US3697573A - Linear alkylphenol sulfate-sulfonate phosphate-free detergent actives - Google Patents

Linear alkylphenol sulfate-sulfonate phosphate-free detergent actives Download PDF

Info

Publication number: US3697573A
Authority: US; United States
Prior art keywords: sulfate; detergent; sulfonate; phosphate; linear
Prior art date: 1970-05-05
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

Application number

US34885A

Other languages

English (en)

Inventor

Mitchell Danzik

Ralph House

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Chevron USA Inc

Original Assignee

Chevron Research and Technology Co

Priority date (The priority date 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 date listed.)

1970-05-05

Filing date

1970-05-05

Publication date

1972-10-10

1970-05-05 Application filed by Chevron Research and Technology Co filed Critical Chevron Research and Technology Co

1972-10-10 Application granted granted Critical

1972-10-10 Publication of US3697573A publication Critical patent/US3697573A/en

1989-10-10 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

239000003599 detergent Substances 0.000 title abstract description 48
125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
150000001875 compounds Chemical class 0.000 claims description 23
-1 alkali metal cation Chemical group 0.000 claims description 14
229910052783 alkali metal Inorganic materials 0.000 claims description 7
239000000463 material Substances 0.000 abstract description 20
229910019142 PO4 Inorganic materials 0.000 abstract description 19
239000010452 phosphate Substances 0.000 abstract description 16
125000000217 alkyl group Chemical group 0.000 abstract description 15
NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 15
239000011149 active material Substances 0.000 abstract description 10
238000005406 washing Methods 0.000 abstract description 7
239000000203 mixture Substances 0.000 description 31
239000000243 solution Substances 0.000 description 19
235000021317 phosphate Nutrition 0.000 description 17
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
229910001868 water Inorganic materials 0.000 description 17
238000006243 chemical reaction Methods 0.000 description 16
239000002689 soil Substances 0.000 description 16
238000009472 formulation Methods 0.000 description 15
238000000034 method Methods 0.000 description 14
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 12
239000004744 fabric Substances 0.000 description 8
239000007788 liquid Substances 0.000 description 7
PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
229910052938 sodium sulfate Inorganic materials 0.000 description 6
235000011152 sodium sulphate Nutrition 0.000 description 6
125000003118 aryl group Chemical group 0.000 description 5
230000007935 neutral effect Effects 0.000 description 5
239000000047 product Substances 0.000 description 5
239000002904 solvent Substances 0.000 description 5
WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 4
150000001340 alkali metals Chemical class 0.000 description 4
239000003795 chemical substances by application Substances 0.000 description 4
238000001816 cooling Methods 0.000 description 4
238000002360 preparation method Methods 0.000 description 4
239000007787 solid Substances 0.000 description 4
239000012086 standard solution Substances 0.000 description 4
239000004094 surface-active agent Substances 0.000 description 4
ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
229910052784 alkaline earth metal Inorganic materials 0.000 description 3
150000001342 alkaline earth metals Chemical class 0.000 description 3
150000001336 alkenes Chemical class 0.000 description 3
150000001768 cations Chemical class 0.000 description 3
230000001747 exhibiting effect Effects 0.000 description 3
239000004615 ingredient Substances 0.000 description 3
229910052920 inorganic sulfate Inorganic materials 0.000 description 3
239000003960 organic solvent Substances 0.000 description 3
150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
238000006277 sulfonation reaction Methods 0.000 description 3
238000012360 testing method Methods 0.000 description 3
239000004711 α-olefin Substances 0.000 description 3
SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
230000029936 alkylation Effects 0.000 description 2
238000005804 alkylation reaction Methods 0.000 description 2
VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
238000004458 analytical method Methods 0.000 description 2
239000007864 aqueous solution Substances 0.000 description 2
125000001204 arachidyl 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])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 2
