US3660313A - High foaming mixtures of fatty alcohol sulfates - Google Patents
High foaming mixtures of fatty alcohol sulfates Download PDFInfo
- Publication number
- US3660313A US3660313A US91145A US3660313DA US3660313A US 3660313 A US3660313 A US 3660313A US 91145 A US91145 A US 91145A US 3660313D A US3660313D A US 3660313DA US 3660313 A US3660313 A US 3660313A
- Authority
- US
- United States
- Prior art keywords
- alcohol
- myristyl
- alcohols
- stearyl
- percent
- 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
- 239000000203 mixture Substances 0.000 title abstract description 79
- -1 fatty alcohol sulfates Chemical class 0.000 title abstract description 29
- 238000005187 foaming Methods 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 66
- 150000001298 alcohols Chemical class 0.000 abstract description 33
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 103
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 34
- 125000001421 myristyl 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])[H] 0.000 description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 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 26
- 229910052782 aluminium Inorganic materials 0.000 description 23
- 239000006260 foam Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 23
- 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 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 239000003599 detergent Substances 0.000 description 16
- 229940043348 myristyl alcohol Drugs 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003240 coconut oil Substances 0.000 description 15
- 235000019864 coconut oil Nutrition 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- 239000003925 fat Substances 0.000 description 13
- 235000019197 fats Nutrition 0.000 description 13
- 239000012535 impurity Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- 238000006073 displacement reaction Methods 0.000 description 8
- 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 8
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004851 dishwashing Methods 0.000 description 3
- 150000002398 hexadecan-1-ols Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 230000019635 sulfation Effects 0.000 description 3
- 238000005670 sulfation reaction Methods 0.000 description 3
- 150000000218 1-tetradecanols Chemical class 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
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-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
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000011260 aqueous acid 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
- 239000002585 base Substances 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 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 2
- 238000002845 discoloration Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 229940096405 magnesium cation Drugs 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl 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])[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WXQWKYFPCLREEY-UHFFFAOYSA-N azane;ethanol Chemical class N.CCO.CCO.CCO WXQWKYFPCLREEY-UHFFFAOYSA-N 0.000 description 1
- 125000000656 azaniumyl group Chemical group [H][N+]([H])([H])[*] 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 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
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 238000005406 washing Methods 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
- C07C29/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only starting from compounds containing carbon-to-metal bonds and followed by conversion of the -O- metal to -OH groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C305/00—Esters of sulfuric acids
- C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
- C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
- C07C305/06—Hydrogenosulfates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
-
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
- C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/03—Organic sulfoxy compound containing
Definitions
- This invention relates to fatty alcohol sulfate or sulfonate compositions. More particularly, the invention relates to sulfates of a mixture of synthetic fatty alcohol components having particularly beneficial properties and not heretofore made or available by conversion of naturally occurring materials. More particularly, the invention relates to a mixture of alcohol sulfates having a substantial proportion of constituency based on myristyl alcohol, or tetradecanol.
- alkyl aryl sulfonates derivatives of naturally occurring fats, including, particularly, coconut oil and animal tallow.
- the alkyl aryl sulfonates are a substantial source of detergent components, but there is indication that these are unsatisfactory for certain reasons, and it is believed that their percentage of the raw material market will decrease in the future.
- the naturally occurring fats are particularly beneficial in that they are readily susceptible to conversion to surface active agents which have certain benefits, relative to the alkyl aryl sulfonates. These benefits are that such derivatives do not exhibit the branching which is so common among the alkyl radicals of the alkyl aryl sulfonates.
- alkyl aryl sulfonates having this high degree of branching are believed more resistant to biodegradation in industrial and domestic sewage effluents, and this resistance has created certain problems to the extent that legislation has been enacted in foreign countries or proposed in the United States, which in effect, limits the use of the alkyl aryl sulfonates.
- the derivatives from the identified naturally occurring fats are straight chain materials, predominantly, and are more susceptible to biodegradation and also are extremely efiicient detergent components.
- the type of processing to convert the above-mentioned fats to detergent components is widely varied, but for present purposes, can be summarized by saying that a large fraction of these materials are converted to the corresponding alcohol components or mixtures and are subsequently treated, for example, by sulfation, to form desirable detergent components.
- Another technique for conversion of the resultant alcohol mixtures involves the reaction with a plurality of mols of alkylene oxide, especially ethylene oxide, and the polyether hydroxy compound resultant, or mixtures of compounds, can be used as components as such, or can also be treated by sulfation or sulfonation.
- the utility of the naturally occurring fats, employed as above outlined, is limited by several factors.
- the relative proportions of components in each of these fats, or in the alcohols derived therefrom, are essentially fixed and not variant, as they represent the result of natural synthesis
- coconut oil predominates in components having 12 through 16 carbon atoms per molecule, so that the alcohols therefrom predominate in lauryl through palmityl alcohols.
- the alcohols derived from animal fats are predominantly alcohols of 16 and 18 carbon atoms.
- the 18 carbon atom alcohol instead of predominating in the saturated compound, includes substantial quantities of the compound having one unsaturated double bond therein.
- lauryl myristyl palmityl the predominant component is the 12 carbon atom alcohol, followed by the 14 and 16 in that order.
- the predominant alcohols are the 18 carbon atom components, followed by the 16, with only very minor quantities of the 14 carbon atom alcohol.
- the presently available natural fats do not provide a substantial source of mixtures rich in 14 and 16 carbon atoms alcohols, viz, myristyl and palmityl alcohols.
- These two alcohols provide properties such that the resultant detergents partake of the particular benefits of detergents made from coconut oil alcohol, as well as detergents made from the tallow alcohols.
- the object of the present invention is to provide derivatives of a synthesized alcohol mixture which are essentially freed of the limitations on composition heretofore experienced. More particularly, an object of the present invention is to provide a new alcohol sulfate product,
- an object of the invention is to provide a new composition derived by synthetic techniques as described hereinafter, wherein the preponderance of the mixture consists of derivatives of the 14-18 carbon atom alcohols, that is, myristyl, palmityl and stearyl alcohols. Other objects will appear hereinafter.
