula: (Formula Removed) or mixtures thereof; wherein a, b. d, ntul e. ate integers, tH-b is from 10 to 16, cMc is from K to 14 and wherein further when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a 4 b ~ 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b ~ 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = M, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a -- b = 16, a is ;m integer from ?. to 15 and b is an integer from 1 to 14; when d -t e - 8, d is tin integer from 2 to 7 and e is an integer from 1 to 6; when d •» c - 9, d is nn integer from 2 to 8 and e is an integer from 1 to 7; when d + e - 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d H c = 11, d is an integer from 2 to 10 and c is an integer from 1 to 9; when d + c - 12, d is an integer fiom 2 to 11 mid c is art integer from 1 to 10; when d -t c • 13, d is an integer from 2 to 1'), and e is ?m integer from 1 to 1); when d i e - 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; and wherein further for this alcohol mixture the average total number of carbon atoms in the branched primary nlkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5; and EO/PO are alkoxy moie.tics selected from cthoxy, propoxy, and mixed cthoxy/propoxy groups, wherein m is at least about 0.01, preferably within the range of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5, Preferred mono-methyl bnme.bcd primary alkyl ethoxyiates are selected from the group consisting of: 3-methyl pentadecanol ethoxylate, 4-methyl pentadecanol ethoxylale, 5-mcthyl pentadecanol cthoxylate, 6-methyl pentadecanol ethoxylate, 7-methyl pentadecanol cthoxylate, 8-methyl pentadecanol ethoxylate, 9-methyl pentadecanol ethoxylate, I0-methyl pentadecanol ethoxylate, 11-methyl pentadecanol ethoxylate, 12-methyl penlaciecnnol ethoxylate, 13-mcthyl pentadecanol ethoxylate, 3-mcthyl hexadccanol ethoxylate, 4-methyl hcxadecanol ethoxylate, 5-mc(hyl hexadccanol ethoxylnte, 6-methyl hexadecanol cthoxylate, 7-nielhyl lu'xadccanol elhoxylate, 8-methyl hexadecanol cthoxylate, 9-methyl hexadecanol ethoxylate,'10-mclhyl hexadccanol ethoxylate, 11-methyl hexadecanol ethoxylate, 12-mcthyl hexadecanol cthoxylate, 13-methyl hcxadecanol ethoxylatc, 14-melbyl hexadecanol ethoxylate, and mixtures thereof, wherein the compounds arc clhoxylated with an average degree of cthoxy lation of from about 0.1 to about 10. Preferred di-rnethyl branched primary alkyl ethoxyiates selected from the group consisting of: 2,3-methyl tctradecnnol cthoxylate, 2,4-methyl IcHradecanol cthoxylate, 2,5-mcthy! tetradecanol ethoxylotc, 2,6-metJiyl tetradecanol ethoxylatc, 2.7-mclhyl tetradecanol ethoxylate, 2,8-mcthyl tetradecanol ethoxylate, 2,9-methyl tetrndccnnol ethoxylatc, 2,10-mcthyl Ictrudccanol cthoxylate, 2,11-mctliyl tetradecanol etlioxylate, 2,12-metliyJ tetradecajiol ethoxylale, 2,3-methyl pentadecanol ethoxylate, 2,4-methyl pentadecanol ethoxylate, 2,5-methyl pcnUidecanol elhoxylatc, 2,6-methyl pentailecajiol clhoxylate, 2,7-inethyl pentadecanol cthoxylatc, 2,8-mcthyl pentadecanol ethoxylate, 2,9-methyl pentadecanol cthoxylatc, 2,10-mcthyl pcntadccnno! ethoxylale, 2.11-methyl pentadecanol ethoxylate, 2,12-methyl pentadecanol etlioxylate, 2,13-methyl pcntadecEinol ethoxylatc, and mixtures thereof, wherein the compounds are ethoxylated with an average degree of cthoxylation of from about 0.1 to about 10. Sulfation Conditions: The Miiration procc.1;1; according to Ihr picf-cnt invention utili/e:. SOj [in the sulfating reagent. 803 concentrations in the range of 4-5%, volume/volume, in air are preferred, although no-air processes can also be used. A slight molar excess of 803, i.e., a mole ratio of SC>3 to alcohol slightly greater than about 1:1, is preferred. Preferred processes further utilize an alcohol feed temperature fo^the sulfation step of the process of less than about 50°C, preferably within the range of from about 10°C to about 50°C, more preferably within the range of from about 15°C to about 45°C, and most preferably from about 20°C to about 35°C. Cooling jacket water temperatures in the range of from about 2Q°C to about 30°C arc typical for the present process. Ilic processes herein may utili/e continuous or batch reactors. Preferred process utilize continuous reactors such as a falling film reactor in which to react the alcohol and the 803. Specific reactors include Chcmithon, Ballestra, and other reactors as described in: Kirk Othmer, Encyclopedia of Chemical Technology, 3rd. lid., Wiley, 1983, Vol. 22, pp 28-45, article entitled "Sulfonation and Sulfation"; W.IJ. De Groot, "sulphonation Technology in the Detergent Industry", Kluwcr Academic Publishers, Boston, 1991; ISDN 0-7923-1202-3; and "Detergent Manufacturing Including Zeolite Builders ajid Other New Materials,", Chemical Technology Review No. 178, Noycs Data Corp., Park Ridge, New Jersey, 1979, pp. 273-310. Neutralization: The step of Neutralizing the alkyl sulfntt1 :ici i or alkyl alkoxylated sulfate acid produced by the sulfation reaction is prcfcrroh conducted irmnediatcly after the sulfation reaction. Typical conditions for this step o: ihc process include neutralization temperatures within the range of from about 25°C to about 35°C, and acid feed temperatures into the ncutralb.er within the range of from about 35°C to about 45°C. Basic neutralizing agents useful herein include any suitable inorganic base. For example, potassium hydroxide, sodium hydroxide, ammonia monoelhanolnminc, and triethanolaminc, may be used. Potassium salts may be useful for further reduction in viscosity of aqueous surfactant pastes. Jt is also preferred that the final alkyl sulfate paste concentration which results Irom the neutralization step be greater than about 20%, preferably greater than about 50%, and most preferably greater than about 60%. As a result of the present process, alky] sulfate and alkyl alkoxylated sulfate surfactants arc produced comprising mid-chain branched primary alky] sulfates and/or mid-chain primary alky] alkoxylated sulfates having the following formulas. The picscnl invention produces surfactant composition}; comprising owl-chain branched primary alky) sulfates having the formula: (Formula Removed) wherein the total number of carbon atoms in me branched primary alkyl moiety of this formula (including the R, R.1, and R^ branching) is from 14 to 20, and wherein further for this surfactant mixture the average total number of carbon atoms in the branched primary alky] moieties having the above formula is within the range of greater than 1-1.5 to about 17.5 (preferably from about 15 to aboul IV); R, R', and R- are each independently selected from hydrogen and CiC3 olky) (preferably methyl), provided R, R1, and R^ are not all hydrogen and, when z is 1, at least R or R' is not hydrogen; M is one or more cations; w is an integer from 0 to 13; x is an integer from 0 to 1 3; y is an integer from 0 to ] 3; 7. is an integer of at least 1 ; and w -I x -» y • The present invention also produces surfactant compositions comprising mid-chain branched primary alkyl alkoxylated sulfates having the formula: (Formula Removed) wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, R', and R-' branching, but not including the carbon atoms in the KU/PO alkoxy moiety) is from 14 to 20, and wherein further for this surfactant mixture the average total number of carbon atoms in the branched primary nlky! moieties having the above formula is within the range of greater than 14.5 to about 17.5 (preferably from about 15 to about 17); R, R', and R^ are each independently selected from hydrogen and Cj-C3 alkyl (preferably methyl), provided R, Rl , and R- arc not all hydrogen and, when / is 1, at least R or R^ is not hydrogen; M is one or more cations; w is an integer from 0 to 13; x is'an integer from 0 to 13; y is mi integer from 0 to 1 3; z is an integer of at least 1 ; w + x + y + z is from 8 to 14; and EO/PO are aJkoxy moieties including for example ethoxy, propoxy, butoxy, etc, preferably selected from ethoxy, propoxy. and mixed cthoxy/propoxy groups, wherein in is at least about 0.01, preferably within th As used herein, M is a salt forming cation depending upon the method of synthesis. Examples of salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amities having the formula (Formula Removed) wherein R3, R4, R5 and R6 are independently hydrogen, C\-Cj2 alkylcnc, 04-022 brandiod alkylene, Cj-C'o' alkanol, C]-C22 alkcuyleiie, 04-022 branched alkenylene, and mixtures tlicreof. Preferred cations are ammonium (R-^, R4, R5 and R^ equal hydrogen), sodium, potassium, mono-, dK and trialkanol ammonium, and mixtures thereof. The rnortoalkanol aJTimonium compounds of the present invention have R.3 equal to Cj-Cg alkanol, R^, R^ and R^ equal to hydrogen; dialkanol ammonium compounds of the present invention hove R^ and R4 equal to C]-C6 alkanol, R^ and R^' equal to hydrogen; trialkanol ammonium cojnpounds of the present invention have R^, R4 and R^ equal to Cj-Of, alkanol, R^ equal to hydrogen, 1'ielerred ulkmiol ammonium salts oi the present invention arc the mono-, di- and tri- quaternary ammonium compounds having the formulas: (Formula Removed) I'referred M is sodium, potassium and the 02 alkanol ammonium salts listed above; most preferred is sodium. Preparation of JV( id-chain Branched Alcohols and Poivoxvalkvlcnc Alcohols The following reaction scheme outlines a general approach to the preparation of the mid-chain branched primary alcohols useful for the present invention process, (Formula Removed) An alkyl halidc is converted to a Grignard reagent and the Grignard is reacted with a haloketone. After conventional acid hydrolysis, acetylation and thermal elimination of acetic acid, an intermediate olefin is produced (not shown in the scheme) which is hydrogenatcd forthwith using any convenient hydrogenation catalyst such as Pd/C. This route is favorable over others in that the branch, in this illustration a 5-mcthyl branch, is introduced early in the reaction sequence. Fonnylalion of the alkyl halidc resulting from Ihc first hydrogenation step yields alcohol product, as shown in the scheme. This may be alkoxylatud using standard tcclmiqucs to yield a mid-chain branched primary alkyl polyoxyalkylene alcohol. There is flexibility to extend the branching one additional carbon beyond thai which is achieved by a single fonnylation. Such extension can, for example, be accomplished by reaction with ethylene oxide. See "Grignard Reactions of Nonmctallic Substances", M.S. Kharasch and O. Reinmulh, Prentice-Hall, N.Y., 1954; J. Org. Chem., J. Cason and W. R. Winans, Vol. 15 (1950), pp 139-147; J. Org Chem., J. Cason et al, Vol. 13 (1948), pp 239-248;,/. Org Chem., J. Cason et al., Vol. 14 (1949), pp 147-154; and J. Org Chem., J. Cason ct al., Vol. 15 (1950), pp 135- 138 all of which are incorporated herein by reference. In variations of the above procedure, alternate haloketoncs or Grignard reagents may be used. PHr3 halogenation of the alcohol from formylation or cthoxylation can be used to accomplish an iterative chain extension. The preferred mid-chained branched primary alkyl alcohols and therefrom the preferred polyoxyalkylene alcohols useful in the present invention can also be readily prepared as follows: (Formula Removed) A conventional bromoalcohol is reacted with triphenylphosphine followed by sodium hydride, suitably in dimcthylsulibxide/tetrahydrofuran, to form a Wittig adduct. The Wittig adduct is reacted with an alpha methyl ketone, forming an internally unsaturatcd methyl-branched alcoholate. Hydrogcnation, optionally followed by alkoxylation, yields tlie desired mid-chain branched primary alkyl alcohols. Although the Wittig approach does nol allow the practitioner to extend the hydrocarbon chain, ns in the Grignard sequence, the Wiltig typically affords higher yields. Sec Agricultural and Biological Chemistiy, M. Horiike et al., vol. 42 (1978), pp 1963-1965 included herein by reference. Any alternative synthetic procedure in accordance with the invention may be used to prepare the branched primary alkyl alcohols. Tlie mid-chain branched primary nlky! alcohols may, in addition be synthcsi/.cd or formulated in the presence of the conventional homologs, for example any of those which may be formed in an industrial process which produces 2-alkyl branching as a result of hydroformylation. In certain preferred embodiments of the alcohol mixtures of the present invention, especially those derived from fossil fuel sources involving commercial processes, comprise at least 1 mid-chain branched primary alkyl alcohol, preferably at least 2, more preferably at least 5, most preferably at least 8. Particularly suitable for preparation of certain alcohol mixtures for the present invention are "oxo" reaction?; wherein a branched chain olefin is subjected to catalytic isomerization and hydroformylation. The preferred processes resulting in such mixtures utilize fossil fuels as the starting material feedstock. PiefeMod processes utilize Oxo reaction on linear olcfins (alpha or internal) with a limited amount of branching. Suitable olefins may be made by dimerization of linear alpha or internal olcfins, by controlled oligomcrization of low molecular weight linear olefins, by skeletal rearrangement of detergent range olefins, by dchydrogenalion/skeletal rearrangement of detergent range paraffins, or by Fischer-Tropsch reaction. These reactions will in general be controlled to: 1) give a large proportion of olefins in the desired detergent range (while allowing for the addition of a carbon atom in the subsequent Oxo reaction), 2) produce a limited number of branches, preferably mid-chain, 3) produce Cj-C^ branches, more preferably ethyl, most preferably methyl. The process described herein above gives the more preferred 5-melhyl-hexadccyl alcohols in higher yield than the le.ss preferred 2/l-dimcthylpcntadecyJ alcohols. This mixture is desirable under the metes and bounds of the present invention in that each product comprises at total of 17 carbon atoms witii linear alkyl chains having at least 13 carbon atoms. The following examples provide methods for synthesizing various compounds useful in the present invention processes. EXAMPLE I I'rcjinration.of.7:tiic(hylhcxadccyl cthoxvlatc (£2) Synthesis of (6-hydioxvhcxyl) triphcnvlphosphoniuni bromide Into a 5L, 3 neck round bottom ilask lilted with nitrogen inlet, condenser, thermometer, mechanical stirring and nitrogen outlet is added 6-bromo-l-hexanol (500g, 2.76 niol), triphcnylphosphine (7fiRp, 2.9mol) and acctonitrilc (1800 nil) under nitrogen. The- reaction mixture is heated to reflux for 72 hr.s. The reaction mixture is cooled to room temperature and transferred into a 5L beaker. The product i;; icuy.slalli/oil from anhydrous ethyl ether (1.51,) al )0°C\ Vacuum filtration followed by washing with ethyl ether and drying in a vacuum oven at 50°C for 2 hrs. gives 1140g of the desired product as white crystals. .Synthesis of 7- methvlhexadecene-1-ol Into a dried 5L, 3 neck round bottom flask fitted with mechanical stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet is added 70.2g of 60% sodium hydride (1.76 mol) in mineral oil. The mineral oil is removed by washing with hexanes. Anhydrous dimethyl sulfoxide (500ml) is added to the flask and the mixture is heated to 70°C until evolution of hydrogen stops. The reaction mixture is cooled to room temperature followed by addition of 1L of anhydrous lelrnbydwfiimn. (6-hyilroxyhcxyl) triphrriylphosphonium bromide (443.'1g, I mol) is slurricd wiih wwni anhydrous dimethyl sulfoxide (SO°C, 500ml) and slovvly added to the reaction mixture through the dropping funnel while keeping it at 25-30°C. The mixture is stirred for 30 minutes at room temperature at which time 2-undecanone (187g, 1.1 mol) is slowly added through a dropping funnel. Reaction is slightly exothermic arid cooling is needed to maintain 25-30°C. The mixture is stirred for 18 Iir. and then poured into a 5L beaker containing 1L purified water with stirring. The oil phase (top) is allowed to separate out in a separatory funnel and the water phase is- removed. The water- phase is washed with hcxflnes (500m!) and the organic phase is separated and combined with the oil phase from the water wash. The organic mixture is then extracted with water 3 times (500ml each) followed by vacuum distillation to collect the clear, oily product (132g) at 140C and 1mm Hg. llvdrop.cnntion of i~ mcthvlhcxndecenc-l-ol Into a 3L rocking autoclave liner is added 7-melhyIhexadecene-l-ol (130g, 0.508mol), methanol (300ml) and platinum on carbon (10% by weight, 35g), The mixture is hydrogenated at 180°C under 1200 psig of hydrogen for 13 lirs., cooled and vacuum filtered thru CeJite 545 with washing of the Celite 545, suitably with methylenc chloride. If needed, the filtration can be repeated to eliminate traces of Pt catalyst, and magnesium sulfatc can be used to dry the product. The solution of product is concentrated on a rotary evaporator to obtain a clear oil (124g). Ajkoxylation of 7-irtethy!hc .adecanol Into n dried JJ. 3 neck round botlom flask fined wiih n nitrogen inlcl, mechanical stirrer, and a y-tubc iilted with a thermometer and a gas outlet is added the. alcohol from the proceeding step. For purposes of removing trace amounts of moisture, the alcohol is sparged with nitrogen for about 30 minutes at 80-100° C. Continuing with a nitrogen sweep, sodium metal is added as the catalyst and allowed to melt with stirring at 120-140° C. With vigorous stirring, eihylenc oxide gas is added in 140 minutes while keeping the reaction temperature at 120-140° C. After the correct weight (equal to two equivalents of ethylene oxide) has been suliU-d. nitrogen is swept through the ,-ippnrnlns for ?0-30 minutes ns the sample is allowed to cool. The desired 7-methylhcxadccyl ethoxylate (average of 2 ethoxylatcs per molecule) product is then collected. EXAMPLE 11 SyntJiesk of 7-mgthvlnentadccvl cthoxylatc (E3) Synthesis of (6-hydiqxyhexvl) Triphenylphosphonium Djomide Into a 5L, 3 neck round bottom flask fitted with nitrogen inlet, condenser, (hennoweter, mechanical stining and nitrogen outlet is added 6-bromo-l-hcxanol (50Ug, 2.76 mol), triphenylphosphine (768g, 2.9mol) and acetonilrile (1§00 ml) under nitrogen. The reaction mixture is heated to reflux for 72 hrs. The reaction mixture is cooled lo room temperature and transferred into a 5L beaker. The product is recrystallixed from anhydrous ethyl ether (] .51.) at JO°C. Vacuum filtration of the mixture followed by washing (he white crystals with ethyl ether and drying in a vacuum oven at 50°C for 2 lirs. gives 1140g of the desired product. .Synthesis of '/_-_ nKMhylpeiiltKlcccnc-1 -ol Into a dried 5L, 3 neck round bottom flask fitted with mechanical stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet is added 80g of (50% sodium hydride (2.0 mol) in mineral oil. The mineral oil is removed by washing with hcxancs. Anhydrous dimethyl sulfoxidc (500ml) is added to the flask and heated lo 70°C until evolution of hydrogen stops. The reaction mixture is cooled 16 room temperature followed by addition of 1L of anhydrous Ictrahydrofuran. (6-hydroxyhexyl)triphenyIphosphonium bromide (443.4g, J mol) is slurried with warm anhydrous dimethyl sulfoxide (50°C, 500ml) and slowly added to the reaction mixture thru the dropping funnel wlu'le keeping the reaction at 25-30°C. The reaction is stirred for .10 minutes at room temperature at which time 2-dccanonc (17l.9g, 1.1 mol) is slowly added thru a dropping funnel. Reaction is slightly exothermic and cooling is needed to maintain 25-30°C, Mixture is stirred for 18 Ins. and then poured into n separator}' funnel containing 600ml of purified water aod 300 ml of hexunes. After shaking the oil phase (top) is allowed to separate out and the water phase is removed. The extractions of the oil phase arc continued using watei until both phases rue clear. The organic phase is collected, vacuum distilled and purified by liquid chromatography (90:10 hcxanesrethyl acetate, silica i gfl stationary phase) to obtain a clear, oily product (119.1g). Hydrogcnation of 7- methylpentadeccnc-l-ol Into a 3L rocking autoclave gloss liner (Autoclave Engineers) is added 7- Mcthylpentadcccne-J-ol (J22g. 0.508mol), mcthanol (300ml) and platinum on carbon (10% by weight, 40g). The mixture is hydrogenated at 180°C under 1200 psig of Iiydrogcn lor 13 hrs., cooled and vacuum filtered thru Celite 545 with washing of Celite 545 with methylcnc chloride. The organic mixture is still dark from platinum catalyst so the filtration procedure is repeated with concentration on a rotary evaporator; dilution is carried out with methylene chloride (500ml) and magnesium sulfate is adcd to dry product. Vacuum filter thru Celite 545 and concentrate filtrate on a rotary evaporator to obtain a clear oil (119g). Alkoxylation of 7-nicjhyjj^ij^decgnoj Into a dried 1L 3 neck round bottom flask fitted with a nitrogen inlet, mechanical stirrer, and a y-tube fitted with a thermometer and a gas outlet is added the alcohol from the proceeding step. For purposes of removing trace amounts of moisture, the alcohol is sparged with nitrogen for about 30 minutes at 80-100* C. Continuing with a nitrogen sweep, sodium metal is added as the catalyst and allowed to melt with stirring at 120-140° C. With vigorous stirring, cthylene oxide gas is added in 140 minutes while keeping the reaction temperature at 120-140° C, After the correct weight (equal to tlircc equivalents of cthylene oxide) has been added, nitrogen is swept through the apparatus for 20-30 minutes as the sample is allowed to cool. The desired 7-methylpentadecyl ethoxylate (average of 3 elhoxylatcs per molecule) product is then collected. 