EP1204465A1 - Low viscosity alkyl diphenyl oxide sulfonic acid blends - Google Patents
Low viscosity alkyl diphenyl oxide sulfonic acid blendsInfo
- Publication number
- EP1204465A1 EP1204465A1 EP00946991A EP00946991A EP1204465A1 EP 1204465 A1 EP1204465 A1 EP 1204465A1 EP 00946991 A EP00946991 A EP 00946991A EP 00946991 A EP00946991 A EP 00946991A EP 1204465 A1 EP1204465 A1 EP 1204465A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- diphenyl oxide
- blend
- alkyl diphenyl
- admixture
- 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.)
- Withdrawn
Links
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 24
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims abstract description 54
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 38
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 34
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 33
- 229930195729 fatty acid Natural products 0.000 claims abstract description 33
- 239000000194 fatty acid Substances 0.000 claims abstract description 33
- 239000004094 surface-active agent Substances 0.000 claims abstract description 26
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 18
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 18
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 claims abstract description 18
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000011054 acetic acid Nutrition 0.000 claims abstract description 12
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims abstract description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 10
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 claims abstract description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 9
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 claims abstract description 9
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019253 formic acid Nutrition 0.000 claims abstract description 9
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 9
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 9
- 229940005605 valeric acid Drugs 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkyl diphenyl oxide Chemical compound 0.000 claims description 15
- 239000003599 detergent Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims 2
- 230000003472 neutralizing effect Effects 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000004973 liquid crystal related substance Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000006277 sulfonation reaction Methods 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 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 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid group Chemical group C(CCCCCC)(=O)O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/02—Alkyl sulfonates or sulfuric acid ester salts derived from monohydric alcohols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Definitions
- R is an alkyl radical having between 6 and 16 carbon atoms; and sulfonating said admixture with a sulfonating agent.
- alkyl diphenyl oxide sulfonic acid blend having between 5 weight percentage and 50 weight percentage of a fatty acid with a carboxylic chain length between 1 and 12.
- R is an alkyl radical having between 6 and 16 carbon atoms
- Figure 1 shows the impact of various levels of octanoic acid upon the viscosity of a DOWFAX alkyl diphenyl oxide sulfonic acid surfactant blend.
- Figure 2 shows the impact of various levels of octanoic acid upon the viscosity of a DOWFAX alkyl diphenyl oxide sulfonic acid surfactant blend in the high viscosity range
- Figure 3 shows the comparative impact of acetic, valeric, octanoic, and decanoic fatty acids on the viscosity of a DOWFAX alkyl diphenyl oxide sulfonic acid surfactant blend.
- Figure 4 shows a ternary phase diagram showing significant liquid crystal phase regions for water, DOWFAX Detergent Acid, and fatty acid (acetic acid and octanoic acid).
- alkyl diphenyl oxide sulfonate surfactants are a Friedel-Crafts reaction product of an olefin and diphenyl oxide using AICI 3 as a catalyst as indicated in Formula I.
- Diphenyl oxide is present in excess and is recycled.
- the reaction yields a mixture of monoalkyl diphenyl oxide and dialkyl diphenyl oxide.
- the ratio of monoalkylation to dialkylation can be optimized depending on the end use of the products.
- the next step in the process is the reaction of the alkylate with a sulfonating agent.
- This reaction (Formula II) is conducted in a solvent to dilute the reactant and to act as a diluent for the S0 3 used in the reaction.
- the reaction generally yields a mixture of monosulfonates and disulfonates according to Formulas III - VI.
- the level of disulfonation is determined by the end use of the product. Generally, the disulfonation level is above 80 percent.
- the predominant component in the commercial reaction mixture is the monoalkyl diphenyl oxide disulfonate (MADS) of Formula IV, with monoalkyl diphenyl oxide monosulfonate (MAMS) of Formula III, dialkyl diphenyl oxide monosulfonate (DAMS) of Formula V, and dialkyl diphenyl oxide disulfonate (DADS) of Formula VI essentially providing the remainder.
- MADS monoalkyl diphenyl oxide disulfonate
- MAMS monoalkyl diphenyl oxide monosulfonate
- DAMS dialkyl diphenyl oxide monosulfonate
- DADS dialkyl diphenyl oxide disulfonate
- Alkyl diphenyloxide sulfonates and their traditional methods of preparation are well-known and reference is made thereto for purposes of describing this invention. Representative methods of preparation and handling are disclosed in U.S. Patents 2,990,375; 3,264,242, 3,634,272; 3,945,437; and 5,015,367.
