USRE28325E - Oh cooh - Google Patents
Oh cooh Download PDFInfo
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- USRE28325E USRE28325E US25882172A USRE28325E US RE28325 E USRE28325 E US RE28325E US 25882172 A US25882172 A US 25882172A US RE28325 E USRE28325 E US RE28325E
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- United States
- Prior art keywords
- cooh
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- chz
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- chy
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 38
- 239000003352 sequestering agent Substances 0.000 abstract description 33
- 239000007788 liquid Substances 0.000 abstract description 22
- 229910018828 PO3H2 Inorganic materials 0.000 abstract description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 abstract 8
- 229910014568 C—O-M Inorganic materials 0.000 abstract 1
- 229910006069 SO3H Inorganic materials 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 20
- 239000013522 chelant Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- 238000006959 Williamson synthesis reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VBZOUUJVGADJBK-UHFFFAOYSA-N 2-bromopropanedioic acid Chemical compound OC(=O)C(Br)C(O)=O VBZOUUJVGADJBK-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- -1 cobaltous ions Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- WRROCBSAWQVHJG-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarbonyl bromide Chemical compound C(CC(O)(C(=O)Br)CC(=O)Br)(=O)Br WRROCBSAWQVHJG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 101150029512 SCG2 gene Proteins 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000001874 trioxidanyl group Chemical group [*]OOO[H] 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/22—Organic compounds, e.g. vitamins
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
-
- 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
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/06—Inorganic compounds
- C11D9/18—Water-insoluble compounds
Definitions
- the present invention relates to sequestering agents and, more particularly, sequestering agents consisting of an ether chelating molecule having carboxylic acid, [phosphoric acid and/or sulfonic acid] groups thereon.
- sequestering agents utilized up to the present time, have not proven as eflicient or as selective of particular ions as desirable in many cases.
- sequestering agents While it has often been desirable in the separation of metals to utilize sequestering agents which show an afiinity for particular metals, such sequestering agents have not been available for all the separations desired.
- M is selected from the group consisting of 0H COOH A I as, and
- X, Y, and Z are selected from the group consisting of H, COOH, and OH; a, b, and c are integers of from 0 to l, at least one member of a, b, and c being 1;
- G is selected from the group consisting of Re. 28,325 Reissued Jan. 28, 1975 COOH A, B, and D are selected from the group consisting of CH COOH, [CH SO H,] A, B and D together having no more than two of the units COOH, H, [SO H, PO H J CHOHCOOH,
- the present compounds are more efiicient sequestering agents than are the citrates, tartrates and other similar materials.
- the present compounds are more useful in metal separations than are the conventional amine sequestering agents, e.g. ethylene diamine tetraacetic acid, since magnesium, calcium, strontium, barium, tin, vanadium, molybdenum, uranium, ferric, and cobaltous ions show a greater affinity for oxygen electron sharing than for nitrogen electron sharing.
- the present compounds are particularly useful in ion exchange resins for multivalent metal separations.
- Example 1 R 0H bHoooH 0- cHi)z0-d-0 0 OH dine 0 OH
- Example 2 CO CH CHiCO OH
- Example 3 ethylene glycol dlmulonate
- 160 gm. sodium carbonate (1 mole) 160 gm. of diethyl malonate (1 mole)
- 450 gm. thiophene-free benzene distilled from sodium.
- 160 gm. of bromine were added slowly over the course of 6 hours. The temperature was maintained at 303S C. After an additional 2 hours stirring, all of the bromine color was gone.
- the bromodiethyl malonate was separated from salts by filtration.
- the reactor was heated to 37 C. and the glycol feed was started. Temperature was maintained by occasional immersion in a methanol bath at 40 C. After one hour all of the diethylene glycol /6 mol) was added. After an additional 10 minutes, no further cooling was required.
- the batch was heated over the course of one hour to 54 C.
- the lithium adduct was a gray thick slurry-solution.
- the bromo diethyl malonate was then started, but after onehalf hour the slurry became extremely thick. It was found that an additional 500 cc. of distilled tetrahydrofurane and a temperature of 70 C. would maintain a fluidized mixture while the additional bromomalonate was added. The bromomalonate was added at 70 C. over an 8-hour period. The mixture was cooled and exposed to the atmosphere for 24 hours in an open tray. Water was added to separate a benzene layer. This benzene layer was found to contain the lithiums parafiin wax. The remainder of the mixture was thinned with 200 cc. of methanol and filtered. cc.