229910052799 carbon Inorganic materials 0.000 description 2
239000003054 catalyst Substances 0.000 description 2
239000007795 chemical reaction product Substances 0.000 description 2
150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
229920001577 copolymer Polymers 0.000 description 2
230000000875 corresponding effect Effects 0.000 description 2
238000004821 distillation Methods 0.000 description 2
238000001035 drying Methods 0.000 description 2
229960001484 edetic acid Drugs 0.000 description 2
238000001704 evaporation Methods 0.000 description 2
230000008020 evaporation Effects 0.000 description 2
239000008233 hard water Substances 0.000 description 2
229910017053 inorganic salt Inorganic materials 0.000 description 2
238000006386 neutralization reaction Methods 0.000 description 2
230000003472 neutralizing effect Effects 0.000 description 2
MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
125000001196 nonadecyl 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])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 2
150000002892 organic cations Chemical class 0.000 description 2
239000002002 slurry Substances 0.000 description 2
239000012085 test solution Substances 0.000 description 2
JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
101100264195 Caenorhabditis elegans app-1 gene Proteins 0.000 description 1
229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
229920000742 Cotton Polymers 0.000 description 1
241000195493 Cryptophyta Species 0.000 description 1
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
239000005977 Ethylene Substances 0.000 description 1
238000005727 Friedel-Crafts reaction Methods 0.000 description 1
JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
239000004115 Sodium Silicate Substances 0.000 description 1
208000027418 Wounds and injury Diseases 0.000 description 1
CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
239000002253 acid Substances 0.000 description 1
239000003377 acid catalyst Substances 0.000 description 1
238000005903 acid hydrolysis reaction Methods 0.000 description 1
239000000654 additive Substances 0.000 description 1
230000002411 adverse Effects 0.000 description 1
150000001298 alcohols Chemical class 0.000 description 1
230000005791 algae growth Effects 0.000 description 1
150000008044 alkali metal hydroxides Chemical class 0.000 description 1
125000003342 alkenyl group Chemical group 0.000 description 1
150000004996 alkyl benzenes Chemical class 0.000 description 1
230000003466 anti-cipated effect Effects 0.000 description 1
239000002585 base Substances 0.000 description 1
125000002511 behenyl 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])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])[H] 0.000 description 1
229940077388 benzenesulfonate Drugs 0.000 description 1
238000004061 bleaching Methods 0.000 description 1
239000007844 bleaching agent Substances 0.000 description 1
150000001642 boronic acid derivatives Chemical class 0.000 description 1
239000004566 building material Substances 0.000 description 1
STRQSIGXGKBISH-UHFFFAOYSA-N butane-1,1-diol;sulfo hydrogen sulfate Chemical class CCCC(O)O.OS(=O)(=O)OS(O)(=O)=O STRQSIGXGKBISH-UHFFFAOYSA-N 0.000 description 1
229910000019 calcium carbonate Inorganic materials 0.000 description 1
150000001721 carbon Chemical group 0.000 description 1
150000004649 carbonic acid derivatives Chemical class 0.000 description 1
239000001768 carboxy methyl cellulose Substances 0.000 description 1
235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
239000008112 carboxymethyl-cellulose Substances 0.000 description 1
238000003442 catalytic alkylation reaction Methods 0.000 description 1
230000003197 catalytic effect Effects 0.000 description 1
XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
239000004927 clay Substances 0.000 description 1
239000008139 complexing agent Substances 0.000 description 1
238000007796 conventional method Methods 0.000 description 1
230000002596 correlated effect Effects 0.000 description 1
230000006378 damage Effects 0.000 description 1
230000002939 deleterious effect Effects 0.000 description 1
238000011033 desalting Methods 0.000 description 1
238000002036 drum drying Methods 0.000 description 1
230000000694 effects Effects 0.000 description 1
230000001815 facial effect Effects 0.000 description 1
238000001914 filtration Methods 0.000 description 1
239000006260 foam Substances 0.000 description 1
230000012010 growth Effects 0.000 description 1
230000026030 halogenation Effects 0.000 description 1