- the commercially available species are predominantly (greater than 85 percent) disulfonates (the DADS and MADS described above) and are a mixture of mono- and di- alkyl with the percentage of dialkylation (the DADS and DAMS described above) being 5 to 25 and the percentage of monoalkylation (the MAMS and MADS described above) being 75 to 95 percent. Most typically, the commercially available species are 85 percent monoalkyl and 15 percent dialkyl.
- the traditional method taught by Steinhauer et al. (U.S. Pat. No. 2,990,375) outlines a series of steps, the first step comprising preparing an alkyldiphenyl ether by reacting an olefin or an olefin ha de, such as t ⁇ propylenes, tetrapropylenes, pentapropylenes or dodecyl bromide, with diphenyl ether at a temperature between 50° C and 100° C in the presence of the F ⁇ edel-Crafts catalyst.
- an olefin or an olefin ha de such as t ⁇ propylenes, tetrapropylenes, pentapropylenes or dodecyl bromide
- the reaction mixture is washed with water to remove the catalyst, the phases separated, and the organic-rich phase subjected to distillation to obtain a fraction consisting of a mixture of monoalkylated diphenyl ether and dialkylated diphenyl ether.
- the number of alkyl substituents per diphenyl ether molecule can be controlled by adjusting the relative proportions of the reactants.
- the distillation can be performed so as to separate the monoalkylated and dialkylated diphenyl ethers from one another and from lower or higher boiling ingredients after which the monoalkylated and dialkylated diphenyl ether fractions can be combined at a desirable ratio.
- the mixture of monoalkylated and dialkylated diphenyl ethers is subsequently reacted with a sulfonating agent, such as chlorosulfonic acid, sulfunc acid, or sulfur t ⁇ oxide, in an inert solvent
- a sulfonating agent such as chlorosulfonic acid, sulfunc acid, or sulfur t ⁇ oxide
- the general process of today uses reaction of an unsaturated hydrocarbon such as an alpha-olefin in the range of 6 to 16 carbons with diphenyl oxide in the presence of AICI 3 .
- Reaction of alpha-olefins in the higher range of 18-30 carbons with diphenyl oxide in the presence of AICI 3 holds some promise for fulfilling future surfactant needs
- the ratio of mono- to dialkylation is controlled by the ratio of olefin to diphenyl oxide. Recycled excess diphenyl oxide is purified and reused.
- the rate of the reaction and the yield are controlled by the amount of catalyst and temperature of the alkylation. Excessively high temperatures as well as excessive amounts of catalyst yield higher levels of dialkylation and tnalkylation.
- Sulfonation is generally carried out in a solvent.
- the solvent provides value in distributing the sulfonating agent, preventing localized burning and yield loss of the reaction product, and acting as a heat removal medium in control of the reaction process temperature.
- Current commercial process routes use sulfur dioxide, methylene chloride, or air as reaction solvents.
- the air sulfonation process eliminates the need for the removal and recycle of the liquid reaction solvent and is amenable to onsite generation of S0 3 Liquid solvents require
- the sulfomc acid is separated from its diluent, (2) the anhydrous acid (HAA) is diluted with water, and (3) neutralization of the diluted acid is optionally executed with an alkaline base such as sodium hydroxide.
- HAA anhydrous acid
- neutralization of the diluted acid is optionally executed with an alkaline base such as sodium hydroxide.
- the material is packaged and sold in drums or bulk shipments as the customer requires.
- the high viscosity of concentrated HAA derives from properties related to liquid crystal presence. This effect initiates at hydrophobe chain lengths above 6, is increasingly pronounced in observed samples to chain lengths of 16, and is expected to extend with greater significance to cases such as those which are contemplated via reaction of alpha- olefins in the higher range of 18-30 carbons with diphenyl oxide. Accordingly, a liquid crystal disrupter, or crystal structure breaker, is highly desirable as an additive for enabling useful viscosity in a useful HAA solids region (that is in an 60-95 percent solids range). In this regard, an additional component in the blend is most desirable which disrupts High Actives Acid (HAA) liquid crystal structure without imparting undesirable attributes to the resulting blend.
- HAA High Actives Acid
- dimethylformamide (DMF) and methyl formamide (MF) effectively disrupt the liquid crystal structure in alkyl diphenyl oxide sulfonic acid blends used in deriving DOWFAX surfactants; but DMF and MF are not favored for use because of asserted health concerns.
