US3475490A - Emulsifying and textile softening phosphonium compounds,processes for preparing the same - Google Patents
Emulsifying and textile softening phosphonium compounds,processes for preparing the same Download PDFInfo
- Publication number
- US3475490A US3475490A US3475490DA US3475490A US 3475490 A US3475490 A US 3475490A US 3475490D A US3475490D A US 3475490DA US 3475490 A US3475490 A US 3475490A
- Authority
- US
- United States
- Prior art keywords
- salts
- chloride
- phosphiniminophosphonium
- salt
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 42
- 239000004753 textile Substances 0.000 title description 42
- 230000001804 emulsifying effect Effects 0.000 title description 5
- 150000004714 phosphonium salts Chemical class 0.000 title description 4
- 150000003839 salts Chemical class 0.000 description 86
- -1 aliphatic radical Chemical group 0.000 description 76
- 239000000203 mixture Substances 0.000 description 65
- 239000003599 detergent Substances 0.000 description 41
- 125000004432 carbon atom Chemical group C* 0.000 description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 239000004902 Softening Agent Substances 0.000 description 21
- 150000003254 radicals Chemical class 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 229910052783 alkali metal Inorganic materials 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- 150000001450 anions Chemical group 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 150000001540 azides Chemical class 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 12
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical class PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 235000019198 oils Nutrition 0.000 description 10
- 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 9
- 239000003995 emulsifying agent Substances 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 150000003003 phosphines Chemical class 0.000 description 9
- 125000002577 pseudohalo group Chemical group 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- XFCIKSSJGIYRMG-UHFFFAOYSA-N [Cl-].C[PH+](NCCCCCCCCCCCC)C Chemical compound [Cl-].C[PH+](NCCCCCCCCCCCC)C XFCIKSSJGIYRMG-UHFFFAOYSA-N 0.000 description 8
- 239000007810 chemical reaction solvent Substances 0.000 description 8
- 150000004820 halides Chemical class 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- QLNAVQRIWDRPHA-UHFFFAOYSA-N iminophosphane Chemical compound P=N QLNAVQRIWDRPHA-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000271 synthetic detergent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- DLOGQHZKMUCSEI-UHFFFAOYSA-N CCCCCCCCCCCCP(C)C.Cl.Cl Chemical compound CCCCCCCCCCCCP(C)C.Cl.Cl DLOGQHZKMUCSEI-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229940096386 coconut alcohol Drugs 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005108 dry cleaning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229950011008 tetrachloroethylene Drugs 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- RIXFPXRYYYJJKF-UHFFFAOYSA-N dodecyl(dimethyl)phosphane Chemical compound CCCCCCCCCCCCP(C)C RIXFPXRYYYJJKF-UHFFFAOYSA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- GPNNERFCOGGDCT-UHFFFAOYSA-N [Cl-].C[PH+](NCCCCCCCCCCCCCC)C Chemical compound [Cl-].C[PH+](NCCCCCCCCCCCCCC)C GPNNERFCOGGDCT-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 1
- SIDULKZCBGMXJL-UHFFFAOYSA-N 1-dimethylphosphoryldodecane Chemical compound CCCCCCCCCCCCP(C)(C)=O SIDULKZCBGMXJL-UHFFFAOYSA-N 0.000 description 1
- ZSGCBBCGHYYEGU-UHFFFAOYSA-N 1-dimethylphosphoryltetradecane Chemical compound CCCCCCCCCCCCCCP(C)(C)=O ZSGCBBCGHYYEGU-UHFFFAOYSA-N 0.000 description 1
- VMWIXXSXYKVMKL-UHFFFAOYSA-N 1-dodecoxy-4-methylsulfinylbutan-2-ol Chemical compound CCCCCCCCCCCCOCC(O)CCS(C)=O VMWIXXSXYKVMKL-UHFFFAOYSA-N 0.000 description 1
- CLHYKAZPWIRRRD-UHFFFAOYSA-N 1-hydroxypropane-1-sulfonic acid Chemical compound CCC(O)S(O)(=O)=O CLHYKAZPWIRRRD-UHFFFAOYSA-N 0.000 description 1
- CGFWIUHIYQFIIQ-UHFFFAOYSA-N 1-methylsulfinyldecan-2-ol Chemical compound CCCCCCCCC(O)CS(C)=O CGFWIUHIYQFIIQ-UHFFFAOYSA-N 0.000 description 1
- CJPDBKNETSCHCH-UHFFFAOYSA-N 1-methylsulfinyldodecane Chemical compound CCCCCCCCCCCCS(C)=O CJPDBKNETSCHCH-UHFFFAOYSA-N 0.000 description 1
- QYRXERZWYVOCEQ-UHFFFAOYSA-N 1-methylsulfinyloctadecane Chemical compound CCCCCCCCCCCCCCCCCCS(C)=O QYRXERZWYVOCEQ-UHFFFAOYSA-N 0.000 description 1
- HYTOZULGKGUFII-UHFFFAOYSA-N 1-methylsulfinyltridecan-3-ol Chemical compound CCCCCCCCCCC(O)CCS(C)=O HYTOZULGKGUFII-UHFFFAOYSA-N 0.000 description 1
- GIFWSCMRWGWNSI-UHFFFAOYSA-N 1-methylsulfinylundecan-2-ol Chemical compound CCCCCCCCCC(O)CS(C)=O GIFWSCMRWGWNSI-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NKFNBVMJTSYZDV-UHFFFAOYSA-N 2-[dodecyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCCCCCCCCCN(CCO)CCO NKFNBVMJTSYZDV-UHFFFAOYSA-N 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- AEDQNOLIADXSBB-UHFFFAOYSA-N 3-(dodecylazaniumyl)propanoate Chemical compound CCCCCCCCCCCCNCCC(O)=O AEDQNOLIADXSBB-UHFFFAOYSA-N 0.000 description 1
