EP0647248A1 - Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides - Google Patents
Surfactants derived from polyoxyalkylenes and substituted succinic anhydridesInfo
- Publication number
- EP0647248A1 EP0647248A1 EP93913432A EP93913432A EP0647248A1 EP 0647248 A1 EP0647248 A1 EP 0647248A1 EP 93913432 A EP93913432 A EP 93913432A EP 93913432 A EP93913432 A EP 93913432A EP 0647248 A1 EP0647248 A1 EP 0647248A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- compound
- formula
- group
- alkyl
- water
- 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- Withdrawn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
- 239000004094 surface-active agent Substances 0.000 title abstract description 33
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 title abstract 2
- 210000002268 wool Anatomy 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 71
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- -1 alkali metal cation Chemical class 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 150000001768 cations Chemical class 0.000 claims description 12
- 239000007762 w/o emulsion Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 239000004166 Lanolin Substances 0.000 claims description 8
- 235000019388 lanolin Nutrition 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 238000009991 scouring Methods 0.000 abstract description 16
- 239000000839 emulsion Substances 0.000 abstract description 10
- 150000002148 esters Chemical class 0.000 abstract description 6
- 150000001408 amides Chemical class 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- 125000003342 alkenyl group Chemical group 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229940014800 succinic anhydride Drugs 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229920001515 polyalkylene glycol Polymers 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 150000005215 alkyl ethers Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 3
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical class CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000847 nonoxynol Polymers 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 241001494479 Pecora Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000011044 succinic acid Nutrition 0.000 description 2
- 150000003444 succinic acids Chemical class 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000004297 Draba Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229920001400 block copolymer Chemical group 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005604 random copolymer Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000002730 succinyl group Chemical group C(CCC(=O)*)(=O)* 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000007056 transamidation reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- 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
- C09K23/22—Amides or hydrazides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F20/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
-
- 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
-
- 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
- C09K23/16—Amines or polyamines
-
- 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
- C09K23/34—Higher-molecular-weight carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B11/00—Recovery or refining of other fatty substances, e.g. lanolin or waxes
-
- 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
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
-
- 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
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- group
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- 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
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01C—CHEMICAL OR BIOLOGICAL TREATMENT OF NATURAL FILAMENTARY OR FIBROUS MATERIAL TO OBTAIN FILAMENTS OR FIBRES FOR SPINNING; CARBONISING RAGS TO RECOVER ANIMAL FIBRES
- D01C3/00—Treatment of animal material, e.g. chemical scouring of wool
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
Definitions
- This invention relates to surfactants and in particular to novel surfactants based on derivatives of substituted succinic acids and to particular end uses for these surfactants.
- EP 0107199 B relates to polvoxyalkylene glycol hemi-esters of CQ to C12 alk(en)yl substituted succinic acids and their salts. These materials are described as anionic surfactants with particular utility at acidic pHs and having hard water tolerance.
- This invention is based on the discovery of compounds which can be derived from alkenyl succinic anhydrides having particularly C14 to C22 alk(en)yl groups and/or substituents of functional groups elsewhere around the molecule give materials which have significantly and surprisingly different properties. In particular they perform well as non-ionic surfactants, particularly in aqueous systems, having unexpected cloud point properties indicating good performance at elevated temperatures and have good behaviour in alkaline conditions. Also the surfactants of this invention have good biodegradation properties.
- the present invention accordingly provides a compound of the formulae (I) or (II):
- R and R 1 is C5 to C22 alkenyl or alkyl and the other is hydrogen;
- A is - 0 - or - R ⁇ -; where R ⁇ is hydrogen or Ci to C alkyl, particularly methyl or ethyl; n is 2 to 100 (and as it is an average it may be non-integral); m is 2 or 3 (and may vary along the polvoxyalkylene chain); R 2 is hydrogen or C]_ to C5 alkyl; A 1 is - 0 -, - 0- or -NR 4 - where R 4 is hydrogen or C*
- Y is a cation, particularly H + , and alkali metal cation especially a sodium or potassium cation, or an ammonium ion (especially NHz,-* " , an amine ammonium or an alkanolamine ammonium ion); and when A 1 is - 0 - or -NR 4 -:
- Y is a C*_ to Cs alkyl group (R 3 ) or a group of the formula (C m H2m°)n- ⁇ where m, n and R 2 are independently as defined above; provided that when A is - 0 - or A 1 is - 0 ⁇ the total number of carbon atoms in the groups R, R 1 and any groups R 2 and R 3 is at least 13, and is desirably 13 to 50; or
- the free acid forms of compounds of the formulae (I) and (II) in are defined with Y as a H + cation.
- Y a H + cation.
- this includes both the ionised form of the free acid that will typically predominate at relatively alkaline pHs and the non-ionised form, that will typically predominate at relatively acidic pHs.
- a and A 1 are desirably both - 0 -, both - NR 4 -, particularly - NH -, or A is - NR 4 -, particularly - NH -, and A 1 is - 0 -. Accordingly, the following particular sub-groups of compounds of the formula (I) form specific aspects of the invention (see also below about R and R**-).
- Y, m, n and R 2 are as defined above formula (I); and R and R 1 are as defined above for formula (I), but particularly where one of R and R 1 is a C1 to C22- especially a C1 to C20» alkenyl or alkyl group and the other is hydrogen.
- the compounds of the general formula (II) can be considered as di(substituted succinyl) functional derivatives of a polyoxyalkylene moiety.
- the respective groups A and A 1 and Y will be the same.
- both groups A are - 0 - or - NR 4 -, particularly - NH -, and both groups A 1 are - 0" with Y being a cation.
- the alk(en)yl groups in the groups R and R**- will usually be the same.
- Y is a cation, it is desirably H + , an alkali metal cation or an ammonium cation, particularly H + , an amine ammonium cation, such as tetramethylammonium or an alkanolamine ammonium ion e.g. H0.CH2CH .NH3 + ; where Y is a Ci to C5 alkyl group, it is particularly a methyl, ethyl or (straight or branched) butyl group.
- R 2 in formulae (I) and (II) is desirably either H or a methyl, ethyl, propyl or butyl (including branched propyl and butyl) group. Where R 2 is H, the products tend to be relatively more
- the compounds of the invention include at least one polyoxyalkylene chain made up of residues of ethylene glycol and/or
- the chain may be a homopolymer chain of either ethylene glycol residues or of propylene glycol residues or a block or random copolymer chain containing both ethylene glycol and propylene glycol residues. In compounds including more than one polyoxyalkylene chain, the chains can be the same or different.
- polyoxyalkylene chain defined as the group (C m H2mO) n in formula (I) (including la, lb and Ic) and (II).