- admixing the fatty acid with the alkyl diphenyl oxide prior to sulfonation also provides reduction of surfactant viscosity and improved handling characteristics in the HAA material
- Formic acid acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, and
- Samples containing straight-chain carboxylic acids from formic to launc acid were blended with a representative alkyl diphenyl oxide sulfonic acid surfactant with a 16-carbon hydrophobe side chain (DOWFAX Detergent Acid, 94 wt percent concentration) at levels of
- a Brookfield programmable rheometer Model HDAV-III, was used to measure the viscosity of DOWFAX acid samples.
- the spindle size used was SC4-21
- the viscosities of the samples were measured at 40 °C, a temperature at which the Thermosel temperature control stage was stable.
- Viscosity 100/RPM * TK * SMC * Torque
- Samples containing various ratios of either acetic or octanoic acid, as representative carboxylic acids, of a representative alkyl diphenyl oxide sulfonic acid surfactant with a 16- carbon hydrophobe side chain (DOWFAX Detergent Acid), and water were prepared. Each sample was blended until homogeneous. Gross visual examination of each sample was made to identify the presence of a solid-like, liquid crystal phase. Data defining the composition of samples exhibiting such a highly viscous phase were plotted on a ternary
- the ternary phase diagram of Figure 4 shows significant liquid crystal phase regions for water, DOWFAX surfactant acid, and two fatty acids (acetic acid and octanoic acid).
- the phase boundary is indicated where the viscosity measures 1 million centipoise or greater at room temperature and pressure.
- the high viscosity area underscores the importance of the method of addition in admixing the alkyl diphenyl oxide sulfomc acid surfactant and fatty acid blend of the described embodiments with water.
- an alkyl diphenyl oxide sulfonic acid surfactant acid / fatty acid admixture should be added to water in use of the highly concentrated HAA in creating a surfactant for use and sale; water should not be added to the alkyl diphenyl oxide sulfonic acid surfactant acid / fatty acid admixture in use of the highly concentrated HAA in creating a surfactant for use and sale.
- the addition of water to the alkyl diphenyl oxide sulfonic acid surfactant acid / fatty acid admixture can function to induce substantive liquid crystal formation in the admixture and render the admixture too viscous for use since the dilution of HAA with water effects entry into the liquid crystal region.
- Octanoic acid at a 10 weight percent concentration based upon expected levels of DOWFAX Detergent Acid was added to aikylate during a sulfonation reaction
- a control reaction containing no octanoic acid under identical conditions yielded DOWFAX Detergent Acid exhibited a viscosity of 40,200 cP.
- the product of the sulfonation reaction containing the 10 weight percent octanoic acid had viscosity of 3,100 cP.
- a method for viscosity control in an alkyl diphenyl oxide sulfomc acid characterized by the step of: admixing a fatty acid having a carboxylic chain length between 1 and 12 into the alkyl diphenyl oxide sulfonic acid blend to provide between 5 weight percentage and 50 weight percentage of fatty acid in the admixture.
- a method for preparation of an alkyl diphenyl oxide sulfonic acid blend characterized by the steps of : admixing formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, or dodecanoic acid to provide between 5 weight percentage and 50 weight percentage of fatty acid in an admixture with an alkyl diphenyl oxide characterized by
- R is an alkyl radical having between 6 and 16 carbon atoms; and sulfonating said admixture with a sulfonating agent.
- a method for preparation of an alkyl diphenyl oxide sulfonic acid blend characterized by the steps of: admixing formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, or dodecanoic acid to provide between 5 weight percentage and 50 weight percentage of fatty acid in an admixture with an alkyl diphenyl oxide sulfomc acid blend characterized by
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Abstract
This invention addresses methods and compositions for providing alkyl diphenyl oxide sulfonic acid blends at useful viscosities for use in surfactants such as DOWFAX - containing surfactants. The low viscosity alkyl diphenyl oxide sulfonic acid blend is made by admixing a fatty acid having a carboxylic chain length between 1 and 12 (for example, formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, or dodecanoic acid into an alkyl diphenyl oxide sulfonic acid reaction product to provide between 5 weight percentage and 50 weight percentage of fatty acid in the admixture.
Description
where R is an alkyl radical having between 6 and 16 carbon atoms; and sulfonating said admixture with a sulfonating agent.