- MNMLTWNKYZNOQA-UHFFFAOYSA-N 3-methoxy-1-methylsulfinyltridecane Chemical compound CCCCCCCCCCC(OC)CCS(C)=O MNMLTWNKYZNOQA-UHFFFAOYSA-N 0.000 description 1
- 238000006677 Appel reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PLZWXBCYYXOXQT-UHFFFAOYSA-N Br.Br.CP(C)C Chemical compound Br.Br.CP(C)C PLZWXBCYYXOXQT-UHFFFAOYSA-N 0.000 description 1
- VCCWZAQTNBYODU-UHFFFAOYSA-N CC(=C)CC(C)CCC(C)=C Chemical group CC(=C)CC(C)CCC(C)=C VCCWZAQTNBYODU-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- ZXUYXFJRAQUVMW-UHFFFAOYSA-N I.Br.Cl Chemical compound I.Br.Cl ZXUYXFJRAQUVMW-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- HWZUDASOMGNLSM-UHFFFAOYSA-N O=P1OCOP(=O)O1 Chemical class O=P1OCOP(=O)O1 HWZUDASOMGNLSM-UHFFFAOYSA-N 0.000 description 1
- JBCMIGPQETVZEP-UHFFFAOYSA-N P1(=O)OC(C)OP(O1)=O.[Na].[Na].[Na] Chemical compound P1(=O)OC(C)OP(O1)=O.[Na].[Na].[Na] JBCMIGPQETVZEP-UHFFFAOYSA-N 0.000 description 1
- KREOUCZKLVCRAQ-UHFFFAOYSA-N P1(=O)OCOP(O1)=O.[K].[K].[K] Chemical compound P1(=O)OCOP(O1)=O.[K].[K].[K] KREOUCZKLVCRAQ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N Taurine Natural products NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- CQWHYFBDNFLDJB-UHFFFAOYSA-N [Cl-].C[PH+](NCCCCCCCCCCCCCCCC)C Chemical compound [Cl-].C[PH+](NCCCCCCCCCCCCCCCC)C CQWHYFBDNFLDJB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- XKCUKNPRINSNLG-UHFFFAOYSA-N aminophosphanium;chloride Chemical class [Cl-].[PH3+]N XKCUKNPRINSNLG-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- KRHIGIYZRJWEGL-UHFFFAOYSA-N dodecapotassium;tetraborate Chemical class [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] KRHIGIYZRJWEGL-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- AKPUJVVHYUHGKY-UHFFFAOYSA-N hydron;propan-2-ol;chloride Chemical compound Cl.CC(C)O AKPUJVVHYUHGKY-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- XNEFVTBPCXGIRX-UHFFFAOYSA-M methanesulfinate Chemical compound CS([O-])=O XNEFVTBPCXGIRX-UHFFFAOYSA-M 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SXQMONVCMHFPDA-UHFFFAOYSA-N nonane Chemical compound CCCCCCCC[CH2-] SXQMONVCMHFPDA-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- OXUCOTSGWGNWGC-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2-] OXUCOTSGWGNWGC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229940045998 sodium isethionate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JZBRFIUYUGTUGG-UHFFFAOYSA-J tetrapotassium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical class [K+].[K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JZBRFIUYUGTUGG-UHFFFAOYSA-J 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- ICUTUKXCWQYESQ-UHFFFAOYSA-N triclocarban Chemical compound C1=CC(Cl)=CC=C1NC(=O)NC1=CC=C(Cl)C(Cl)=C1 ICUTUKXCWQYESQ-UHFFFAOYSA-N 0.000 description 1
- AVCVDUDESCZFHJ-UHFFFAOYSA-N triphenylphosphane;hydrochloride Chemical compound [Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 AVCVDUDESCZFHJ-UHFFFAOYSA-N 0.000 description 1
- SFDBJFMMXUVCFG-UHFFFAOYSA-K trisodium;hydroxy(phosphonatomethyl)phosphinate Chemical compound [Na+].[Na+].[Na+].OP([O-])(=O)CP([O-])([O-])=O SFDBJFMMXUVCFG-UHFFFAOYSA-K 0.000 description 1
- KCYJBQNPOFBNHE-UHFFFAOYSA-K trisodium;hydroxy-(1-hydroxy-1-phosphonatoethyl)phosphinate Chemical compound [Na+].[Na+].[Na+].OP(=O)([O-])C(O)(C)P([O-])([O-])=O KCYJBQNPOFBNHE-UHFFFAOYSA-K 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000000080 wetting agent Substances 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
-
- 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
- C07F9/535—Organo-phosphoranes
- C07F9/5355—Phosphoranes containing the structure P=N-
-
- 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
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5463—Compounds of the type "quasi-phosphonium", e.g. (C)a-P-(Y)b wherein a+b=4, b>=1 and Y=heteroatom, generally N or O
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/60—Sulfonium or phosphonium 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/07—Organic amine, amide, or n-base containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2352—Coating or impregnation functions to soften the feel of or improve the "hand" of the fabric
Definitions
- This invention relates to novel phosphiniminophosphonium salts which are textile softening agents and emulsifying agents. It further relates to processes for preparing these novel compounds and other compounds which are antibacterial agents. It further relates to novel intermediate compounds which are employed in one of these processes.
- phosphiniminophosphonium is used herein to denote a compound containing a linkage, which linkage is explained hereinafter. Compounds containing this linkage have been described in the prior art. However, compounds containing this linkage which are effective textile softening agents and effective emulsifying agents are not known to have been so described.
- a durable softening agent that is a softening agent which resist removal even after several washings of the textile, is advantageous to the consumer in that the necessity of continual reapplication of softening agent is eliminated.