- the chain length of this group i.e. the value of the parameter n, will generally be chosen to provide the desired properties in the intended product.
- the polyoxyalkylene chain is a
- polyethylene glycol chain it will usually have 3 to 50, particularly 3 to 35 e.g. 10 to 35, ethylene glycol residues and where it is a polyoxypropylene chain it will usually have 10 to 50 and more preferably 12 to 20 propylene glycol residues.
- the chain is a block or random copolymer of ethylene and propylene glycol residues
- the chain length chosen will typically correspond to the above ranges but numerically according to the proportion of ethylene and propylene glycol residues in the chain. Of course, numerical values of the > repeat length of the polyoxyalkylene chain are average values. As is common to surfactants containing a polyoxyalkylene chain, the longer
- compounds where the group R or R 1 is an alkenyl group are more desirable than those where the group is alkyl.
- Compounds where the group R or R 1 is an alkenyl group, particularly a C14 to C20 alkenyl group form a specific aspect of the invention.
- the compounds of this invention, and particularly those where the group R or R 1 is a C1 to C22 alkenyl or alkyl group have properties that are entirely unexpected in that the cloud point tends to rise with increasing length of the chain R or R , particularly where this chain is an alkenyl chain. The step from C12 to £3.4 chains is often particularly notable.
- the cloud point may tend to fall back somewhat, but often stays significantly above that for compounds with a chain length of say C ⁇ _2. This trend in cloud point indicates increasing water solubility of the compounds with increasing chain length which is completely unexpected and runs counter to previous experience with surfactants. However, at longer chain lengths the compounds tend to be less effective wetters, which is consistent with the increasingly hydrophobic nature of the group R/R 1 .
- surfactants are usually most effective at or near their cloud points.
- Higher cloud points indicate materials that are likely to be effective at comparably higher temperatures and surfactants are often used at moderately superambient temperatures.
- the longer chain lengths are linked with increased oil solubility so the cloud point behaviour indicates that better oil , solubility is likely to be linked to higher effective temperatures.
- the product is typically a mixture of isomers corresponding to the two senses of the anhydride ring opening reaction.
- the alkenyl or alkyl chain seems to have a minor steric effect on the isomer ratio with the isomer ration being typically about 60:40, the major isomer arising from nucleophilic attack at the anhydride carbonyl group remote from the alkenyl or alkyl group.
- Y is a different cation
- Y is an alkali metal or ammonium cation formation of the salts is straightforward by reaction with the corresponding base e.g. alkali metal such as sodium or potassium, hydroxide or carbonate, ammonia or amine, including alkanolamines such as ethanolamine.
- alkali metal such as sodium or potassium
- hydroxide or carbonate ammonia or amine
- alkanolamines such as ethanolamine.
- a 1 is other than -0 ⁇ i.e. Y is other than a cation
- further reaction is by preparation of an ester, particularly an ester with a C_ to C5 or polyalkylene glycol alkyl ether alcohol.
- esters and the corresponding amides can be made from esters with short chain alcohols, especially methyl or ethyl esters, by trans-esterification or amidation with the corresponding alcohol (YOH) or amine (YNH2) (where Y is as defined above).
- the esterification of the free acid can be carried out in a conventional manner for example using an acid catalyst which may be sulphuric, toluene sulphonic or a phosphoric acid.
- Phosphoric acids can be particularly useful as, after neutralisation, they may be a useful component of detergent compositions which include the surfactants of this invention.
- the compounds of the invention may be made by other methods.
- the anhydride may be reacted with a lower alcohol and the resulting half ester esterified with a polyalkylene glycol or polyalkylene glycol alkyl ether or condensed with an alkylene oxide and if desired end capped with a further lower alcohol.
- the poly ⁇ alkylene glycol chain length can be controlled by using a polyalkylene glycol or polyalkylene glycol alkyl ether of a narrow range of molecular weight, whereas the latter process gives a wide distribution of chain lengths.
- Alkenyl succinic anhydrides may be produced by reacting maleic anhydride preferably with an excess of an olefin having 6 to 22, particularly 14 to 22, carbon atoms for example a 50 to 200Z excess at a temperature in the range 150 to 400°C and preferably 180 to 250°C and removing excess olefin for example by distillation which is suitably carried out under vacuum. No catalyst is necessary, but is is preferred than an antioxidant be present.
- These anhydrides are well known commercial materials. In alkenyl succinic anhydrides prepared as described above the double bond normally lies in the 2-position in the alkenyl substituent.
- the unsaturated products can be hydrogenated or, and preferably, the intermediate alkenyl succinic anhydride can be hydrogenated to give an alkyl succinic anhydride.
- the hydrogenation is carried out over a hydrogenation catalyst such as Raney nickel or a Pd/C catalyst. Temperatures of from 15 to 100°C and pressures of 0 - 200 bar absolute may be used and, if desired a solvent may be present.
- the hydrogenation reaction on an alkenyl succinic anhydride may be carried out at 20°C using 5Z w/w of Pd/C catalyst over a period of for example 6 to 24 hours.
- the R, R 1 alkyl or alkenyl group of the compounds of the invention has a straight chain. Where the chain is not straight it is desirable that it has at most a total of two and preferably only one branch(es) on average. Preferably the whole molecule comprises at most three branches in total in all alkyl and alkenyl groups present.
- the products are readily made with low odour and, since polyalkylene glycols and polyalkylene glycol alkyl ether or their amine derivatives are readily transportable can be made at locations distant from alkylene oxide plants if they are used as reactants.
- Compounds according to the invention have emulsification properties and wetting and dispersion capabilities. These include use in oil in water emulsions for metal working fluids, based on semi-soluble oil and synthetics and for crude oil transportation and fuel systems, emollients for personal (skin) care; domestic detergent composition for example laundry liquids; the dispersion or organic and inorganic powders in paints and coatings (e.g. filler and pigments) and agrochemical formulations (e.g. pesticides); wetters in so-called industrial and institutional cleaning products (e.g. traffic film removers, bottle washes).
- industrial and institutional cleaning products e.g. traffic film removers, bottle washes.
- the surfactants of this invention include wool scouring and as inverting agents in the manufacture of acrylamide or similar products. These applications are described in more detail below.
- the woollen fleece includes, in addition to the wool fibre, a variety of materials including wool wax. Wool wax is a complex mixture of fatty materials secreted onto the wool by the skin of the sheep. Wool wax is removed from the wool, prior to use of the wool in textiles, by washing the wool with an aqueous mix including surfactants typically at moderately elevated temperatures e.g. 40 to 80°C, particularly 50 to 70°C. This process is called wool scouring.