3 - An alkyl diphenyl oxide sulfonic acid blend having between 5 weight percentage and 50 weight percentage of a fatty acid with a carboxylic chain length between 1 and 12.
4 - An admixture composition of-
formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, or dodecanoic acid to provide between 5 weight percentage and 50 weight percentage of fatty acid in the admixture composition; and
alkyl diphenyl oxide characterized by
where R is an alkyl radical having between 6 and 16 carbon atoms
Turning now to an overview of the Figures, Figure 1 shows the impact of various levels of octanoic acid upon the viscosity of a DOWFAX alkyl diphenyl oxide sulfonic acid surfactant blend.
Figure 2 shows the impact of various levels of octanoic acid upon the viscosity of a DOWFAX alkyl diphenyl oxide sulfonic acid surfactant blend in the high viscosity range
Figure 3 shows the comparative impact of acetic, valeric, octanoic, and decanoic fatty acids on the viscosity of a DOWFAX alkyl diphenyl oxide sulfonic acid surfactant blend.
Figure 4 shows a ternary phase diagram showing significant liquid crystal phase regions for water, DOWFAX Detergent Acid, and fatty acid (acetic acid and octanoic acid).
In further discussion of details in the preferred embodiments, alkyl diphenyl oxide sulfonate surfactants are a Friedel-Crafts reaction product of an olefin and diphenyl oxide using AICI3 as a catalyst as indicated in Formula I.
Formula l
Olefin
Diphenyl oxide is present in excess and is recycled. The reaction yields a mixture of monoalkyl diphenyl oxide and dialkyl diphenyl oxide. The ratio of monoalkylation to dialkylation can be optimized depending on the end use of the products.
The next step in the process is the reaction of the alkylate with a sulfonating agent. This reaction (Formula II) is conducted in a solvent to dilute the reactant and to act as a diluent for the S03 used in the reaction.
Formula II
The reaction generally yields a mixture of monosulfonates and disulfonates according to Formulas III - VI. The level of disulfonation is determined by the end use of the product. Generally, the disulfonation level is above 80 percent. The predominant component in the commercial reaction mixture is the monoalkyl diphenyl oxide disulfonate (MADS) of Formula IV, with monoalkyl diphenyl oxide monosulfonate (MAMS) of Formula III, dialkyl diphenyl oxide monosulfonate (DAMS) of Formula V, and dialkyl diphenyl oxide disulfonate (DADS) of Formula VI essentially providing the remainder.
Forrnula iπ
Formula IV
Alkyl diphenyloxide sulfonates and their traditional methods of preparation are well-known and reference is made thereto for purposes of describing this invention. Representative methods of preparation and handling are disclosed in U.S. Patents 2,990,375; 3,264,242, 3,634,272; 3,945,437; and 5,015,367. The commercially available species are predominantly (greater than 85 percent) disulfonates (the DADS and MADS described above) and are a mixture of mono- and di- alkyl with the percentage of dialkylation (the DADS and DAMS described above) being 5 to 25 and the percentage of monoalkylation (the MAMS and MADS described above) being 75 to 95 percent. Most typically, the commercially available species are 85 percent monoalkyl and 15 percent dialkyl.
The traditional method taught by Steinhauer et al. (U.S. Pat. No. 2,990,375) outlines a series of steps, the first step comprising preparing an alkyldiphenyl ether by reacting an olefin or an
olefin ha de, such as tπpropylenes, tetrapropylenes, pentapropylenes or dodecyl bromide, with diphenyl ether at a temperature between 50° C and 100° C in the presence of the Fπedel-Crafts catalyst. The reaction mixture is washed with water to remove the catalyst, the phases separated, and the organic-rich phase subjected to distillation to obtain a fraction consisting of a mixture of monoalkylated diphenyl ether and dialkylated diphenyl ether. The number of alkyl substituents per diphenyl ether molecule can be controlled by adjusting the relative proportions of the reactants. Alternatively, the distillation can be performed so as to separate the monoalkylated and dialkylated diphenyl ethers from one another and from lower or higher boiling ingredients after which the monoalkylated and dialkylated diphenyl ether fractions can be combined at a desirable ratio.