238000005658 halogenation reaction Methods 0.000 description 1
235000019589 hardness Nutrition 0.000 description 1
238000010438 heat treatment Methods 0.000 description 1
125000000755 henicosyl 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])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
229910052739 hydrogen Inorganic materials 0.000 description 1
239000001257 hydrogen Substances 0.000 description 1
125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
239000012442 inert solvent Substances 0.000 description 1
238000002329 infrared spectrum Methods 0.000 description 1
208000014674 injury Diseases 0.000 description 1
150000007529 inorganic bases Chemical class 0.000 description 1
229910052806 inorganic carbonate Inorganic materials 0.000 description 1
229910010272 inorganic material Inorganic materials 0.000 description 1
239000011147 inorganic material Substances 0.000 description 1
229910052816 inorganic phosphate Inorganic materials 0.000 description 1
125000002463 lignoceryl 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])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])C([H])([H])[H] 0.000 description 1
235000014666 liquid concentrate Nutrition 0.000 description 1
239000006193 liquid solution Substances 0.000 description 1
ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
239000001095 magnesium carbonate Substances 0.000 description 1
229910000021 magnesium carbonate Inorganic materials 0.000 description 1
238000003760 magnetic stirring Methods 0.000 description 1
238000012423 maintenance Methods 0.000 description 1
VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
239000011976 maleic acid Substances 0.000 description 1
125000002960 margaryl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
229910000000 metal hydroxide Inorganic materials 0.000 description 1
229910044991 metal oxide Inorganic materials 0.000 description 1
150000004706 metal oxides Chemical class 0.000 description 1
WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
230000004048 modification Effects 0.000 description 1
238000012986 modification Methods 0.000 description 1
229910052757 nitrogen Inorganic materials 0.000 description 1
150000007530 organic bases Chemical class 0.000 description 1
125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
238000005191 phase separation Methods 0.000 description 1
239000000843 powder Substances 0.000 description 1
239000002243 precursor Substances 0.000 description 1
238000012545 processing Methods 0.000 description 1
150000003254 radicals Chemical class 0.000 description 1
239000000376 reactant Substances 0.000 description 1
239000011541 reaction mixture Substances 0.000 description 1
238000011160 research Methods 0.000 description 1
150000003839 salts Chemical class 0.000 description 1
210000002374 sebum Anatomy 0.000 description 1
239000003352 sequestering agent Substances 0.000 description 1
239000000344 soap Substances 0.000 description 1
239000011734 sodium Substances 0.000 description 1
229910000029 sodium carbonate Inorganic materials 0.000 description 1
229910001415 sodium ion Inorganic materials 0.000 description 1
159000000000 sodium salts Chemical class 0.000 description 1
NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
229910052911 sodium silicate Inorganic materials 0.000 description 1
235000019832 sodium triphosphate Nutrition 0.000 description 1
ZAWGLAXBGYSUHN-UHFFFAOYSA-M sodium;2-[bis(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CC([O-])=O ZAWGLAXBGYSUHN-UHFFFAOYSA-M 0.000 description 1
239000012265 solid product Substances 0.000 description 1
238000001179 sorption measurement Methods 0.000 description 1
125000004079 stearyl 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])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
238000003756 stirring Methods 0.000 description 1
230000019635 sulfation Effects 0.000 description 1
238000005670 sulfation reaction Methods 0.000 description 1
150000003871 sulfonates Chemical class 0.000 description 1
125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
239000004753 textile Substances 0.000 description 1
238000004448 titration Methods 0.000 description 1
VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
125000002469 tricosyl 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])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])[H] 0.000 description 1
238000003911 water pollution Methods 0.000 description 1
238000005303 weighing Methods 0.000 description 1
239000011592 zinc chloride Substances 0.000 description 1
235000005074 zinc chloride Nutrition 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof

Definitions

This invention is concerned with novel linear alkylphenol sulfate-sulfonate compounds which are effective in detergent applications as detergent actives.
liquid heavy duty detergent compositions achieves many desirable results. They are easy to package and measure, and their use opens the possibility of automatic dispensing in washing machines.
it has been impracticable to formulate heavy duty detergents in liquid form because of the insufficient solubility of the inorganic ingredients (phosphate builders, etc.) required for heavy duty applications and the high cost of organic substitutes for such inorganic ingredients. It is therefore highly desirable to provide detergent active materials having good water solubility and which, because of their excellent detergency without builders, can be formulated into effective, reasonably priced, heavy duty liquid detergent formulations.
Heavy duty detergent materials comprise alkylphenol sulfate-sulfonates of the formula R s 03X in which R is a substantially linear alkyl group of from about 16 to 24 carbon atoms and X is H or a water soluble salt-forming cation.
the compounds of this invention do not require the presence of a builder to achieve good heavy duty detergency, and while they are effective over a broad pH range, reach their maximum effectiveness at a pH near neutral in detergent solutions. Thus washing at a pH of 6.5 to 8.0, preferably 6.5 to 7.5, will give maximum soil removal while securing the previously mentioned advantages which inhere in the use of neutral washing solutions. Further, the compounds may be easily compounded into effective liquid heavy duty formulations because of the substantial solubility of the compounds in water and because of the lack of need for large adjunctive portions of inorganic materials such as builders.
the salt-forming cation X may be any of numerous materials such as alkali metal, alkaline earth metal, ammonium, or various organic cations.
suitable organic cations include nitrogen-containing organic cations such as diethanolammonium and triethanolammonium cations.
the alkali metal cations are preferred, and sodium ions are particularly preferred.
alkyl groups represented by R are, as previously noted, substantially linear, although the presence of a random methyl radical upon the linear chain, for example, may not adversely affect the performance of the compounds.
Alkyl radicals representative of R include hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, and tetracosyl.
the preferred compounds will have as alkyl substituents octadecyl, nonadecyl, and eicosyl groups.
alkylphenols which are suitable for the preparation of the compounds of this invention are prepared by conventional techniques. Such techniques include thermal and catalytic alkylation of phenol with olefms, al-
Catalytic methods include the use of Friedel-Crafts catalysts such as aluminum chloride, zinc chloride, etc., and various acid catalysts and clay catalysts.
the alkyl groups are generally derived from alcohols, olefins, or haloparaffins.
the position of the attachmentrof the aromatic nucleus on the alkyl chain may beat any point.
alpha olefins the predominant point of attachment of the alkylation product will be end group attachment-thatis, either at the l or 2 but principally at the 2 position of the chain.
an isomerized mixture of olefins or olefins derived from haloparaffms which have, in turn, been produced by halogenation of paraffins, the position of the double bond will be generally completely random on the chain, and thus the corresponding aromatic nucleus attachment will be random.
the sulfonation and sulfation of the alkylphenols to produce the compounds of this invention is accomplished by reacting the alkylphenol with a sulfonating agent capable of (1) converting the aromatic hydroxyl radical to a sulfate and (2).forming a ring-substituted SO H under conditions such that the reaction product contains both an -OSO H and an SO H radical attached to the aromatic nucleus.
a sulfonating agent satisfying these reaction prerequisites is sulfur trioxide.
the sulfur trioxide may be employed in mixtures with an appropriate liquid solvent such as a chlorinated hydrocarbon or liquid 80,. Complexed 80;, may also be used to effect the reaction.
Typical complexing agents are dioxane and dimethylaniline, triethylamine, etc.
the alkylphenol sulfate-sulfonate compounds .of this invention .thus aresuitably prepared by the reaction of an alkyl-phenol with sulfur trioxide.
the reaction is carriedout in an anhydrous inert solvent such as the chlorinated hydrocarbons, e.g., dichloroethane.
the quantity of sulfur trioxide to be used should equal or exceed 2 moles per mole of alkylphenol for 100% conversion of the. latter.
Mole ratios of S0,, to alkylphenol I ashigh as 10:1 may be employed, but preferably the ratio is in the range of 3:1 to 5:1.
reaction temperatures are generally in the range of -l to 10 C, preferably about to 0 C.