- the eflluent was evaporated and found to be malonic acid.
- the second fraction was passed through an ion-exchange column and evaporated.
- the product was a thick yellow liquid with some crystals.
- the product was dissolved in acetone and the acetone evaporated.
- the product was titrated with sodium hydroxide, found 70.3 gm. per carboxyl (77 g. theoretical).
- the product was titrated with ferric chloride at a pH of 4, salicylic acid indicator, found l.l moles Fe ion per 310 gms. (one mole theoretically).
- the third fraction was apparently either decarboxylated malonateglycol-malonate, or partly reacted glycol malonate.
- Two fractions were isolated therefrom, fraction (a) insoluble in cold acetone, sodium hydroxide titre 230 gm. per carboxyl; and fraction (b) soluble in acetone, 120 gm. per carboxyl.
- Example 12 00011 00 OH H-(J-O-(CI-hh- H OOH OOH Citric acid is reacted with HBr to form citric bromide which in turn is reacted with alkaline salicylic acid.
- Example 16 CHBCOOH CHaCOOH
- Example 17 Example 18 C O OH CHQC O OH 0-CHz-CH-CHr-N OOH CHaCOOH
- M M--O-(CHX),(CHY) (CHZ) G wherein M is selected from the group consisting of X, Y, and Z are selected from the group consisting of H, COOH, and OH;
- a, b, and c are integers of from 0 to 1, at least one member of a, b, and c being 1;
- G is selected from the group consisting of COOII A, B, and D are selected from the group consisting of CH COOH, CH SO H, A, B and D together having no more than two of the units COOH, H, -SO H, PO H -CHOHCOOH,
- E and F are selected from the group consisting of CH COOH, CH(COOH)z, H, -CH CH OH, -CH CH OCH CH OH,
- p being an integer of from 0 to 2.
- HaCCOOH 0-fL-COOH 15000011 16 The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
- G is selected from the group consisting 0] COOH and O(CHX),,(CHY),,(CHZ),.OM
- A, B and D are selected from the group consisting of CH COOH, CH 50,11, -COOH, --H,
- G is selected from the group consisting ofi' COOH and O-(CHX),(CHY) (CHZ) O-M A, B and D being selected from the group consisting of -CH COOH, --COOH, H, CHOHCO0H,
- G being selected from the group consisting of:
- A, B and D being selected from the group consisting of: CH;COOH, CO0H, -H, CHOHCO0H, and (CHZ) (CHY) (CHX) 0-M with no more than two of the units A, B and D being (CHZ) (CHY) (CHX),,OM.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Hydrology & Water Resources (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
THEREFROM WHICH COMPRISES CONTACTING SAID LIQUID MEDIA WITH A SEQUESTERING AGENT OF THE FORMULA:
M-O-(CHX)A(CHY)B(CHZ)C-G
WHERIN M IS SELECTED FROM THE GROUP CONSISTING OF
-C(-A)(-B)-D , 2-(HO-)PHENYL ,AND 2-(HOOC-)PHENYL
X=Y=-H,-COOH Z=--OH,-COOH A=B=O,1 C=O,1 WITH AT LEAST ONE OF A, B, AND C BEING 1; G IS SELECTED FROM THE GROUP CONSISTING OF
-O-C(-A)(-B)-D , -C(-A)(-D)-Y , -O-(2-(HO-)PHENYL) ,
-O-(2-(HOOC-)PHENYL)
AND-O-(CHX)A(CHY)B(CHZ)C-O-M A,B AND D AARE SELECTED FROM THE GROUP CONSISTING OF -CH2COOH,-CH2SO3H,-COOH,-H -SO2H,-PO2H2, -CHOHCOOH,
2-(HOOC-)PHENYL , 2-(HO-)PHENYL
AND -(CHZ)C(CHY)B(CHX)A-O-M WITH NO MORE THAN TWO OF THE UNITS A, B AND D BEING -COOH,-H -SO3H, -PO3H2, -CHORCOOH,
2-(HOOC-)PHENYL , 2-(HO-)PHENYL
AND NO MORE THAN ONE OF THE UNITS A, B AN D BEING -(CHZ)C(CHY)B(CHX)A-O-M.