The mixture of monoalkylated and dialkylated diphenyl ethers is subsequently reacted with a sulfonating agent, such as chlorosulfonic acid, sulfunc acid, or sulfur tπoxide, in an inert solvent
The general process of today uses reaction of an unsaturated hydrocarbon such as an alpha-olefin in the range of 6 to 16 carbons with diphenyl oxide in the presence of AICI3. Reaction of alpha-olefins in the higher range of 18-30 carbons with diphenyl oxide in the presence of AICI3 holds some promise for fulfilling future surfactant needs The ratio of mono- to dialkylation is controlled by the ratio of olefin to diphenyl oxide. Recycled excess diphenyl oxide is purified and reused. The rate of the reaction and the yield are controlled by the amount of catalyst and temperature of the alkylation. Excessively high temperatures as well as excessive amounts of catalyst yield higher levels of dialkylation and tnalkylation. Low temperatures result in a low conversion of olefin. The ratios of concentration, catalyst and temperature are critical in keeping the reaction products consistent throughout the production cycle. The catalyst is removed from the process stream and the crude reaction mixture is then stripped of excess diphenyl oxide. Additional purification is optionally effected prior to the sulfonation reaction.
Sulfonation is generally carried out in a solvent. The solvent provides value in distributing the sulfonating agent, preventing localized burning and yield loss of the reaction product, and acting as a heat removal medium in control of the reaction process temperature. Current commercial process routes use sulfur dioxide, methylene chloride, or air as reaction solvents. The air sulfonation process eliminates the need for the removal and recycle of the liquid reaction solvent and is amenable to onsite generation of S03 Liquid solvents require
7
the use of liquid S03 that is diluted into the solvent prior to addition to the sulfonation reactors. Sulfur tnoxide and chlorosulfonic acid are the two most common sulfonating agents.
After sulfonation, (1 ) the sulfomc acid is separated from its diluent, (2) the anhydrous acid (HAA) is diluted with water, and (3) neutralization of the diluted acid is optionally executed with an alkaline base such as sodium hydroxide. The material is packaged and sold in drums or bulk shipments as the customer requires.
The high viscosity of concentrated HAA derives from properties related to liquid crystal presence. This effect initiates at hydrophobe chain lengths above 6, is increasingly pronounced in observed samples to chain lengths of 16, and is expected to extend with greater significance to cases such as those which are contemplated via reaction of alpha- olefins in the higher range of 18-30 carbons with diphenyl oxide. Accordingly, a liquid crystal disrupter, or crystal structure breaker, is highly desirable as an additive for enabling useful viscosity in a useful HAA solids region (that is in an 60-95 percent solids range). In this regard, an additional component in the blend is most desirable which disrupts High Actives Acid (HAA) liquid crystal structure without imparting undesirable attributes to the resulting blend. In this regard, dimethylformamide (DMF) and methyl formamide (MF) effectively disrupt the liquid crystal structure in alkyl diphenyl oxide sulfonic acid blends used in deriving DOWFAX surfactants; but DMF and MF are not favored for use because of asserted health concerns.
It has been discovered that addition of fatty acids, for instance, caprylic (octanoic) or launc acid, to highly concentrated surfactant sulfonic acid can greatly reduce the surfactant viscosity and improve handling characteristics of HAA. The use of such an additive to form particular blends enables the manufacture and use of concentrated acid forms of these surfactants.
In an alternative embodiment, admixing the fatty acid with the alkyl diphenyl oxide prior to sulfonation also provides reduction of surfactant viscosity and improved handling characteristics in the HAA material
Formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, and
8
dodecanoic (lauπc) acid all provide benefit in low viscosity HAA formulations as further described with reference to the sample data in the Examples and Figures.
EXAMPLE 1
Samples containing straight-chain carboxylic acids from formic to launc acid were blended with a representative alkyl diphenyl oxide sulfonic acid surfactant with a 16-carbon hydrophobe side chain (DOWFAX Detergent Acid, 94 wt percent concentration) at levels of
10 wt percent carboxylic acid based upon DOWFAX amount. The viscosities of these samples were measured at 40 °C. The results are listed in Table 1
A Brookfield programmable rheometer, Model HDAV-III, was used to measure the viscosity of DOWFAX acid samples. The spindle size used was SC4-21 The viscosities of the samples were measured at 40 °C, a temperature at which the Thermosel temperature control stage was stable.