- phosphiniminophosphonium salts having the following structural formula are effective and durable textile softening agents and effective emulsifying agents:
- R is an aliphatic radical containing from 1 to about 18 carbon atoms
- R R R and R are aliphatic radicals containing from 1 to about 4 carbon atoms
- R is an aliphatic radical containing from about 12 to about 18 carbon atoms
- X is an anion which permits adequate solubility and hydrolytic stability of the salt.
- This structural formula and more particularly the linkage in this structural formula is a resonance structure.
- this structural formula represents the following structural formulas which are in resonance and in which R, R R R R R R R and X are defined as above:
- the salts defined by this structural formula can be symmetrical or unsymmetrical.
- R, R R R and R can each be of different chain lengths within the same compound.
- the aliphatic radicals in this structural formula can be saturated or unsaturated and branched or straight chain.
- these aliphatic radicals can be alkyl, substituted alkyl, alkenyl and substituted alkenyl radicals.
- alkyl is used herein to include only saturated carbon chains.
- alkenyl is used herein to include carbon chains containing one or more double :bonds.
- X in the above structural formula can suitably be, for example, a halide, such as chloride, bromide, iodide, or fluoride; a pseudohalide, such as cyanide, azide or thiocyanate; a sulfonate, such as methane sulfonate or p-toluene sulfonate; a sulfinate, such as methane sulfinate; a fluoroborate; sulfate, sulfite, nitrate, nitrite, phosphate, borate, methosulfate, chlorate, 'bisulfate, bisulfite, acetate, hexachloroantimonate and other anions.
- a halide such as chloride, bromide, iodide, or fluoride
- a pseudohalide such as cyanide, azide or thiocyanate
- a sulfonate such as methan
- the aliphatic radicals in the present phosphiniminophosphonium salts are alkyl radicals and the anion, X, is selected from the group consisting of halides and pseudohalides.
- Symmetrical phosphiniminophosphonium salts of the present invention are especially preferred for textile softening agents.
- Emulsifying and textile softening phosphiniminophosphonium salts are set forth in Table I below wherein R, R R R R, R and X are applied in the structural formula set forth above.
- R R R R R X methyl methyl methyl methyl methyl methyl trideeyl SO4- butyl methyl methyl propyl methyl dodecyl Br butyl butyl butyl methyl methyl dodecyl C1 octyl 3-iodopropenyl ethyl methyl methyl tetradeeyl I- dodecyl methyl methyl methyl dodecyl Cldodccyl ethyl ethyl ethyl ethyl dodecyl CHJCOO' dodecyl ethylene methyl methyl ethylene dodecyl N0 tetradecyl methyl methyl methyl methyl tetradceyl Cltetradecyl chloromethyl nethyl methyl methyl tetradeeyl b13- tetradecyl hydroxymethyl methyl methyl methyl tetradeeyl C N- t
- phosphiniminophosphonium salts are especially useful as emulsifying agents.
- These salts ordinarily can be used to produce oil-in-water emulsions that are stable for more than one hour, the weight ratio of emulsifier to oil phase generally ranging from about 1:1000 to about 3:1.
- these salts provide stable water emulsions of dry cleaning solvents, such as tetrachloroethylene, and of other organic solvents, such as carbon tetrachloride.
- these salts provide stable water emulsions of glyceride oils, such as cottonseed oil or soybean oil.
- the phosphiniminophosphoniu1n salt is preferably first dispersed in the oil phase to be emulsified, and the oil-emulsifier combination is then mixed with the water phase. This is because these phosphiniminophosphonium salts tend to cause the formation of viscous solutions or gels when added by themselves to the water phase thereby making it difficult to emulsify oil phase which is added to the water phase thereafter.
- these phosphiniminophosphonium salts are especially useful as textile softening agents.
- they effectively soften textiles, for example, towels, thereby reducing or eliminating harsh feel.
- they are durable softening agents and after application to textiles resist removal and provide softening effect even after five to ten washings of such textiles.
- these salts are suitably used as active ingredients in textile softener compositions, as softening agents in industrial textile treatment where durable softening effect is desirable or necessary, and as additives to detergent compositions.
- the textile softener compositions referred to above can be in the form of liquids, granular products, tablets, and in other forms.
- a liquid textile softener composition can comprise from about 1% to about 15% by weight phosphiniminophosphonium salt and from about 85% to about 99% water.
- Such compositions also contain preferably from about 1% to about 50%, and more preferably from about 1% to about by weight of an alcohol containing from 1 to about 4 carbon atoms, such as, for example, ethanol or isopropanol, in place of an equal weight of water.
- This alcoholic component reduces the viscosity of the softener composition thereby causing it to be more readily pourable and also reduces the tendency of the composition to become a gel.
- a preferred liquid textile softener composition herein consists essentially by weight of from about 1% to about phosphiniminophosphonium salt, from about 1% to about 50% alcohol, and from about 35% to about 98% water while an especially preferred liquid textile softener composition herein consists essentially by weight of from about 1% to about 15% phosphiniminophosphonium salt, from about 1% to about 10% alcohol and from about 75% to about 98% water.
- Optional ingredients for the present liquid textile softener compositions include, for example, perfume,
- coloring agent and up to about 1% or more of a nonionic detergent such as, for example, nonyl phenoxy polyoxyethylene ethanol, containing 5 to 25 moles of ethylene oxide per mole of phenol, to help stabilize the composition.
- a nonionic detergent such as, for example, nonyl phenoxy polyoxyethylene ethanol, containing 5 to 25 moles of ethylene oxide per mole of phenol, to help stabilize the composition.
- a granular textile softener composition can be prepared simply by mixing urea with the present phosphiniminophosphonium salts. These compositions can comprise, for example, from about 5% to about 50% phosphiniminophosphonium salt and from about 50% to about urea.
