US3687999A - Inhibition of color formation during sulfation of ethoxylated alcohols and alkyl phenols - Google Patents
Inhibition of color formation during sulfation of ethoxylated alcohols and alkyl phenols Download PDFInfo
- Publication number
- US3687999A US3687999A US877016A US3687999DA US3687999A US 3687999 A US3687999 A US 3687999A US 877016 A US877016 A US 877016A US 3687999D A US3687999D A US 3687999DA US 3687999 A US3687999 A US 3687999A
- Authority
- US
- United States
- Prior art keywords
- ethoxylated
- alcohol
- sulfation
- borohydride
- color
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 alkyl phenols Chemical class 0.000 title abstract description 21
- 238000005670 sulfation reaction Methods 0.000 title abstract description 18
- 230000019635 sulfation Effects 0.000 title abstract description 12
- 150000001298 alcohols Chemical class 0.000 title description 8
- 230000015572 biosynthetic process Effects 0.000 title description 6
- 230000005764 inhibitory process Effects 0.000 title description 3
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 10
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000001180 sulfating effect Effects 0.000 abstract description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 31
- 239000000047 product Substances 0.000 description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- XEFJFCAXFQMSSY-UHFFFAOYSA-N 13-hydroxytridecanal Chemical compound OCCCCCCCCCCCCC=O XEFJFCAXFQMSSY-UHFFFAOYSA-N 0.000 description 2
- PTMRDOLOEDPHLB-UHFFFAOYSA-N 2,3-dipentylphenol Chemical compound CCCCCC1=CC=CC(O)=C1CCCCC PTMRDOLOEDPHLB-UHFFFAOYSA-N 0.000 description 2
- RGVIYLQXUDJMCP-UHFFFAOYSA-N 2-tridecylphenol Chemical class CCCCCCCCCCCCCC1=CC=CC=C1O RGVIYLQXUDJMCP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- FLLNLJJKHKZKMB-UHFFFAOYSA-N boron;tetramethylazanium Chemical compound [B].C[N+](C)(C)C FLLNLJJKHKZKMB-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 229940043348 myristyl alcohol Drugs 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- JKTAIYGNOFSMCE-UHFFFAOYSA-N 2,3-di(nonyl)phenol Chemical compound CCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCC JKTAIYGNOFSMCE-UHFFFAOYSA-N 0.000 description 1
- ARHAISXOLPRHQN-UHFFFAOYSA-N 2,3-dihexylphenol Chemical compound CCCCCCC1=CC=CC(O)=C1CCCCCC ARHAISXOLPRHQN-UHFFFAOYSA-N 0.000 description 1
- IXKVYSRDIVLASR-UHFFFAOYSA-N 2,3-dioctylphenol Chemical compound CCCCCCCCC1=CC=CC(O)=C1CCCCCCCC IXKVYSRDIVLASR-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- ABMULKFGWTYIIK-UHFFFAOYSA-N 2-hexylphenol Chemical compound CCCCCCC1=CC=CC=C1O ABMULKFGWTYIIK-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 241001633942 Dais Species 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- NQZKZGHOYUYCHU-UHFFFAOYSA-N boron;tetraethylazanium Chemical compound [B].CC[N+](CC)(CC)CC NQZKZGHOYUYCHU-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- LBIYNOAMNIKVKF-FPLPWBNLSA-N palmitoleyl alcohol Chemical compound CCCCCC\C=C/CCCCCCCCO LBIYNOAMNIKVKF-FPLPWBNLSA-N 0.000 description 1
- LBIYNOAMNIKVKF-UHFFFAOYSA-N palmitoleyl alcohol Natural products CCCCCCC=CCCCCCCCCO LBIYNOAMNIKVKF-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- XAMMKFSEEQGBIC-UHFFFAOYSA-N tetra(propan-2-yl)azanium Chemical compound CC(C)[N+](C(C)C)(C(C)C)C(C)C XAMMKFSEEQGBIC-UHFFFAOYSA-N 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
Definitions
- ABSTRACT Light-colored sulfates of ethoxylated long chain [52] US. Cl ..260/458 aliphatic alcohols and of ethoxylated alkylphenols are [51] Int. Cl ..C07c 141/02. produced by carrying out the Sulfation, using sulfur trioxide dissolved in liquid sulfur dioxide as the sulfatlTeld of Search ..260/458 ing agent, in the presence of small amount of a borohydride such as sodium borohydride.