Alkylphenol, dissolved in the solvent is cooledto the reaction temperature and then 80;, dissolved in the same solvent is added.
the reaction is exthermic, and cooling meansmust be employed to keep the temperature within the desired range.
the rate of addition of S0 is such thatthe cooling means can hold this temperature.
the time required for reaction varies as to efficiency of cooling, size of reaction mass, etc., but generally the addition will be complete within to 120 minutes for small sized batches. Continuous procedure ispreferred for large batches. In continuous processing, the reactants, dissolved in an appropriate solvent and cooled to reaction temperature, are charged to a cooled tubular reactor, wherein the average residence time is only a few minutes or less.
the .reaction product may be neutralized with a water-soluble, salt-formingcationic neutralizing agent, usually a metal oxide or hydroxide, and more preferably an alkaline earth metal or alkali metal hyroxide.
a water-soluble, salt-formingcationic neutralizing agent usually a metal oxide or hydroxide, and more preferably an alkaline earth metal or alkali metal hyroxide.
the alkali metal hydroxides are preferred, and sodium hydroxide is most preferredsln addition to the inorganic bases described above, the neutralizing agent may be any of various organic bases. Sufficient base is added to neutralize both acid sites, that is about two moles. The final of the neutralized mixture should be about 7, butpl-l values within the range of 6 to 8 are satisfactory.
the inert organic solvent is removed for reuse. Thismay be done by phase separation, or preferably by distillation.
the organic solvent free material comprises an aqueous solution of the organic surface active materials and any inorganic salt, such as sodium sulfate.
the neutralized product which will contain a substantial quantity of waterand from 1 to 4 parts of a normally inorganic sulfate from the neutralization of excess SO, (e.g., Na,SO may be used, as is, in combination with conventional detergent additives. to formulate liquid heavy duty detergents.
SO normally inorganic sulfate from the neutralization of excess SO, (e.g., Na,SO may be used, as is, in combination with conventional detergent additives. to formulate liquid heavy duty detergents.
water may be removed in any quantity to complete dryness by. conventional concentration techniques such as evaporation, distillation, drum drying, etc., to yield a concentrated solution,-a slurry, or a dry particulate solid which .may then be blended to form a heavy
the solid product isolated as described above may be desalted by the usual procedures as used in the alkyl benzene sulfonate art.
thesolid material is mixed with about a /30 alcohol/water solution.
the insoluble inorganic sulfate is removed by filtration, and the organic surfactant may be used as such or isolated by evaporation of the solvent.
the liquid concentrates and slurries may be treated in similar fashion with allowance made for the quantity of water already present.
Example 3 Drying of Aqueous Alkylphenol Sulfate- Sulfonate Solution
An aqueous solution of octadecylphenol sulfate-sulfonate prepared as described in Example 1 was neutralized with sufficient sodium hydroxide to give a pH of 7.
the dichloroethane was removed by heating under vacuum at about 25-30 C. The temperature was then raised, and all of the water was removed to leave a particulate solid mass weighing 5.15 g. Analysis showed that this material contained 31 percent octadecylphenol sulfate-sulfonate, a small amount of water, and the remainder sodium sulfate.
the above isolated solid was a free-flowing powder.
the compounds of this invention are useful as heavy duty detergent actives.
heavy duty detergent formulations useful for removing soil from textiles have comprised an organic surfactant (detergent) and an inorganic phosphate builder; the phosphate being present by weight, in an amount of from one to four times that of the detergent.
the compounds of the present invention are excellent soil removers without the aid of any phosphate builder. That is, the compounds of this invention satisfy all need for both organic surfactant and builder in the final heavy duty detergent formulation.
One way that this may be accomplished is by preparing a mixture of the sulfate-sub fonate materials of the instant invention and an inert material, e.g. water, sodium sulfate, sodium carbonate, etc.
Such mixtures may contain any amount of sulfatesulfonate in excess of about 10 percent, preferably 15 percent or more.
One useful composition comprises from to 50 percent sulfate-sulfonate and the remainder, sodium sulfate.
Many other combinations make useful formulations and may be either liquid solutions or particulate solids.
the sulfate-sulfonate compounds will be used in wash water at concentrations of about 0.01 percent to about 0.10 percent. This is within the same range of concentrations as are employed with the present day commercial detergents.