Approximately 8 mLs of sample were placed into the rheometer chamber. The spindle was inserted into the chamber so that the sample covered to 1/8 inch of the spindle shaft The chamber was placed into the temperature control stage and the spindle connected to the rheometer. The rheometer was auto-zeroed. Stirring was started at 1 RPM and the sample was allowed to temperature equilibrate for ten minutes. After the ten minutes, the motor was stopped, the sample was allowed to sit for five minutes, then the motor was started again. A reading was taken after the spindle made 5 revolutions The stirring was increased and the torque recorded until the allowable torque range on the instrument was exceeded The equation below was used to convert torque to viscosity in units of cP
Viscosity = 100/RPM * TK * SMC * Torque
Torque constant (TK) = 2
Spindle Multiply Constant (SMC) = 5
TABLE 1
Structure - Viscosity Modification Attributes of Carboxylic Acid Additives in DOWFAX Detergent Surfactant
[9.1 wt percent carboxylic acid, 85 5 wt percent DOWFAX Detergent, 5 4 wt percent water]
Carboxylic Acid Viscosity, cP Common (Systematic) (@ 40 8 °C)
Formic (methanoic) 7030
Acetic (ethanoic) 5847
Propanoic (propanoic) 4965
Butyric (butanoic) 5227
Valeric (pentanoic) 4970
Caproic (hexanoic) 6333
Enanthic (heptanoic) 6290
Capryhc (octanoic) 9360
Pelargonic (nonanoic) 9120
Capπc (decanoic) 15820
Laurie (dodecanoic) 18040
EXAMPLE 2
Samples containing a variety of concentrations (from 2 to 50 wt percent based upon DOWFAX acid amount) of a representative carboxylic acid, octanoic acid, were blended with a representative alkyl diphenyl oxide sulfonic acid surfactant with a 16-carbon hydrophobe side chain (DOWFAX Detergent Acid, or DD-HAA in Figures 1 and 2) at a variety of aqueous dilution levels (from 44 to 94 wt percent DOWFAX acid) Each sample was blended until homogeneous The viscosities of these samples were measured at 40 °C by the method indicated in Example 1 The results of these measurements are shown in Figures 1 and 2
Some of the samples (a) exhibited liquid crystal behavior with very high viscosities and (b) turned solid-like in consistency These samples typically exhibited viscosities exceeding the
10
upper measuring limit of the rheometer (1 ,000,000 cP), and these samples are shown as having viscosities of 1 ,000,000 cP in the Figures. The behavior of DOWFAX Detergent Acid containing no carboxylic acid ("0 wt percent OA") is shown for comparison purposes in both Figures 1 and 2.
The onset of the liquid crystal phase in Figure 1 is apparent at the rapid rise of viscosity with decrease of solids in the 69 percent to 90 percent solids range (depending on the particular concentration of octanoic acid). Only at 30 percent octanoic acid is the liquid crystal phase evidently suppressed.
EXAMPLE 3.
Samples containing a variety of concentrations (from 2 to 30 wt percent) of four representative carboxylic acids (acetic, valeric, octanoic, and decanoic acids) each were blended with a representative alkyl diphenyl oxide sulfonic acid surfactant with a 16-carbon hydrophobe side chain (DOWFAX Detergent Acid, 94 wt percent concentration). Each sample was blended until homogeneous. The viscosities of these samples were measured at 40 °C by the method indicated in Example 1. The results of these measurements are shown in Figure 3. The behavior of DOWFAX Detergent Acid containing no carboxylic acid (at "0 wt percent additive concentration" on the graph) is shown for comparison.
Comparison of the data for all acids at concentrations above 0 percent in Figure 3 with the 0 percent case help to further illustrate the general viscosity reducing influence of fatty acids on an HAA such as the tested DOWFAX Detergent Acid
The data of Figure 3 indicate a higher significance of fatty acid chain length toward viscosity reduction at the 5 weight percent fatty acid concentration.