1-XAMPLE III Synthesis of 7-rnethylhepiadecvl^thQXvlate CE1.5) Synthesis ol(6-11 ydn)xylicxvl) Triphcrivl]>hosphoiiiuiii broinicle Into a 5L, 3 neck round bottom flask fitted with nitrogen inlet, condenser, thermometer, mechanical stirring and nitrogen outlet is added 6-bromo-l-hexanol (500g, 2.76 mol), triphenylphosphine (768g, 2.9mol) and acetonkrile (1800 ml) under nitrogen. The reaction mixture is healed to reflux for 72 hrs. The reaction mixture is cooled to room temperature and transferred into a 5L beaker. The product is recryslallized from anhydrous ethyl ether (1.5L) at 10°C. Vacuum filtration of the mixture followed by washing the white crystals with ethyl ether and drying in a i vacuum oven at 50°C for 2 hrs. gives 1140g of the desired product. Synthcsis oOr, meIhyjheptadcccne-1-o) Into 'A dried 5Lt 3 neck round bottom flask fitted with mechanical stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet is added 80g of 60% sodium hydride (2.0 mol) in mineral oil. The mineral oil is removed by washing with hexanes, Anhydrous dimethyl .sulfoxidc (500ml) is added to the flask and heated to 70°C until evolution of hydrogen stops. The reaction mixture is cooled to room tcmpemtme followed by addition of 11, of anhydrous tcirahydrofuran. (6-hydroxyhexyl) triphcnylphosphonium bromide (443.4g, 1 mol) is slum'ed with warm anhydrous dimethyl sulfoxidc (50°C, 500ml) and slowly added to the reaction mixture thru the dropping funnel while keeping the reaction at 25'30°C. The reaction is stirred for 30 minutes at room temperature at wjjich time 2-dodecanone (184.3g, I.I mol) is slowly added thru, a dropping funnel. Reaction is slightly exothermic and cooling is needed to maintain 25-30°C. Mixture is stirred for 18 lirs. and then poured into a scparatory funnel containing 600ml of purified water nnd 300 ml of hcxancs. After .shaking the oil phase (top) is allowed to separate out and the water phase is removed which is cloudy. The extractions are continued using water until the water phase and the organic phase become clear. The organic phase is collected nnd purified by liquid chiomatoginphy (mobile phase-hcxanes, stationary phase-silica gel) to obtain a clear, oily product (116g). HNMR of the final product (in deuterium oxide) indicates a CH^-OSC^ triplet at the 3.8 ppm resonance, CH2-CH2-OS03' multiple! at the 1.5 ppm resonance, CH2 of the alkyl chain at the 0.9-1.3 ppm resonance and CII-CH^ branch point overlapping the R-Cl 12QLI3 terminal methyl group at the 0.8 ppm resonance. Hydrogenation of 7- methylhcptadeccnc-1-ol Into a 3L rocking autoclave glass liner (Autoclave Engineers) is added 7-Methylheptadecene-1-ol (1) 6g, 0.433mol), methanol (300ml) and platinum on carbon (10% by weight, 40g). The mixture is hydtogen.'itcd at 180°C under 1200 psig of hydrogen for 13 hrs., cooled and vacuum filtered thru Celite 545 with washing of Cclitc 545 with mcthylene chloride. Vacuum filter thru Cclitc 545 and concentrate filtiaie on a iotary evaporator to obtain a clear oil (108g), Alkoxvlation of 7-mcthvlheptadecanpi Into a dried 1L 3 neck round bottom flask fitted with a nitrogen inlet, mechanical stirrcr, and a y-tube fitted with a thermometer and a gas outlet is added * the alcohol from the proceeding step. For purposes of removing trace amounts of moisture, the alcohol is sparged with nitrogen for about 30 minutes at 80-100° C. Continuing with a nitrogen sweep, sodium metal is added as the catalyst and allowed to melt with stirring at 120-140" C, With vigorous stirring, ethylcnc oxide gas is added in 140 minutes while keeping the reaction temperature at 120-140° C. After the correct weight (equal to 1 .5 equivalents of cthylene oxide) has been added, nitrogen is swept through the apparatus for 20-30 minutes as the sample is allowed to cool. The desired 7-methylheptadecyl cthoxylate (average of 1 .5 ethoxylates per molecule) product is then collected. EXAMPLE IV The following Shell Research experimental test alcohol samples,are cthoxylated (average ethoxylatiori of 2.5) by the following procedure. Results For Branched Alcohols Prepared (Table Removed) Into a dried 250ml 3 neck round bottom flask fitted with a nitrogen inlet, mechanical slirrer, and a y-tube fitted with a thermometer and a gas outlet is added the C16 alcohol (48.4p,. 0.2 mol) above. For purposes of removing trace amounts of moisture, the alcohol is sparged with nitrogen for about 30 minutes at 80-100° C. Continuing with a nitrogen sweep, sodium metal (0.23g, 0.01 mo)) is added as the catalyst and allowed to melt with stirring at 120-140° C. >With vigorous stirring, ethylene oxide gas (22g, 0.5 mol) is added in 140 minutes while keeping the reaction temperature at 120-140° C. After the correct weight of ethylcnc oxide (average 2.5 cthoxylatcs per molecule) lias been added, nitrogen is swept through the apparatus for 20-30 minutes as the sample is allowed to cool. The gold liquid product (69g, 0.1% mol) is bottled under nitrogen. QXAMPLl: V The alcohol of F.xnmple 111 (90 parts) is mixed with n-hcxadecanol (10 pails). The starting alcohol mixture has a total carbonyl impurity level of no more than about 5ppm, by wcight.The mixture is sulfated in a falling film reactor using the following conditions: mole ratios: conventional, i.e., slight excess of S03 over fatty alcohol; typical 803 concentrations: 4-5% , v/v in air, though no-aif processes can also be used; typical fatty alcohol feed temperature: 10-25 deg. C (compare 55-60 which would be essential for tallow); cooling jacket water: 20-30 deg. C (compare 45 and above which would be needed for tallow alcohol, stearyl alcohol and the like); neutralisation: 25-35 deg. C (compare 40-45 deg C for tallow alcohol); acid feed to ncutralizer: 35-45 deg. C (compare tallow alcohol at 55 deg C). Final paste concentrations above 30% by weight are possible (compare tallow which typically sets up solid almost independently of paste concentration when there is no LAB orethanol used). The following two analytical methods for characterizing branching in the present invention surfactant compositions are useful: 1) Separation and Identification of Components in Fatty Alcohols prior to alkoxylation. The position and length of branching found in the precursor fatty alcohol materials is determined by GC/MS techniques [see: D. J. Harvey, Biomed, linviron. Mass Spectrom (1989). 18(9), 719-23; D. J. Harvey, J. M. Tiffany, J. Chromatogr. (1984), 301(1), 173-87; K. A. Karlsson, B. E. Samuelsson, G. O. Stccn, Chcin. Phys. Lipids (1973), 11 (1), 17-38]. 2) Identification of Separated Fatty Alcohol Components prior to alkoxylation by MS/MS techniques. The position and length of branching is also dctcrminable by Ion Spray-MS/MS or FAB-MS/MS techniques on previously isolated fatty alcohol components. Having identified isolated alcohol components, alkoxylation of the isolated alcohols yields sUuulaids useful for calibrating and interpreting GC cliromatograms of mid-chain branched primary alkyl polyoxyalkylene surfactants. The uvcinge tolal carbon atoms of the bianchcd primary alkyl polyoxyalkylenes herein can be calculated from the hydroxyl value of the precursor fatty alcohol mix according to common procedures, such as outlined in "Bailey's Industrial Oil and Fat Products", Volume 2, Fourth Ikiition, edited by Daniel Swcrn, We Claims 1. A method for manufacturing longer chain alkyl sulfate surfactant mixture compositions, said method comprising the steps of: (a) sulfating with 803, preferably in a falling film reactor, a long chain aliphatic alcohol mixture having an average carbon chain length of at least 14.5 to 17.5, said alcohol mixture comprising at least 10 %, preferably at least 25%, more preferably at least 50%, still more preferably at least 75%, and most preferably at-least 95%, of a mid-chain branched aliphatic alcohol having the formula: (Formula Removed) wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula, including the R, lO, and R^ branching, is from 14 to 20, and wherein further for this alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to 17.5, preferably greater than 15 to 17; R, R', and 1 (b) neutralizing the alkyl sulfate acid produced by step (a), preferably utilizing a base selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonia monoethanolamine, triethanolamine, and mixtures thereof. 2. The method according to Claim 1 wherein the alcohol feed temperature for a step (a) is less than 50°C, preferably within the range of from 10°C to 50°C, more preferably within the range of from 15°C to 45°C, and most preferably from 20°C to 35°C. 3. The process according to cither of Claims 1 or 2 wherein the aliphatic alcohol sulfaU-d in step («) comprises at least 10%, preferably at least 25%, more preferably at least 50%, still more piefcrably at least 75%, and most preferably at least 95%, by weight of a mixture of two or more mid-chain branched alcohols having the formula: (Formula Removed) or mixtures thereof; wherein a, b, d, and c arc integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further when a + b - 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a •»• b = 11, a is an integer from 2 to 10 and b is an integer from Ho 9; when a + b = 12, n is an integer from 2 to 11 and b is an integer from 1 to 10; when a •» b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b - 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b •= 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d -i e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e - 10, d is an integer from 2 to 9 and c is an integer from 1 to 8; when cH e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and c is an integer from 1 to 10; when d + e r- 13, d is an integer from 2 to 12 and c is an integer from 1 to 11; when d + c - 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein for this alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to 17.5. 4. A method for manufacturing longer chain alkyl alkoxylated sulfatc surfactant mixture compositions, said method comprising the steps of: (a) alkoxylating a long chain aliphatic alcohol mixture having an average carbon chain length of at least 14.5 to 17.5, said alcohol mixture comprising at least 10%, preferably at least 25%, more preferably at least 50%, still more preferably at least 75%, and most preferably at least 95%, of a mid-chain branched aliphatic alcohol having the formula: (Formula Removed) wherein tbf total number of carbon atoms in the branched primary alkyl moiety of this formula, including the R, Rl, and R2 branching, is from 14 to 20, and wherein further for this alcohol mixture the average total number of carbon atoms in the branched primary alky) moieties having the above formula is -within the range of greater than 14.5 to 17.5, preferably greater than 15 to 17; R, R.', and R^ arc each independently selected from hydrogen and Cj-C3 alkyl, preferably methyl, provided R, R1, HI id R2 are not all hydrogen mid, when z is 1, m least R or R' is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to ] 3; z is nn integer of at least 1 ; and w •» x •+ y + z is from 8 to 14; (b) sulfaiing the polyoxyalkylenc alcohol produced by step (a) with 863; and (c) neutralizing the alkyl alkoxylate sulfate acid produced by step (b), preferably utilizing u base selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonia monoethanolamine, triethanolamine, and mixtures thereof. 5. The method according to Claim 4 wherein the polyoxyalkylene alcohol feed temperature for a step (b) is less than 50°C, preferably within the range of from 10°C to 50°C, more preferably within the range of from 15"C to 45°C, and most preferably from 20°C to 35°C. 6. The process according to either of Claims 4 or 5 wherein the aliphatic alcohol alkoxylatcd in step (a) comprises at least 10%, preferably at least 25%, more preferably at least 50%, still more preferably at least 75%, and most preferably at least 95%, by weight of a mixture of two or more mid-chain branched alcohols having the formula: (Formula Removed) or mixtures thereof; wherein a, b, d, and c are integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further \vhen a •' b ^ 10, a is nn integer from 2 to 0 niicl b is nn integer from 1 to 8; when a H- b -• 1 1 , a is an integer from 2 to 1 0 and b is an integer from 1 to 9; when a •» b = 12, a is an integer from 2 to 1 1 and b is an integer from 1 to 10; when a • when cH- e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e ~- 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + c = 11, d is an integer from 2 to 10 mid e is an integer from 1 to 9; when d + c - 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d H e - 13, d is an integer from 2 to 12 and c is an integer from 1 to 11; when d + c = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein for this alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to 17.5. -« 7. A method for manufacturing longer chain alkyl alkoxylated sulfate surfactant mixture compositions, said method comprising the steps of: (a) sulfating with 863 a long chain aliphatic polyoxyalkylene alcohol mixture having an average aliphatic alcohol carbon chain length of at least 14.5 to 17.5, said polyoxyalkylene alcohol mixture comprising at least 10% (preferably at least 25%, more preferably at least 50%, still more preferably at least 75%, and most preferably at least 95%) of a mid-chain branched aliphatic polyoxyalkylene alcohol having the formula: (Formula Removed) wherein the total number of carbon atoms in the branched primary alky) moiety of this formula, including the R, Rl, and R^ branching, but not including the carbon atoms in the EO/PO alkoxy moiety, is from 14 to 20, and wherein further for this polyoxyalkylene alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to 17.5, preferably from 15 to 17; R, Rl, and R^ arc each independently selected from hydrogen and Cj-C3 nlkyl, preferably methyl, provided R, R1, and R2 are not all hydrogen and, when z is 1, at least R or R1 is not hydrop.cn; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer Jiom 0 to 13; 7. is an integer of at least 1; w -I x -t- y •)- 7. is from 8 to 14; and EO/PO arc alkoxy moieties, preferably selected from cthoxy, propoxy, and mixed etboxy/propoxy groups, wherein m is at least 0.01, preferably within the range of from 0.1 to 30, more preferably from 0.5 to 10, and most preferably from 1 to 5; and (b) neutralizing the alkyl alkoxylated sulfate acid produced by step (a), preferably utilizing a base selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonia monocthanolaminc, tricthanolamine, and mixtures thereof. 8. The method according to Claim 7 wherein the polyoxyalkylcnc alcohol feed temperature for a step (a) is less than 50°C, preferably within the range of from 10°C to 50°C, more preferably within the range of from 15°C to 45°C, and most preferably from 20°C to 3 5°C . 9. The process acording to any of Claims 1-8 wherein the neutralization temperature is within the range of from 25°C to 35°C and the acid feed temperature into the neutral izcr is within the range of from 35C to 45°C. 10. The process acording to any of Claims 1-9 wherein the cooling jacket water temperature for the sulfation reactor used for step (a) is in the range of from 20°C to 30°C. 1 1 . The process according to any of Claims 7- 1 0 wherein the aliphatic polyoxyalkylenc alcohol sulfatcd in step (a) comprises at least 10%, preferably at least 25%, more pioferably at least 50%, still more preferably at least 75%, and most preferably at least 95%, by weight of a mixture of two or more mid-chain branched alcohols having the formula: (Formula Removed) or mixtures thereof; wherein a, b, d, and c are integers, a+b is from 10 to 16, d-t-c is from 8 to 1 4 and wherein further when a + b ** 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 1 J , a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is on integer from 2 to 1 1 and b is an integer from 1 to 10; when a + b = 1 3, a is an integer from 2 to 12 and b is an integer from 1 to 1 1; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when u + b =• J 5, a is an imc-ycr JViun 2 to 14 and b is mi integer from 1 to 13; when a + b = 1 6, a is an integer from 2 to 1 5 and b is an integer from 1 to 14; when (1 i- c j' K, cl is an inlegiT from 2 lo 7 uiicl c is an integer from 1 to 6; when cl I e • 9, d is an integer from ?. to K mul c is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e ^ 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e ~ 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and c is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein for this poJyoxyalkylcne alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to 17.5; and wherein EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least 0.01, preferably within the range of from 0.1 to 30, more preferably from 0.5 to 10, and most preferably from 1 to 5. 12. A method for m;i n u f a c tuning Longer chain alkyl sulfate surfacted mixtures substantially as hereinbefore described in any of the Examples.