M-O-(CHX)A(CHY)B(CHZ)C-G
WHERIN M IS SELECTED FROM THE GROUP CONSISTING OF
-C(-A)(-B)-D , 2-(HO-)PHENYL ,AND 2-(HOOC-)PHENYL
X=Y=-H,-COOH Z=--OH,-COOH A=B=O,1 C=O,1 WITH AT LEAST ONE OF A, B, AND C BEING 1; G IS SELECTED FROM THE GROUP CONSISTING OF
-O-C(-A)(-B)-D , -C(-A)(-D)-Y , -O-(2-(HO-)PHENYL) ,
-O-(2-(HOOC-)PHENYL)
AND-O-(CHX)A(CHY)B(CHZ)C-O-M A,B AND D AARE SELECTED FROM THE GROUP CONSISTING OF -CH2COOH,-CH2SO3H,-COOH,-H -SO2H,-PO2H2, -CHOHCOOH,
2-(HOOC-)PHENYL , 2-(HO-)PHENYL
AND -(CHZ)C(CHY)B(CHX)A-O-M WITH NO MORE THAN TWO OF THE UNITS A, B AND D BEING -COOH,-H -SO3H, -PO3H2, -CHORCOOH,
2-(HOOC-)PHENYL , 2-(HO-)PHENYL
AND NO MORE THAN ONE OF THE UNITS A, B AN D BEING -(CHZ)C(CHY)B(CHX)A-O-M.
Description
XR RE28325 United States Patent Int. Cl. C02b 5/06 US. Cl. 210-58 14 Claims Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
This is a continuation-in-part of application Serial No. 765,924, tiled October 8, 1958, and now abandoned.
The present invention relates to sequestering agents and, more particularly, sequestering agents consisting of an ether chelating molecule having carboxylic acid, [phosphoric acid and/or sulfonic acid] groups thereon.
sequestering agents, utilized up to the present time, have not proven as eflicient or as selective of particular ions as desirable in many cases. In addition, while it has often been desirable in the separation of metals to utilize sequestering agents which show an afiinity for particular metals, such sequestering agents have not been available for all the separations desired.
It is therefore an object of the present invention to overcome the disadvantages inherent in the prior art, such as those indicated above.
It is another object of the present invention to provide sequestering agents useful for the textile and soap industries in the preparation of cleaning products.
It is another object of the present invention to provide a new group of metal deactivators and carriers in both aqueous and organic solutions.
It is another object of the present invention to provide new sequestering agents.
It is another object of the present invention to provide sequestering agents which are easily and inexpensively synthesized.
It is another object of the present invention to utilize as sequestering agents, materials which comprise an ether chelating molecule having acid groups thereon.
These and other objects and the nature and advantages of the present invention will be apparent from the following description.
The compounds of the present invention fall within the general formula:
wherein M is selected from the group consisting of 0H COOH A I as, and
X, Y, and Z are selected from the group consisting of H, COOH, and OH; a, b, and c are integers of from 0 to l, at least one member of a, b, and c being 1;
G is selected from the group consisting of Re. 28,325 Reissued Jan. 28, 1975 COOH A, B, and D are selected from the group consisting of CH COOH, [CH SO H,] A, B and D together having no more than two of the units COOH, H, [SO H, PO H J CHOHCOOH,
COOH OH and no more than one unit of (CHZ) (CHY);,(CHX) O-M [E and F are selected from the group consisting of CH COOH, CH(COOH)z, H, CH CH OH, CH CH OCH CH OH on on on cmo u-' $0011 i cin).,rono
(CH SO H, and no more than one unit of omcmN and p is an integer of from 0 to 2.]
These materials are all broadly ethers and may be synthesized by the conventional ether producing reactions, such as the Williamson ether synthesis.
The present compounds are more efiicient sequestering agents than are the citrates, tartrates and other similar materials. In addition, the present compounds are more useful in metal separations than are the conventional amine sequestering agents, e.g. ethylene diamine tetraacetic acid, since magnesium, calcium, strontium, barium, tin, vanadium, molybdenum, uranium, ferric, and cobaltous ions show a greater affinity for oxygen electron sharing than for nitrogen electron sharing. In addition, the present compounds are particularly useful in ion exchange resins for multivalent metal separations.