- These softener compositions are applied, for example, by the housewife to textiles during laundering.
- the housewife can cause the application of such a softener composition simply by adding it, for example, by pouring, into the rinse water which is present during the rinse cycle of washing machine operation.
- the textile softener composition is added to the rinse water in amount sufiicient to provide a concentration of phosphiniminophosphonium salt in the rinse water ranging from about 10 ppm. to about 500 ppm. and preferably from about 25 ppm. to about ppm.
- the present phosphiniminophosphonium salts are advantageously employed in many industrial textile treating operations where durable softening effect is desired.
- the above described textile softener composition can be applied to yard goods by passing such yard goods through a pad containing this composition.
- yard goods can be treated with the present phosphiniminophosphonium salts at the same time they are treated with wash wear resins, for example, cyclic ethylene urea, to provide softer feel since treatment with wash wear resins alone usually produces textiles having harsh feed.
- these phosphiniminophosphonium salts can be employed as durable softening agent additives to various detergent compositions, and ordinarily comprise from about 1% to about 15 by weight of such detergent compositions.
- the detergent active in these detergent compositions is any detergent which is compatible with the phosphiniminophosphonium salt additive.
- This detergent active is preferably a nonionic synthetic detergent or a zwitterionic synthetic detergent since the phosphiniminophosphonium salt being cationic is compatible with these detergents while such salt may not be compatible with soap and with anionic synthetic detergents.
- the phosphiniminophosphonium salt additive can also be used in combination with cationic detergents or with ampholytic or amphoteric detergents with the pH of the system adjusted so that such detergents are cationic detergents.
- the detergent active ordinarily comprises from about 5% to about 95% by weight of these detergent compositions.
- nonionic synthetic detergents may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
- the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Nonionic synthetic detergents are made available on the market under the trade name Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
- the hydrophobic portion of the molecule which, of course, exhibits water insolubility, has a molecular weight of about 1500 to 1800.
- the addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the products is retained up to the point where polyoxyethylene content is about 50% of the total Weight of the condensation product.
- nonionic synthetic detergents include:
- the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl radical containing from about 6 to 12 carbon atoms in either straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
- the alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.
- Trialkyl amine oxides and trialkyl phosphine oxides wherein one alkyl radical contains from about 10 to about 18 carbon atoms, from to about 5 ether linkages, and from 0 to about 2 hydroxy groups and wherein the other two alkyl radicals each contain from 1 to about 3 carbon atoms, from 0 to about 2 ether linkages, and from 0 to about 2 hydroxy groups.
- Specific examples are dodecyl diethanol amine oxide and tetr-adecyl dimethyl phosphine oxide.
- Dialkyl sulfoxide detergents having the formula wherein R is a hydrocarbon group containing from about to about 20 carbon atoms, from 0 to about 5 ether linkages, and from 0 to about 3 hydroxyl groups, there being at least one moiety of R which constitutes a carbon chain containing no ether linkages and containing about 10 to 18 carbon atoms, and wherein R is a short alkyl chain containing from about 1 to about 3 carbon atoms having 0-2 hydroxyl groups attached to said short alkyl chain.
- sulfoxides are octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradeeyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3- methoxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, 2-hydroxyundecyl methyl sulfoxide, 2-hydroxydecyl methyl sulfoxide, and Z-decoxyethyl-2-hydroxyethyl sulfoxide.
- Suitable zwitterionic detergents include detergents such as betaine and betaine-like detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic values.
- suitable zwitterionic detergents include those having the formula R0 Ra 11fl wherein R contains from about 10 to about 18 carbon atoms and from about 0 to about 5 other linkages, wherein R and R are each selected from the group consisting of alkyl groups containing from 1 to about 3 carbon atoms, wherein R is selected from the group consisting of alkylene and hydroxy substituted alkylene groups containing from 1 to about 4 carbon atoms, and wherein Z is selected from the group consisting of ii -o-o and groups.
- ampholytic and amphoteric detergents mentioned above are represented by detergents such as dodocyl-betaalanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of US. 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching of US. 2,438,091, and the products sold under the trade name Miranol and described in US. Patent 2,528,378.
- the detergent compositions herein contain from about 0% to preferably from 10% to 90%, by weight of water-soluble alkaline detergency builder salts, either of the organic or inorganic types, and should provide a washing solution pH of from about 9 to about 12.
- the ratio of builder salts to organic detergent is preferably from about 1:4 to about 20:1, more preferably from about 0.7:1 to about 9:1.
- suitable watersoluble inorganic alkaline detergency builder salts are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Specific examples of such salts are sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, orthophosphates, and hexametaphosphates.
- suitable organic alkaline detergency builder salts are: 1) water-soluble aminopolycarboxylates (e.g., sodium and potassium ethylenediamine-tetraacetates, nitro triacetates, and N-(Z-hydroxyethyl)-nitrilo diacetates); (2) water-soluble salts of phytic acid (e.g., sodium and potassium phytatessee US. Patent 2,739,942); (3) watersoluble salts of ethane-l-hydroxy-1,1-diphosphonate (e.g., the trisodium and tripotassium salts-see US.
- water-soluble aminopolycarboxylates e.g., sodium and potassium ethylenediamine-tetraacetates, nitro triacetates, and N-(Z-hydroxyethyl)-nitrilo diacetates
- phytic acid e.g., sodium and potassium phytatessee US. Patent 2,739,942
- Patent 3,159,581 water-soluble salts of methylene diphosphonic acid (e.g., trisodium and tripotassium methylene diphosphonate and the other salts described in the copending application of Francis L. Diehl, Ser .No. 266,025, filed Mar. 18, 1963, now US. Patent 3,213,030; (5) water-soluble salts of substituted methylene diphosphonic acids (e.g., trisodium and tripotassium ethylidene, isopropylidene, benzylmethylidene, and halomethylidene diphosphonates and the other substituted methylene diphosphonates disclosed in the copending application of Clarence H. Roy, Ser. No.