- the fatty alcohols of the present process are generated by making a trialkyl aluminum mixture, then oxidizing said trialkyl aluminum components to aluminum alkoxides, and then hydrolyzing said aluminum alkoxides with water or acidified water, whereby a mixture of alcohols according to the present invention and an aluminum salt of an inorganic acid are produced.
- the product of the invention differs appreciably from derivatives of any alcohol mixture obtained from naturally occurring fats or fatty oils and is further significantly desirable in exhibiting high quality standards with respect to a variety of experimental criteria, for example, the acid value, the unsaturation, carbonyl oxygen and ester content and certain other attributes.
- the product of the present invention can be made by several different specific variants within the above described general procedure.
- a particularly preferred manufacturing method results in the conjoint production of the product with an alcohol stream corresponding essentially to an alcohol derived from a coconut oil. It is found that the high myristyl alcohol derivatives of the present invention can be thus jointly made with coconut oil, so that the relative proportions are from about 2 to 6 or 7 parts by weight of coconut oil alcohol per part of the high myristyl alcohol product.
- the initial product mixture includes relatively minor components content of derivatives of alcohols of lower than 12 carbon atoms.
- a product is derivable which differs greatly in the weight or molecular weight distribution from that which would be predicted or anticipated by any of the prior art.
- the invention relates to water soluble salts of alcohol (ROH) sulfates, expressed ROSO Me wherein the alcohol equivalent constituency (ROH) has the following distribution on a hydrocarbon impurity-free basis:
- Alcohol Weight percent Lower than myristyl Not over about 2. Myristyl -50.
- Palmityl -45 Stearyl 15-30. Higher than stearyl Not over about 2.
- the alcohol has the distribution, same basis:
- the alcohol has the distribution, same basis: (So
- Me indicates a solubility radical such as alkali metal or ammonio radical.
- Typical alkali metals are 75 sodium, potassium and lithium with sodium most preferred from cost and convenience of reactivity viewpoints.
- Typical ammonia radicals are ammonium (NHJ), and lower alkanol ammonium having up to about 5 carbon atoms per alkanol group; such as, monoethanol amine, diethanol amine and triethanol amine.
- a crude mixture is obtained, from which is separated the synthetic coconut oil alcohol fraction and the desired high myristyl alcohol product.
- An illustrative, but non-limiting composition of the crude alcohol, made according to the above mentioned preferred route, is as follows:
- the high myristyl alcohol product has an approximate composition range as given below:
- Weight Alcohol percent Myristyl 25-50 Palmityl 30-45 Stearyl 15-30 This product is generally also limited to not over about 2 weight percent, each, of components lower and higher than those listed.
- the intermediate cut corresponding generally to a coconut oil alcohol, is controlled within the following range of compositions:
- Alcohol Weight percent Lower than lauryl 3 max. Lauryl -70. Myristyl 20-30. Palmityl 10 max. Higher alcohols 2 max.
- compositions are on the basis of the alcohol analysis, i.e. exclusive of other impurities, principally hydrocarbons, which may be present in proportions of up to about four percent without seriously affecting the properties of the products.
- the hydrocarbon impurities are generally alkane and alkene components.
- Acid value The free fatty acids or acid values of the streams are determined by the A.O.C.S. method Ca 5a-40. It is expressed in terms of milligrams of potassium hydroxide necessary to neutralize one gram of sample.
- Iodine value The iodine value is significant in indicating the degree of unsaturation of a particular product. It is determined by A.O.C.S. method Cd l-25, and is expressed in terms of centigrams of iodine absorbed per gram of sample.
- Ester value The ester content is determined as the difference between the A.O.C.S. saponification value (Cd 3-25) and the acid value, as already defined.
- Moisture value The moisture value is determined according to A.O.C.S. procedure Ca 2a-55.
- Clarity or color is usually determined using, for example, the American Public Health Association scale (A.P.H.A.).
- Carbonyl oxygen The total amount of carbonyl oxygen present in the sample is determined using, for example, the method described in Analytical Chemistry 31, 760 (1959).
- Hydroxyl value The measure of the amount of hydroxyl value of a sample is determined according to A.O.C.S. procedure Cd 13-60. It is defined in terms of milligrams potassium hydroxide equivalent to the hydroxyl content of one gram of sample.
- Hydrocarbon impurity As previously mentioned, another quality criterion is the amount of hydrocarbon impurity. This is efficiently determined by gas chromatography.
- the amount of esters, carbonyl oxygen and the hydroxyl value of the product are probably the most important.
- the amount of discoloration or degradation of a specimen, when exposed to strong sulfuric acid is frequently determined, particularly for the alcohols of the coconut oil t e.
- compositions such preferred high myristyl alcohol products exhibit additional high quality attributes, including, particularly in that the carbonyl oxygen content does not exceed about 0.05 weight percent, and a hydroxyl value of at least 225, as mg. KOH/ g. Further a total non-alcohol impurity concentration of not over about 3 weight percent is experienced. Additional typical quality attributes of less significance include the following:
- the chemical reactions involved in preparing the alcohols of the present invention include the chain growth of ethylene on a lower alkyl-trialkyl aluminum to obtain higher alkyl-trialkyl aluminum com pounds. These are then oxidized to aluminum alkoxide materials which are then hydrolyzed by reaction with an aqueous acid and form thereby alcohols corresponding to the alkyl group and aluminum salts corresponding to the acid of the aqueous acid used.
- the chain growth of ethylene on a lower alkyl-trialkyl aluminum compound is well known, generally, but performing this operation in the heretofore known conventional manner will not produce gross trialkyl aluminum mixtures having alkyl groups distributed by chain length as required for the present invention.
- the alcohols derived thereby will include substantial proportions of lower than desired alcohols than is required for most efficient performance.
- the alcohol mixture of the present invention is separated by fractionation, resulting in substantial quantities of alcohol components outside the range of the desired product.