The following specific examples are presented by way of illustration only and are not intended as limiting the invention. The compounds of Examples 1, 2, 3, 5, 6, 7, 8, 9, 10, 12 and 13 are produced by the Williamson ether synthesis and when tested provide good sequestering agents.
Example 1 R 0H bHoooH 0- cHi)z0-d-0 0 OH dine 0 OH Example 2 CO CH CHiCO OH Example 3 ethylene glycol dlmulonate To a. three-neck flask, fitted with stirrer, dropping funnel, thermometer, and N, inlet was charged 160 gm. sodium carbonate (1 mole), 160 gm. of diethyl malonate (1 mole) and 450 gm. thiophene-free benzene distilled from sodium. 160 gm. of bromine were added slowly over the course of 6 hours. The temperature was maintained at 303S C. After an additional 2 hours stirring, all of the bromine color was gone. The bromodiethyl malonate was separated from salts by filtration. To another three-neck flask fitted with stirrer, thermometer, nitrogen inlet, reflux condenser and dropping funnel, was charged 1 mole of lithium dispersion in wax and 250 cc. of sodium dried benzene. Diethylene glycol dried 8 hours in a 60 C. vacuum oven was then added dropwise. The reactor was heated to 37 C. and the glycol feed was started. Temperature was maintained by occasional immersion in a methanol bath at 40 C. After one hour all of the diethylene glycol /6 mol) was added. After an additional 10 minutes, no further cooling was required. The batch was heated over the course of one hour to 54 C. The lithium adduct was a gray thick slurry-solution. The bromo diethyl malonate was then started, but after onehalf hour the slurry became extremely thick. It was found that an additional 500 cc. of distilled tetrahydrofurane and a temperature of 70 C. would maintain a fluidized mixture while the additional bromomalonate was added. The bromomalonate was added at 70 C. over an 8-hour period. The mixture was cooled and exposed to the atmosphere for 24 hours in an open tray. Water was added to separate a benzene layer. This benzene layer was found to contain the lithiums parafiin wax. The remainder of the mixture was thinned with 200 cc. of methanol and filtered. cc. of 20% hydrogen peroxide was added, stirred in, 300 cc. water was then stirred in and the mix allowed to settle for 18 hours. The upper layer was discarded and the lower layer was hydrolyzed with a solution of 90 gm. sodium hydroxide, 90 gm. water, 200 cc. methanol. The mixture exothermed and was allowed to stand 18 hours. Water was added to dissolve the mixture and the mixure was heated. The 600 cc. of solution was filtered and heated an additional 4 hours at 60-70 C. Alcohol was then added continuously and three fractions were filtered off. The least soluble fraction was passed through an acidified Dowex 50 (sulfonated polystyrene) ion exchange column. The eflluent was evaporated and found to be malonic acid. The second fraction was passed through an ion-exchange column and evaporated. The product was a thick yellow liquid with some crystals. The product was dissolved in acetone and the acetone evaporated. The product was titrated with sodium hydroxide, found 70.3 gm. per carboxyl (77 g. theoretical). The product was titrated with ferric chloride at a pH of 4, salicylic acid indicator, found l.l moles Fe ion per 310 gms. (one mole theoretically). The third fraction was apparently either decarboxylated malonateglycol-malonate, or partly reacted glycol malonate. Two fractions were isolated therefrom, fraction (a) insoluble in cold acetone, sodium hydroxide titre 230 gm. per carboxyl; and fraction (b) soluble in acetone, 120 gm. per carboxyl.
4 [Example 5 Clip- H CH COOH Example 6 CHnP 03H,
HO O C- O(CH;)1N
HzCOOH CHaS OaH Example 7 CHaCHa-N CH COOH Example 8 CHzCHzO CHzCHzOH [Example 9 Example 10 CHICHI OH Example 11 COOH COOH This compound is found to have good sequestering properties.
Example 12 00011 00 OH H-(J-O-(CI-hh- H OOH OOH Citric acid is reacted with HBr to form citric bromide which in turn is reacted with alkaline salicylic acid.