- a polyelectrolyte builder material comprising a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to the acid form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment to the polymer chain of any carboxyl-containing radical being separated by not more than 3 carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical.) Specific examples are polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene, and
- Mixtures of organic and/or inorganic builders can be used and are generally desirable. Especially preferred are the mixtures of builders disclosed in the copending application of Burton H. Gedge, Ser. No. 398,705, filed Sept. 23, 1964, now US. Patent 3,392,121, e.g., ternary mixtures of sodium tripolyphosphate, sodium nitrilotriactate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
- These detergent compositions can optionally contain from about 1% to about 50%, preferably about 1% to about 10%, by weight of an alcohol containing 1 to about 4 carbon atoms such as, for example, isopropanol or ethanol, to reduce the viscosity of the composition thereby causing it to be more readily pourable and also to reduce the tendency of the composition to become a gel.
- an alcohol containing 1 to about 4 carbon atoms such as, for example, isopropanol or ethanol
- detergent compositions can also contain any of the usual adjuvants, diluents and additives, for example, perfumes, anti-tarnishing agents (e.g., sodium and potassium silicates and benzotriazole), anti-redeposition agents (e.g., alkali metal and ammonium salts of carboxymethyl cellulose), bacteriostatic agents, dyes or pigments (including optical brighteners), suds builders, suds depressors,
- the organic detergent components, the builders the phosphiniminophosphonium salt component, and the minor ingredients are incorporated into the composition prior to conversion into final product form, e.g., detergent granules, flakes, etc., but they can also be added individually in the form of particles or as liquids.
- these salts can be prepared by any of a number of processes but preferably are prepared according to one of two novel processes described hereinafter. These novel processes can be used to prepare not only the above phosphiniminophosphonium salts which are effective and durable softening agents and effective emulsifying agents, but also other phosphiniminophosphonium salts known in the prior art which do not possess these advantageous softening and emulsifying properties but which are effective antibacterial agents.
- symmetrical phosphiniminophosphonium salts are prepared by heating an aminophosphonium salt having the formula wherein R is a radical selected from the group consisting of aliphatic radicals containing from 1 to 18 carbon atoms, phenyl and substituted phenyl; R and R are radicals selected from the group consisting of aliphatic radicals containing 1 to about 4 carbon atoms, phenyl and substituted phenyl; and Y is an anion selected from the group consisting of halides (such as chloride, bromide and iodide), cyanide, and azide.
- R R and R can each be of different chain lengths within the same compound.
- the aliphatic radicals in this formula can be saturated or unsaturated and branched or straight chain.
- these aliphatic radicals can be alkyl, alkenyl, substituted alkyl, and substituted alkenyl radicals, the terms alkyl and alkenyl being defined as previously.
- Suitable aminophosphonium salts are set forth in Table II below wherein R R R and Y are applied in the structural formula set forth above.
- reaction solvent it is preferred that no reaction solvent be employed in this process since the use of a reaction solvent lowers the concentration of aminophosphonium salt and can therefore necessitate longer reaction times. If no reaction solvent is employed a reaction temperature at least 20 C. above the melting point of the aminophosphonium Salt reactant is essential. If a reaction solvent is employed, such reaction solvent must be inert with respect to the aminophosphonium salt and any reaction product and is preferably a high boiling point aromatic or aliphatic hydrocarbon, such as, for example, dodecane.
- the phosphiniminophosphonium product is separated from by-product by any conventional separation technique, for example, by selectively dissolving the product in a solvent, separating the dissolved product from undissolved by-product by filtration, and evaporating the filtrate to yield substantially pure product.
- aminophosphonium salt reactant of this process while not readily available commercially, can be easily prepared.
- aminophosphonium chlorides are conveniently prepared by reacting the appropriate trisubstituted phosphine in an inert atmosphere and at room temperature with chloramine gas.
- the preparation of trisubstituted phosphines is described in Hays, Ser. No. 461,669, filed June 7, 1965.
- this process can be employed to prepare either symmetrical or unsymmetrical phosphiniminophosphonium salts.
- an N-alkali-metal phosphinimine is reacted with a trisubstituted phosphine dihalide or dipseudohalide.
- the N-alkali-metal phosphinimine for use herein is believed to be a novel compound. It has the structural formula wherein R is a radical selected from the group consisting of aliphatic radicals containing from 1 to about 18 carbon atoms, phenyl, and substituted phenyl; R and R are radicals selected from the group consisting of aliphatic radicals containing 1 to about 4 carbon atoms, phenyl, and substituted phenyl; and M is an alkali metal selected from the group consisting of sodium, potassium, and lithium.
- R R and R can each be of different chain lengths within the same compound and can be saturated or unsaturated and branched or straight chain.
- these aliphatic radicals can be alkyl, alkenyl, substituted alkyl, and substituted alkenyl radicals, the terms alkyl and alkenyl being defined as hereinbefore.
- N-alkali-metal phosphinimines are set forth in Table III below wherein R R R and M are applied in the structural formula set forth above.
- the trisubstituted phosphine dihalide or dipseudohalide for use herein has the structural formula R18R19R20PY21 wherein R is a radical selected from the group consisting of aliphatic radicals containing from 1 to about 18 carbon atoms, phenyl, and substituted phenyl; R and R are radicals selected from the group consisting of aliphatic radicals containing from 1 to about 4 carbon atoms, phenyl, and substituted phenyl; and Y is selected from the group consisting of (l) halogens, such as chlorine, bromine, and iodine, and (2) pseudohalogens selected from the group consisting of cyanide and azide.
- R R and R can each be of different chain lengths within the same compound and can be saturated or unsaturated and branched or straight chain.