- the most preferred synthesis utilizes a novel process wherein the alkyl groups of the trialkyl aluminum intermediate stream are generated in anti-statistical, or non- Poisson proportions. The characteristics of this highly preferred preparatory process are summarized below.
- the essential feature of the preferred preparatory process is the use of at least two displacement processes, whereby the distribution of alkyl groups to a non-statistical spectrum is achieved.
- the operations include the following steps:
- the ethylene to be utilized in chain growth is divided into two portions, and only a fraction usually of about one-half to three-fourths is reacted with the initial lower alkyl-trialkyl aluminum, preferably triethyl aluminum, in a first chain growth reaction.
- the chain grown trialkyl aluminum effiuent from the first chain growth reaction is then subjected to a displacement reaction with a mixture of olefins predominating in olefins of less than 12 carbon atoms, whereby a displacement product mixture from this first displacement reaction is obtained which includes olefins enriched in higher olefins of above 12 carbon atoms and trialkyl aluminum mixture enriched in alkyl groups of less than 12 carbon atoms.
- the trialkyl aluminum mixture from the first displacement reaction is then subjected to a second chain growth reaction with the remainder of the ethylene to be reacted.
- the trialkyl aluminum from the second chain growth reaction is then processed in a second displacement reaction, wherein reaction is carried out with olefins, concentrated in olefins of 12 and higher carbon atoms, as a result of which the trialkyl aluminum feed is converted to trialkyl aluminum mixtures appreciably enriched in alkyl aluminum groups of 12 and higher carbon atoms.
- the trialkyl aluminum thus obtained exhibits a unique non-Poisson distribution of alkyl group lengths.
- This mixture is then oxidized with an oxygen containing gas to convert a substantial proportion of the alkyl aluminum bonds to the corresponding alkoxide aluminum bonds, and the oxidized mixture is then hydrolyzed or reacted with a dilute aqueous added acid to form the desired alcohol mixture.
- Upon separation of certain impurities from the resultant alcohol mixture it is then ready for fractionation and separation of a cut corresponding to a coconut oil alcohol, and the desired myristyl alcohol fraction of the present invention.
- a variation of the process utilizes a single chain growth reaction, but processes a mixture of fresh low alkyl trialkyl aluminum and trialkyl aluminum, which is generated in a first displacement reaction.
- at least two displacement reactions are carried out, utilizing circulating olefin streams to continually adjust the identity and proportions of the alkyl groups of the trialkyl aluminum stream.
- the crude alcohol mixture from which the preferred myristyl-rich alcohol product is derived, has the following composition:
- Alcohol Weight percent Lower than lauryl 3 max. Lauryl 65:2. Myristyl 25:4. Palmityl 7:3. Stearyl and higher 1 max.
- the above described alcohol mixture as in the case of the novel high myristyl alcohol product also exhibits additional high quality attributes. Among these are good resistance to discoloration on exposure to acids, low values for acid, iodine, ester, moisture and carbonyl oxygen content.
- composition of alcohols from animal tallow is of interest:
- compositions of the present invention are readily reacted at 100 F. with chlorosulfonic acid to produce alkyl sulfates for use in detergents.
- the reaction proceeds according to the following equation and the equilibrium is favored for the desired product by low temperatures of the order of 100 F.
- Sodium alkyl sulfate detergents are obtained by reacting the alkyl sulfate with caustic or nitrogen base compound containing the desired cation. Samples of such material are tested and rated for various properties using standard techniques. One technique is a foam test identified as the Ross-Miles test. This compares the amount of foam obtained from different materials at selected temperatures and concentrations. An important temperature for this is 40 C. which is representative of temperatures used in hand dishwashing operations. A 0.2 wt. percent concentration represents the start of a dishwashing while the 0.1 Wt. percent represents the end of effective dishwashing before adding new cleaning agent. When the test is made according to a conventional procedure, foam heights are as follows.
- the 0.2 percent data for the blend for example, shows a foam height improvement of 13.3 percent over that predictable from the components.
- Palmityl and stearyl in effect require a solubilizing action to make them useful in applications such as the above.
- Myristyl alcohol provides this eifect in the present compositions.
- prior art compositions based on eflicient and economical utilization of starting materials it is necessary to obtain the solubilizing eifect through unsaturated a1-
- the results of Examples II and III are clearly inferior to those of Example I.
- EXAMPLE IV cohols particularly C
- the use of unsaturated alcohols Example I Was repeated using an alcohol with the has significant adverse effects since they impart undesired following distribution and the product tested similarly. properties such as color, odor, rancidity, and instability to The foam height results are tabulated based 0H h i percent concentration of the water soluble sodium alkyl EXAMPLE I sulfate salt in water of 150 p.p.m. hardness with a calcium cation/magnesium cation weight ratio of 3/2.
- composition of claim 1 wherein the water soluble salts are alkali metal salts.
- composition of claim 1 wherein the water soluble salts are sodium salts.
- composition of claim 1 wherein the water soluble salts are selected from the group consisting of ammonium salts and lower alkanol ammonium salts, wherein the alkanol groups contain up to about 5 carbon atoms per alkanol group.
- composition of claim 1 wherein the water soluble salts are ammonium salts.
- composition of claim 1 wherein the Water soluble salts are triethanol ammonium salts.
- Alcohol Weight percent 'Lower than myristyl 1.5 max. Myristyl 36-46. Palmityl 32-40. Stearyl 16-25. Higher than stearyl 2.0 max.
Abstract
HIGHER ALCOHOL SULFATE COMPOSITIONS ARE DISCLOSED WHICH ARE PRIMARILY DERIVATIVES OF MIXTURES OF MYRISTYL, PALMITYL, AND STEARYL ALCOHOLS CONTAINING SMALL QUANTITIES OF ALCOHOLS OF LOWER MOLECULAR WEIGHT.