Full Text

Case 6405
INDUSTRIAL SULFAT10N Daniel Sicdman Connor Thomas Anthony Cripe R. Craig Jacobs Mike C. Jansen FIF.T.D OF THE INVENTION
The present invention relates to methods for producing longer chain length • alkyl sulfatc and/or alkyl alkoxylated sulfate surfactant compositions. This method utilizes the presence of a significant amount of mid-chain branched alcohol and/or mid-chain branched polyoxyalkylcne alcohol in the sulfation reaction to significantly reduce the reaction temperature, thereby improving product quality and" saving energy,
BACKGROUND OF THE INVENTION
Sulfpnution/sulfatkm of nnionie surfactants worldwide is done on a very large scale, on the order of millions of tons each year. Such processes are well defined and are thoroughly characterized in the art. [Sec for example, Everett E. Gilbert, "Sulfation aiul Related Reactions", copyright 1965 by John Willcy and Son, Inc., pages 345-354; and "Sulfonation Technology in the Detergent Industry", by W. Herman dc Ciroot, copyright 1991 by Kluwer Academic Publishers, especially pages 213-215.]
The art recognizes that for lower chain length alcohols, such as lauryl alcohol, the feed temperature for the reaction can be kept low, in the 25-3Q°C range. However, longer chain length alcohols, like the C]6-18 tallow alcohol, require feed temperatures in the 55-60° jnnpc. At such higher temperatures, in addition to the added energy needed to run in the process, there is a need to carefully control the reaction conditions, (e.g., to control the flow rates and reactor temperature dissipation) to avoid producing products with poor physical chnrncteristics, such ns off-odor and/or color. [See for example, pages 213-214 of "Sulfonation Technology in the Detergent Industry", ibid]
More specifically, side reactions that may occur, at least In part owing to conventional temperatures and the vigor of the sulfating agent include: dehydration of alkyl sulfatc to form olefin; elimination of water between two molecules to form
an ether; oxidation to the aldehyde followed by further oxidation to the acid; and esterification of the acid with fatly alcohol [see: David D. Whyte, J.A.O.C.S., Vol. 32, pp313-316, (1955)].
Thus, milder conditions for such longer chain alcohols is highly sought after
in the industry. It has been discovered by the present invention that inclusion of at least 10% of a mid-chain branched, longer chain alcohol mixture into the longer chain length (at least about C]^ 5 average) alcohol mixture to be sulfatcd permits avoidance of high peak instantaneous reaction temperatures of the sulfation reaction, sufficiently Objects of the present invention therefore include one or more of the following: better economy by virtue of lower energy input in preparing tlv? alcohol for the sulfation process and the ability to avoid having to melt out and control the feed alcohol temperature; faster reaction times; the ability to provide a more mass-effective product, by avoiding the need to include diluents and viscosity reducers; better color compared with high-temperature processing, such as required for tallow alcohols, and thereby avoiding the need for a subsequent bleaching operation; lower viscosity of the "acid mix" (the term used to describe the product of sulfation prior to being neutralized), which in turn impiovcs the case and quality of the neutralization step; lower viscosity of the finished surfactant paste at identical temperature compared to the process required for the tallow alcohol analog, which thereby permits the manufacture of more concentrated paste for use in so called "compact" or "ultra" determent products, the ability to reduce or eliminate alcohol or similar1 materials which are frequently used to thin the final paste; the ability to manufacture new alkyl sulfate products which are completely linear alkyl benzene sulfonatc- free (typical current practice is to co-react tallow alcohol nnd linear alky) benzene to make a mixed tallow alcohol sulfate and linear alkyl benzene sulfonatc product); (lie ability to more easily pump and handle all materials in the sulfation process from starting material to final product; the ability to avoid or eliminate hot storage steps, and the associated costs and potential discoloration of product that may thereby be produced; the ability to use relatively low-cost sulfonation plants which under normal circumstances would be intoleranl of, or could not handle, neat C16-18 alcohols; and the ability to limit side-reactions during sulfation, thereby giving a cleaner product. These and other objects of the present invention will he apparent from the detailed description hereinafter.
BACKGROUND ART
Sec: Kirk dinner, Kncyclopedht of Chemical Technology, 3/d. Ed., Wiley, 1983, Vol. 22, pp 28-45, article entitled "Sulfonation and Sulfation"; W.H. De Orooi. "siilphonniion Trdmolnpy in Ihr* Dcicrgont Industry", Kluwcr Academic Publishers, Boston, 1991; ISBN 0-7923-1202-3; and "Detergent Manufacturing
Including Zeolite Builders arid Other New Materials,", Chemical Technology Review No. 128, Noyes Data Corp., Park Ridge, New Jersey, 1979, pp. 273-310,
SUMMARY OF THE INVENTION
The present invention relates to a method for manufacturing longer chain alkyl sulfalc surfactant mixture compositions, said method comprising the steps of: (a) sulfating with 863 (preferably in a falling film reactor) a long chain aliphatic alcohol mixture having an average carbon chain length of at least )4.5 lo about J7.5, said alcohol mixture comprising at least about 1 0 % (preferably at least about 25%, more preferably at least about 50%, still more preferably at least about 7$%, and most preferably at least nbout 95%) of a mid-chain branched aliphatic alcohol having the formula:
(Formula Removed)
wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, R*, and R^ branching) is from 14 to 20, and wherein further for this alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14,5 to about 17.5 (preferably greater than about 15 to about 17); R, Rl, and R?- arc each independently selected from hydrop.cn and C]-C3 alkyl (preferably methyl), provided R, R' , and R2 are not all hydrogen and, when z is 1 , nt least R or RJ is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 1 3 ; z is an integer of at least 1 ; and w + x + y •»• z is from 8 to 1 4; and (b) neutralizing the nlkyl .sulfate acid produced by step (a).
Preferred processes further utilize an ulcoho' teed temperature for a step (a) of less than about 50°C, preferably within the range T" from about 10°C to about 50°C, more preferably within the range of from aboi ..: 15°C to about 45°C, and most preferably from about 20°C to about 35°C. Typical conditions also include: a mole ratio of SO_3 to alcohol slightly greater than about 1:1; 803 concentrations in the range of 4-5%, volume/volume, in air or nitrogen (although no-air processes can also be used); cooling jacket water temperatures in the range of from about 20*C to about 30°C; neulrnli'/ntion temperatures within the range of from about 25°C to
t
about 35°C; acid feed temperature into the neutralize!' within ihc range of from about 35°C to nbout 45°C. It is also preferred that the final alkyl sulfate paste concentration be greater than about 20%, preferably greater than about 50%, and most preferably greater than about 60%.
Preferably, the aliphatic alcohol used in the above process comprises at least about 10% (preferably at least about 25%, more preferably at least about 50%, still wore preferably at least about 75%, and most preferably at least about 95%) by weight ofa mixture of two or more mid-chain branched alcohols having the
formula:
(Formula Removed)
or mixtures thereof; wherein a, b, d, and e are integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further
when a -f b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b ~ 11, a is an integer from 2 to 10 and b is an integer from 3 to 9; when a -»- b ~ 12, a Is an integer from 2 to 11 and b is an integer from 1 to 10; when a -f b = 13, a is an integer from 2 to 12 find b is an integer from 1 to 11; when a •»- b - 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b - 15, u is an integer from 2 to H and b is an integer from 1 to 33; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to H; when d + c = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d f• e = 9, d is tin integer from 2 to 8 and e is an integer from 1 to 7; when d + c = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d -t- e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d +• c = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d •*• e ~ 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d -i e - 14, d is an integer from 2 to 13 and c is fln integer from 1 to 12; wherein for this alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5.
Optionally, the present invention process may include a first alkoxylation . step whereby a long chain mid-chain branched polyoxyalkylcnc alcohol compound is produced, which thereafter is sulfatcd to produce alkyl alkoxylated sulfates according to the present invention. Such processes comprise the steps of: (a) alkoxylatiny s\ long chum mid-chain branched aliphatic alcohol mixture having an average carbon chain length of at least 14.5 to about 17.5, said alcohol mixture ccmipiisinj', nt least about 10% (preferably at Jcnst about 25%, more preferably at least about 50%, still more preferably at least about 75%, and most preferably at
least about 95%) of a mid-chain branched aliphatic alcohol having the formula:
(Formula Removed)
wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, R' , and R^ branching) is from 14 to 20, and wherein further for this alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to about 17.5 (preferably greater than about 15 to abouU?); R, R*, and R^ are each independently selected from hydrogen and Cj'C} alky) (preferably methyl), provided R, R1, and R^ are not all hydrogen and, when z is 1, at least R or R! is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; 7. is an integer of at least 1; and w + x + y + 7. is from 8 to 14;
(b) sulfating the polyoxyalkylene alcohol produced by step (a) with 803; and
(c) ncutriili/inp. the alkyl alkoxylate r.ulfntc ncid produced by step (b).
The present invention therefore also may produce alkyl alkoxylatcd sulfatcs directly starting from a polyoxyalkylene alcohol. Such method comprises the steps of:
(a) sulfating with 803 a long chain aliphatic polyoxyalkylene alcohol mixture having an average aliphatic alcohol carbon chain length of at least 14.5 to about 17.5, said polyoxyalkylcnc nlcohol mixture comprising at least about 10% (preferably at least about 25%, more preferably at least about 50%, still more preferably at least about 75%, and most preferably at least about 95%) of a inid-chain branched aliphatic polyoxyalkylene alcohol having the formula:
(Formula Removed)
wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, Rl, and R^ branching, but not including the carbon atoms in the EO/PO alkoxy moiety) is from 14 to 20, and wherein further for this polyoxyalkylene alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14,5 to about 17.5 (preferably from about 15 to about .17); R, Rl, and \0- arc each independently selected from hydrogen and Cj-C^ alkyl (preferably methyl), provided R, Rl, and R2 are not all hydrogen and, when z is 1, at least R or l\l is not hydrogen; \v is nn ink-pcr from 0 to 11; x is on integer from 0 to 13; y is nn integer from 0 to 13; z is an integer of at Icnst 1; w + x H- y -I- z is from B to 14; and
F.O/PO arc alkoxy moieties including lor cx.'implc cthoxy, propoxy, butoxy, etc. preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is ai least about 0.01, preferably within the ranp.c of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 lo nboul 5 fit i.1; to be re.eoj'.m'/ed that the (HO/PO),,, moiety may bc-friiher n distribution with average degree oi'ulkoxylation concsponding to in, or It may be a single specific chain with alkoxylation (e.g., ethoxylation and/or propoxylation) of exactly the number of units corresponding to m); ami (b) neutralizing the alkyl alkoxylated sulfate acid produced by step (a). ,.-,
Preferably, the aliphatic polyoxyalkylene alcohol used in step (a) of this process comprises at least about 10% (preferably at least about 25%, more preferably at least about 50%, still more preferably at least about 75%, and most preferably at least about 95%) by weight of a mixture of two or more mid-chain branched aliphatic polyoxyalkylene alcohols having the formula:
(Formula Removed)
or mixtures thereof; wherein a, b, d, and e are integers, a+b is from 10 to 16, d+e is from 8 to 1 4 and wherein further
when alb1 )(), a is an integer from 2 to 9 and b is an integer from 1 to 8; when a -t • b - 1 1 , a is an integer from 2 to 1 0 and b is an integer from 1 to 9; when a I b - 12, a is an integer from 2 to 1 1 and b is an integer from 1 to 10; when a + b *= 1 3, a is an integer from 2 to 1 2 and b is ai\ integer from 1 to 1 1 ; when a + b = 14, a is an integer from 2 to 13 and b is an integer fronvl to 12; when a + b - 1 5, a is an integer from 2 to 14 and b is an integer from 1 lo 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and c is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7;
when d + c = 1 0, d is an integer from 2 to 9 and e is an integer from 1 to 8;
i.
when d -I 0 " 1 1, d is an integer from ? to 10 and e is an integer from 1 to 9; when d + e = 1 2, d is an integer from 2 to 1 1 and e is an integer from 1 to 1 0; when d + e = 1 3, d is an integer from ?. lo 12 and e is an integer from 1 to 1 1 ; when d i e ": H, d is an inle^u1 from '). to 13 and c is an integer from 1 to 12;
wherein for this polyoxyalkylcne alcohol mixture the average total number of carbon atoms in the branched primai-y alkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5; and
wherein EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and niixed cthoxy/propoxy groups, wherein m is at least about 0.01, preferably within the range of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5,
All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless.pthcnvise specified. All documents cited arc in relevant part, incorporated herein by reference.
PETAILEP DESCRIPTION OF THEJNVBNT10N The present invention sulfation process may start with alcohols arid/or polyoxyalkylenc alcohols essentially comprising at least about 10% (preferably at least about 25%, more preferably at least about 50%, still more preferably at least about 75%, and most preferably at least about 95%) by weight of the following mid-chain branched materials, (a) .Mid-chain branchedhiliphntic alcohols:
Mid-chain branched aliphatic alcohols useful in the present invention .';iilf;ition process hnve the formula:
(Formula Removed)
The alcohol mixtures useful in the present invention comprise molecules having a linear primary alkyl chain backbone (i.e., the longest linear carbon chain which includes the hydroxylated carbon atom). These alkyl chain backbones comprise from 12 to 19 carbon atoms; and further the molecules comprise a branched primary alkyl moiety having at least a total of 14, but not more than 20, carbon atoms. In addition, the alcohol mixture has an average total number of carbon atoms for the branched primary alkyl moieties within the range of from greater than M.5 to about 17.5. Thus, the present invention mixtures comprise at least one branched primary alkyl alcohol compound having a longest linear carbon chain of not less than 12 carbon moms or more than J9 carbon atoms, and the total
k
number of carbon atoms including branching must be al least 14, and further the avciagc total number of carbon atoms for the branched primary alky] chains is williin the ninye of j'.ieatrr than H.5 (o about 17.5.
For example, a C16 total carbon primary alkyl alcohol having 13 carbon
atoms in the backbone must have ) , 2, or 3 branching units (i.e., R, R1 and/or R3) whereby total number of carbon atom?; in the molecule is ot least 16. In this example, the C16 total carbon requirement may be satisfied equally by having, for example, one propyl branching unit or three methyl branching units.
R, R1, and R^ arc each independently selected from hydrogen and C)-C3 alkyl (preferably hydrogen or Cj-C2 alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R' , and R^ are not all hydrogen. Further, when * is 1 , at least R or R' is not hydiogen,
Although for the purposes of the present invention alcohol compositions having the above formula do not include molecules wherein the units R, R1 , and R^ are all hydrogen (i.e., linear non-branched primary alkyl sulfates), it is to be recognized that the present invention compositions may still further comprise some amount of linear, non-brtmched primary alkyl nlcohol. Further, this linear non-branched primary alkyl alcohol surfactant may be present as the result of the process used to manufacture the alcohol mixture having the requisite one or more mid-chain branched primary alkyl sulfates according to the present invention, or for purposes of formulating detergent compositions some amount of linear non-branched primary alkyl alcohol may be admixed into the alcohol mixture.
Further regarding the above formula, vv is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at hast 1 ; and w I x •! y i '/. is an integer from 8 to I A.
Certain points of branching (i.e., the location along the chain of the R, Rl, and/or R^ moieties it) the above foimulu) arc preferred over other points of branching along the backbone of the alcohol. The formula below illustrates the mid-chain branching range (i.e., where points of branching occur), preferred mid-chain branching range, and more preferred mid-chain branching range for mono-methyl substituted linear alkyl alcohols (the same applies to the polyoxyalkylenc alcohols described in detail herein after) of the present invention.
I more preferred range
preferred range. — — mid-ehiiin blanching rtinyc
It should be noted that for the mono-methyl substituted alcohols these ranges i-xcluiif the (wo tciniinnl imrlxui atom-; i>Hhc chain mul the two carbon rUom.'i immediately adjacent to the- hydroxyl (or polyoxyalkylenc moieties) group. For