- the term aliphatic is de fined as hereinbefore.
- Each Y can be different in the same compound.
- the above N-alkali-metal phosphinimines are reacted with the above trisubstituted phosphine dihalides or dipseudohalides in an inert atmosphere, for example under argon, at a temperature ranging from about 0 C. to about 50 C. for a period ranging from about 0.5 hour to about 30 hours to provide essentially complete reaction.
- Room temperature is a preferred reaction temperature. Reaction times ranging from about 1 hour to about 20 hours are preferred.
- reaction solvent is employed in this process which is compatible with the above reactants and with the reaction product.
- This reaction solvent is preferably an aliphatic or aromatic hydrocarbon uch as benzene, hexane, dodecane, and the like.
- N-alkali-metal phosphinimines can be prepared by reacting an aminophosphonium halide or pseudohalide, e.g., chloride, the preparation of which is described hereinbefore, with aliphtic hydrocarbon alkalimetal salt.
- an aminophosphonium halide or pseudohalide e.g., chloride
- aliphtic hydrocarbon alkalimetal salt e.g., aliphtic hydrocarbon alkalimetal salt.
- R M Two equivalents of aliphatic hydrocarbon alkali-metal, R M, are employed for each equivalent of aminophosphonium halide or pseudohalide,
- R R R and M are defined as previously;
- R is an aliphatic radical containing from 1 to about 12 carbon atoms, the term aliphatic being defined as previously; and
- Y is selected from the group consisting of chloride, bromide, iodide, azide, and cyanide.
- the reaction is conveniently carried out without external heating at a temperature ranging from about 10 C. to about C. in an inert atmosphere, such as argon, with a reaction time ranging from about 0.5 hour to about 10 hours or more.
- the following equation represents a typical example of the preparation of an N-alkali-metal phosphinimine:
- the trisubstituted dihalide or dipseudohalide can be conveniently prepared, for example, by reacting trisubstituted phosphines with a halogen or pseudohalogen.
- the reactants in the above two novel processes for the production of phosphinimino-phosphonium salts contain as anion-producing constituents only halogens and the pseudohalogens, azide and cyanide.
- This limitation in the structure of the reactants is essential for the production of high yields of phosphiniminophosphonium salt since reactants containing oxygen-containing anion-producing constituents for example produce high yields of by-products.
- these two novel processes are advantageously used directly only to produce phosphiniminophosphonium halides, azides and cyanides.
- the anions in the phosphiniminophosphonium salt products produced by these novel processes can be converted to other anions by means of conventional techniques, for example, by means of an ion exchange column.
- 12 2s 3 2 -NH Cl was prepared as follows: A 500-ml. three-necked roundbottom flask was fittted with a gas inlet tube, a paddle stirrer driven by an electric motor, and a gas outlet tube connected to a mineral oil bubbler. Twelve grams of dimethyldodecylphosphine prepared according to the method of Hays, Ser. No. 461,669, filed June 7, 1965, was added to the flask which previously had been evacuated and filled with argon. Then 300 ml. of dry benzene was added. The gas inlet tube was arranged so as to extend below the surface of the benzene and then was connected to a chloramine gas generator.
- symmetrical phosphiniminophosphonium salts are prepared if molar equivalents of other aminophosphonium salts are substituted for the aminophosphonium salts in the above examples.
- trimethylphosphiniminotrimethylphosphonium bromide is prepared if trimethylaminophosphonium bromide is substituted for the dimethyldodecylaminophosphonium chloride of Example I;
- dibutylundecylphosphiniminodibutylundecylphosphonium iodide is prepared if dibutylundecylaminophosphonium iodide is substituted for the dimethyltetradecylaminophosphonium chloride of Example II;
- dimethyloleylphosphiniminodimethyloleylphosphonium azide is prepared if dimethyloleylaminophosphonium azide is substituted for the dimethylhexadecylaminophosphonium chlo ride in Example III
- one-necked round-bot tomed flask was placed 11.57 grams (45.7 moles) of trin-butylaminophosphonium chloride, (n-C H P NH C1 and 30 ml. of benzene under an atmosphere of argon.
- a solution of tri-n-ibutylaminophosphonium chloride in benzene was then formed by means of vigorous stirring with a magnetic stirrer.
- To this solution at room temperature was added 57.4 ml. of 1.59 normal solution of n-butyl lithium-hexane solution (91.2 mmoles of n-butyl lithium or about 2 equivalents), and vigorous heat and gas evolution occurred.
- the resulting yellow solution was stirred for three hours under argon without addition of external heat.
- the resulting solution containing N-lithiotributylphosphini mine was used hereinafter without isolation or purification of the formed intermediate.
- the above tri-n-butylaminophosphonium chloride was synthesized in a manner similar to the dimethyldodecylaminophosphonium chloride of Example I.
- Dimethyldodecylphosphine dichloride was then prepared as follows: In a one-necked 100 ml. round-bottom flask equipped with a rubber cap and filled with argon was placed 7.05 grams (30.7 mmoles) of dimethyldodecylphosphine, and 50 ml. of dry benzene. The formed solution was vigorously stirred while 772 ml. of chlorine gas was injected into the capped flask. The reaction mixture was then stirred for one hour at room temperature. The resulting solution containing dimethyldodecylphosphine dichloride was used hereinafter without isolation or purification of the formed intermediate. The above dimethyldodecylphosphine was prepared by the method of Hays, previously referred to.
- phosphiniminophosphonium salts are prepared by the method of this example if molar equivalent of other N-alkali-metal phosphinimines are substituted for the N-lithiphosphinimine above and/ or molar equivalents of other trisubstituted phosphine dihalides or dipseudohalides are substituted for the dimethyldodecylphosphine dichloride above.