CONa HOH Br- COOH H2 COOH COOH ail-C OOH -O-C-COOH NaOH NaBr The compounds of the following Examples 15 and 17 are also prepared by the Williamson ether synthesis and are found to be excellent sequestering agents:
Example 16 CHBCOOH CHaCOOH Example 17 Example 18 C O OH CHQC O OH 0-CHz-CH-CHr-N OOH CHaCOOH It will be obvious to those skilled in the art that various changes may be made without departing from the spirit of the invention and therefore the invention is not limited to what is described in the specification, but only as indicated in the appended claims.
What is claimed is:
[1. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
M--O-(CHX),(CHY) (CHZ) G wherein M is selected from the group consisting of X, Y, and Z are selected from the group consisting of H, COOH, and OH;
a, b, and c are integers of from 0 to 1, at least one member of a, b, and c being 1;
G is selected from the group consisting of COOII A, B, and D are selected from the group consisting of CH COOH, CH SO H, A, B and D together having no more than two of the units COOH, H, -SO H, PO H -CHOHCOOH,
and no more than one unit of E and F are selected from the group consisting of CH COOH, CH(COOH)z, H, -CH CH OH, -CH CH OCH CH OH,
'(CH2) PO3H2, (CHQ)DSO3H, and E and F [O- gether having no more than one unit of -crncH,N
p being an integer of from 0 to 2.]
2. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
3. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
COOH
CHaCOOH H- -O(CHCOOH);O H
HaCOOH therefrom which comprises contacting said media with a sequestering agent of the formula:
[6. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
CH PO;H:
H H OCHOHN OH HICOOH CH OOOH [7. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
[8. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
COOH
H -o cu) 2- H crncoon oon ClhCH -N CH(COOH):
[9. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
C O O H CHACHQ O CH CHaOH HO-O-(CHOHh-N OOH CH;
[10. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
8 [11. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
CHsCOOH JOOH): CHICOOH 12. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
COOH COOH 13. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
COOH C OOH H-JJ-O-(Clhh- H OOH OOH 14. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
15. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
OOOH
HaCCOOH 0-fL-COOH 15000011 16. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
CHgC OOH 0-CHz-CHy-O-C-C O OH CHgCOOH [17. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
coon orneoon nd-o-cm-oa-cmn on H cmooon 18. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
v 9; Q a [1-9. The method of treating liquid media to chelate ions therefrom which comprises contacting said media with a sequestering agent of the formula:
COOH
CH, C 0H 5 O-Cm-C H CH,-N
O OH CH: C O OH 20. The method of treating a liquid media to chelate ions therefrom which comprises contacting said liquid media with a sequestering agent of the formula:
MO-(CHX),,(CHY) ,(CHZ) G wherein M is selected from the group consisting of OH 000H 2 B, and i X Y=--H, COOH Z =-OH -C OOH a: b =0, 1 c=0, 1
with at least one of a, b and c being I; G is selected from the group consisting 0] COOH and O(CHX),,(CHY),,(CHZ),.OM
A, B and D are selected from the group consisting of CH COOH, CH 50,11, -COOH, --H,
-SO H, PO H CHOHCOOH,
COOH OH and -(CHZ) (CHY);,(CHX) -0M with no more than two of the units A, B and D being CO0H, -H -S0 H, PO H --CHOHCOOH,
C0 OH OH iii) MO(CHX) )CHY) (CHZ) -G wherein M is selected from the group consisting of 1 0 a b 0, 1 0:0, I
with at least one of a, b and c being I; G is selected from the group consisting ofi' COOH and O-(CHX),(CHY) (CHZ) O-M A, B and D being selected from the group consisting of -CH COOH, --COOH, H, CHOHCO0H,
COOH OH iii) and -(CHX),,(CHY) ,(CHZ) OM with no more than two units of A, B and D being --CO0H, H CHOHCO0H,
COOH 0H s w s and no more than one unit of A, B and D being -(CHZ) (CHY) ,(CHX) OM.
22. The method of treating a liquid media to chelate ions therefrom which comprises contacting said liquid media with a sequestering agent of the formula:
wherein M is A l F B X Y=H. COOH; Z=OH, CO0H; a=b=0, 1 0:0, I
with at least one of a, b and c being I; G being selected from the group consisting of:
and 0-(CHX),,(CHY];,(CHZ) -O-M A, B and D being selected from the group consisting of: CH;COOH, CO0H, -H, CHOHCO0H, and (CHZ) (CHY) (CHX) 0-M with no more than two of the units A, B and D being (CHZ) (CHY) (CHX),,OM.