- alkali metal borohydrides alkaline earth metal borohydrides and quaternary alkyl ammonium borohydrides wherein the alkyl moieties contain, for instance, from one to four carbon atoms, illustrative examples of which are the borohydrides of sodium, potassium, lithium, calcium, barium, magnesium, strontium and lithium-aluminum; tetramethylammonium borohydride, tetraethylammonium borohydride, tetrapropylammonium borohydride, tetraisopropylammonium borohydride, and tetrabutylammonium borohydrides.
- sodium borohydride particularly satisfactory is sodium borohydride.
- the borohydrides are utilized in quite small proportions, generally of the order of 0.01 to 0.2 percent based upon the weight of the sulfated ethoxylated alkylphenol, particularly satisfactory in most cases being about 0.05 to 0.1 percent.
- ethoxylated long chain aliphatic alcohols and ethoxylated alkylphenols which are sulfated in accordance with our invention, in the presence of a color inhibiting amount of a borohydride, are conveniently made by adducting a long chain, C to C aliphatic alcohol or C to C alkylphenol with ethylene oxide.
- the number of moles of ethylene oxide per mole of long chain aliphatic alcohol or alkylphenol is variable within wide limits but, in general, there is at least 1 mole and there may be up to 30 or more moles of ethylene oxide per mole of the long chain aliphatic alcohol or alkylphenol, preferably from 4 to 20 and particularly from 6 to 15 moles of the ethylene oxide per mole of the long chain aliphatic alcohol or alkylphenol.
- the long chain aliphatic alcohols and the alkylphenols the ethylene oxide adducts of which are sulfated in accordance with our present invention include, by way of illustration, aliphatic (including cycloaliphatic) straight chain and branched chain alcohols, such as octyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, oleyl alcohol, palmitoleyl alcohol, stearyl alcohol; oxo alcohols such as the primary monohydric saturated aliphatic alcohols of about 10 to 20 carbon atoms produced by the 0X0 process as, for instance, oxo tridecyl alcohol and oxo hexadecyl alcohol (see US.
- aliphatic (including cycloaliphatic) straight chain and branched chain alcohols such as octyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol,
- alkylphenols including monoand di-alkylphenols in which the alkyl radicals contain from five to 15 carbon atoms, exemplified by amylphenol, diamylphenol, hexylphenol, dihexylphenol, octylphenol, dioctylphenol, and monoand di-nonyl, decyl, undecyl, dodecyl and tridecyl phenols.
- the ethylene oxide may be replaced, in part, by propylene oxide and/or butylene oxide, generally up to about 25 percent by weight of the total of the alkylene oxides present in the molecules of the adducts and, in the making of said adducts, mixtures of the ethylene oxide and propylene and/or butylene oxides can be used, or, alternatively, the adduction of the long chain aliphatic alcohol or alkylphenol may first be effected with the ethylene oxide, followed by the propylene and/or butylene oxide; or the adduction with the propylene oxide and/or butylene oxide may be effected followed by the adduction with the ethylene oxide.
- the straight ethylene oxide adducts are utilized without any propylene oxide or butylene oxide.
- Illustrative examples of the ethoxylated long chain aliphatic alcohols and ethoxylated alkylphenols which can be sulfated in accordance with the present invention to obtain highly desirable light colored sulfated products are the following, the letters E.O. standing for ethylene oxide, the letters P.O. standing for propylene oxide and the number precedingthe same standing for the number of moles thereof adducted or reacted with 1 mole of the stated alcohol or alkyl phenol.