EXAMPLE 4:
Samples containing various ratios of either acetic or octanoic acid, as representative carboxylic acids, of a representative alkyl diphenyl oxide sulfonic acid surfactant with a 16- carbon hydrophobe side chain (DOWFAX Detergent Acid), and water were prepared. Each sample was blended until homogeneous. Gross visual examination of each sample was made to identify the presence of a solid-like, liquid crystal phase. Data defining the composition of samples exhibiting such a highly viscous phase were plotted on a ternary
1 1
phase diagram to ascertain the phase boundary. Boundary regions for blends with either acetic acid or octanoic acid are shown in Figure 4
The ternary phase diagram of Figure 4 shows significant liquid crystal phase regions for water, DOWFAX surfactant acid, and two fatty acids (acetic acid and octanoic acid). The phase boundary is indicated where the viscosity measures 1 million centipoise or greater at room temperature and pressure. The high viscosity area underscores the importance of the method of addition in admixing the alkyl diphenyl oxide sulfomc acid surfactant and fatty acid blend of the described embodiments with water. It should be noted successful combination of HAA with water requires attentiveness to the issue of progression in component concentration with respect to phase control according to the depiction of Figure 4 In this regard, an alkyl diphenyl oxide sulfonic acid surfactant acid / fatty acid admixture should be added to water in use of the highly concentrated HAA in creating a surfactant for use and sale; water should not be added to the alkyl diphenyl oxide sulfonic acid surfactant acid / fatty acid admixture in use of the highly concentrated HAA in creating a surfactant for use and sale. In this regard, with reference to Figure 4, the addition of water to the alkyl diphenyl oxide sulfonic acid surfactant acid / fatty acid admixture can function to induce substantive liquid crystal formation in the admixture and render the admixture too viscous for use since the dilution of HAA with water effects entry into the liquid crystal region.
EXAMPLE 5:
Octanoic acid at a 10 weight percent concentration based upon expected levels of DOWFAX Detergent Acid was added to aikylate during a sulfonation reaction A control reaction containing no octanoic acid under identical conditions yielded DOWFAX Detergent Acid exhibited a viscosity of 40,200 cP. The product of the sulfonation reaction containing the 10 weight percent octanoic acid had viscosity of 3,100 cP.
The beneficial results from use of fatty acids in the described embodiments indicate that fatty alcohols, fatty amines, or even linear alkanes in the C6 - C18 range warrant consideration and empirical study in contemplated embodiment blends.
12
We claim:
1. A method for viscosity control in an alkyl diphenyl oxide sulfomc acid, characterized by the step of: admixing a fatty acid having a carboxylic chain length between 1 and 12 into the alkyl diphenyl oxide sulfonic acid blend to provide between 5 weight percentage and 50 weight percentage of fatty acid in the admixture.
2. A method for preparation of an alkyl diphenyl oxide sulfonic acid blend characterized by the steps of : admixing formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, or dodecanoic acid to provide between 5 weight percentage and 50 weight percentage of fatty acid in an admixture with an alkyl diphenyl oxide characterized by
where R is an alkyl radical having between 6 and 16 carbon atoms; and sulfonating said admixture with a sulfonating agent.
3. The method of Claim 2 wherein a plurality of said fatty acids are admixed in said admixing step with said alkyl diphenyl oxide blend.
4. A method for preparation of an alkyl diphenyl oxide sulfonic acid blend characterized by the steps of: admixing formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, or dodecanoic acid to provide between 5 weight percentage and 50 weight percentage of fatty acid in an admixture with an alkyl diphenyl oxide sulfomc acid blend characterized by
13
Claims
where R is an alkyl radical having between 6 and 16 carbon atoms.
5. The method of Claim 4 wherein a plurality of said fatty acids are admixed admixed in said admixing step with said alkyl diphenyl oxide sulfonic acid blend.
6. The method of either of Claims 4 or 5 wherein the alkyl diphenyl oxide sulfonic acid blend prior to admixing of said fatty acid is characterized by:
between 5 to 25 weight percent
14
between 75 to 95 respective weight percent
greater than 85 weight percent
7. The method of either of Claims 2 or 3 wherein the alkyl diphenyl oxide blend prior to admixing of said fatty acid is characterized by:
between 5 to 25 weight percent
between 75 to 95 respective weight percent
15
8. An alkyl diphenyl oxide sulfomc acid blend having between 5 weight percentage and 50 weight percentage of a fatty acid with a carboxylic chain length between 1 and 12.
9. An admixture composition of:
formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, or dodecanoic acid to provide between 5 weight percentage and 50 weight percentage of fatty acid in the admixture composition; and
alkyl diphenyl oxide characterized by
where R is an alkyl radical having between 6 and 16 carbon atoms
10. The admixture composition of Claim 9 having a plurality of said fatty acids
11. An alkyl diphenyl oxide sulfomc acid blend characterized by:
formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, or dodecanoic acid to provide between 5 weight percentage and 50 weight percentage of fatty acid in the blend; and
alkyl diphenyl oxide sulfomc acid characterized by
16
where R is an alkyl radical having between 6 and 16 carbon atoms.