Description
limited States Patent U11 US. Cl. 252-545 Claims ABSTRACT or ran nrscrosunn Higher alcohol sulfate compositions are disclosed which are primarily derivatives of mixtures of myristyl, palmityl, and stearyl alcohols containing small quantities of alcohols of lower molecular weight.
CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of our copending application Ser. No. 2,670, filed Jan. 13, 1970 now U.S. Pat. 3,598,747; which application is a continuation-in-part of abandoned application Ser. No. 558,237, filed June 17, 1966; which application in turn is a continuation-in-part of abandoned application Ser. No. 277,078, filed May 1, 1963.
BACKGROUND OF THE INVENTION Field of the invention 7 This invention relates to fatty alcohol sulfate or sulfonate compositions. More particularly, the invention relates to sulfates of a mixture of synthetic fatty alcohol components having particularly beneficial properties and not heretofore made or available by conversion of naturally occurring materials. More particularly, the invention relates to a mixture of alcohol sulfates having a substantial proportion of constituency based on myristyl alcohol, or tetradecanol.
Description of the prior art Heretofore, the synthetic detergent industry in the United States has been based predominantly upon surface active agents derived from several particular sources, viz,
alkyl aryl sulfonates derivatives of naturally occurring fats, including, particularly, coconut oil and animal tallow.
The alkyl aryl sulfonates are a substantial source of detergent components, but there is indication that these are unsatisfactory for certain reasons, and it is believed that their percentage of the raw material market will decrease in the future. The naturally occurring fats, however, are particularly beneficial in that they are readily susceptible to conversion to surface active agents which have certain benefits, relative to the alkyl aryl sulfonates. These benefits are that such derivatives do not exhibit the branching which is so common among the alkyl radicals of the alkyl aryl sulfonates. The alkyl aryl sulfonates having this high degree of branching are believed more resistant to biodegradation in industrial and domestic sewage effluents, and this resistance has created certain problems to the extent that legislation has been enacted in foreign countries or proposed in the United States, which in effect, limits the use of the alkyl aryl sulfonates. On the other hand, the derivatives from the identified naturally occurring fats are straight chain materials, predominantly, and are more susceptible to biodegradation and also are extremely efiicient detergent components.
The type of processing to convert the above-mentioned fats to detergent components is widely varied, but for present purposes, can be summarized by saying that a large fraction of these materials are converted to the corresponding alcohol components or mixtures and are subsequently treated, for example, by sulfation, to form desirable detergent components. Another technique for conversion of the resultant alcohol mixtures involves the reaction with a plurality of mols of alkylene oxide, especially ethylene oxide, and the polyether hydroxy compound resultant, or mixtures of compounds, can be used as components as such, or can also be treated by sulfation or sulfonation.
Generally, the utility of the naturally occurring fats, employed as above outlined, is limited by several factors. For example, the relative proportions of components in each of these fats, or in the alcohols derived therefrom, are essentially fixed and not variant, as they represent the result of natural synthesis Thus, coconut oil predominates in components having 12 through 16 carbon atoms per molecule, so that the alcohols therefrom predominate in lauryl through palmityl alcohols. On the other hand, the alcohols derived from animal fats are predominantly alcohols of 16 and 18 carbon atoms. In some products, the 18 carbon atom alcohol, instead of predominating in the saturated compound, includes substantial quantities of the compound having one unsaturated double bond therein.
Each of the above described naturally occurring fats has particularly desirable attributes with respect to subsequently manufactured detergents. The relatively invariant compositions of these fats, and of the alcohols derived therefrom, does create some limitations with respect to most elfective and economical manufacture. Thus, in the case of coconut oil alcohol, the quantities of individual alcohols rank as follows:
lauryl myristyl palmityl In other words, the predominant component is the 12 carbon atom alcohol, followed by the 14 and 16 in that order. With respect to alcohols derived from tallow, the predominant alcohols are the 18 carbon atom components, followed by the 16, with only very minor quantities of the 14 carbon atom alcohol. Thus, the presently available natural fats do not provide a substantial source of mixtures rich in 14 and 16 carbon atoms alcohols, viz, myristyl and palmityl alcohols. These two alcohols provide properties such that the resultant detergents partake of the particular benefits of detergents made from coconut oil alcohol, as well as detergents made from the tallow alcohols. The economics of the industry have dictated that these natural fats be processed as unitary mixtures, as the resolution of resultant alcohol mixtures into individual pure alcohol components would be prohibitive in cost and would also mean that the less desired individual components would not find ready usage. Hence, for practical purposes there has not heretofore been available an efiicient and economical source of alcohols which are high in myristyl and palmityl alcohols, because of the relatively invariant compositions of naturally occurring raw materials.
The object of the present invention is to provide derivatives of a synthesized alcohol mixture which are essentially freed of the limitations on composition heretofore experienced. More particularly, an object of the present invention is to provide a new alcohol sulfate product,
high in myristyl alcohol derivatives, and a particularly beneficial detergent material. More particularly, an object of the invention is to provide a new composition derived by synthetic techniques as described hereinafter, wherein the preponderance of the mixture consists of derivatives of the 14-18 carbon atom alcohols, that is, myristyl, palmityl and stearyl alcohols. Other objects will appear hereinafter.
The fatty alcohols of the present process are generated by making a trialkyl aluminum mixture, then oxidizing said trialkyl aluminum components to aluminum alkoxides, and then hydrolyzing said aluminum alkoxides with water or acidified water, whereby a mixture of alcohols according to the present invention and an aluminum salt of an inorganic acid are produced. The product of the invention differs appreciably from derivatives of any alcohol mixture obtained from naturally occurring fats or fatty oils and is further significantly desirable in exhibiting high quality standards with respect to a variety of experimental criteria, for example, the acid value, the unsaturation, carbonyl oxygen and ester content and certain other attributes.
The product of the present invention can be made by several different specific variants within the above described general procedure. A particularly preferred manufacturing method, as described more fully hereinafter, results in the conjoint production of the product with an alcohol stream corresponding essentially to an alcohol derived from a coconut oil. It is found that the high myristyl alcohol derivatives of the present invention can be thus jointly made with coconut oil, so that the relative proportions are from about 2 to 6 or 7 parts by weight of coconut oil alcohol per part of the high myristyl alcohol product.