the soil removal properties of the present compounds are essentially equivalent to the soil removal properties of an equal amount of the current commercial surfactant combined with at least an equal amount of phosphate.
Detergency of the compounds of the present invention is measured by their ability to remove natural sebum soil from cotton cloth.
small swatches of cloth, soiled by rubbing over face and neck are washed with test solutions of detergents in a miniature laboratory washer.
the quantity of soil removed by this washing procedure is determined by measuring the reflectances of the new cloth, the soiled cloth, and the washed cloth, the results being expressed as per cent soil removal. Because of variations in degree and type of soiling, in water and in cloth, and other unknown variables, the absolute value of per cent soil removal is not an accurate measure of detergent effectiveness and cannot be used to compare various detergents. Therefore, the art has developed the method of using relative detergency ratings for comparing detergent effectiveness.
the relative detergency ratings are obtained by comparing and correlating the per cent soil removal results from solutions containing the detergents being tested with the results from two defined standard solutions.
the two standard solutions are selected to represent a detergent system exhibiting relatively high detersive characteristics and a system exhibiting relatively low detersive characteristics.
the systems are assigned detergency ratings of 6.3 and 2.2, respectively.
the two standard solutions are identical in formulation but are employed at different hardnesses.
Control B The standard exhibiting high detersive characteristics is prepared by dissolving the above formulation (1.0 g.) in 1 liter of 50 ppm hard water (calculated as two-thirds calcium carbonate and one-third magnesium carbonate).
the low detersive standard (Control A) contained the formulation (1.0 g.) dissolved in one liter of ppm water (same basis).
RDRs Relative detergency ratings
% Telt Cuntrol A Detergency results obtained on a variety of the subject compounds are given in the following table. Each value shown is the average of at least fourtests- For comparison, the detergency rating is given for a linear alkylbenzene sulfonate (LAS) (having from 11 to 14 carbon straight chain alkyl groups) both with and without phosphate builder.
LAS linear alkylbenzene sulfonate
Each formulation tested comprised 25 weight percent'of the test material along with 1 percent carboxymethylcellulose, 7 percent sodium silicate, 8 percent water, and 59 percent sodium sulfate.
the LAS comparison formulations were prepared in the same way except that. in Test 2 40 percent of the sodium sulfate was replaced by an equal amount of sodium tripolyphosphate and only 20 percent of LAS was used.
the formulations were tested at several concentrations in water ranging from 0.1 to 0.2 weight percent. These concentrationswere chosen in order to bracket the 0.15 percent concentration typical of household use.
the test results were obtained at a pH of 7, except for the two LASexamples, which were run at a pH of 9 (without phosphate) and 10(with phosphate).
compositions of this invention include those materials which com-.
alkylphenol sulfate-sulfonates may be employed in combination with other detergent active materials.
dianionic' materials examples of which include linear alkyl and alkenyl disulfates and disulfonates.
a particularly useful class of materials for use in detergent active combinations is that of linear 2-alkenyl or linear 2-alkyl l ,4-
butane diol disulfates in which the alkenyl or alkyl groups contain from 15 to 20 carbon atoms.
Another particularly effective class of materials are the alkylphenol disulfonates described in our previously mentioned copending patent application.
detergent active materials of this invention may be formulated with additional compatible ingredients being optionally incorporated to enhance the detergent properties.
additional compatible ingredients may include but are not limited to anticorrosion, antiredeposition, bleaching and sequestering agents, and certain organic and inorganic alkali metal and alkaline earth metalsalts such as inorganic sulfates, carbonates, or borates.
nonphosphate builders may be included in the composition. Examples of these builders include the sodium salts of nitrilotriacetic acid, ethylene diamine tetraacetic acid, and ethylene-maleic acid copolymers, etc. Also small quantities of phosphate builders may be included in the compositions, although, of course, they are not necessary for effective detergency.
R is a linear alkyl radical of 16 to 24 carbon atoms and X is hydrogen'or a cation selected from the group consisting of alkali metal, alkaline earth metal, ammonium, diethanolammonium and triethanolammonium cations.
R is an alkyl radical of 18 to 20 carbon atoms.