alcohol mixtures comprising two or more of R, R1, or R^, alkyl branching at the 2-carbon atom is within the scope of the present invention. Alcohols having chains longer than ethyl (i.e. €3 alky) substitutents) on the 2-carbon atom, however, are less preferred,
The formula below illustrates the mid-chuin branching range, prcfcncd mid-chain branching range, and more preferred mid-chain branching range for di-methyl substituted linear alkyl alcohols (the same applies to the polyoxyalkylene alcohols described in detail herein after) of the present invention,
A e
more preferred rang
preferred range mid-chain branching range-
When di-alkyl substituted primary nlkyl alcohol;; ore combined with mono-substituted mid-chain branched primary alky] alcohols, the di-alkyl substituted primary alkyl alcohols having one methyl substitution on the 2-carboo position and another methyl substitution in the preferred range as indicated above, are within the present invention.
MIC preferred alcohol mixtures of the present invention have nt Icfi.si 0.001%, more preferably at least 5%, most preferably at least 20% by weight, of the mixture one or more branched primary alkyl sul fates having the formula
(Formula Removed)
wherein the total number of carbon atoms, including branching, is from 15 to 18, and wherein further for this alcohol mixture the average total number of carbon atoms in the branched primary alkyi moieties havimi the above formula is within the range of greater than 14,5 to about 17.5; R^ and R2 are each independently hydrogen or C j -C.% alkyl; x is from 0 to 1 1 ; y is from 0 to 11; 7, is at least 2; and x + y + / is from 9 to 13; provided R^ and R^ are not both hydrogen. More preferred are compositions having at least 5% of the mixture comprising one or more mid-chain branched primary alkyl sul fates wherein x •» y is equal to 9 and z is at least 2.
Preferably, the mixtures of alcohols comprise at least 5% of a mid chain branched primary alkyl alcohol having R! and R^ independently hydrogen, methyl, provided R 1 and R^ are not both hydrogen; x + y is equal to 8, 9, or 10 and z is at least 2. More preferably the mixtures of alcohol comprise at least 20% of a rnid
chain branched primary alkyl alcohol having lO and R2 independently hydrogen, methyl, provided R1 and R2 arc not botli hydrogen; x + y is equal to 8,9, or 10 and z is at least 2.
Preferred alcohol mixtures according to the present invention comprise from about 0.001% to about 99% of a mixture of mid-chain branched primary alkyl alcohols, said mixture comprising at least about 5 % by weight of two or more mid-
chain branched alkyl alcohols having the formula:
(Formula Removed)
or mixtures thereof; wheieina, b, d, ajid e are integers, a+b is from 10 to 16, d+c is from 8 to 14 and wherein further
when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 1 1 , a is an integer from 2 lo 1 0 and b is an integer from 1 to 9; when a + b - 12, a is an integer from 2 to 1 1 and b is an integer from 1 to 1 0; when a -f b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b - 14, a is an integer from 2 to 1 3 and b is an integer from 1 to 12; when a •*• b - ] 5, a is an integer from ?. to 14 and b is nn integer from 1 to 13; when a + b - 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + c = 8, d is an integer from 2 to 7 and c is an integer from 1 to 6; \vhcn d H r •-' V, d is tin intern liom '}. to K mid c is nn integer from 1 lo 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + c = 1 1 , d is an integer from 2 to 1 0 and e is an integer from 1 to 9; when d + e = 12, d is an integer from' 2 to 1 1 and c is an integer from 1 to 10; when d + e = 1 3, d is an integer from 2 to 1 2 and e is an integer from 1 to 1 1 ; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein further for this surfactant mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5.
Preferred mono-methyl branched primary alkyl alcohols useful in the present process are selected from the group consisting of: 3-mclhyl pcntadecanol , 4-mcthyl
peiitaclecanol , 5-methyl pcntadecanol , 6-methyl pcntadecanol , 7-mcthyl pentadecatiol , 8-methyl pcntadecanol , 9-methyl pcntadecanol , 10-methyl pc-madeeano) , 1 1 -methyl pcnladociuiol , 12-mHhyl prntadccanol , 13-methyl pcntadecanol » 3-methyl hexadecaiiol , 4-mcthyl hcxadecanol , 5-methyl
hexadecanol, 6-methyl hexadecanol, 7-methyl hcxadecanol, 8-methyl hexadecanol , 9-rnelhyl hexadecanol , 10-methyl liexadecanol, 11-methyl hexadecanol, 12-mcthyl hexadecanol, 13-methyl hexadecanol, 14-methyl hexadecanol. and mixtures thereof.
Preferred di-methyl branched primary nlkyl alcohols arc selected from the group consisting of: 2,3-mcthy) tctradecanol, 2,4-methyl tetradccanol , 2,5-methyl tctradccnnol, 2,6-niethyl ictradccanol , 2,7-meihyl tctradecanol, 2,8-mcthyJ tetradccanol, 2,9-mcthyI tetradecanol, 2,10-rncthyl tetradecanol, 2,11-methyl tetradecanol, 2,12-methyI tetradecanol, 2,3-methyl pentadecanol, 2,4-methyl pcnladecanol, 2,5-mcthyl pentadecanol, 2,6-mcthyl pcnUidccanol, 2,7-mcthyl pentadecanol, 2,8-methyl pentadecanol, 2,9-methyI pentadecanol»2,10-methyl pentadecanol, 2,11-methyl pentadecanol, 2,12-mcthyl pentadecanol, 2,13-methyl pentadecanol, and mixtures thereof. (b) Mid-chain branched aliphatic polyoxvalkvlene alcohols:
Mid-chain branched aliphatic polyoxyalkylcnc alcohols useful in the present invention sulfation process have the formula:
(Formula Removed)
These alcohol mixtures of the present invention comprise molecules having a linear primary polyoxyalkylene chain backbone (i.e., the longest linear carbon chain which includes the ulkoxylated carbon atom). These alkyl chain backbones comprise from 12 to 19 carbon atoms; and further the molecules comprise a branched primary alkyl moiety having at least a total of 14, but not more than 20, carbon atoms. In addition, the alcohol mixture has an average total number of carbon atoms for the branched primary alkyl moieties within the range of from greater than 14.5 to about 17.5. Thus, the present invention mixtures comprise at least one polyoxyalkylene compound having a longest linear carbon chain of not less than 12 carbon atoms or more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl chains is within the range of greater than H..*> to about 17.$.
For example, a C16 total carbon (in the alkyl chain) primary polyoxyalkylene alcohol having 15 carbon atoms in the backbone must have a methyl biandiing unil (fitlicr R, R' ot J?2 is mctliyl) whereby ON? toUtl number oT carbon atoms in the molecule is 16.
R, R1 „ and R2 are each independently selected from hydrogen and C\-C$ alkyl (preferably hydrogen or Ci-Co alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided R, R' , and R2 are not all hydrogen. Further, when z is ], at least R or R1 is not hydrop.en.
Although for tin- purposes of the present invention alcohol compositions the above formula does no! include molecules wherein the units R, lO, and R^ arc all hydrogen (i.e., linear non-branched primary polyoxyulkylenes), it is to be recognized that the present invention compositions may still further comprise some amount of linear, non-branched primary polyoxynlkylenc. Further, this linear non-btanched primary polyoxyalkylcnc alcohol may be present as the result of the piocess used to manufacture the alcohol mixture having the requisite mid-chain branched primary polyoxyalkylenes according to the present invention, or for purposes of formulating deleigcnt compositions some amount of linear non-branched primary polyoxyalkylene may be admixed into the final product formulation.
Further it is to be similarly recognized that non-alkoxylutcd mid-chain branched alcohol may comprise some amount of the present invention polyoxyalkylenc-containing compositions. Such materials may be present as the result of incomplete alkoxylation of the alcohol used to prepare the polyoxyalkylene alcohol, or these alcohols may be separately added to the present invention alcohol mixtures along with n mid-chain branched polyoxynlkylenc alcohol iior.ordiny to the present invention.
Further regarding the above formula, w is an integer from 0 to 13; x is an integer from 0 to 1 3; y is an integer from 0 lo 13; z is an integer of at least ]; and w •i- x H y + z is an integer from 8 to 14.
F.O/PO are alkoxy moieties, preferably selected from cthoxy, propoxy, and mixed elhoxy/propoxy groups, wherein m is at least about 0.01, preferably within the. range of from about 0,1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5. The (E0/P0)ni moiety may be either o distribution with average degree of alkoxylation (e.g., ethoxylation and/or propoxylation) corresponding to in, or it may be a single specific chain with nlkoxyhilion (e.g., elhoxyhtion and/or propoxylation) ol exactly the number of units corresponding to m.
The preferred alcohol mixtures of the present invention have at least 0.001%,
4
more preferably at least 5%, most preferably at least 20% by weight, of the mixture one or more mid-chain branched primary alkyl polyoxyalkylencs having the formula
(Formula Removed)
wherein the total number of carbon atoms, including branching is from 15 to 18, and wherein further for this alcohol mixture the overage total number of carbon atoms in (lu- bi;mduxl piimaiy alkyl moieties having the above formula is within the range of greater (hnn H.5 to about 17.5; R1 and R2 are each independently hydrogen or C]-€3 alkyl; x is from 0 to 11; y is from 0 to 11; z is at least 2; and x + y H z is from 9 to 13; provided R1 and R2 are not both hydrogen; and EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propQjy groups, wherein in is nt least about 0.01, preferably within the range of from about O.I to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5. More preferred are compositions having at least 5% of the mixture comprising one or more mid-chain branched primary polyoxyalkylencs wherein / is at least 2.
Preferably, the mixtures of surfactant comprise at least 5%, preferably at least about 20%, of a mid chain branched primary alkyl polyoxyalkylenc having R1 and R^ independently hydrogen or methyl, provided R' and R^ ore not both hydrogen; x -(- y is equal to 8, 9 or 10 and z is at least 2.
Preferred alcohol mixtures according to the present invention comprise from about 0.001% to about 99% of a mixture of mid-chain branched primary alkyl polyoxyalkylene alcohols, said mixture comprising at least about 5 % by weight of one or more mid-chain branched alkyl polyoxyalkylencs having the formula:
(Formula Removed)
or mixtures thereof; wherein a, b. d, ntul e. ate integers, tH-b is from 10 to 16, cMc is from K to 14 and wherein further
when a + b = 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a 4 b ~ 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b ~ 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = M, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a -*- b = 16, a is ;m integer from ?. to 15 and b is an integer from 1 to 14; when d -t e - 8, d is tin integer from 2 to 7 and e is an integer from 1 to 6;
when d •» c - 9, d is nn integer from 2 to 8 and e is an integer from 1 to 7; when d + e - 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d H c = 11, d is an integer from 2 to 10 and c is an integer from 1 to 9; when d + c - 12, d is an integer fiom 2 to 11 mid c is art integer from 1 to 10; when d -t c • 13, d is an integer from 2 to 1'), and e is ?m integer from 1 to 1); when d i e - 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; and wherein further for this alcohol mixture the average total number of carbon atoms in the branched primary nlkyl moieties having the above formulas is within the range of greater than 14.5 to about 17.5; and EO/PO are alkoxy moie.tics selected from cthoxy, propoxy, and mixed cthoxy/propoxy groups, wherein m is at least about 0.01, preferably within the range of from about 0.1 to about 30, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 5,
Preferred mono-methyl bnme.bcd primary alkyl ethoxyiates are selected from the group consisting of: 3-methyl pentadecanol ethoxylate, 4-methyl pentadecanol ethoxylale, 5-mcthyl pentadecanol cthoxylate, 6-methyl pentadecanol ethoxylate, 7-methyl pentadecanol cthoxylate, 8-methyl pentadecanol ethoxylate, 9-methyl pentadecanol ethoxylate, I0-methyl pentadecanol ethoxylate, 11-methyl pentadecanol ethoxylate, 12-methyl penlaciecnnol ethoxylate, 13-mcthyl pentadecanol ethoxylate, 3-mcthyl hexadccanol ethoxylate, 4-methyl hcxadecanol ethoxylate, 5-mc(hyl hexadccanol ethoxylnte, 6-methyl hexadecanol cthoxylate, 7-nielhyl lu'xadccanol elhoxylate, 8-methyl hexadecanol cthoxylate, 9-methyl hexadecanol ethoxylate,'10-mclhyl hexadccanol ethoxylate, 11-methyl hexadecanol ethoxylate, 12-mcthyl hexadecanol cthoxylate, 13-methyl hcxadecanol ethoxylatc, 14-melbyl hexadecanol ethoxylate, and mixtures thereof, wherein the compounds arc clhoxylated with an average degree of cthoxy lation of from about 0.1 to about 10.
Preferred di-rnethyl branched primary alkyl ethoxyiates selected from the group consisting of: 2,3-methyl tctradecnnol cthoxylate, 2,4-methyl IcHradecanol cthoxylate, 2,5-mcthy! tetradecanol ethoxylotc, 2,6-metJiyl tetradecanol ethoxylatc, 2.7-mclhyl tetradecanol ethoxylate, 2,8-mcthyl tetradecanol ethoxylate, 2,9-methyl tetrndccnnol ethoxylatc, 2,10-mcthyl Ictrudccanol cthoxylate, 2,11-mctliyl tetradecanol etlioxylate, 2,12-metliyJ tetradecajiol ethoxylale, 2,3-methyl pentadecanol ethoxylate, 2,4-methyl pentadecanol ethoxylate, 2,5-methyl pcnUidecanol elhoxylatc, 2,6-methyl pentailecajiol clhoxylate, 2,7-inethyl pentadecanol cthoxylatc, 2,8-mcthyl pentadecanol ethoxylate, 2,9-methyl pentadecanol cthoxylatc, 2,10-mcthyl pcntadccnno! ethoxylale, 2.11-methyl pentadecanol ethoxylate, 2,12-methyl pentadecanol etlioxylate, 2,13-methyl
pcntadecEinol ethoxylatc, and mixtures thereof, wherein the compounds are ethoxylated with an average degree of cthoxylation of from about 0.1 to about 10.
Sulfation Conditions:
The Miiration procc.1;1; according to Ihr picf-cnt invention utili/e:. SOj [in the sulfating reagent. 803 concentrations in the range of 4-5%, volume/volume, in air are preferred, although no-air processes can also be used. A slight molar excess of 803, i.e., a mole ratio of SC>3 to alcohol slightly greater than about 1:1, is preferred.
Preferred processes further utilize an alcohol feed temperature fo^the sulfation step of the process of less than about 50°C, preferably within the range of from about 10°C to about 50°C, more preferably within the range of from about 15°C to about 45°C, and most preferably from about 20°C to about 35°C. Cooling jacket water temperatures in the range of from about 2Q°C to about 30°C arc typical for the present process.
Ilic processes herein may utili/e continuous or batch reactors. Preferred process utilize continuous reactors such as a falling film reactor in which to react the alcohol and the 803. Specific reactors include Chcmithon, Ballestra, and other reactors as described in: Kirk Othmer, Encyclopedia of Chemical Technology, 3rd. lid., Wiley, 1983, Vol. 22, pp 28-45, article entitled "Sulfonation and Sulfation"; W.IJ. De Groot, "sulphonation Technology in the Detergent Industry", Kluwcr Academic Publishers, Boston, 1991; ISDN 0-7923-1202-3; and "Detergent Manufacturing Including Zeolite Builders ajid Other New Materials,", Chemical Technology Review No. 178, Noycs Data Corp., Park Ridge, New Jersey, 1979, pp. 273-310.
Neutralization:
The step of Neutralizing the alkyl sulfntt1 :ici i or alkyl alkoxylated sulfate acid produced by the sulfation reaction is prcfcrroh conducted irmnediatcly after the sulfation reaction. Typical conditions for this step o: ihc process include neutralization temperatures within the range of from about 25°C to about 35°C, and acid feed temperatures into the ncutralb.er within the range of from about 35°C to about 45°C.
Basic neutralizing agents useful herein include any suitable inorganic base. For example, potassium hydroxide, sodium hydroxide, ammonia monoelhanolnminc, and triethanolaminc, may be used. Potassium salts may be useful for further reduction in viscosity of aqueous surfactant pastes.
Jt is also preferred that the final alkyl sulfate paste concentration which results Irom the neutralization step be greater than about 20%, preferably greater
than about 50%, and most preferably greater than about 60%.
As a result of the present process, alky] sulfate and alkyl alkoxylated sulfate surfactants arc produced comprising mid-chain branched primary alky] sulfates and/or mid-chain primary alky] alkoxylated sulfates having the following formulas.
The picscnl invention produces surfactant composition}; comprising owl-chain branched primary alky) sulfates having the formula:
(Formula Removed)
wherein the total number of carbon atoms in me branched primary alkyl moiety of this formula (including the R, R.1, and R^ branching) is from 14 to 20, and wherein further for this surfactant mixture the average total number of carbon atoms in the branched primary alky] moieties having the above formula is within the range of greater than 1-1.5 to about 17.5 (preferably from about 15 to aboul IV); R, R', and R- are each independently selected from hydrogen and Ci*C3 olky) (preferably methyl), provided R, R1, and R^ are not all hydrogen and, when z is 1, at least R or R' is not hydrogen; M is one or more cations; w is an integer from 0 to 13; x is an integer from 0 to 1 3; y is an integer from 0 to ] 3; 7. is an integer of at least 1 ; and w -I x -» y • The present invention also produces surfactant compositions comprising mid-chain branched primary alkyl alkoxylated sulfates having the formula:
(Formula Removed)
wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, R', and R-' branching, but not including the carbon atoms in the KU/PO alkoxy moiety) is from 14 to 20, and wherein further for this surfactant mixture the average total number of carbon atoms in the branched primary nlky! moieties having the above formula is within the range of greater than 14.5 to about 17.5 (preferably from about 15 to about 17); R, R', and R^ are each independently selected from hydrogen and Cj-C3 alkyl (preferably methyl), provided R, Rl , and R- arc not all hydrogen and, when / is 1, at least R or R^ is not hydrogen; M is one or more cations; w is an integer from 0 to 13; x is'an integer from 0 to 13; y is mi integer from 0 to 1 3; z is an integer of at least 1 ; w + x + y + z is from 8 to 14; and EO/PO are aJkoxy moieties including for example ethoxy,