In addition to the principal cuts which are actually provided, the initial product mixture includes relatively minor components content of derivatives of alcohols of lower than 12 carbon atoms. However, it is surprisingly discovered that a product is derivable which differs greatly in the weight or molecular weight distribution from that which would be predicted or anticipated by any of the prior art.
SUMMARY OF THE INVENTION The invention relates to water soluble salts of alcohol (ROH) sulfates, expressed ROSO Me wherein the alcohol equivalent constituency (ROH) has the following distribution on a hydrocarbon impurity-free basis:
Alcohol: Weight percent Lower than myristyl Not over about 2. Myristyl -50.
Palmityl -45. Stearyl 15-30. Higher than stearyl Not over about 2.
In a preferred aspect the alcohol has the distribution, same basis:
Alcohol:
Weight percent Lower than myristyl 1.5 max. Myristyl 36-46. Palmityl 32-40. Stearyl 16-25. Higher than stearyl 2.0 max.
In a more preferred aspect the alcohol has the distribution, same basis: (So
Alcohol: Weight percent Lower than myristyl 1.5 max. Myristyl 42:4. Palmityl 36:4. Stearyl 19:3. Higher than stearyl 2 max.
The term Me indicates a solubility radical such as alkali metal or ammonio radical. Typical alkali metals are 75 sodium, potassium and lithium with sodium most preferred from cost and convenience of reactivity viewpoints. Typical ammonia radicals are ammonium (NHJ), and lower alkanol ammonium having up to about 5 carbon atoms per alkanol group; such as, monoethanol amine, diethanol amine and triethanol amine.
DISCUSSION In the preferred mode of preparing the present product, as explained above, a crude mixture is obtained, from which is separated the synthetic coconut oil alcohol fraction and the desired high myristyl alcohol product. An illustrative, but non-limiting composition of the crude alcohol, made according to the above mentioned preferred route, is as follows:
Weight Alcohol: percent Ethyl 1 Butyl l Hexyl 1.5
' Octyl 3.3 Decyl 7.8 Dodecyl or lauryl 34.8 Tetradecyl or myristyl 25.8 Hexadecyl or palmityl 16.4 Octadecyl or stearyl 8.7 Eicosyl or arachidyl and higher 3 The crude stream, of which the foregoing is an illustrative composition, is fractionated into the desired high myristyl alcohol fraction, a fraction high in lauryl alcohol, generally corresponding to a coconut oil alcohol, and a low alcohol fraction predominating in octyl and decyl alcohols. Small amounts of lower-than-octyl, and higher than stearyl alcohols are also separated.
The high myristyl alcohol product has an approximate composition range as given below:
Weight Alcohol: percent Myristyl 25-50 Palmityl 30-45 Stearyl 15-30 This product is generally also limited to not over about 2 weight percent, each, of components lower and higher than those listed.
The intermediate cut, corresponding generally to a coconut oil alcohol, is controlled within the following range of compositions:
Alcohol: Weight percent Lower than lauryl 3 max. Lauryl -70. Myristyl 20-30. Palmityl 10 max. Higher alcohols 2 max.
The foregoing compositions are on the basis of the alcohol analysis, i.e. exclusive of other impurities, principally hydrocarbons, which may be present in proportions of up to about four percent without seriously affecting the properties of the products. The hydrocarbon impurities are generally alkane and alkene components.
In addition to the distribution of the alcohol components in the product, and in the synthetic coconut oil alcohol which is customarily concurrently made, various other recognized quality tests are frequently applied. Generally, such tests or product criteria are determined by procedures of the American Oil Chemists Society, and some of these are referred to below.
Acid value: The free fatty acids or acid values of the streams are determined by the A.O.C.S. method Ca 5a-40. It is expressed in terms of milligrams of potassium hydroxide necessary to neutralize one gram of sample.
Iodine value: The iodine value is significant in indicating the degree of unsaturation of a particular product. It is determined by A.O.C.S. method Cd l-25, and is expressed in terms of centigrams of iodine absorbed per gram of sample.
Ester value: The ester content is determined as the difference between the A.O.C.S. saponification value (Cd 3-25) and the acid value, as already defined.
Moisture value: The moisture value is determined according to A.O.C.S. procedure Ca 2a-55.
Color: Clarity or color is usually determined using, for example, the American Public Health Association scale (A.P.H.A.).
Carbonyl oxygen: The total amount of carbonyl oxygen present in the sample is determined using, for example, the method described in Analytical Chemistry 31, 760 (1959).
Hydroxyl value: The measure of the amount of hydroxyl value of a sample is determined according to A.O.C.S. procedure Cd 13-60. It is defined in terms of milligrams potassium hydroxide equivalent to the hydroxyl content of one gram of sample.
Hydrocarbon impurity: As previously mentioned, another quality criterion is the amount of hydrocarbon impurity. This is efficiently determined by gas chromatography.
Among the foregoing quality or identifying tests, the amount of esters, carbonyl oxygen and the hydroxyl value of the product are probably the most important. The amount of discoloration or degradation of a specimen, when exposed to strong sulfuric acid is frequently determined, particularly for the alcohols of the coconut oil t e.
llie most preferred form of the high myristyl alcohol materials of the present invention is obtained in conjunction with about twice its quantity of a product corresponding in general compoistion to a coconut oil alcohol. The composition of such a preferred high myristyl alcohol mixture is as given below:
Alcohol: Weight percent Lower than myristyl Not over about 1.5. Myristyl 42:4.
Palmityl 36:314. Stearyl 19:3. Higher than stearyl 2 max.