23. The method of treating a liquid media to chelate ions therefrom which comprises contacting said liquid media with a sequestering agent of the formula:
M-ocHx cHY cHz ,-o
wherein M is 1 1 X: Y=H; Re. 22,352 g 1 2,936,242 1 3,128,287 with at least I of a, b and 0 being I; 59,418 A, B and D being selected from the group consisting 2,240,957 of: -H, -CO0H, -CH;COOH, with no more 2,311,003 than two of the units A, B and D being the same; 3 G being selected from the group consisting of 2,727,867 2,868,724 2,894,905 3,130,153 3 1 3,234,124 -Y, -0- -B,
References Cited The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.
12 UNITED STATES PATENTS Teeters 102-1 Brauer 106-35 Berg 252-351 X Lawrence 210-58 Munz 252-117 Tucker 210-58 Ryznar 252-321 Denman 252-321 Zech 210-58 Bernard 210-58 Keller 210-58 Irani 210-38 FOREIGN PATENTS 6/1939 Germany.
US. Cl. X.R.
252-180, 189; 260-429 I, 507 R, 513 N, 519, 520,
THOMAS G. WYSE, Primary Examiner
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US25882172 USRE28325E (en) | 1958-10-08 | 1972-06-01 | Oh cooh |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US76592458A | 1958-10-08 | 1958-10-08 | |
US356629A US3293176A (en) | 1964-04-01 | 1964-04-01 | Method of chelating with an ethergroup-containing sequestering agent |
US25882172 USRE28325E (en) | 1958-10-08 | 1972-06-01 | Oh cooh |
Publications (1)
Publication Number | Publication Date |
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USRE28325E true USRE28325E (en) | 1975-01-28 |
Family
ID=27401173
Family Applications (1)
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US25882172 Expired USRE28325E (en) | 1958-10-08 | 1972-06-01 | Oh cooh |
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US (1) | USRE28325E (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US4143125A (en) | 1976-12-27 | 1979-03-06 | Monsanto Company | Calculus-inhibiting compositions and method |
US4182905A (en) | 1974-05-17 | 1980-01-08 | Monsanto Company | Chemical compounds |
US4663071A (en) | 1986-01-30 | 1987-05-05 | The Procter & Gamble Company | Ether carboxylate detergent builders and process for their preparation |
US4798907A (en) | 1988-02-26 | 1989-01-17 | The Procter & Gamble Company | Controlled temperature process for making 2,2'-oxodisuccinates useful as laundry detergent builders |
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US2240957A (en) * | 1935-10-30 | 1941-05-06 | Gen Aniline & Film Corp | Process for avoiding and rendering harmless the precipitates of water insoluble metal salts |
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US3128287A (en) * | 1963-01-31 | 1964-04-07 | Pfizer & Co C | 2,2'-oxodisuccinic acid, derivatives thereof, and process for preparing |
US3130153A (en) * | 1959-05-13 | 1964-04-21 | Jr Howard F Keller | Treatment of water to prevent scaling or corrosion |
US3234124A (en) * | 1962-10-18 | 1966-02-08 | Monsanto Co | Sequestration of metal ions |
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US22352A (en) * | 1858-12-21 | And james r | ||
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DE677600C (en) * | 1933-10-07 | 1939-06-29 | August Chwala Dipl Ing Dr | Process for the production of sulfonic acids of higher molecular weight aliphatic amino ethers |
US2240957A (en) * | 1935-10-30 | 1941-05-06 | Gen Aniline & Film Corp | Process for avoiding and rendering harmless the precipitates of water insoluble metal salts |
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US4182905A (en) | 1974-05-17 | 1980-01-08 | Monsanto Company | Chemical compounds |
US4143125A (en) | 1976-12-27 | 1979-03-06 | Monsanto Company | Calculus-inhibiting compositions and method |
US4663071A (en) | 1986-01-30 | 1987-05-05 | The Procter & Gamble Company | Ether carboxylate detergent builders and process for their preparation |
US4798907A (en) | 1988-02-26 | 1989-01-17 | The Procter & Gamble Company | Controlled temperature process for making 2,2'-oxodisuccinates useful as laundry detergent builders |
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