- the surfactants of this invention are very effective wool scouring surfactants, in particular retaining their activity well after multiple scouring cycles, even when used in scouring wool with very fine fibres e.g. merino wool, which is difficult to scour because the proportion of wool fat is relatively high and the fibres have a high surface area to be treated.
- very fine fibres e.g. merino wool
- R 2 is a C**_ to CQ alkyl group, especially a methyl group are especially effective.
- the surfactant in this application is typically used at a concentration of from 0.1 to 5, particularly from 0.2 to 1.5, g.1-1.
- the invention accordingly includes a method of treating wool to remove wool wax which method comprises washing the wool, containing wool wax, with an aqueous mix including an effective amount of a compound of the formulae (I) or (II) above, in particular a compound of the formula (la) above, especially where m is 2, n is from 3 to 10 and where R 2 is a Ci to CQ alkyl group, particularly a methyl group.
- the invention also includes the use of such compounds of the invention as wool scouring surfactants.
- polymers such as polyacrylamide
- an emulsion polymerisation route in which the polymer is accumulated in an aqueous phase (in which it is soluble).
- aqueous phase in which it is soluble
- polyacrylamides can give aqueous solutions having high viscosities even at low concentrations; this is the basis of their use as thickeners and viscosity enhancers in aqueous systems. If the aqueous phase during polymerisation were the continuous phase, it would rapidly become very viscous, leading to difficulties in agitation and recovery of the product. To avoid this problem, the aqueous phase is normally the dispersed phase in an oil continuous phase i.e.
- a compound within the invention for this end use will depend on the specific operating conditions, we have found that compounds of the formula (la) above, particularly where m is 2, n is from 8 to 25, particularly 10 to 15, and where R 2 is H or a Ci to C5 alkyl group, particularly a methyl, ethyl, propyl or butyl group, are especially effective.
- the amount of surface active agent used to invert such emulsions will depend on the emulsion, in particular the proportion of disperse aqueous phase and the polymer concentration in the aqueous phase. Generally amounts in the range 1 to 5Z of the water in oil emulsion are typical.
- the invention accordingly includes a method of inverting a water in oil emulsion containing polyacrylamide in the aqueous phase which comprises including in the water in oil emulsion a compound of the formulae (I) or (II) above, in particular a compound of the formula (ia) above, especially m is 2, n is from 8 to 25, particularly 10 to 15, and where R 2 is H or a Ci to Cs alkyl group, particularly a methyl, ethyl, propyl or butyl group, and subsequently diluting the water in oil emulsion into water.
- the invention also includes the use of compounds of the invention as polyacrylamide water in oil emulsion inverting agents.
- Draves wetting was assessed using the skein test (ASTM D 2281 - 68); results are in seconds (s) [or minutes (m) - for slow wetters].
- 's' indicates that the substituent is an alkyl group; for R 2 H » hydrogen and a number the length of an alkyl group, for Y H indicates Y • » H + and a number the alkyl chain length.
- n may be rounded values; for compounds of the formula (II) the value for 'n* in this table is n+p in formula (II) as given above (with p » m) .
- Semi aqueous cleaning involves the cleaning of, e.g. metal, components with a solvent followed by a water rinse stage. Frequently solvents derived from terpenes are used in this application.
- Surface active agents can be added to expedite the removal of the solvent from the components being cleaned during the water rinse stage.
- Such surface active agents, or rinse aids as they are known must fulfil two criteria. Firstly they must effect good solvent removal and be soluble in the cleaning solvent. Secondly they must not stabilise mixtures of the solvent and water thus preventing effective separation of the mixture with adverse implications on waste disposal.
- Materials A and B below have the desired surface active properties to be effective rinse aids in semi aqueous cleaning formulations. They are also soluble in terpene solvents. Surprisingly tests have demonstrated that they exhibit rapid and more effective solvent and water separation as compared to other surfactants commonly used in this application.
- Complete separation means oil layer of 10Z and a water layer of 90Z of 0 the total volume.
- the following mixture was polymerised by heating to about 40°C using as the primary emulsifier a commercially available polymeric surfactant sold under the trade name "HYPERMER” 2296.
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Abstract
Polyoxylalkylene esters and amides of alk(en)yl succinic anhydrides, of the formulae (I) YA1.OC(HR)CC(HR1)CO.A(C¿m?H2m0)n.R?2¿ and (II) YA1.OC(HR)CC(HR1)CO.A(C¿m?H2m0)n.CpH2pA.CO(HR?1¿)CC(HR)CO.A1Y where R, R?1, A, A1, Y, R2¿, m, n and p are as defined, particularly where the alk(en)yl group is a C¿14? to C22 group, are effective surfactants. They are especially notable because, very surprisingly, the cloud point tends to rise with increasing alk(en)yl group chain lenght. The surfactants are effective in scouring wool and inverting polyacrylamide water in oil emulsions into water.
Description
SURFACTANTS DERIVED FROM POLYOXYALKYLENES AND SUBSITUTED SUCCINIC ANHYDRIDES.
This invention relates to surfactants and in particular to novel surfactants based on derivatives of substituted succinic acids and to particular end uses for these surfactants.
In recent years there has been an increasing desire to replace well established surfactants with materials of increased biodegrad- ability. There is, however, great practical difficulty in devising alternatives to substances of excellent performance which have maintained an important position in the market for several decades.
EP 0107199 B relates to polvoxyalkylene glycol hemi-esters of CQ to C12 alk(en)yl substituted succinic acids and their salts. These materials are described as anionic surfactants with particular utility at acidic pHs and having hard water tolerance.
This invention is based on the discovery of compounds which can be derived from alkenyl succinic anhydrides having particularly C14 to C22 alk(en)yl groups and/or substituents of functional groups elsewhere around the molecule give materials which have significantly and surprisingly different properties. In particular they perform well as non-ionic surfactants, particularly in aqueous systems, having unexpected cloud point properties indicating good performance at elevated temperatures and have good behaviour in alkaline conditions. Also the surfactants of this invention have good biodegradation properties.