- n-octyl alcohol 4 E.O. iso-octyl alcohol 3 E.O. lauryl alcohol 10 E.O. myristyl alcohol 11 E.O. hexadecyl alcohol 15 E.O. octadecyl alcohol 18 E.O. oleyl alcohol 17 E.O. Oxo tridecyl alcohol 8 E.O. Oxo pentadecyl alcohol 12 E.O. diamylphenol 4 E.O. nonylphenol 8 E.O. dinonylphenol 10 E.O. dodecylphenol 7 E.O. tridecylphenol 9 E.O. lauryl alcohol 4 E.O. & 1 P0. hexadecyl alcohol 10 E.O. 2 PD. nonylphenol 7 E.O. l P.O.
- the sulfation is carried out under vigorous stirring or agitation and under substantially anhydrous conditions, preferably under controlled temperature and utilizing an excess of the sulfating agent. Generally speaking, it is advantageous to carry out the sulfation at temperatures in the range of to -20C.
- the sulfated products can be neutralized in well known ways to form, for instance, the sodium, potassium, am-
- Example 1 Example 1 was repeated, except that only 0.166 grams of NaBI-L (0.1 percent by weight) was added to the alcohol. On addition of $0 -$0 the color of the sulfate ester remained colorless except during the addition of the final 25 percent of $0 -$0 the sulfate turned a light brown. On stripping of S0 the color was a transparent brown. Neutralization gave a Klett color of 475 which after 3 dais reduced to 220.
- Example 1 was repeated except that no NaBl-I, was added. Immediately upon addition of SO,SO the mixture darkened in color. The color before and after stripping of S0 was dark brown. On neutralization, the Klett color of the finished product was 950 and in 2 days had only dropped to 650.
- EXAMPLE 4 The process of example 1 is carried out except that 0.5 mol of a 5 mol ethylene oxide adduct of nonylphenol is used with 425 grams of the sulfating solution. A light colored sulfated ethoxylated nonylphenol is obtained.
- EXAMPLE 5 The process of example 1 is carried out except that 0.75 grams of lithium borohydride is used in place of the sodium borohydride. A light colored sulfated ethoxylated alcohol is obtained.
- EXAMPLE 6 The process of example 2 is carried out except that 0.80 grams of tetramethylammonium borohydride is used in place of the sodium borohydride. A light colored sulfated ethoxylated alcohol is obtained.
- borohydride is sodium borohydride and which is present in proportions of from about 0.01 to 0.2 percent based upon the weight of the sulfated ethoxylated product produced.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Light-colored sulfates of ethoxylated long chain aliphatic alcohols and of ethoxylated alkylphenols are produced by carrying out the sulfation, using sulfur trioxide dissolved in liquid sulfur dioxide as the sulfating agent, in the presence of small amount of a borohydride such as sodium borohydride.
Description
United States Patent Kapur et al. 1 Aug. 29, 197 2 [54] INHIBITION OF COLOR FORMATION [56] References Cited DURING SULFATION OF I UNITED STATES PATENTS ETHOXYLATED ALCOHOLS AND 3 150 161 9/1964 N 260/458 unn 2,928,860 3/1960 Havington ..260/458 Inventors: u J- Kap 325 18th 3,376,333 4/1968 Ernst et a1. ..260/458 Paterson, NJ. 07524; Marvin L. Mausner, 531 Cumberland Ave., imary Ex miner-Leon Zitver Teaneck, NJ, 07666 Assistant Examiner-Leo B. DeCrescente Attorne Wallenstein, S an enber Hattis and 22 Flledz Nov. 14, 1969 swamp; p g g [21] Appl.No.: 877,016
[ ABSTRACT Light-colored sulfates of ethoxylated long chain [52] US. Cl ..260/458 aliphatic alcohols and of ethoxylated alkylphenols are [51] Int. Cl ..C07c 141/02. produced by carrying out the Sulfation, using sulfur trioxide dissolved in liquid sulfur dioxide as the sulfatlTeld of Search ..260/458 ing agent, in the presence of small amount of a borohydride such as sodium borohydride.
3 Claims, No Drawings INHEITION OF COLOR FORMATION DURING SULFATION F ETHOXYLATED ALCOHOLS AND ALKYL PHENOLS Our invention is directed to improvements in the production of sulfated ethoxylated long chain aliphatic alcohols and sulfated ethoxylated alkylphenols specifically in regard to the production of light colored sulfated products, by inhibiting the formation of colored bodies through the inclusion, during the sulfation reaction, of color inhibiting amounts of certain compounds described in detail below.