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Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Life Sciences & Earth Sciences (AREA)
Engineering & Computer Science (AREA)
Chemical Kinetics & Catalysis (AREA)
Oil, Petroleum & Natural Gas (AREA)
Wood Science & Technology (AREA)
Detergent Compositions (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

US34885A 1970-05-05 1970-05-05 Linear alkylphenol sulfate-sulfonate phosphate-free detergent actives Expired - Lifetime US3697573A (en)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
US3488570A	1970-05-05	1970-05-05
US00130449A US3836484A (en)	1970-05-05	1971-04-01	Phosphate-free detergent concentrates containing sulfated and sulfonated linear alkylphenols

Publications (1)

Publication Number	Publication Date
US3697573A true US3697573A (en)	1972-10-10

Family

ID=26711524

Family Applications (2)

Application Number	Title	Priority Date	Filing Date
US34885A Expired - Lifetime US3697573A (en)	1970-05-05	1970-05-05	Linear alkylphenol sulfate-sulfonate phosphate-free detergent actives
US00130449A Expired - Lifetime US3836484A (en)	1970-05-05	1971-04-01	Phosphate-free detergent concentrates containing sulfated and sulfonated linear alkylphenols

Family Applications After (1)

Application Number	Title	Priority Date	Filing Date
US00130449A Expired - Lifetime US3836484A (en)	1970-05-05	1971-04-01	Phosphate-free detergent concentrates containing sulfated and sulfonated linear alkylphenols

Country Status (8)

Country	Link
US (2)	US3697573A (fr)
BE (1)	BE766707A (fr)
CA (1)	CA946407A (fr)
DE (1)	DE2120494A1 (fr)
FR (1)	FR2090856A5 (fr)
GB (1)	GB1321001A (fr)
NL (1)	NL7106160A (fr)
SE (1)	SE360107B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3919429A (en) *	1972-01-18	1975-11-11	Hoechst Ag	Dispersing and wetting agents for use in organic biocides
JPS511501A (ja) *	1974-06-26	1976-01-08	Lion Fat Oil Co Ltd	Ryujosenzainoseizoho
US5928948A (en) *	1997-03-10	1999-07-27	Steris Corporation	Method for the assessment and validation of cleaning processes
US20100240752A1 (en) *	2007-11-07	2010-09-23	Reckitt Benckiser Inc.	Aqueous Acidic Hard Surface Cleaning and Disinfecting Compositions
CN101585786B (zh) *	2009-07-09	2012-05-23	江南大学	一种用so3-空气混合物经膜式磺化器磺化烷基酚生产烷基酚磺酸及其盐的方法
CN103265462A (zh) *	2013-06-14	2013-08-28	杨锌荣	一种烷氧基烷基苯磺酸盐及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4269789A (en) *	1979-12-31	1981-05-26	Phillips Petroleum Company	Petroleum sulfonation
US4360515A (en) *	1980-07-25	1982-11-23	Johnson & Johnson Products, Inc.	Sulfonated alkoxynaphthalenes as dental plaque barriers
US4360514A (en) *	1980-07-25	1982-11-23	Johnson & Johnson Products Inc.	Sulfonated alkylnaphthalenes as dental plaque barriers
GB2232665A (en) *	1989-05-31	1990-12-19	Exxon Chemical Patents Inc	Sulphonic acid derivatives and their use as emulsifiers

1970
- 1970-05-05 US US34885A patent/US3697573A/en not_active Expired - Lifetime
1971
- 1971-03-25 CA CA108,738A patent/CA946407A/en not_active Expired
- 1971-04-01 US US00130449A patent/US3836484A/en not_active Expired - Lifetime
- 1971-04-27 DE DE19712120494 patent/DE2120494A1/de active Pending
- 1971-04-28 FR FR7115149A patent/FR2090856A5/fr not_active Expired
- 1971-05-03 GB GB1281571*[A patent/GB1321001A/en not_active Expired
- 1971-05-04 BE BE766707A patent/BE766707A/fr unknown
- 1971-05-04 SE SE05752/71A patent/SE360107B/xx unknown
- 1971-05-05 NL NL7106160A patent/NL7106160A/xx unknown