The present invention accordingly provides a compound of the formulae (I) or (II):
Y.A1.0C.(H )C.C(H ?-).C0.A.(CmH2m0)n. 2 (I)
where one of R and R1 is C5 to C22 alkenyl or alkyl and the other is hydrogen;
A is - 0 - or - R^ -; where R^ is hydrogen or Ci to C alkyl, particularly methyl or ethyl; n is 2 to 100 (and as it is an average it may be non-integral); m is 2 or 3 (and may vary along the polvoxyalkylene chain);
R2 is hydrogen or C]_ to C5 alkyl; A1 is - 0 -, - 0- or -NR4- where R4 is hydrogen or C*|_ to C5 alkyl, particularly methyl or ethyl; such that when A**- is - 0":
Y is a cation, particularly H+, and alkali metal cation especially a sodium or potassium cation, or an ammonium ion (especially NHz,-*", an amine ammonium or an alkanolamine ammonium ion); and when A1 is - 0 - or -NR4-:
Y is a C*_ to Cs alkyl group (R3) or a group of the formula (CmH2m°)n-^ where m, n and R2 are independently as defined above; provided that when A is - 0 - or A1 is - 0~ the total number of carbon atoms in the groups R, R1 and any groups R2 and R3 is at least 13, and is desirably 13 to 50; or
Y.Ai.OC. (HR)C.C(HR1) .CO.A. (CmH2m0)n-cpH2p-A.C0. (HR-Mc.CdπOCO.A-i-.Y
where: (II) n, m and each R, R1, A, A1 and Y are independently as defined above; and p is 2 or 3.
For convenience of definition, the free acid forms of compounds of the formulae (I) and (II) in are defined with Y as a H+ cation. Of course, this includes both the ionised form of the free acid that will typically predominate at relatively alkaline pHs and the non-ionised form, that will typically predominate at relatively acidic pHs.
In the general formula (I), A and A1 are desirably both - 0 -, both - NR4 -, particularly - NH -, or A is - NR4 -, particularly - NH -, and A1 is - 0 -. Accordingly, the following particular sub-groups of compounds of the formula (I) form specific aspects of the invention (see also below about R and R**-).
(la) Y.-OOC.(HR)C.C(HR1).COO.(CmH2mO)n.R2 where m, n and R2 are as defined above for formula (I); Y is a cation as defined above for formula (I); and one of R and R1 is a C1 to c22» especially a C14 to C20- alkenyl or alkyl group and the other is hydrogen.
(lb) Y.0.0C.(HR)C.C(HR*L).C0.0.(CmH2m0)n.R2 where m, n and R2 are as defined above formula (I) ; Y is a Ci to C5 alkyl group or a group of the formula (CmH2mO)n.R2 as defined above for formula (I); and R and ΕL- are as defined above for formula (I), but particularly where one of R and R*-** is a C14 to c22> especially a C14 to C20» alkenyl or alkyl group and the other is hydrogen.
(Ic) Y.0.0C.(HR)C.C(HR1).C0.NH.(CmH2m0)n.R2 where
Y, m, n and R2 are as defined above formula (I); and R and R1 are as defined above for formula (I), but particularly where one of R and R1 is a C1 to C22- especially a C1 to C20» alkenyl or alkyl group and the other is hydrogen.
(Id) R2. (CmH2m0)n.NH.0C. (HR)C.C(HR1) .C0.NH. (CmH2m0)n-R2 where each m, n and R2 is independently as defined above for formula (I); and R and R1 are as defined above for formula (I), but particularly where one of R and Rl is a C1 to C22» especially a C]_ to C20t alkenyl or alkyl group and the other is hydrogen.
The compounds of the general formula (II) can be considered as di(substituted succinyl) functional derivatives of a polyoxyalkylene moiety. Usually, the respective groups A and A1 and Y will be the same. Desirably both groups A are - 0 - or - NR4 -, particularly - NH -, and both groups A1 are - 0" with Y being a cation. Similarly the alk(en)yl groups in the groups R and R**- will usually be the same.
Where, in formulae (I) and (II) Y is a cation, it is desirably H+, an alkali metal cation or an ammonium cation, particularly H +, an amine ammonium cation, such as tetramethylammonium or an alkanolamine ammonium ion e.g. H0.CH2CH .NH3+; where Y is a Ci to C5 alkyl group, it is particularly a methyl, ethyl or (straight or branched) butyl group.
The group R2 in formulae (I) and (II) is desirably either H or a methyl, ethyl, propyl or butyl (including branched propyl and butyl) group. Where R2 is H, the products tend to be relatively more
10 hydrophilic and where it is an alkyl group, relatively less hydrophilic. The choice of the group R2 will be determined by the desired overall properties of the compound.
The compounds of the invention include at least one polyoxyalkylene chain made up of residues of ethylene glycol and/or
15 propylene glycol. The chain may be a homopolymer chain of either ethylene glycol residues or of propylene glycol residues or a block or random copolymer chain containing both ethylene glycol and propylene glycol residues. In compounds including more than one polyoxyalkylene chain, the chains can be the same or different.
20 Referring specifically to the polyoxyalkylene chain defined as the group (CmH2mO)n in formula (I) (including la, lb and Ic) and (II). The chain length of this group, i.e. the value of the parameter n, will generally be chosen to provide the desired properties in the intended product. Typically, where the polyoxyalkylene chain is a
25 polyethylene glycol chain it will usually have 3 to 50, particularly 3 to 35 e.g. 10 to 35, ethylene glycol residues and where it is a polyoxypropylene chain it will usually have 10 to 50 and more preferably 12 to 20 propylene glycol residues. Where the chain is a block or random copolymer of ethylene and propylene glycol residues
™ the chain length chosen will typically correspond to the above ranges but numerically according to the proportion of ethylene and propylene glycol residues in the chain. Of course, numerical values of the > repeat length of the polyoxyalkylene chain are average values. As is common to surfactants containing a polyoxyalkylene chain, the longer
-" the chain and the higher the proportion of ethylene glycol residues, the more hydrophilic the product. In compounds of the formula (II),
if along the polyoxyalkylene chain m is constant then p will usually be the same as m.
Among the compounds of the invention, those where the group R or R**- is a C]_ to C22> particularly a C_4 to C20 a* c*** very particularly a C14 to C]_8. alkenyl or alkyl group are especially desirable.
Similarly, compounds where the group R or R1 is an alkenyl group are more desirable than those where the group is alkyl. Compounds where the group R or R1 is an alkenyl group, particularly a C14 to C20 alkenyl group form a specific aspect of the invention. The compounds of this invention, and particularly those where the group R or R1 is a C1 to C22 alkenyl or alkyl group have properties that are entirely unexpected in that the cloud point tends to rise with increasing length of the chain R or R , particularly where this chain is an alkenyl chain. The step from C12 to £3.4 chains is often particularly notable. At chain lengths longer than C1 , the cloud point may tend to fall back somewhat, but often stays significantly above that for compounds with a chain length of say Cτ_2. This trend in cloud point indicates increasing water solubility of the compounds with increasing chain length which is completely unexpected and runs counter to previous experience with surfactants. However, at longer chain lengths the compounds tend to be less effective wetters, which is consistent with the increasingly hydrophobic nature of the group R/R1. By way of example in the series of compounds of the formula: H+.-00C.(HR)C.C(HR1) .CO.O.(C2H4θ)n.R2 where n and R2 as given below; the cloud points (°C) for compounds with R or R1 groups in the range 10 to 18 are as follows:
(The compounds in this table where R2 - H and R/R1 chain length is 12 or less are not compounds of this invention.)