It is well known that, in the sulfation of ethoxylated long chain aliphatic alcohols and of ethoxylated alkylphenols, colored byproduct bodies are formed which are objectionable since it is a desirable attribute of the finished sulfated products that they possess a light color. Various approaches have, accordingly, been suggested to overcome such objections as, for instance, the carrying out of the sulfation reaction in the presence of such agents as hypophosphorous acid and salts, as is disclosed in British Pat. No. 903,204. Other procedures which have been suggested, in relation to eliminating objectionable color from sulfated products such as sulfated long chain alcohols, have been to effect bleaching of the sulfated long chain alcohols after the completion of the sulfation reaction, as shown, for instance, in U.S. Pat. No. 2,846,457; and by carrying out of the sulfation reaction in the presence of thioamides such as thiourea and thioacetamide, as shown in US. Pat. No. 2,928,860.
We have discovered that, by carrying out the sulfation of the ethoxylated-long chain aliphatic alcohols or the ethoxylated alkylphenols in the presence of a small or minor amount of a borohydride, the resulting sulfated products possess a highly desirable light color. The color bodies the inhibition of formation of which is achieved by the practice of our invention are those which result from carrying out the sulfonations with sulfur trioxide dissolved in liquid sulfur dioxide.
Various borohydrides can be employed in the practice of our invention, namely, alkali metal borohydrides, alkaline earth metal borohydrides and quaternary alkyl ammonium borohydrides wherein the alkyl moieties contain, for instance, from one to four carbon atoms, illustrative examples of which are the borohydrides of sodium, potassium, lithium, calcium, barium, magnesium, strontium and lithium-aluminum; tetramethylammonium borohydride, tetraethylammonium borohydride, tetrapropylammonium borohydride, tetraisopropylammonium borohydride, and tetrabutylammonium borohydrides. Particularly satisfactory is sodium borohydride. The borohydrides are utilized in quite small proportions, generally of the order of 0.01 to 0.2 percent based upon the weight of the sulfated ethoxylated alkylphenol, particularly satisfactory in most cases being about 0.05 to 0.1 percent.
The ethoxylated long chain aliphatic alcohols and ethoxylated alkylphenols which are sulfated in accordance with our invention, in the presence of a color inhibiting amount of a borohydride, are conveniently made by adducting a long chain, C to C aliphatic alcohol or C to C alkylphenol with ethylene oxide. The number of moles of ethylene oxide per mole of long chain aliphatic alcohol or alkylphenol is variable within wide limits but, in general, there is at least 1 mole and there may be up to 30 or more moles of ethylene oxide per mole of the long chain aliphatic alcohol or alkylphenol, preferably from 4 to 20 and particularly from 6 to 15 moles of the ethylene oxide per mole of the long chain aliphatic alcohol or alkylphenol.
The long chain aliphatic alcohols and the alkylphenols the ethylene oxide adducts of which are sulfated in accordance with our present invention include, by way of illustration, aliphatic (including cycloaliphatic) straight chain and branched chain alcohols, such as octyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, oleyl alcohol, palmitoleyl alcohol, stearyl alcohol; oxo alcohols such as the primary monohydric saturated aliphatic alcohols of about 10 to 20 carbon atoms produced by the 0X0 process as, for instance, oxo tridecyl alcohol and oxo hexadecyl alcohol (see US. Pat. No. 2,965,678 for a more detailed disclosure of such oxo alcohols); alkylphenols, including monoand di-alkylphenols in which the alkyl radicals contain from five to 15 carbon atoms, exemplified by amylphenol, diamylphenol, hexylphenol, dihexylphenol, octylphenol, dioctylphenol, and monoand di-nonyl, decyl, undecyl, dodecyl and tridecyl phenols.