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3919429A (en) *	1972-01-18	1975-11-11	Hoechst Ag	Dispersing and wetting agents for use in organic biocides
JPS511501A (ja) *	1974-06-26	1976-01-08	Lion Fat Oil Co Ltd	Ryujosenzainoseizoho
US5928948A (en) *	1997-03-10	1999-07-27	Steris Corporation	Method for the assessment and validation of cleaning processes
US20100240752A1 (en) *	2007-11-07	2010-09-23	Reckitt Benckiser Inc.	Aqueous Acidic Hard Surface Cleaning and Disinfecting Compositions
US8268334B2 (en) *	2007-11-07	2012-09-18	Reckitt Benckiser Llc	Aqueous acidic hard surface cleaning and disinfecting compositions
CN101585786B (zh) *	2009-07-09	2012-05-23	江南大学	一种用so3-空气混合物经膜式磺化器磺化烷基酚生产烷基酚磺酸及其盐的方法
CN103265462A (zh) *	2013-06-14	2013-08-28	杨锌荣	一种烷氧基烷基苯磺酸盐及其制备方法

Also Published As

Publication number	Publication date
NL7106160A (fr)	1971-11-09
CA946407A (en)	1974-04-30
SE360107B (fr)	1973-09-17
DE2120494A1 (de)	1971-11-25
GB1321001A (en)	1973-06-20
BE766707A (fr)	1971-11-04
US3836484A (en)	1974-09-17
FR2090856A5 (fr)	1972-01-14

Publication	Publication Date	Title
US3320174A (en)	1967-05-16	Detergent composition
US3332876A (en)	1967-07-25	Detergent composition
US3686098A (en)	1972-08-22	Novel detergent composition
US3697573A (en)	1972-10-10	Linear alkylphenol sulfate-sulfonate phosphate-free detergent actives
US3708437A (en)	1973-01-02	2-olefin sulfonate for liquid detergents
US3346629A (en)	1967-10-10	Process for preparing beta-ethylenically unsaturated organic sulfonates
US3766254A (en)	1973-10-16	Linear alkylphenol disulfonate phosphate free detergent actives
JPS5923358B2 (ja)	1984-06-01	水性ビルト液体洗浄剤組成物
US3793226A (en)	1974-02-19	Detergent composition containing monoamide hydrocarbyl sulfonic acid salts of hydrocarbyl succinic acid
US4162236A (en)	1979-07-24	Detergent compositions containing mixtures of alkylbenzene sulfonates as the detergent active
US2427577A (en)	1947-09-16	Production of ether sulphonates
US3821272A (en)	1974-06-28	Dialkylphenol sulfate-sulfonate
US2379703A (en)	1945-07-03	Process for the production of derivatives of polyhydroxy alcohols
US2298696A (en)	1942-10-13	Detergent composition
US3923856A (en)	1975-12-02	Phosphate-free carboxylate-sulfate detergents
US2223363A (en)	1940-12-03	Alkyl-hydroxy-diphenyl sulphonates and method of producing them
US3896057A (en)	1975-07-22	Composite olefin sulfonate
US4088680A (en)	1978-05-09	Linear alkyl hydrocarbyloxybenzene disulfonates
US3021284A (en)	1962-02-13	Liquid detergent compositions
US2787639A (en)	1957-04-02	Long-chain alkane 1, 2-disulfonic acids and salts thereof
US4104023A (en)	1978-08-01	Ring polysulfonated alkylphenoxy alkylols as detergents
US2694086A (en)	1954-11-09	Sulfonation of poly-alkyl substituted aromatic hydrocarbons
US2676185A (en)	1954-04-20	Production of alkylated aryl sulfonate detergents
US3651119A (en)	1972-03-21	Sulfur-linked linear alkyl vicinal disulfates
US3346628A (en)	1967-10-10	Nu-substituted amino-alkane sulphonic acids