propoxy, butoxy, etc, preferably selected from ethoxy, propoxy. and mixed cthoxy/propoxy groups, wherein in is at least about 0.01, preferably within th As used herein, M is a salt forming cation depending upon the method of synthesis. Examples of salt forming cations are lithium, sodium, potassium, calcium, magnesium, quaternary alkyl amities having the formula
(Formula Removed)
wherein R3, R4, R5 and R6 are independently hydrogen, C\-Cj2 alkylcnc, 04-022 brandiod alkylene, Cj-C'o' alkanol, C]-C*22 alkcuyleiie, 04-022 branched alkenylene, and mixtures tlicreof. Preferred cations are ammonium (R-^, R4, R5 and R^ equal hydrogen), sodium, potassium, mono-, dK and trialkanol ammonium, and mixtures thereof. The rnortoalkanol aJTimonium compounds of the present invention have R.3 equal to Cj-Cg alkanol, R^, R^ and R^ equal to hydrogen; dialkanol ammonium compounds of the present invention hove R^ and R4 equal to C]-C6 alkanol, R^ and R^' equal to hydrogen; trialkanol ammonium cojnpounds of the present invention have R^, R4 and R^ equal to Cj-Of, alkanol, R^ equal to hydrogen, 1'ielerred ulkmiol ammonium salts oi the present invention arc the mono-, di- and tri- quaternary ammonium compounds having the formulas:
(Formula Removed)
I'referred M is sodium, potassium and the 02 alkanol ammonium salts listed above; most preferred is sodium.
Preparation of JV( id-chain Branched Alcohols and Poivoxvalkvlcnc Alcohols
The following reaction scheme outlines a general approach to the preparation
of the mid-chain branched primary alcohols useful for the present invention process,
(Formula Removed)
An alkyl halidc is converted to a Grignard reagent and the Grignard is reacted with a haloketone. After conventional acid hydrolysis, acetylation and thermal elimination of acetic acid, an intermediate olefin is produced (not shown in the scheme) which is hydrogenatcd forthwith using any convenient hydrogenation catalyst such as Pd/C.
This route is favorable over others in that the branch, in this illustration a 5-mcthyl branch, is introduced early in the reaction sequence.
Fonnylalion of the alkyl halidc resulting from Ihc first hydrogenation step yields alcohol product, as shown in the scheme. This may be alkoxylatud using standard tcclmiqucs to yield a mid-chain branched primary alkyl polyoxyalkylene alcohol. There is flexibility to extend the branching one additional carbon beyond thai which is achieved by a single fonnylation. Such extension can, for example, be accomplished by reaction with ethylene oxide. See "Grignard Reactions of Nonmctallic Substances", M.S. Kharasch and O. Reinmulh, Prentice-Hall, N.Y., 1954; J. Org. Chem., J. Cason and W. R. Winans, Vol. 15 (1950), pp 139-147; J. Org Chem., J. Cason et al, Vol. 13 (1948), pp 239-248;,/. Org Chem., J. Cason et al., Vol. 14 (1949), pp 147-154; and J. Org Chem., J. Cason ct al., Vol. 15 (1950), pp 135- 138 all of which are incorporated herein by reference.
In variations of the above procedure, alternate haloketoncs or Grignard reagents may be used. PHr3 halogenation of the alcohol from formylation or cthoxylation can be used to accomplish an iterative chain extension.
The preferred mid-chained branched primary alkyl alcohols and therefrom the preferred polyoxyalkylene alcohols useful in the present invention can also be readily prepared as follows:
(Formula Removed)
A conventional bromoalcohol is reacted with triphenylphosphine followed by sodium hydride, suitably in dimcthylsulibxide/tetrahydrofuran, to form a Wittig adduct. The Wittig adduct is reacted with an alpha methyl ketone, forming an internally unsaturatcd methyl-branched alcoholate. Hydrogcnation, optionally followed by alkoxylation, yields tlie desired mid-chain branched primary alkyl alcohols. Although the Wittig approach does nol allow the practitioner to extend the hydrocarbon chain, ns in the Grignard sequence, the Wiltig typically affords higher yields. Sec Agricultural and Biological Chemistiy, M. Horiike et al., vol. 42 (1978), pp 1963-1965 included herein by reference.
Any alternative synthetic procedure in accordance with the invention may be used to prepare the branched primary alkyl alcohols. Tlie mid-chain branched primary nlky! alcohols may, in addition be synthcsi/.cd or formulated in the presence of the conventional homologs, for example any of those which may be formed in an industrial process which produces 2-alkyl branching as a result of hydroformylation.
In certain preferred embodiments of the alcohol mixtures of the present invention, especially those derived from fossil fuel sources involving commercial processes, comprise at least 1 mid-chain branched primary alkyl alcohol, preferably at least 2, more preferably at least 5, most preferably at least 8.
Particularly suitable for preparation of certain alcohol mixtures for the present invention are "oxo" reaction?; wherein a branched chain olefin is subjected to catalytic isomerization and hydroformylation. The preferred processes resulting in such mixtures utilize fossil fuels as the starting material feedstock. PiefeMod processes utilize Oxo reaction on linear olcfins (alpha or internal) with a limited amount of branching. Suitable olefins may be made by dimerization of linear alpha or internal olcfins, by controlled oligomcrization of low molecular weight linear olefins, by skeletal rearrangement of detergent range olefins, by dchydrogenalion/skeletal rearrangement of detergent range paraffins, or by Fischer-Tropsch reaction. These reactions will in general be controlled to:
1) give a large proportion of olefins in the desired detergent range (while allowing
for the addition of a carbon atom in the subsequent Oxo reaction),
2) produce a limited number of branches, preferably mid-chain,
3) produce Cj-C^ branches, more preferably ethyl, most preferably methyl.
The process described herein above gives the more preferred 5-melhyl-hexadccyl alcohols in higher yield than the le.ss preferred 2/l-dimcthylpcntadecyJ alcohols. This mixture is desirable under the metes and bounds of the present invention in that each product comprises at total of 17 carbon atoms witii linear alkyl chains having at least 13 carbon atoms.
The following examples provide methods for synthesizing various compounds useful in the present invention processes.
EXAMPLE I I'rcjinration.of.7:tiic(hylhcxadccyl cthoxvlatc (£2)
Synthesis of (6-hydioxvhcxyl) triphcnvlphosphoniuni bromide Into a 5L, 3 neck round bottom ilask lilted with nitrogen inlet, condenser, thermometer, mechanical stirring and nitrogen outlet is added 6-bromo-l-hexanol (500g, 2.76 niol), triphcnylphosphine (7fiRp, 2.9mol) and acctonitrilc (1800 nil) under nitrogen. The- reaction mixture is heated to reflux for 72 hr.s. The reaction mixture is cooled to room temperature and transferred into a 5L beaker. The product i;; icuy.slalli/oil from anhydrous ethyl ether (1.51,) al )0°C\ Vacuum filtration followed by washing with ethyl ether and drying in a vacuum oven at 50°C for 2 hrs. gives 1140g of the desired product as white crystals.
.Synthesis of 7- methvlhexadecene-1-ol
Into a dried 5L, 3 neck round bottom flask fitted with mechanical stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet is added 70.2g of
60% sodium hydride (1.76 mol) in mineral oil. The mineral oil is removed by washing with hexanes. Anhydrous dimethyl sulfoxide (500ml) is added to the flask and the mixture is heated to 70°C until evolution of hydrogen stops. The reaction mixture is cooled to room temperature followed by addition of 1L of anhydrous lelrnbydwfiimn. (6-hyilroxyhcxyl) triphrriylphosphonium bromide (443.'1g, I mol) is slurricd wiih wwni anhydrous dimethyl sulfoxide (SO°C, 500ml) and slovvly added to the reaction mixture through the dropping funnel while keeping it at 25-30°C. The mixture is stirred for 30 minutes at room temperature at which time 2-undecanone (187g, 1.1 mol) is slowly added through a dropping funnel. Reaction is slightly exothermic arid cooling is needed to maintain 25-30°C. The mixture is stirred for 18 Iir. and then poured into a 5L beaker containing 1L purified water with stirring. The oil phase (top) is allowed to separate out in a separatory funnel and the water phase is- removed. The water- phase is washed with hcxflnes (500m!) and the organic phase is separated and combined with the oil phase from the water wash. The organic mixture is then extracted with water 3 times (500ml each) followed by vacuum distillation to collect the clear, oily product (132g) at 140C and 1mm Hg.
llvdrop.cnntion of i~ mcthvlhcxndecenc-l-ol
Into a 3L rocking autoclave liner is added 7-melhyIhexadecene-l-ol (130g, 0.508mol), methanol (300ml) and platinum on carbon (10% by weight, 35g), The mixture is hydrogenated at 180°C under 1200 psig of hydrogen for 13 lirs., cooled and vacuum filtered thru CeJite 545 with washing of the Celite 545, suitably with methylenc chloride. If needed, the filtration can be repeated to eliminate traces of Pt catalyst, and magnesium sulfatc can be used to dry the product. The solution of product is concentrated on a rotary evaporator to obtain a clear oil (124g).
Ajkoxylation of 7-irtethy!hc .adecanol
Into n dried JJ. 3 neck round botlom flask fined wiih n nitrogen inlcl, mechanical stirrer, and a y-tubc iilted with a thermometer and a gas outlet is added the. alcohol from the proceeding step. For purposes of removing trace amounts of moisture, the alcohol is sparged with nitrogen for about 30 minutes at 80-100° C. Continuing with a nitrogen sweep, sodium metal is added as the catalyst and allowed to melt with stirring at 120-140° C. With vigorous stirring, eihylenc oxide gas is added in 140 minutes while keeping the reaction temperature at 120-140° C. After the correct weight (equal to two equivalents of ethylene oxide) has been suliU-d. nitrogen is swept through the ,-ippnrnlns for ?0-30 minutes ns the sample is allowed to cool. The desired 7-methylhcxadccyl ethoxylate (average of 2
ethoxylatcs per molecule) product is then collected.
EXAMPLE 11 SyntJiesk of 7-mgthvlnentadccvl cthoxylatc (E3)
Synthesis of (6-hydiqxyhexvl) Triphenylphosphonium Djomide Into a 5L, 3 neck round bottom flask fitted with nitrogen inlet, condenser, (hennoweter, mechanical stining and nitrogen outlet is added 6-bromo-l-hcxanol (50Ug, 2.76 mol), triphenylphosphine (768g, 2.9mol) and acetonilrile (1§00 ml) under nitrogen. The reaction mixture is heated to reflux for 72 hrs. The reaction mixture is cooled lo room temperature and transferred into a 5L beaker. The product is recrystallixed from anhydrous ethyl ether (] .51.) at JO°C. Vacuum filtration of the mixture followed by washing (he white crystals with ethyl ether and drying in a vacuum oven at 50°C for 2 lirs. gives 1140g of the desired product.
.Synthesis of '/_-_ nKMhylpeiiltKlcccnc-1 -ol
Into a dried 5L, 3 neck round bottom flask fitted with mechanical stirring, nitrogen inlet, dropping funnel, thermometer and nitrogen outlet is added 80g of (50% sodium hydride (2.0 mol) in mineral oil. The mineral oil is removed by washing with hcxancs. Anhydrous dimethyl sulfoxidc (500ml) is added to the flask and heated lo 70°C until evolution of hydrogen stops. The reaction mixture is cooled 16 room temperature followed by addition of 1L of anhydrous Ictrahydrofuran. (6-hydroxyhexyl)triphenyIphosphonium bromide (443.4g, J mol) is slurried with warm anhydrous dimethyl sulfoxide (50°C, 500ml) and slowly added to the reaction mixture thru the dropping funnel wlu'le keeping the reaction at 25-30°C. The reaction is stirred for .10 minutes at room temperature at which time 2-dccanonc (17l.9g, 1.1 mol) is slowly added thru a dropping funnel. Reaction is slightly exothermic and cooling is needed to maintain 25-30°C, Mixture is stirred for 18 Ins. and then poured into n separator}' funnel containing 600ml of purified water aod 300 ml of hexunes. After shaking the oil phase (top) is allowed to separate out and the water phase is removed. The* extractions of the oil phase arc continued using watei until both phases rue clear. The organic phase is collected, vacuum distilled and purified by liquid chromatography (90:10 hcxanesrethyl acetate, silica
i
gfl stationary phase) to obtain a clear, oily product (119.1g).
Hydrogcnation of 7- methylpentadeccnc-l-ol Into a 3L rocking autoclave gloss liner (Autoclave Engineers) is added 7-
Mcthylpentadcccne-J-ol (J22g. 0.508mol), mcthanol (300ml) and platinum on carbon (10% by weight, 40g). The mixture is hydrogenated at 180°C under 1200 psig of Iiydrogcn lor 13 hrs., cooled and vacuum filtered thru Celite 545 with washing of Celite 545 with methylcnc chloride. The organic mixture is still dark from platinum catalyst so the filtration procedure is repeated with concentration on a rotary evaporator; dilution is carried out with methylene chloride (500ml) and magnesium sulfate is adcd to dry product. Vacuum filter thru Celite 545 and concentrate filtrate on a rotary evaporator to obtain a clear oil (119g).
Alkoxylation of 7-nicjhyjj^ij^decgnoj
Into a dried 1L 3 neck round bottom flask fitted with a nitrogen inlet, mechanical stirrer, and a y-tube fitted with a thermometer and a gas outlet is added the alcohol from the proceeding step. For purposes of removing trace amounts of moisture, the alcohol is sparged with nitrogen for about 30 minutes at 80-100* C. Continuing with a nitrogen sweep, sodium metal is added as the catalyst and allowed to melt with stirring at 120-140° C. With vigorous stirring, cthylene oxide gas is added in 140 minutes while keeping the reaction temperature at 120-140° C, After the correct weight (equal to tlircc equivalents of cthylene oxide) has been added, nitrogen is swept through the apparatus for 20-30 minutes as the sample is allowed to cool. The desired 7-methylpentadecyl ethoxylate (average of 3 elhoxylatcs per molecule) product is then collected.
1-XAMPLE III Synthesis of 7-rnethylhepiadecvl^thQXvlate CE1.5)
Synthesis ol(6-11 ydn)xylicxvl) Triphcrivl]>hosphoiiiuiii broinicle Into a 5L, 3 neck round bottom flask fitted with nitrogen inlet, condenser, thermometer, mechanical stirring and nitrogen outlet is added 6-bromo-l-hexanol (500g, 2.76 mol), triphenylphosphine (768g, 2.9mol) and acetonkrile (1800 ml) under nitrogen. The reaction mixture is healed to reflux for 72 hrs. The reaction mixture is cooled to room temperature and transferred into a 5L beaker. The product is recryslallized from anhydrous ethyl ether (1.5L) at 10°C. Vacuum filtration of the mixture followed by washing the white crystals with ethyl ether and drying in a
i
vacuum oven at 50°C for 2 hrs. gives 1140g of the desired product.
Synthcsis oOr, meIhyjheptadcccne-1-o) Into 'A dried 5Lt 3 neck round bottom flask fitted with mechanical stirring,
nitrogen inlet, dropping funnel, thermometer and nitrogen outlet is added 80g of 60% sodium hydride (2.0 mol) in mineral oil. The mineral oil is removed by washing with hexanes, Anhydrous dimethyl .sulfoxidc (500ml) is added to the flask and heated to 70°C until evolution of hydrogen stops. The reaction mixture is cooled to room tcmpemtme followed by addition of 11, of anhydrous tcirahydrofuran. (6-hydroxyhexyl) triphcnylphosphonium bromide (443.4g, 1 mol) is slum'ed with warm anhydrous dimethyl sulfoxidc (50°C, 500ml) and slowly added to the reaction mixture thru the dropping funnel while keeping the reaction at 25'30°C. The reaction is stirred for 30 minutes at room temperature at wjjich time 2-dodecanone (184.3g, I.I mol) is slowly added thru, a dropping funnel. Reaction is slightly exothermic and cooling is needed to maintain 25-30°C. Mixture is stirred for 18 lirs. and then poured into a scparatory funnel containing 600ml of purified water nnd 300 ml of hcxancs. After .shaking the oil phase (top) is allowed to separate out and the water phase is removed which is cloudy. The extractions are continued using water until the water phase and the organic phase become clear. The organic phase is collected nnd purified by liquid chiomatoginphy (mobile phase-hcxanes, stationary phase-silica gel) to obtain a clear, oily product (116g). HNMR of the final product (in deuterium oxide) indicates a CH^-OSC^ triplet at the 3.8 ppm resonance, CH2-CH2-OS03' multiple! at the 1.5 ppm resonance, CH2 of the alkyl chain at the 0.9-1.3 ppm resonance and CII-CH^ branch point overlapping the R-Cl 12QLI3 terminal methyl group at the 0.8 ppm resonance.
Hydrogenation of 7- methylhcptadeccnc-1-ol
Into a 3L rocking autoclave glass liner (Autoclave Engineers) is added 7-Methylheptadecene-1-ol (1) 6g, 0.433mol), methanol (300ml) and platinum on carbon (10% by weight, 40g). The mixture is hydtogen.'itcd at 180°C under 1200 psig of hydrogen for 13 hrs., cooled and vacuum filtered thru Celite 545 with washing of Cclitc 545 with mcthylene chloride. Vacuum filter thru Cclitc 545 and concentrate filtiaie on a iotary evaporator to obtain a clear oil (108g),
Alkoxvlation of 7-mcthvlheptadecanpi
Into a dried 1L 3 neck round bottom flask fitted with a nitrogen inlet, mechanical stirrcr, and a y-tube fitted with a thermometer and a gas outlet is added
*
the alcohol from the proceeding step. For purposes of removing trace amounts of moisture, the alcohol is sparged with nitrogen for about 30 minutes at 80-100° C. Continuing with a nitrogen sweep, sodium metal is added as the catalyst and allowed to melt with stirring at 120-140" C, With vigorous stirring, ethylcnc oxide
gas is added in 140 minutes while keeping the reaction temperature at 120-140° C. After the correct weight (equal to 1 .5 equivalents of cthylene oxide) has been added, nitrogen is swept through the apparatus for 20-30 minutes as the sample is allowed to cool. The desired 7-methylheptadecyl cthoxylate (average of 1 .5 ethoxylates per molecule) product is then collected.
EXAMPLE IV
The following Shell Research experimental test alcohol samples,are cthoxylated (average ethoxylatiori of 2.5) by the following procedure.
Results For Branched Alcohols Prepared