The ethylene oxide may be replaced, in part, by propylene oxide and/or butylene oxide, generally up to about 25 percent by weight of the total of the alkylene oxides present in the molecules of the adducts and, in the making of said adducts, mixtures of the ethylene oxide and propylene and/or butylene oxides can be used, or, alternatively, the adduction of the long chain aliphatic alcohol or alkylphenol may first be effected with the ethylene oxide, followed by the propylene and/or butylene oxide; or the adduction with the propylene oxide and/or butylene oxide may be effected followed by the adduction with the ethylene oxide. For best results, however, the straight ethylene oxide adducts are utilized without any propylene oxide or butylene oxide.
Illustrative examples of the ethoxylated long chain aliphatic alcohols and ethoxylated alkylphenols which can be sulfated in accordance with the present invention to obtain highly desirable light colored sulfated products are the following, the letters E.O. standing for ethylene oxide, the letters P.O. standing for propylene oxide and the number precedingthe same standing for the number of moles thereof adducted or reacted with 1 mole of the stated alcohol or alkyl phenol.
n-octyl alcohol 4 E.O. iso-octyl alcohol 3 E.O. lauryl alcohol 10 E.O. myristyl alcohol 11 E.O. hexadecyl alcohol 15 E.O. octadecyl alcohol 18 E.O. oleyl alcohol 17 E.O. Oxo tridecyl alcohol 8 E.O. Oxo pentadecyl alcohol 12 E.O. diamylphenol 4 E.O. nonylphenol 8 E.O. dinonylphenol 10 E.O. dodecylphenol 7 E.O. tridecylphenol 9 E.O. lauryl alcohol 4 E.O. & 1 P0. hexadecyl alcohol 10 E.O. 2 PD. nonylphenol 7 E.O. l P.O.
Other ethoxylated long chain aliphatic alcohols and ethoxylated alkylphenols which can be sulfated in accordance with our invention are disclosed in numerous patents, illustrative of which is the aforementioned British Pat. No. 903,204.
No novelty is claimed in the sulfation procedure per se which is utilized in the production of the sulfated ethoxylated long chain aliphatic alcohols or ethoxylated alkylphenols. Sulfur trioxide dissolved in sulfur dioxide is a well known sulfating system and is disclosed in numerous patents and other printed publications, illustrative of said US. Patents being Nos. 2,928,867 and 2,831,020. In those cases in which the ethoxylated long chain aliphatic alcohol or ethoxylated alkylphenol is a solid at room temperature, it should be heated to above its melting point before the sulfating agent is added thereto. The sulfation is carried out under vigorous stirring or agitation and under substantially anhydrous conditions, preferably under controlled temperature and utilizing an excess of the sulfating agent. Generally speaking, it is advantageous to carry out the sulfation at temperatures in the range of to -20C. After completion of the sulfation reaction, the sulfated products can be neutralized in well known ways to form, for instance, the sodium, potassium, am-
monium, calcium, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethylamine, isopropylamine, cyclohexylamine,
dicyclohexylamine or other amine or other salts.
We are aware of the fact that borohydrides have heretofore been suggested for use in certain reactions to produce improved color in the resulting reaction products, as, for instance, in the purification of crude phthalic anhydride (US. Pat. No. 3,328,429). This type of chemical reaction bears no relationship to the considerations which apply to inhibiting objectionable color formation in the sulfation of ethoxylated long chain aliphatic alcohols and ethoxylated alkylphenols.
The following examples are illustrative of the practice of our invention and are not to be construed as in any way limitative thereof since various changes can be made in the light of the guiding principles and teachings disclosed herein.
EXAMPLE 1 To 166 grams of a 3mol ethylene oxide adduct of a mixture of C and C linear aliphatic alcohols was added 0.83 grams of NaBH Then 166 grams of liquid S0 at 5C was added. The mixture was stirred for 1 hour until all the alcohol dissolved in the S0 Next was added a mixture of 43 grams S0 and 380 grams S0 Throughout the addition of the SO SO the color of the sulfate ester formed remained colorless. After stripping of S0 the sulfate ester was a light yellow color. On neutralization the Klett color of the finished product was 123.
EXAMPLE 2 Example 1 was repeated, except that only 0.166 grams of NaBI-L (0.1 percent by weight) was added to the alcohol. On addition of $0 -$0 the color of the sulfate ester remained colorless except during the addition of the final 25 percent of $0 -$0 the sulfate turned a light brown. On stripping of S0 the color was a transparent brown. Neutralization gave a Klett color of 475 which after 3 dais reduced to 220.