We have been unable to account for this behaviour and so far as we know it is unique in surfactants. It is of considerable practical importance in that in aqueous systems surfactants are usually most effective at or near their cloud points. Higher cloud points indicate
materials that are likely to be effective at comparably higher temperatures and surfactants are often used at moderately superambient temperatures. The longer chain lengths are linked with increased oil solubility so the cloud point behaviour indicates that better oil , solubility is likely to be linked to higher effective temperatures.
This is a very useful combination of properties. This effect is more noticeable for compounds where the group R or R is an alkenyl group, particularly as compounds where it is alkyl generally have lower cloud points than the corresponding alkenyl compounds. The compounds of formula (I) where A1 is -0" and Y is H+ can be made by reacting an alkenyl or alkyl succinic anhydride with a compound of the formula:
H.A. (CmH2mO)n' R2 (where A, m, n and R2 are as defined above). The reaction between the anhydride and the polyalkylene glycol, poly- alkylene glycol mono alkyl ether or corresponding amine derivatives can be readily carried out, with or without catalysts, by bringing the glycol or amine derivative into contact with the alkenyl or alkyl succinic anhydride. Reaction occurs typically at temperatures below 200°C and even below 100°C. The reactants will usually be used in.at least approximately stoichiometric proportions. Particularly where stoichiometric proportions are used, further purification does not usually appear to be necessary, but can be carried out if desired.
The product is typically a mixture of isomers corresponding to the two senses of the anhydride ring opening reaction. We have noted that the alkenyl or alkyl chain seems to have a minor steric effect on the isomer ratio with the isomer ration being typically about 60:40, the major isomer arising from nucleophilic attack at the anhydride carbonyl group remote from the alkenyl or alkyl group.
Compounds of the invention where Y is a different cation can be made by salt formation from the free acid (Y ■ H+) . Where Y is an alkali metal or ammonium cation formation of the salts is straightforward by reaction with the corresponding base e.g. alkali metal such as sodium or potassium, hydroxide or carbonate, ammonia or amine, including alkanolamines such as ethanolamine. < Compounds of the invention where A1 is other than -0~ i.e. Y is other than a cation, can be made by reaction from the free acid. Typically, further reaction is by preparation of an ester,
particularly an ester with a C_ to C5 or polyalkylene glycol alkyl ether alcohol. Generally longer chain esters and the corresponding amides can be made from esters with short chain alcohols, especially methyl or ethyl esters, by trans-esterification or amidation with the corresponding alcohol (YOH) or amine (YNH2) (where Y is as defined above). The esterification of the free acid can be carried out in a conventional manner for example using an acid catalyst which may be sulphuric, toluene sulphonic or a phosphoric acid. Phosphoric acids can be particularly useful as, after neutralisation, they may be a useful component of detergent compositions which include the surfactants of this invention.
Compounds of the formulae la, lb, Ic and Id can, thus, be made as follows:
la reacting a polyoxyalkylene glycol or derivative of the formula: HO. (CmH2mO)n*.R2 with a Cτ_4to C22 alk(en)yl succinic anhydride to give a compound of the formula:
HOOC. (HR)C.C(HR1) .C0.0. (CmH2m0)n.R2 and (where Y is other than H) reaction with an alkali material.
lb esterifying a compound of the formula la, especially where Y is H, with a low molecular weight alcohol, particularly methanol, ethanol or a butanol, followed, if necessary, by a trans- esterification with an alcohol YOH to give the desired product.
Ic reacting a amino polyoxyalkylene glycol or derivative of the formula: H7N. Cπ-H9π.0)ττR2 with an alk(en)yl succinic anhydride to give a compound of the formula:
HOOC. (HR)C.C(HR1) .CO.NH. (CmH2m0)n-R2 and (where Y is other than H) reaction with an alkali material.
Id reacting a amino polyoxyalkylene glycol or derivative of the formula: H2N. (CmH2mO)n-R2 with an alk(en)yl succinic anhydride to give a compound of the formula: H00C.(HR)C.C(HR1).C0.NH.(CmH2m0)n-R2 followed by esterification with a low molecular weight alcohol,
particularly methanol or ethanol, followed by an amidation reaction with an amine YNH2 to give the desired product.
Compounds of the formula (II) where Y is H+ can be made by reacting 2 moles of an alk(en)yl succinic anhydride with one mole of a compound of the formula:
H.A.(CmH2m0)I1.CpH2p.A.H ' where m, n, p and each A are independently as defined above. Compounds where Y is another cation or a Ci to CQ alkyl group (R3) or a group of the formula (CmH2mO)n.R2 where m, n and R2 are independently as defined above; can be made as described above for compounds of the formula (I).
The compounds of the invention may be made by other methods. For example, the anhydride may be reacted with a lower alcohol and the resulting half ester esterified with a polyalkylene glycol or polyalkylene glycol alkyl ether or condensed with an alkylene oxide and if desired end capped with a further lower alcohol. The poly¬ alkylene glycol chain length can be controlled by using a polyalkylene glycol or polyalkylene glycol alkyl ether of a narrow range of molecular weight, whereas the latter process gives a wide distribution of chain lengths.
Alkenyl succinic anhydrides may be produced by reacting maleic anhydride preferably with an excess of an olefin having 6 to 22, particularly 14 to 22, carbon atoms for example a 50 to 200Z excess at a temperature in the range 150 to 400°C and preferably 180 to 250°C and removing excess olefin for example by distillation which is suitably carried out under vacuum. No catalyst is necessary, but is is preferred than an antioxidant be present. These anhydrides are well known commercial materials. In alkenyl succinic anhydrides prepared as described above the double bond normally lies in the 2-position in the alkenyl substituent.
To make products where the group R or R1 is an alkyl group then either the unsaturated products can be hydrogenated or, and preferably, the intermediate alkenyl succinic anhydride can be hydrogenated to give an alkyl succinic anhydride. Typically, the hydrogenation is carried out over a hydrogenation catalyst such as
Raney nickel or a Pd/C catalyst. Temperatures of from 15 to 100°C and pressures of 0 - 200 bar absolute may be used and, if desired a solvent may be present. For example, the hydrogenation reaction on an alkenyl succinic anhydride may be carried out at 20°C using 5Z w/w of Pd/C catalyst over a period of for example 6 to 24 hours.