- N-sodiodimethylpalmitoleylphosphinimine is reacted with dimethylpalmitoleylphosphine diazide to produce dimethylpalmitoleylphosphiniminodimethylpalmitoleylphosphonium azide; N-potassiotributylphosphinimine is reacted with trimethylphosphine dibromide to produce tributylphosphiniminotrimethylph osphonium bromide; and N-lithiodimethyl-p-ethylphosphinimine is reacted with tributylphosphinemonoiodidemonacyanide to form a mixture of dimethyl-p-ethylphenylphosphiniminotributylphosphonium iodide and cyanide.
- halide and pseudohalide anions of the phosphiniminophosphonium salts formed in Examples I-V above can be converted to other anions by conventional ion exchange techniques.
- the dimethyldodecylphosphiniminotributylphosphonium chloride formed above can be converted to dimethyldodecylphosphinirninotributylphosphonium nitrate in this manner.
- EXAMPLE VI Emulsions of carbon tetrachloride
- One-fourth gram of dimethyldodecylphosphiniminotributylphosphonium chloride prepared in Example V was mixed with 4 ml. of carbon tetrachloride. This mixture was mixed with 4 ml. of water to provide a carbon tetrachloride/water emulsion which is stable for more than twelve hours.
- this composition can be diluted to contain as much as 50% Water. After being mixed, this diluted composition is an emulsion which is stable for at least 1 hour, and as such is suitable for application to textiles for dry cleaning purposes.
- phosphiniminophosphonium salts for example, the compounds prepared in Examples I, II, and III can replace the dimethyldodecylphosphiniminotributylphosphonium chloride in the above example to provide stable emulsions upon dilution of the composition.
- useful dry cleaning compositions consist essentially of from about 0.5% to about 5% phosphiniminophosphonium salt, from about 0.5% to about 50% water and from about 45% to about 99% tetrachloroethylene.
- compositions containing the new phosphiniminophosphonium salts are applied to textiles as water solutions containing 50 p.p.m. posphiniminophos phoniu-m salt. When so applied these compositions provide effective and durable softening. The softening efi'ect remains even after five washings of the treated textile.
- a suitable liquid textile softener composition contains:
- a suitable granular textile softener composition contains:
- EXAMPLE X In the manufacture of sheeting, 80 x 80 cotton sheeting is pass through a pad containing a water solution of dimethyloctadecylphosphiniminodimethyloctadecylphosphonium chloride. The water solution contains 75 p.p.m. of the phosphiniminophosphonium salt. The sheeting is effectively softened and retain this softened effect even after the consumer has washed it five times with no application of textile softener.
- Examples XI-XVII illustrate heavy-duty laundry detergent compositions which contain as a softening agent the new phosphiniminophosphonium salts of this invention. These detergent compositions can be used to clean and soften textiles such as sheets and towels.
- component A is a tertiary amine oxide having a long alkyl chain derived from middle cut coconut alcohol (containing 2%-C 66%-C 23%- C and 9%C and two methyl groups.
- phosphiniminophosphonium salts can be substituted for the phosphiniminophosphonium salts of Examples XI-XIX to provide laundry detergents.
- dimethyltetradecyphosphiniminodimethyltetradecylphosphonium chloride can be substituted for the dimethyldodecylphosphiniminodimethyldodecylphosphonium chloride of Example XIX to provide a lightduty liquid detergent having softening properties.
- various other detergent actives can be substituted for the detergent actives in Examples XI-XIX above.
- ampholytic detergents e.g., dodecylbeta-alanine, the sodium salt of N-dodecyl taurine, or disodium N-dodecyl asparate
- component A can replace component A in Examples XVIII and XIX above to provide light-duty liquid detergents, having softening properties.
- wetting agents wetting agents, detergents, solubilizing agents, waterproofing agents, and gelling or thickening agents.
- These salts also are very soluble and thus are very advantageously used in various compositions such as softener compositions and detergent compositions; this is because they remain in solution even though the composition containing them freezes and later thaws.
- additives which are suspended in such compositions tend to separate from the rest of the composition under these same freezing-thawing circumstances.
- N-lithiodimethyldodecylphosphinimine was prepared by reacting dimethyldodecylaminophosphonium chloride with n-butyl lithium according to the method for preparing N-lithiotributylphosphinimine in Example V.
- This prepared compound is a reactive intermediate and can be used in the preparation of the novel phosphiniminophosphonium salts of this invention according to the second of the two novel processes described herein.
- this N-lithiodimethyldodecylphosphinimine can be reacted with tn'butylphosphine dichloride to produce dimethyldodecylphosphiniminotributylphosphonium chloride.
- a phosphiniminophosphonium salt having the structural formula wherein R is selected from the group consisting of alkyl radicals containing from 1 to about 18 carbon atoms; R R R and R are selected from the group consisting of alkyl radicals having from 1 to about 4 carbon atoms; R is selected from the group consisting of alkyl radicals containing from about 12 to about 18 carbon atoms; and X is an anion which permits solubility and hydrolytic stability of the salt.
- R, R R R R and R are alkyl radicals and X is an anion selected from the group consisting of halides and pseudohalides.
- X is an anion selected from the group consisting of chloride, bromide, iodide, azide, and cyanide.
- Y is selected from the group consisting of chlorine and bromine.
- reaction time ranges from about 0.5 hour to about 30 hours.
- reaction time ranges from about 1 hour to about 20 hours.
- An N-alkali metal phosphinimine having the structural formula R R R P NM wherein R is a radical selected from the group consisting of alkyl radicals containing from 1 to about 18 carbon atoms; R and R are radicals selected from the group consisting of alkyl radicals containing 1 to about 4 carbon atoms; and M is an alkali metal selected from the group consisting of sodium, potassium, and lithium.