In addition to the foregoing compositions such preferred high myristyl alcohol products exhibit additional high quality attributes, including, particularly in that the carbonyl oxygen content does not exceed about 0.05 weight percent, and a hydroxyl value of at least 225, as mg. KOH/ g. Further a total non-alcohol impurity concentration of not over about 3 weight percent is experienced. Additional typical quality attributes of less significance include the following:
Acid value Max. 1.0 mg. KOH/ g. Iodine value Max. 1.0 cg. 1 g.
Ester value Max. 1.5 mg. KOH/ g. Moisture Max. about 0.15 percent.
As already described the chemical reactions involved in preparing the alcohols of the present invention include the chain growth of ethylene on a lower alkyl-trialkyl aluminum to obtain higher alkyl-trialkyl aluminum com pounds. These are then oxidized to aluminum alkoxide materials which are then hydrolyzed by reaction with an aqueous acid and form thereby alcohols corresponding to the alkyl group and aluminum salts corresponding to the acid of the aqueous acid used. The chain growth of ethylene on a lower alkyl-trialkyl aluminum compound is well known, generally, but performing this operation in the heretofore known conventional manner will not produce gross trialkyl aluminum mixtures having alkyl groups distributed by chain length as required for the present invention. Hence, if the conventional process sequence is obtained, the alcohols derived thereby will include substantial proportions of lower than desired alcohols than is required for most efficient performance. When the above general or conventional procedure is followed, the alcohol mixture of the present invention is separated by fractionation, resulting in substantial quantities of alcohol components outside the range of the desired product. The most preferred synthesis, however, utilizes a novel process wherein the alkyl groups of the trialkyl aluminum intermediate stream are generated in anti-statistical, or non- Poisson proportions. The characteristics of this highly preferred preparatory process are summarized below.
The essential feature of the preferred preparatory process is the use of at least two displacement processes, whereby the distribution of alkyl groups to a non-statistical spectrum is achieved. In carrying out an embodiment of such a process, the operations include the following steps:
The ethylene to be utilized in chain growth is divided into two portions, and only a fraction usually of about one-half to three-fourths is reacted with the initial lower alkyl-trialkyl aluminum, preferably triethyl aluminum, in a first chain growth reaction.
The chain grown trialkyl aluminum effiuent from the first chain growth reaction is then subjected to a displacement reaction with a mixture of olefins predominating in olefins of less than 12 carbon atoms, whereby a displacement product mixture from this first displacement reaction is obtained which includes olefins enriched in higher olefins of above 12 carbon atoms and trialkyl aluminum mixture enriched in alkyl groups of less than 12 carbon atoms.
The trialkyl aluminum mixture from the first displacement reaction is then subjected to a second chain growth reaction with the remainder of the ethylene to be reacted.
The trialkyl aluminum from the second chain growth reaction is then processed in a second displacement reaction, wherein reaction is carried out with olefins, concentrated in olefins of 12 and higher carbon atoms, as a result of which the trialkyl aluminum feed is converted to trialkyl aluminum mixtures appreciably enriched in alkyl aluminum groups of 12 and higher carbon atoms.
The trialkyl aluminum thus obtained exhibits a unique non-Poisson distribution of alkyl group lengths. This mixture is then oxidized with an oxygen containing gas to convert a substantial proportion of the alkyl aluminum bonds to the corresponding alkoxide aluminum bonds, and the oxidized mixture is then hydrolyzed or reacted with a dilute aqueous added acid to form the desired alcohol mixture. Upon separation of certain impurities from the resultant alcohol mixture, it is then ready for fractionation and separation of a cut corresponding to a coconut oil alcohol, and the desired myristyl alcohol fraction of the present invention.
Instead of employing two separate chain growth operations, as described above, a variation of the process utilizes a single chain growth reaction, but processes a mixture of fresh low alkyl trialkyl aluminum and trialkyl aluminum, which is generated in a first displacement reaction. In all of these preferred methods of generating the non-Poisson, trialkyl aluminum mixtures from which the desired alcohol product is obtained, at least two displacement reactions are carried out, utilizing circulating olefin streams to continually adjust the identity and proportions of the alkyl groups of the trialkyl aluminum stream.
In a typical operation, according to the preferred process first described above, the crude alcohol mixture, from which the preferred myristyl-rich alcohol product is derived, has the following composition:
In addition to the preferred high myristyl alcohol fraction already described, a mixture corresponding to a coconut oil fraction is separated having the following approximate composition range:
Alcohol: Weight percent Lower than lauryl 3 max. Lauryl 65:2. Myristyl 25:4. Palmityl 7:3. Stearyl and higher 1 max.
The above described alcohol mixture as in the case of the novel high myristyl alcohol product also exhibits additional high quality attributes. Among these are good resistance to discoloration on exposure to acids, low values for acid, iodine, ester, moisture and carbonyl oxygen content.
By contrast to the high myristyl alcohol mixtures of the present invention, the composition of alcohols from animal tallow is of interest:
Alcohol: Weight percent Lower than myristyl 0.3 Myristyl 2.5 Palmityl 27.2 Stearyl 69.2 Higher than stearyl 0.8
From the foregoing it is seen that alcohols from animal fats are virtually devoid of the very desirable myristyl alcohol component whereas the product of the present invention contains from one-fourth to about one-half myristyl alcohol content and in the particularly preferred composition, about 42 percent of this component.
The compositions of the present invention are readily reacted at 100 F. with chlorosulfonic acid to produce alkyl sulfates for use in detergents. The reaction proceeds according to the following equation and the equilibrium is favored for the desired product by low temperatures of the order of 100 F.
The equilibrium is not favorable to this reaction with palmityl and stearyl alcohols per se because of their high melting point.
Sodium alkyl sulfate detergents are obtained by reacting the alkyl sulfate with caustic or nitrogen base compound containing the desired cation. Samples of such material are tested and rated for various properties using standard techniques. One technique is a foam test identified as the Ross-Miles test. This compares the amount of foam obtained from different materials at selected temperatures and concentrations. An important temperature for this is 40 C. which is representative of temperatures used in hand dishwashing operations. A 0.2 wt. percent concentration represents the start of a dishwashing while the 0.1 Wt. percent represents the end of effective dishwashing before adding new cleaning agent. When the test is made according to a conventional procedure, foam heights are as follows.