It is desirable that the R, R1 alkyl or alkenyl group of the compounds of the invention has a straight chain. Where the chain is not straight it is desirable that it has at most a total of two and preferably only one branch(es) on average. Preferably the whole molecule comprises at most three branches in total in all alkyl and alkenyl groups present.
The products are readily made with low odour and, since polyalkylene glycols and polyalkylene glycol alkyl ether or their amine derivatives are readily transportable can be made at locations distant from alkylene oxide plants if they are used as reactants. Compounds according to the invention have emulsification properties and wetting and dispersion capabilities. These include use in oil in water emulsions for metal working fluids, based on semi-soluble oil and synthetics and for crude oil transportation and fuel systems, emollients for personal (skin) care; domestic detergent composition for example laundry liquids; the dispersion or organic and inorganic powders in paints and coatings (e.g. filler and pigments) and agrochemical formulations (e.g. pesticides); wetters in so-called industrial and institutional cleaning products (e.g. traffic film removers, bottle washes).
Particular end uses for the surfactants of this invention include wool scouring and as inverting agents in the manufacture of acrylamide or similar products. These applications are described in more detail below. AS sheared from the sheep, the woollen fleece includes, in addition to the wool fibre, a variety of materials including wool wax. Wool wax is a complex mixture of fatty materials secreted onto the wool by the skin of the sheep. Wool wax is removed from the wool, prior to use of the wool in textiles, by washing the wool with an aqueous mix including surfactants typically at moderately elevated temperatures e.g. 40 to 80°C, particularly 50 to 70°C. This process is called wool scouring. Our testing indicates that the surfactants
of this invention are very effective wool scouring surfactants, in particular retaining their activity well after multiple scouring cycles, even when used in scouring wool with very fine fibres e.g. merino wool, which is difficult to scour because the proportion of wool fat is relatively high and the fibres have a high surface area to be treated. Although the particular choice of a compound within the invention for this end use will depend on the specific operating \ conditions, we have found that compounds of the formula (la) above, particularly where m is 2, n is from 2 to 25, particularly 3 to 10, and where R2 is a C**_ to CQ alkyl group, especially a methyl group are especially effective. The surfactant in this application is typically used at a concentration of from 0.1 to 5, particularly from 0.2 to 1.5, g.1-1.
The invention accordingly includes a method of treating wool to remove wool wax which method comprises washing the wool, containing wool wax, with an aqueous mix including an effective amount of a compound of the formulae (I) or (II) above, in particular a compound of the formula (la) above, especially where m is 2, n is from 3 to 10 and where R2 is a Ci to CQ alkyl group, particularly a methyl group. The invention also includes the use of such compounds of the invention as wool scouring surfactants.
The manufacture of polymers such as polyacrylamide is usually carried out by an emulsion polymerisation route in which the polymer is accumulated in an aqueous phase (in which it is soluble). It is well known that polyacrylamides can give aqueous solutions having high viscosities even at low concentrations; this is the basis of their use as thickeners and viscosity enhancers in aqueous systems. If the aqueous phase during polymerisation were the continuous phase, it would rapidly become very viscous, leading to difficulties in agitation and recovery of the product. To avoid this problem, the aqueous phase is normally the dispersed phase in an oil continuous phase i.e. as a water in oil emulsion, including an emulsifier to stabilise the water in oil emulsion. The viscosity of the oily phase does not increase during polymerisation, as does the aqueous phase, because the polymer remains in the aqueous phase. However, the polymer is typically used in a aqueous environments, so at some point the emulsion must be inverted to give an aqueous continuous phase.
This is typically done on dilution of the water in oil emulsion into water. Usually, a surface active agent that promotes such inversion is added to the water in oil emulsion before dilution into water. Our testing indicates that the compounds of this invention are effective inverting agents for such emulsions. Although the particular choice of a compound within the invention for this end use will depend on the specific operating conditions, we have found that compounds of the formula (la) above, particularly where m is 2, n is from 8 to 25, particularly 10 to 15, and where R2 is H or a Ci to C5 alkyl group, particularly a methyl, ethyl, propyl or butyl group, are especially effective. The amount of surface active agent used to invert such emulsions will depend on the emulsion, in particular the proportion of disperse aqueous phase and the polymer concentration in the aqueous phase. Generally amounts in the range 1 to 5Z of the water in oil emulsion are typical.
The invention accordingly includes a method of inverting a water in oil emulsion containing polyacrylamide in the aqueous phase which comprises including in the water in oil emulsion a compound of the formulae (I) or (II) above, in particular a compound of the formula (ia) above, especially m is 2, n is from 8 to 25, particularly 10 to 15, and where R2 is H or a Ci to Cs alkyl group, particularly a methyl, ethyl, propyl or butyl group, and subsequently diluting the water in oil emulsion into water. The invention also includes the use of compounds of the invention as polyacrylamide water in oil emulsion inverting agents.
The following Examples illustrate the invention including the manufacture and properties of the compounds of the invention and their end uses, particularly illustrating the versatility and utility of the compounds of the invention. All parts and percentages are by weight unless otherwise specified.
Test Methods
Cloud Point (CP) was measured by ASTM D 2024 - 65; results are in °C
Wetting (Wtg)
Draves wetting was assessed using the skein test (ASTM D 2281 - 68); results are in seconds (s) [or minutes (m) - for slow wetters].
Foam height (FH)
Ross Miles foam height was assessed by ASTM D 1173-53 at 60°C; results are in mm.
Surface Tension (ST) was measured on a 0.1Z w/w solution by the drop method at 23°C; results are in mN.m"1 (1 mN.m"1 •**• 1 dyne.cm-1).
Synthesis Examples SE1 to SE24
Various compounds of the invention were made by reacting stoichiometric mixtures of an alkenyl succinic anhydride and poly-, ethylene glycol (PEG), an alkyl polyethylene glycol ether or amine derivative, as set out in Table 1 below, by heating the mixture to about 100°C. Samples taken every 30 minutes until the reaction was complete as determined by infra red spectroscopy and/or the acid value of the mixture.
Corresponding sodium salts were made by addition of NaOH solution to the acid product until the pH had risen to 9. The sodium salt was then isolated by stripping or used as a solution in water.
Corresponding methyl esters were made by the addition of sulphuric acid and methanol. Methanol was distilled through the reaction at such a rate as to keep the volume constant for 2-12 hours. Sodium hydrogen carbonate was then added to neutralise the sulphuric acid and the product filtered. Other low alcohol esters were made by corresponding methods. Comparative materials of similar structure were also prepared by the general method described but substituting the appropriate starting materials. These are identified by the prefix 'C before a number.
Various properties of the compounds were measured and the results are given in Table 2 below. For further illustration a commercially available nonyl phenol ethoxylate (with 9 moles of EO per mole phenol) is included in Table 2 under the reference 'NPE' .