E AMPLE 3 Example 1 was repeated except that no NaBl-I, was added. Immediately upon addition of SO,SO the mixture darkened in color. The color before and after stripping of S0 was dark brown. On neutralization, the Klett color of the finished product was 950 and in 2 days had only dropped to 650.
EXAMPLE 4 The process of example 1 is carried out except that 0.5 mol of a 5 mol ethylene oxide adduct of nonylphenol is used with 425 grams of the sulfating solution. A light colored sulfated ethoxylated nonylphenol is obtained.
EXAMPLE 5 The process of example 1 is carried out except that 0.75 grams of lithium borohydride is used in place of the sodium borohydride. A light colored sulfated ethoxylated alcohol is obtained.
EXAMPLE 6 The process of example 2 is carried out except that 0.80 grams of tetramethylammonium borohydride is used in place of the sodium borohydride. A light colored sulfated ethoxylated alcohol is obtained.
We claim:
1. In that method of producing sulfated ethoxylated C to C aliphatic alcohols and sulfated ethoxylated C to C monoand dialkyl phenols, wherein the sulfation is effected by means of sulfur trioxide dissolved in liquid sulfur dioxide, the improvement which comprises carrying out said sulfation reaction in the presence of a color inhibiting amount of a borohydride selected from the group consisting of alkali metal borohydrides, alkaline earth metal borohydrides and quaternary alkyl ammonium borohydrides, wherein the alkyl moieties contain from one to four carbon atoms.
2. The method of claim 1 in which the borohydride is sodium borohydride.
3. The method of claim 1 in which the borohydride is sodium borohydride and which is present in proportions of from about 0.01 to 0.2 percent based upon the weight of the sulfated ethoxylated product produced.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,687 999 Dated Ag gugt Z2 1Q Z2 Inventor(s) Brij L. Kapur, et. a1.
It is certified that error appears in the above-identified patent. and that said Letters Patent are hereby corrected as shown below:
On the cover sheet, insert-"r?- [731- Assignors To Witco Chemical Corporation, New York, N.Y. a Corporation of Delaware.
Signed and sealed this 20th day of March 1973.
(SEAL) 1s Attest:
EDWARD M. FLETCHER, JR. ROBERT coT'rscHAfiK Attesting Officer Commissioner of Patents FORM PO-1050 (10-69) USCOMM-DC 6O376-F69 U.5. GOVERNMENT PRINTING OFFICE: 1969 0-366-33L
Claims (2)
- 2. The method of claim 1 in which the borohydride is sodium borohydride.
- 3. The method of claim 1 in which the borohydride is sodium borohydride and which is present in proportions of from about 0.01 to 0.2 percent based upon the weight of the sulfated ethoxylated product produced.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US87701669A | 1969-11-14 | 1969-11-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3687999A true US3687999A (en) | 1972-08-29 |
Family
ID=25369081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US877016A Expired - Lifetime US3687999A (en) | 1969-11-14 | 1969-11-14 | Inhibition of color formation during sulfation of ethoxylated alcohols and alkyl phenols |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3687999A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4337369A (en) * | 1981-01-30 | 1982-06-29 | Texaco Inc. | Method of decolorizing mixtures of t-butyl alkylphenols |
| US4356330A (en) * | 1981-07-20 | 1982-10-26 | Texaco Inc. | Method of decolorizing mixtures of T-butyl alkylphenols with N-(2-hydroxyethyl)oxazolidine |
| US4959468A (en) * | 1987-06-12 | 1990-09-25 | Henkel Kommanditgesellschaft Auf Aktien | Color stabilization method for glycoside products |
| US6255275B1 (en) * | 1996-12-06 | 2001-07-03 | Nippon Shokubai Co., Ltd. | Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition |
| US6346509B1 (en) | 1997-12-05 | 2002-02-12 | Nippon Shokubai Co., Ltd. | Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2928860A (en) * | 1956-05-23 | 1960-03-15 | Eastman Kodak Co | Inhibition of color formation during sulfation |