FOAM BY ROSS-MILES TEST AT 40 C.
The 0.2 percent data for the blend, for example, shows a foam height improvement of 13.3 percent over that predictable from the components.
EFFECTIVENESS CALCULATED FROM COMPONENTS 1150 mm. foam height] The 0.1 percent data show a foam height improvement of 18.4 percent over that predictable from the components.
EFFECTIVENESS CALCULATED FROM COMPONENTS [152 mm. ioarn height] Percentage lndivldual effective- Fraetion foam ness, mm.
0.4 X 185 74. 0. 4 X 175 70. Stearyl. 0. 2 X 40 8.
Total 152.0
Actual effectiveness 180 Difference 28 28 NorE.Percentage improvement over prediction X=18.4
152 percent.
From the foregoing it is evident that myristyl (C alcohol provides the most profuse foaming cleaning agents of this type and that the blend is almost as good as that individual material despite the fact that the individual characteristics of the components, particularly stearyl and to a smaller extent, palmityl, are much lower.
The data also show that stearyl alcohol is of little value per se; however, when used in a composition (mixture) according to the present application, it is almost as good as myristyl alcohol and that the overall value for the mixture is better than that of any of the individual components other than myristyl.
The data show that the present compositions have a superiority of about 15 percent over the percentage-effectiveness sums for the components. In other words, the effectivenes of the combination based on the claimed alcohol composition exceeded the sum of effectiveness of the components when tested individually.
Another important criteria in this connection is the detersive (cleaning) ability. Again a standard test procedure was used, with a Launder-O-Meter of the U8. Testing Company using soiled test cloths. This test was made at F. which is a typical home laundering temperature. The detergent sodium alkyl sulfate was used at a 0.1 percent concentration (weight) with 0.05 percent sodium metasilicate as builder.
Increase in reflect- Detergent sodium alkyl sulfate: ance of the Wash Alkyl=Lauryl (C 17.0 Myristyl (C 33.5 Palmityl (C 32.5 -Stearyl (C18) Blend 40/40/20 MPS 33.0
From this it is evident that detergency also peaks at C under the conditions selected and that the composition is practically equal to the peak detergency in cleaning efliciency despite the content of stearyl (C Similar desirable characteristics are found with the compositions in preparing detergent bars for personal use. Profuse foam and good cleaning properties are obtained in hand washing and bathing.
Palmityl and stearyl in effect require a solubilizing action to make them useful in applications such as the above.
Myristyl alcohol provides this eifect in the present compositions. In prior art compositions based on eflicient and economical utilization of starting materials it is necessary to obtain the solubilizing eifect through unsaturated a1- The results of Examples II and III are clearly inferior to those of Example I.
EXAMPLE IV cohols, particularly C The use of unsaturated alcohols Example I Was repeated using an alcohol with the has significant adverse effects since they impart undesired following distribution and the product tested similarly. properties such as color, odor, rancidity, and instability to The foam height results are tabulated based 0H h i percent concentration of the water soluble sodium alkyl EXAMPLE I sulfate salt in water of 150 p.p.m. hardness with a calcium cation/magnesium cation weight ratio of 3/2. The temafi fii iifiifiiflhii 3.233553%?311.3535;i P333133 3.3 tests was Foam heights were hol (by weight) was made and tested using 0.2 weight measured lmtlany and after 5 mmutes standing percent concentration of the sodium alkyl sulfate pastes of the alcohols in a standard water solution of 0 p.p.m. (parts per million) hardness as equivalent calcium car- 15 Foam height bonate. The hardness was achieved by use of a mixture (millimeters) of calcium chloride and magnesium sulfate to provide a After 5 calcium cation/magnesium cation weight ratio of 3/2. Component Wt.percent Initial minutes The temperature of each solution during the test was 2 Myristyl (CH) 4040 95 F. O Palmityl ow 30.0} 30 05 'In the test the activity of a sodium alkyl sulfate paste is Steam (C15) related to the height of the foam it produces. In other Total 0.0 words, the higher the foam, the more active the substance under test. In addition, it is desirable that the foam exhibit stability and therefore the height of the foam is measured not only as soon as it has been formed but also after stand- EXAMPLE V ing 5 minutes- Another alcohol composition containing wt. percent The results of the tests are tabulated hereinafter. by vapor phase chromatography analysis) 17 C12 l hol, 36.86 C alcohol, 37.76 C alcohol, 24.58 C alco- Foam helght (millimeters) hol, and 0.62 C and higher alcohols was sulfated with After S0 Initial fiminutes The alcohol had the following wet chemical analysis: comnosltwn 140 125 Add value u 0.32 mg KOH/gram. Ester value 1.05 mg. KOH/ gram. EXAMPLE II Carbonyl oxygen 0.014 Weight percent. In a comparative test, a sodium alkyl sulfate detergent Iodine Value 8- 2 gramderived from a different starting alcohol mixture was Y F Y Value 233 KOH/gramtested as in Example L Mo1sture (H O) 0.16 weight percent.
Color (APHA) 10.
am ht 396.2 grams of alcohol was diluted to one liter with Mixture, (Immmeters) Freon 113 and reacted with S0 at 40 C. in a falling film p s y after 5 retactor at about atmospheric pressure. 1.08 mols of S0 mmponent Welght Imtlal mmutes was used per mol of alcohol. The product was collected Decyl 6 in a flask, the Freon evaporated and parts of the remaing 3 45 ing solution reacted with the desired base to produce Palmityl 40 various Me alkyl sulfate compositions. To produce the Stem'yl 20 potassium alkyl sulfate, one portion of the sulfation prod- Total 50 uct was reacted 'wtih 20.7 grams of KOH in 350 milliliters of water and 400 milliliters of percent ethyl EXAMPLE HI EllCOllOl l0 a pH Of 8.5.