(Table Removed)
Into a dried 250ml 3 neck round bottom flask fitted with a nitrogen inlet, mechanical slirrer, and a y-tube fitted with a thermometer and a gas outlet is added the C16 alcohol (48.4p,. 0.2 mol) above. For purposes of removing trace amounts of moisture, the alcohol is sparged with nitrogen for about 30 minutes at 80-100° C. Continuing with a nitrogen sweep, sodium metal (0.23g, 0.01 mo)) is added as the catalyst and allowed to melt with stirring at 120-140° C. >With vigorous stirring, ethylene oxide gas (22g, 0.5 mol) is added in 140 minutes while keeping the reaction temperature at 120-140° C. After the correct weight of ethylcnc oxide (average 2.5 cthoxylatcs per molecule) lias been added, nitrogen is swept through the apparatus for 20-30 minutes as the sample is allowed to cool. The gold liquid product (69g,
0.1% mol) is bottled under nitrogen. QXAMPLl: V
The alcohol of F.xnmple 111 (90 parts) is mixed with n-hcxadecanol (10 pails). The starting alcohol mixture has a total carbonyl impurity level of no more than about 5ppm, by wcight.The mixture is sulfated in a falling film reactor using the following conditions: mole ratios: conventional, i.e., slight excess of S03 over fatty alcohol; typical 803 concentrations: 4-5% , v/v in air, though no-aif processes can also be used; typical fatty alcohol feed temperature: 10-25 deg. C (compare 55-60 which would be essential for tallow); cooling jacket water: 20-30 deg. C (compare 45 and above which would be needed for tallow alcohol, stearyl alcohol and the like); neutralisation: 25-35 deg. C (compare 40-45 deg C for tallow alcohol); acid feed to ncutralizer: 35-45 deg. C (compare tallow alcohol at 55 deg C). Final paste concentrations above 30% by weight are possible (compare tallow which typically sets up solid almost independently of paste concentration when there is no LAB orethanol used).
The following two analytical methods for characterizing branching in the present invention surfactant compositions are useful:
1) Separation and Identification of Components in Fatty Alcohols prior to
alkoxylation. The position and length of branching found in the precursor fatty
alcohol materials is determined by GC/MS techniques [see: D. J. Harvey, Biomed,
linviron. Mass Spectrom (1989). 18(9), 719-23; D. J. Harvey, J. M. Tiffany, J.
Chromatogr. (1984), 301(1), 173-87; K. A. Karlsson, B. E. Samuelsson, G. O.
Stccn, Chcin. Phys. Lipids (1973), 11 (1), 17-38].
2) Identification of Separated Fatty Alcohol Components prior to
alkoxylation by MS/MS techniques. The position and length of branching is also
dctcrminable by Ion Spray-MS/MS or FAB-MS/MS techniques on previously
isolated fatty alcohol components.
Having identified isolated alcohol components, alkoxylation of the isolated alcohols yields sUuulaids useful for calibrating and interpreting GC cliromatograms of mid-chain branched primary alkyl polyoxyalkylene surfactants.
The uvcinge tolal carbon atoms of the bianchcd primary alkyl polyoxyalkylenes herein can be calculated from the hydroxyl value of the precursor fatty alcohol mix according to common procedures, such as outlined in "Bailey's Industrial Oil and Fat Products", Volume 2, Fourth Ikiition, edited by Daniel Swcrn,