| US3150161A (en) * | 1959-12-01 | 1964-09-22 | Gen Aniline & Film Corp | Process for preparating organo-sulfates |
| US3376333A (en) * | 1964-11-16 | 1968-04-02 | Textilana Corp | Sulfuric acid esters of linear secondary alcohol ethoxylates and salts thereof and method of producing same |
-
1969
- 1969-11-14 US US877016A patent/US3687999A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2928860A (en) * | 1956-05-23 | 1960-03-15 | Eastman Kodak Co | Inhibition of color formation during sulfation |
| US3150161A (en) * | 1959-12-01 | 1964-09-22 | Gen Aniline & Film Corp | Process for preparating organo-sulfates |
| US3376333A (en) * | 1964-11-16 | 1968-04-02 | Textilana Corp | Sulfuric acid esters of linear secondary alcohol ethoxylates and salts thereof and method of producing same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4337369A (en) * | 1981-01-30 | 1982-06-29 | Texaco Inc. | Method of decolorizing mixtures of t-butyl alkylphenols |
| US4356330A (en) * | 1981-07-20 | 1982-10-26 | Texaco Inc. | Method of decolorizing mixtures of T-butyl alkylphenols with N-(2-hydroxyethyl)oxazolidine |
| US4959468A (en) * | 1987-06-12 | 1990-09-25 | Henkel Kommanditgesellschaft Auf Aktien | Color stabilization method for glycoside products |
| US6255275B1 (en) * | 1996-12-06 | 2001-07-03 | Nippon Shokubai Co., Ltd. | Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition |
| US6346509B1 (en) | 1997-12-05 | 2002-02-12 | Nippon Shokubai Co., Ltd. | Higher secondary alcohol alkoxylate compound composition, method for production thereof, and detergent and emulsifier using the composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2230073A1 (en) | Alpha-substituted beta-sulfosuccinic acids and their use as builders in detergents | |
| GB1064169A (en) | Surface active sulpho compounds | |
| US4188311A (en) | Detergent compositions containing ether sulfates | |
| US3687999A (en) | Inhibition of color formation during sulfation of ethoxylated alcohols and alkyl phenols | |
| DE1568754A1 (en) | Process for the production of capillary-active sulfates | |
| KR970011314B1 (en) | Use of mixtures containing (a) alkali, ammonium and/or amine salts of sulfonated unsaturated fatty acids, and(b) alkoxylated alkyl alcohol, as wetting agents | |
| US3029264A (en) | Preparation of a mixture of fattyacyl-oxyalkane sulphonates | |
| GB1064125A (en) | 1,2,5-oxathiazine derivatives | |
| US3376333A (en) | Sulfuric acid esters of linear secondary alcohol ethoxylates and salts thereof and method of producing same | |
| WO1991018871A1 (en) | Process for producing glycerin ether sulphates | |
| Kapur et al. | Summary of the technology for the manufacture of higher alpha‐sulfo fatty acid esters | |
| GB1012944A (en) | ª‰-hydroxy-alkane-ª‡-sulphonic anhydrides and secondary products thereof, and a process for their manufacture | |
| US3150161A (en) | Process for preparating organo-sulfates | |
| US2868812A (en) | Manufacture of fatty acid monoesters of glycerol monosulfuric acid and salts thereof | |
| US3492239A (en) | Light-colored sulfonation products | |
| GB1459830A (en) | Process for the preparation of thiocarbamic acid o-esters | |
| US2427577A (en) | Production of ether sulphonates | |
| US4169076A (en) | Process for producing clear aqueous solution of magnesium salt of anionic surface active agent | |
| US2204210A (en) | Preparation of secondary alkyl sulphonic acids | |
| US2603654A (en) | Polyethylene glycol esters of alpha-(alkylmercapto) propionic acid | |
| US2346568A (en) | Process for the production of sulphonyl bromide derivatives | |
| US2099214A (en) | Process fob forming the sulphuric | |
| GB1338935A (en) | Sulphonation process | |
| US2427576A (en) | Ether sulphonates and their production | |
| US4269786A (en) | Alkyl glyceryl ether sulfate salts and process for their preparation |