The properties of compound SE1 are as follows:
Surface Tension (0.1Z w/w solution)
(Drop Method at 23°C) mN.m"1 28.4
Pour Point (°C) -15
Viscosity (cps/25°C) 165
Foam Heights (mm) 0 min 5 min (Ross Miles at 60°C) 7.5 3
Density (g.cm-3 at 23°C) 1.006
Wetting (Draves - seconds) 10.5 sees
Cloud Point °C 40 - 53
TABLE 1
the number of carbon atoms in the substituent chain is given, for R/R1 'u' indicates that the substituent is an alkenyl group
's' indicates that the substituent is an alkyl group; for R2 H » hydrogen and a number the length of an alkyl group, for Y H indicates Y •» H+ and a number the alkyl chain length.
integral values for n may be rounded values; for compounds of the formula (II) the value for 'n* in this table is n+p in formula (II) as given above (with p » m) .
TABLE 2
Applications Examples AE1 to AE4
Example AE1 - Semi Aqueous Cleaners
Semi aqueous cleaning involves the cleaning of, e.g. metal, components with a solvent followed by a water rinse stage. Frequently solvents derived from terpenes are used in this application. Surface active agents can be added to expedite the removal of the solvent from the components being cleaned during the water rinse stage. Such surface active agents, or rinse aids as they are known, must fulfil two criteria. Firstly they must effect good solvent removal and be soluble in the cleaning solvent. Secondly they must not stabilise mixtures of the solvent and water thus preventing effective separation of the mixture with adverse implications on waste disposal. Materials A and B below have the desired surface active properties to be effective rinse aids in semi aqueous cleaning formulations. They are also soluble in terpene solvents. Surprisingly tests have demonstrated that they exhibit rapid and more effective solvent and water separation as compared to other surfactants commonly used in this application.
The following experimental data demonstrate the effect. Mixtures of 0.6Z surfactant, 9.4Z terpene solvent and 90Z water were prepared by shaking 5 times in a measuring cylinder. The mixtures were allowed to stand at room temperature for twenty hours, during which time a periodic assessment of the level of phase separation was made. The following table records the results obtained.
Surfactant Appearance after Comments 20 Hours
None Both layers clear Separation complete after 0.5 hours
CIO alcohol 3 E0 Oil and water layers Separation incomplete cloudy after 20 hours
o Alkyl phenol Oil and water layers Separation complete 4.5 EO slightly cloudy after 10 hours
SE10 Oil and water layers Separation complete very slightly cloudy after 12 hours 5
SE1 Slight haze in both Separation complete layers after 8 hours
Complete separation means oil layer of 10Z and a water layer of 90Z of 0 the total volume.
Example AE2 - Wool Scouring
Ten 20g samples of wool were washed successfully in the same bath 5 of a 0.1Z w/w solution of surfactant in water (1 litre) at 60°C. The residual grease in the last sample to be washed was then measured by extraction with an organic solvent, typically dichloromethane or chloroform. The results are set out in the following table:
0 Product Z Residual Grease
'SYNPERONIC" NP9 **, ) 1.71 •SYNPERONIC" 87K (*) 2.16 SE1 1.24
5 ** Commercially available Ci3_**_5 alcohol alkoxylate * Commercially available nonyl phenol ethoxylate
Example AE3 - Wool Scouring
Further tests of wool scouring were carried out using fine merino wool (ca. 20 μm diameter fibres) at a surfactant dose of 0.5 g.l-1 in an aqueous scouring solution containing 4Z by weight of KC1 (to simulate salt accumulation during repeated use of the scouring solution) . The scouring was operated at 65°C in the scour detergent bowls and at 50°C in the rinse bowls. The scouring solutions were, reused a number of times and the weight percentage of residual wool wax on the wool after each treatment was noted and is given in Table 3 below. The product of SE1 was compared with four other scouring surfactants:
Code Product Name Source Description
C3 Lissapol TN450 ICI Australia nonyl phenol ethoxylate
C4 Lissapol BD20 ICI Australia biodegradable wool scourer
C5 Lissapol BD30 ICI Australia biodegradable wool scourer
C6 Softanol 90 Nippon Shokubai secondary alcohol ethoxylate
Table 3
The results given in Table 3 show that the compound of this invention performs well as a wool scouring agent and in particular shows good retention of performance as compared with current agents, even in treating a wool that is known to be difficult to scour.
Example AE4 - Polyacrylamide Emulsion Inversion
The following mixture was polymerised by heating to about 40°C using as the primary emulsifier a commercially available polymeric surfactant sold under the trade name "HYPERMER" 2296.
Acrylamide 135.Og
Acrylic acid 58.Og
Demin Water 179.Og Hydrocarbon Solvent (Isopar L) 168.Og
Sodium hydroxide up to pH 6
Ethylene diamine tetra acetic acid 5.2g
(EDTA) (5Z)
Azobisisobutyronitrile (AIBN) 0.4g Primary emulsifier 8-12g
3Z of each of the surfactants below was added as an inverting agent to a sample of the polymer emulsion and the mixture allowed to rest for 2-3 days. A sample of emulsion was then taken and a IZ blend in water produced. After 2 minutes of stirring the viscosity was measured. Stirring was then continued and after 15 minutes the viscosity was measured again. The measured viscosities were:
Viscosity (mPa.s)
These results show that SE11 is equivalent to the conventional inverting agent "SYNPERONIC" NP9 and SE19 is superior and that compound C3 does not act effectively as an inverting agent.
Claims
Claims
1 A compound of the formulae (I) or (II):
Y.A1.OC.(HR)C.C(HR1).CO.A.(CmH2πιO)n-R2 (D
where one of R and R1 is C5 to C22 alkenyl or alkyl and the other is hydrogen;
A is - 0 - or or -NR4-, where R4 is hydrogen or Ci to CQ alkyl; n is 2 to 100; m is 2 or 3 (and may vary along the polyoxyalkylene chain); R2 is hydrogen or Ci to Cs alkyl; A1 is - 0 -, - 0" or -NR4-, where R4 is hydrogen or C**_ to CQ alkyl; such that when A1 is - 0", Y is a cation; and when A1 is - 0 - or -NR4-:
Y is a Ci to Cζ alkyl group (R3) or a group of the formula
(CmH2m°)n' R2. where m, n and R2 are independently as defined above; provided that when A is - 0 - or A1 is - 0* the total number of carbon atoms in the groups R, R1 and any groups R2 and R3 is at least 13. or Y.A1.OC.(HR)C.C(HR1).CO.A.(CmH2mO)n-cpH2p-A-CO.(HR1)C.C(HR)CO.A1Y
where: (II) n, m and each R, R1, A, A1 and Y are independently as defined above; and p is 2 or 3.