12. The blend of Claim 11 having a plurality of said fatty acids.
13. The blend of either of Claims 11 or 12 wherein the alkyl diphenyl oxide sulfonic acid blend without consideration of the weight of said fatty acid is characterized by:
between 5 to 25 weight percent
17
between 75 to 95 respective weight percent
greater than 85 weight percent
14. The method of either of Claims 2 or 3 wherein the alkyl diphenyl oxide blend without consideration of the weight of said fatty acid is characterized by:
between 5 to 25 weight percent
between 75 to 95 respective weight
18
15. A method for preparation of a surfactant characterized by the steps of:
admixing formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, or dodecanoic acid to provide between 5 weight percentage and 50 weight percentage of fatty acid in an admixture with an alkyl diphenyl oxide characterized by
where R is an alkyl radical having between 6 and 16 carbon atoms; sulfonating said admixture with a sulfonating agent; blending the sulfonated admixture into water; and neutralizing the blend of water and sulfonated admixture.
16. A method for preparation of a surfactant characterized by the steps of:
admixing formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, or dodecanoic acid to provide between 5 weight percentage and 50 weight percentage of fatty acid in an admixture with an alkyl diphenyl oxide sulfonic acid blend characterized by
between 5 to 25 weight percent
19
between 75 to 95 respective weight percent
greater than 85 weight percent
blending the sulfonated admixture into water; and neutralizing the blend of water and sulfonated admixture; where R is an alkyl radical having between 6 and 16 carbon atoms.
20
VISCOSITIES OF AQUEOUS DILUTIONS OF DOWFAX DETERGENT CONTAINING VARIOUS LEVELS OF OCTANOIC ACID ADDITIVE
30 40 50 60 70 80 90 100
DD CONCENTRATION, WT % SOLIDS
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14639599P | 1999-07-30 | 1999-07-30 | |
| US146395P | 1999-07-30 | ||
| PCT/US2000/018287 WO2001008793A1 (en) | 1999-07-30 | 2000-06-30 | Low viscosity alkyl diphenyl oxide sulfonic acid blends |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1204465A1 true EP1204465A1 (en) | 2002-05-15 |
Family
ID=22517176
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00946991A Withdrawn EP1204465A1 (en) | 1999-07-30 | 2000-06-30 | Low viscosity alkyl diphenyl oxide sulfonic acid blends |
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| Country | Link |
|---|---|
| EP (1) | EP1204465A1 (en) |
| JP (1) | JP2003505520A (en) |
| CN (1) | CN1365299A (en) |
| CA (1) | CA2379347A1 (en) |
| MX (1) | MXPA02001105A (en) |
| TW (1) | TW524716B (en) |
| WO (1) | WO2001008793A1 (en) |
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| KR100553594B1 (en) * | 2002-10-14 | 2006-02-20 | (주)에스앤에프 | Hydrosetting Polyurethane Casting Sheet |
| EP2903950B1 (en) * | 2012-10-01 | 2019-02-13 | Huntsman Petrochemical LLC | Surfactant formulation for release of underground fossil fluids |
| CN109415621A (en) * | 2016-07-12 | 2019-03-01 | 陶氏环球技术有限责任公司 | The foaming and molding composition of oil recycling is assisted for steam |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE4203439B4 (en) * | 1992-02-06 | 2006-04-13 | Showa Denko K.K. | Process for the preparation of chlorinated polyolefins |
-
2000
- 2000-06-30 MX MXPA02001105A patent/MXPA02001105A/en not_active Application Discontinuation
- 2000-06-30 CN CN00810905A patent/CN1365299A/en active Pending
- 2000-06-30 WO PCT/US2000/018287 patent/WO2001008793A1/en not_active Ceased
- 2000-06-30 CA CA002379347A patent/CA2379347A1/en not_active Abandoned
- 2000-06-30 EP EP00946991A patent/EP1204465A1/en not_active Withdrawn
- 2000-06-30 JP JP2001513513A patent/JP2003505520A/en active Pending
- 2000-07-13 TW TW089113966A patent/TW524716B/en active
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| Title |
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| See references of WO0108793A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| MXPA02001105A (en) | 2002-08-20 |
| WO2001008793A1 (en) | 2001-02-08 |
| CN1365299A (en) | 2002-08-21 |
| JP2003505520A (en) | 2003-02-12 |
| TW524716B (en) | 2003-03-21 |
| CA2379347A1 (en) | 2001-02-08 |
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