We Claims
1. A method for manufacturing longer chain alkyl sulfate surfactant mixture
compositions, said method comprising the steps of:
(a) sulfating with 803, preferably in a falling film reactor, a long chain aliphatic
alcohol mixture having an average carbon chain length of at least 14.5 to 17.5, said
alcohol mixture comprising at least 10 %, preferably at least 25%, more preferably
at least 50%, still more preferably at least 75%, and most preferably at-least 95%, of
a mid-chain branched aliphatic alcohol having the formula:
(Formula Removed)
wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula, including the R, lO, and R^ branching, is from 14 to 20, and wherein further for this alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to 17.5, preferably greater than 15 to 17; R, R', and 1 (b) neutralizing the alkyl sulfate acid produced by step (a), preferably utilizing a
base selected from the group consisting of potassium hydroxide, sodium hydroxide,
ammonia monoethanolamine, triethanolamine, and mixtures thereof.
2. The method according to Claim 1 wherein the alcohol feed temperature for a step
(a) is less than 50°C, preferably within the range of from 10°C to 50°C, more
preferably within the range of from 15°C to 45°C, and most preferably from 20°C to
35°C.
3. The process according to cither of Claims 1 or 2 wherein the aliphatic alcohol
sulfaU-d in step («) comprises at least 10%, preferably at least 25%, more preferably
at least 50%, still more piefcrably at least 75%, and most preferably at least 95%, by
weight of a mixture of two or more mid-chain branched alcohols having the
formula:

(Formula Removed)
or mixtures thereof; wherein a, b, d, and c arc integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further
when a + b - 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a •»• b = 11, a is an integer from 2 to 10 and b is an integer from Ho 9; when a + b = 12, n is an integer from 2 to 11 and b is an integer from 1 to 10; when a •» b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b - 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b •= 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d -i e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e - 10, d is an integer from 2 to 9 and c is an integer from 1 to 8; when cH e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and c is an integer from 1 to 10; when d + e r- 13, d is an integer from 2 to 12 and c is an integer from 1 to 11; when d + c - 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein for this alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to 17.5.
4. A method for manufacturing longer chain alkyl alkoxylated sulfatc surfactant mixture compositions, said method comprising the steps of: (a) alkoxylating a long chain aliphatic alcohol mixture having an average carbon chain length of at least 14.5 to 17.5, said alcohol mixture comprising at least 10%, preferably at least 25%, more preferably at least 50%, still more preferably at least 75%, and most preferably at least 95%, of a mid-chain branched aliphatic alcohol having the formula:
(Formula Removed)
wherein tbf total number of carbon atoms in the branched primary alkyl moiety of this formula, including the R, Rl, and R2 branching, is from 14 to 20, and wherein
further for this alcohol mixture the average total number of carbon atoms in the branched primary alky) moieties having the above formula is -within the range of greater than 14.5 to 17.5, preferably greater than 15 to 17; R, R.', and R^ arc each independently selected from hydrogen and Cj-C3 alkyl, preferably methyl, provided R, R1, HI id R2 are not all hydrogen mid, when z is 1, m least R or R' is not hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to ] 3; z is nn integer of at least 1 ; and w •» x •+ y + z is from 8 to 14;
(b) sulfaiing the polyoxyalkylenc alcohol produced by step (a) with 863; and
(c) neutralizing the alkyl alkoxylate sulfate acid produced by step (b), preferably
utilizing u base selected from the group consisting of potassium hydroxide, sodium
hydroxide, ammonia monoethanolamine, triethanolamine, and mixtures thereof.

5. The method according to Claim 4 wherein the polyoxyalkylene alcohol feed
temperature for a step (b) is less than 50°C, preferably within the range of from
10°C to 50°C, more preferably within the range of from 15"C to 45°C, and most
preferably from 20°C to 35°C.
6. The process according to either of Claims 4 or 5 wherein the aliphatic alcohol
alkoxylatcd in step (a) comprises at least 10%, preferably at least 25%, more
preferably at least 50%, still more preferably at least 75%, and most preferably at
least 95%, by weight of a mixture of two or more mid-chain branched alcohols
having the formula:
(Formula Removed)
or mixtures thereof; wherein a, b, d, and c are integers, a+b is from 10 to 16, d+e is from 8 to 14 and wherein further
\vhen a •' b ^ 10, a is nn integer from 2 to 0 niicl b is nn integer from 1 to 8; when a H- b -• 1 1 , a is an integer from 2 to 1 0 and b is an integer from 1 to 9; when a •» b = 12, a is an integer from 2 to 1 1 and b is an integer from 1 to 10; when a • when cH- e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7;
when d + e ~- 10, d is an integer from 2 to 9 and e is an integer from 1 to 8;
when d + c = 11, d is an integer from 2 to 10 mid e is an integer from 1 to 9;
when d + c - 12, d is an integer from 2 to 11 and e is an integer from 1 to 10;
when d H e - 13, d is an integer from 2 to 12 and c is an integer from 1 to 11;
when d + c = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12;
wherein for this alcohol mixture the average total number of carbon atoms in the
branched primary alkyl moieties having the above formulas is within the range of
greater than 14.5 to 17.5. -*«
7. A method for manufacturing longer chain alkyl alkoxylated sulfate surfactant mixture compositions, said method comprising the steps of: (a) sulfating with 863 a long chain aliphatic polyoxyalkylene alcohol mixture having an average aliphatic alcohol carbon chain length of at least 14.5 to 17.5, said polyoxyalkylene alcohol mixture comprising at least 10% (preferably at least 25%, more preferably at least 50%, still more preferably at least 75%, and most preferably at least 95%) of a mid-chain branched aliphatic polyoxyalkylene alcohol having the formula:
(Formula Removed)
wherein the total number of carbon atoms in the branched primary alky) moiety of this formula, including the R, Rl, and R^ branching, but not including the carbon atoms in the EO/PO alkoxy moiety, is from 14 to 20, and wherein further for this polyoxyalkylene alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formula is within the range of greater than 14.5 to 17.5, preferably from 15 to 17; R, Rl, and R^ arc each independently selected from hydrogen and Cj-C3 nlkyl, preferably methyl, provided R, R1, and R2 are not all hydrogen and, when z is 1, at least R or R1 is not hydrop.cn; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer Jiom 0 to 13; 7. is an integer of at least 1; w -I x -t- y •)- 7. is from 8 to 14; and EO/PO arc alkoxy moieties, preferably selected from cthoxy, propoxy, and mixed etboxy/propoxy groups, wherein m is at least 0.01, preferably within the range of from 0.1 to 30, more preferably from 0.5 to 10, and most preferably from 1 to 5; and
(b) neutralizing the alkyl alkoxylated sulfate acid produced by step (a), preferably utilizing a base selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonia monocthanolaminc, tricthanolamine, and mixtures thereof.
8. The method according to Claim 7 wherein the polyoxyalkylcnc alcohol feed
temperature for a step (a) is less than 50°C, preferably within the range of from 10°C
to 50°C, more preferably within the range of from 15°C to 45°C, and most
preferably from 20°C to 3 5°C .
9. The process acording to any of Claims 1-8 wherein the neutralization temperature
is within the range of from 25°C to 35°C and the acid feed temperature into the
neutral izcr is within the range of from 35*C to 45°C.
10. The process acording to any of Claims 1-9 wherein the cooling jacket water
temperature for the sulfation reactor used for step (a) is in the range of from 20°C to
30°C.
1 1 . The process according to any of Claims 7- 1 0 wherein the aliphatic polyoxyalkylenc alcohol sulfatcd in step (a) comprises at least 10%, preferably at least 25%, more pioferably at least 50%, still more preferably at least 75%, and most preferably at least 95%, by weight of a mixture of two or more mid-chain branched
alcohols having the formula:
(Formula Removed)
or mixtures thereof; wherein a, b, d, and c are integers, a+b is from 10 to 16, d-t-c is from 8 to 1 4 and wherein further
when a + b ** 10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a + b = 1 J , a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is on integer from 2 to 1 1 and b is an integer from 1 to 10; when a + b = 1 3, a is an integer from 2 to 12 and b is an integer from 1 to 1 1; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when u + b =• J 5, a is an imc-ycr JViun 2 to 14 and b is mi integer from 1 to 13; when a + b = 1 6, a is an integer from 2 to 1 5 and b is an integer from 1 to 14;
when (1 i- c j' K, cl is an inlegiT from 2 lo 7 uiicl c is an integer from 1 to 6; when cl I e • 9, d is an integer from ?. to K mul c is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e ^ 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e ~ 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and c is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein for this poJyoxyalkylcne alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having the above formulas is within the range of greater than 14.5 to 17.5; and
wherein EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is at least 0.01, preferably within the range of from 0.1 to 30, more preferably from 0.5 to 10, and most preferably from 1 to 5.
12. A method for m;i n u f a c tuning Longer chain alkyl sulfate surfacted mixtures substantially as hereinbefore described in any of the Examples.

Documents:

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Patent Number

214865

Indian Patent Application Number

958/DEL/1997

PG Journal Number

10/2008

Publication Date

07-Mar-2008

Grant Date

18-Feb-2008

Date of Filing

15-Apr-1997

Name of Patentee

THE PROCTER & GAMBLE COMPANY

Applicant Address

ONE PROCTER & GAMBLE PLAZA, CINCINNATI, OHIO 45202, U.S.A.

Inventors:

#	Inventor's Name	Inventor's Address
1	CONNOR, DANIEL STEDMAN	9217 SAGEMEADOW DRIVE CINCINNATI, OHIO 45251, U.S.A.
2	CRIPE, THOMAS ANTHONY	599 THREE CHIMNEYS LANE LOVELAND, OHIO 45140-7345, U.S.A.
3	JENSEN, MICHAEL CHRIS	3811 DRAKEWOOD DRIVE CINCINNATI, OHIO 45209, U.S.A.
4	JACOBS, ROGER CRAIG	515 WENCELLA DRIVE HAMILTON, OHIO 45013 U.S.A.

PCT International Classification Number

C07D 215/20

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	60/015,523	1996-04-16	U.S.A.
2	60/015,521	1996-04-16	U.S.A.
3	60/031,761	1996-11-26	U.S.A.