2 A compound as claimed in claim 1 in which one of R and R1 is C14 to C22 alkenyl or alkyl and the other is hydrogen.
A compound as claimed in claim 1 of the formula (la):
(la) Y.-00C.(HR)C.C(HR1) .COO. (CmH2m0)n.R2
where m, n and R2 are as defined in claim 1; Y is a cation and one of R and R1 is a C14 to C22 alkenyl or alkyl group and the other is hydrogen.
A compound as claimed in claim 1 of the formula (lb):
(lb) Y.00C.(HR)C.C(HR1).C00.(CmH2m0)n-R2
where R, R1, m, n and R2 are as defined in claim 1; and Y is a C*j_ to C5 alkyl group or a group of the formula (CmH2mO)n.R2 where m, n and R2 are independently as defined in claim 1.
A compound as claimed in claim 1 of the formula (Ic):
(Ic) Y.-00C.(HR)C.C(HR1).C0.NH.(CmH2m0)n.R2
where R, R1, m, n and R2 are as defined in claim 1 and Y is a cation.
A compound as claimed in claim 1 of the formula (Id):
(Id) R2. (CπιH2m0)n-N.H.0C. (HR)C.C(HR1) .CO.NH. (CmH2m0)n-R2
where R and R1 and each m, n and R2 is independently as defined in claim 1.
A compound as claimed in any one of claims 4 to 6 in which one of R and R1 is a C1 to C22 alkenyl group and the other is hydrogen.
A compound as claimed in any one of claims 1 to 7 wherein m is 2; p, if present, is 2; n is from 3 to 50 and
Y is a cation it is H+, an alkali metal cation, or an ammonium cation, or a methyl, ethyl or butyl group.
A method of treating wool to remove wool wax which method comprises washing the wool, containing wool wax, with an aqueous mix including an effective amount of a compound of the formulae (I) or (II) as defined in any one of claims 1 to 8.
A method as claimed in claim 9 wherein the compound is a compound of the formula (la) where m is 2, n is from 3 to 10 and where R2 is a Ci to Cβ alkyl group.
A method of inverting a water in oil emulsion containing polyacrylamide in the aqueous phase which comprises including in the water in oil emulsion a compound of the formulae (I) or (II) as defined in any one of claims 1 to 8 and subsequently diluting the water in oil emulsion into water to invert it.
A method as claimed in claim 11 wherein the compound is a compound of the formula (la) where m is 2, n is from 8 to 25, and R2 is H or a Ci to Cβ alkyl group.
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Application Number | Priority Date | Filing Date | Title |
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GB929213571A GB9213571D0 (en) | 1992-06-26 | 1992-06-26 | Surfactants |
GB9213571 | 1992-06-26 | ||
PCT/GB1993/001335 WO1994000508A1 (en) | 1992-06-26 | 1993-06-25 | Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides |
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EP0647248A1 true EP0647248A1 (en) | 1995-04-12 |
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EP93913432A Withdrawn EP0647248A1 (en) | 1992-06-26 | 1993-06-25 | Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides |
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JP (1) | JPH07508546A (en) |
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AU (1) | AU679918B2 (en) |
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CZ (1) | CZ328094A3 (en) |
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GB (2) | GB9213571D0 (en) |
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RU (1) | RU2118641C1 (en) |
SK (1) | SK159694A3 (en) |
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Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
HU184618B (en) * | 1979-10-26 | 1984-09-28 | Chinoin Gyogyszer Es Vegyeszet | Surface active materials containing carboxyl group stable in hard water |
IL70368A (en) * | 1982-12-13 | 1987-11-30 | Chevron Res | Nonionic emulsifier and substituted succinic anhydride compositions therewith |
US4661275A (en) * | 1985-07-29 | 1987-04-28 | The Lubrizol Corporation | Water-based functional fluid thickening combinations of surfactants and hydrocarbyl-substituted succinic acid and/or anhydride/amine terminated poly(oxyalkylene) reaction products |
US4968321A (en) * | 1989-02-06 | 1990-11-06 | Texaco Inc. | ORI-inhibited motor fuel composition |
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1992
- 1992-06-26 GB GB929213571A patent/GB9213571D0/en active Pending
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1993
- 1993-06-22 ZA ZA934479A patent/ZA934479B/en unknown
- 1993-06-24 GB GB939313096A patent/GB9313096D0/en active Pending
- 1993-06-25 AU AU43505/93A patent/AU679918B2/en not_active Ceased
- 1993-06-25 HU HU9403701A patent/HUT68780A/en unknown
- 1993-06-25 JP JP6502165A patent/JPH07508546A/en active Pending
- 1993-06-25 RU RU94046395A patent/RU2118641C1/en active
- 1993-06-25 SK SK1596-94A patent/SK159694A3/en unknown
- 1993-06-25 CA CA002139003A patent/CA2139003A1/en not_active Abandoned
- 1993-06-25 KR KR1019940704735A patent/KR950702215A/en not_active IP Right Cessation
- 1993-06-25 EP EP93913432A patent/EP0647248A1/en not_active Withdrawn
- 1993-06-25 NZ NZ253297A patent/NZ253297A/en unknown
- 1993-06-25 WO PCT/GB1993/001335 patent/WO1994000508A1/en not_active Application Discontinuation
- 1993-06-25 CZ CZ943280A patent/CZ328094A3/en unknown
- 1993-06-26 TW TW082105101A patent/TW256854B/zh active
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1994
- 1994-12-23 FI FI946075A patent/FI946075A0/en unknown
Non-Patent Citations (1)
Title |
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See references of WO9400508A1 * |
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CA2139003A1 (en) | 1994-01-06 |
AU4350593A (en) | 1994-01-24 |
CZ328094A3 (en) | 1995-06-14 |
FI946075A (en) | 1994-12-23 |
HUT68780A (en) | 1995-07-28 |
RU94046395A (en) | 1996-11-20 |
GB9213571D0 (en) | 1992-08-12 |
GB9313096D0 (en) | 1993-08-11 |
WO1994000508A1 (en) | 1994-01-06 |
SK159694A3 (en) | 1995-06-07 |
JPH07508546A (en) | 1995-09-21 |
AU679918B2 (en) | 1997-07-17 |
KR950702215A (en) | 1995-06-19 |
NZ253297A (en) | 1997-02-24 |
TW256854B (en) | 1995-09-11 |
RU2118641C1 (en) | 1998-09-10 |
ZA934479B (en) | 1995-03-22 |
FI946075A0 (en) | 1994-12-23 |
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