To produce a typical ammonio salt, one portion of Exafnple H repeated 1n another comPal'atlve exam the sulfated alcohols was reacted with 20 grams of ample using a sodium alkyl sulfate paste derived from an- 55 monium hydroxide in 200 milliliters of wvater and 200 other Startlng alcohol mlXtllremilliliters of 95 percent ethyl alcohol to a pH of about 8.5. The water soluble salts obtained by the neutralization Foam height reactions were tested in a Ross-Miles foam test using Mixture (mlmmeters) 0.20 wt. percent concentration of the ammonium salt in parts a; Aiter5 0 water and 0.10 wt. percent concentration of the salt in Cmnponent Weight Initial minutes the water, the tests being run with water of 25 ppm. 30 hardness and with water of 1.50 ppm. hardness Ca/Mg i8} 45 15 ratio 3/2). As in previous examples, the foam was measured initially and after 5 minutes to determine foam 65 stability.
ROSS-MILES FOAM [95 F., mm. of foam] 25 ppm. water p.p.m. water Sample Initial 5min. Initial 5 min.
Ammonium salt (0.20 wt. percent cone.) 185 180 155 Ammonium salt (0.10 wt. percent cone.) 150 50 30 Potassium salt (0.20 wt. percent cone.) 50 170 65 Potassium salt (0.10 wt. percent cone.) 165 80 45 25 1 1 We claim: 1. The water soluble salts of the sulfates of alcohols having the following distribution on a hydrocarbon impurity free basis:
Alcohol: Weight percent Lower than myristyl Not over about 2. Myristyl 25-50.
Palmityl 30-45. Stearyl 15-30. Higher than stearyl Not over about 2.
2. The water soluble salts of the sulfates of alcohols having the following distribution on a hydrocarbon impurity free basis:
Alcohol: Weight percent Lower than myristyl 1.5 max. Myristyl 36-46. Palmityl 32-40.
Stearyl 16-25.
Higher than stearyl 2.0 max.
3. The water soluble salts of the sulfates of alcohols having the following distribution on a hydrocarbon impurity free basis:
Alcohol: Weight percent Lower than myristyl 1.5 max. Myristyl -3 42:4. Palmityl 36:4.
Stearyl 19:3. Higher than stearyl 2 max.
4. The composition of claim 1 wherein the water soluble salts are alkali metal salts.
5. The composition of claim 1 wherein the water soluble salts are sodium salts.
6. The composition of claim 1 wherein the water soluble salts are selected from the group consisting of ammonium salts and lower alkanol ammonium salts, wherein the alkanol groups contain up to about 5 carbon atoms per alkanol group.
7. The composition of claim 1 wherein the water soluble salts are ammonium salts.
8. The composition of claim 1 wherein the Water soluble salts are triethanol ammonium salts.
9. The sodium salts of the sulfates of alcohols having the following distribution on a hydrocarbon impurity free basis:
Alcohol: Weight percent 'Lower than myristyl 1.5 max. Myristyl 36-46. Palmityl 32-40. Stearyl 16-25. Higher than stearyl 2.0 max.
10. The sodium salts of the sulfates of alcohols having the following distribution on a hydrocarbon impurity free basis:
OTHER REFERENCES Use Evaluation of Alcohol Derivatives in Detergent Formulations, by T. P. Matson, J.A.O.C.S., vol. 40, pp. 636-640.
LEON D. ROSDOL, Primary Examiner D. L. ALBRECHT, Assistant Examiner US. Cl. X.R.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27707863A | 1963-05-01 | 1963-05-01 | |
| US267070A | 1970-01-13 | 1970-01-13 | |
| US9114570A | 1970-11-19 | 1970-11-19 | |
| DE2105910A DE2105910B2 (en) | 1963-05-01 | 1971-02-09 | Mixture of alkali metal or ammonium salts of sulfated alcohols |
| GB8422/71A GB1291196A (en) | 1963-05-01 | 1971-04-01 | Alcohol mixtures and products therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3660313A true US3660313A (en) | 1972-05-02 |
Family
ID=27510145
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2670A Expired - Lifetime US3598747A (en) | 1963-05-01 | 1970-01-13 | Alcohol mixtures adapted for use in making detergent sulfates |
| US91145A Expired - Lifetime US3660313A (en) | 1963-05-01 | 1970-11-19 | High foaming mixtures of fatty alcohol sulfates |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2670A Expired - Lifetime US3598747A (en) | 1963-05-01 | 1970-01-13 | Alcohol mixtures adapted for use in making detergent sulfates |
Country Status (3)
| Country | Link |
|---|---|
| US (2) | US3598747A (en) |
| DE (1) | DE2105910B2 (en) |
| GB (1) | GB1291196A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8811672D0 (en) * | 1988-05-17 | 1988-06-22 | Unilever Plc | Detergent composition |
| DE4322968A1 (en) * | 1993-07-09 | 1995-01-12 | Henkel Kgaa | Process for the preparation of alkyl sulfates |
| DE4432365A1 (en) * | 1994-09-12 | 1996-03-14 | Henkel Kgaa | Anhydrous surfactant mixtures |
| US6174849B1 (en) * | 1996-10-30 | 2001-01-16 | Henkel Kommanditgesellschaft Auf Aktien | Water-free surfactant mixtures containing alcohol sulfates |
| WO2023051978A1 (en) * | 2021-09-29 | 2023-04-06 | Unilever Ip Holdings B.V. | Composition |
-
1970
- 1970-01-13 US US2670A patent/US3598747A/en not_active Expired - Lifetime
- 1970-11-19 US US91145A patent/US3660313A/en not_active Expired - Lifetime
-
1971
- 1971-02-09 DE DE2105910A patent/DE2105910B2/en active Pending
- 1971-04-01 GB GB8422/71A patent/GB1291196A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2105910B2 (en) | 1974-11-21 |
| GB1291196A (en) | 1972-10-04 |
| DE2105910A1 (en) | 1972-08-24 |
| US3598747A (en) | 1971-08-10 |
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