- a process for preparing a symmetrical ph0sphiniminophosphonium salt comprising the step of heating to an elevated temperature and in an inert atmosphere an aminophosphonium salt having the formula wherein R is a radical selected from the group consisting of alkyl radicals containing from 1 to about 18 carbon atoms; R and R are radicals selected from the group consisting of alkyl radicals containing from 1 to about 4 carbon atoms; and wherein Y is an anion selected from the group consisting of halides, azide and cyanide; said elevated temperature being at least 20 C. in excess of the melting point of said aminophosphonium salt.
- a process for preparing a dimethyldodecylphosphiniminedimethyldodecylphosphonium salt comprising the step of heating at a temperature ranging from about 100 C. to about 300 C. in the presence of an inert solvent and in an inert atmosphere a dimethyldodecylaminophosphonium salt having the formula R R R P NH Y wherein R is dodecyl; R and R each are methyl; and Y is an anion selected from the group consisting of halides, azide and cyanide.
- Y is selected from the group consisting of chloride, iodide, bromide, azide, and cyanide.
- reaction time ranges from about 0.5 hour to about 30 hours.
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Description
United States Patent EMULSIFYING AND TEXTILE SOFTENING PHOS- PHONIUM COMPOUNDS, PROCESSES FOR PRE- PARING THE SAME Terence William Rave, Cincinnati, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Dec. 30, 1965, Ser. No. 517,826
Int. Cl. C07g 9/54; A611: 27/00; D06m 13/44 US. Cl. 260-551 20 Claims ABSTRACT OF THE DISCLOSURE Novel phosphonium compounds and processes for their preparation are disclosed. These novel phosphonium compounds are useful as textile softening agents, emulsifying agents and anti-bacterial agents.
This invention relates to novel phosphiniminophosphonium salts which are textile softening agents and emulsifying agents. It further relates to processes for preparing these novel compounds and other compounds which are antibacterial agents. It further relates to novel intermediate compounds which are employed in one of these processes.
The term phosphiniminophosphonium is used herein to denote a compound containing a linkage, which linkage is explained hereinafter. Compounds containing this linkage have been described in the prior art. However, compounds containing this linkage which are effective textile softening agents and effective emulsifying agents are not known to have been so described.
There are several textile softening agents which are presently known to be commercially available which are of much different chemical structure from the compounds of the present invention. Some of these softening agents while effectively softening textiles thereby reducing or eliminating harsh feel, do not resist removal. In other words, if the softened textile is washed without reapplication of softening agent, the previously applied softening agent is removed by the washing from the textile, and harsh feel is again present. A durable softening agent, that is a softening agent which resist removal even after several washings of the textile, is advantageous to the consumer in that the necessity of continual reapplication of softening agent is eliminated.
It is, therefore, an object of this invention to provide novel phosphiniminophosphonium salts which are effective and durable textile softening agents and effective emulsifying agents.
It is a further object of this invention to prepare phosphiniminophosphonium salts by heating aminophosphonium salts.
It is a further object of this invention to prepare phosphiniminophosphonium salts :by reacting N-alkali-metal phosphinimines with trisubstituted phosphine dihalides or dipseudohalides.
It is another object of this invention to provide novel N-alkali-metal phosphinimines which can be employed in the above process.
These and other objects will be apparent from the description of the invention which follows.
According to this invention, it has been found that phosphiniminophosphonium salts having the following structural formula are effective and durable textile softening agents and effective emulsifying agents:
wherein R is an aliphatic radical containing from 1 to about 18 carbon atoms; R R R and R are aliphatic radicals containing from 1 to about 4 carbon atoms; R is an aliphatic radical containing from about 12 to about 18 carbon atoms; and X is an anion which permits adequate solubility and hydrolytic stability of the salt. This structural formula and more particularly the linkage in this structural formula is a resonance structure. Thus, this structural formula represents the following structural formulas which are in resonance and in which R, R R R R R and X are defined as above:
The salts defined by this structural formula can be symmetrical or unsymmetrical. R, R R R and R can each be of different chain lengths within the same compound. The aliphatic radicals in this structural formula can be saturated or unsaturated and branched or straight chain. For example, these aliphatic radicals can be alkyl, substituted alkyl, alkenyl and substituted alkenyl radicals. The term alkyl is used herein to include only saturated carbon chains. The term alkenyl is used herein to include carbon chains containing one or more double :bonds.
The exact nature of the anionic portion of the above phosphiniminophosphonium salts is thought to be immaterial so far as the textile softening and emulsifying properties of these new compounds are concerned. Accordingly, virtually any organic or inorganic anion which permits adequate solubility of the phosphiniminophosphonium salts and which permits hydrolytic stability of the salts, that is, which provides stable anionic and cationic moieties upon solution in water, may be found suitable depending upon availability and cost factors. Thus, X in the above structural formula can suitably be, for example, a halide, such as chloride, bromide, iodide, or fluoride; a pseudohalide, such as cyanide, azide or thiocyanate; a sulfonate, such as methane sulfonate or p-toluene sulfonate; a sulfinate, such as methane sulfinate; a fluoroborate; sulfate, sulfite, nitrate, nitrite, phosphate, borate, methosulfate, chlorate, 'bisulfate, bisulfite, acetate, hexachloroantimonate and other anions.
Preferably, the aliphatic radicals in the present phosphiniminophosphonium salts are alkyl radicals and the anion, X, is selected from the group consisting of halides and pseudohalides. Symmetrical phosphiniminophosphonium salts of the present invention are especially preferred for textile softening agents.
Emulsifying and textile softening phosphiniminophosphonium salts, none of which are known to be described in the prior art and exemplary of those within the present invention, are set forth in Table I below wherein R, R R R R, R and X are applied in the structural formula set forth above.
TABLE I R R R R R R X methyl methyl methyl methyl methyl trideeyl SO4- butyl methyl methyl propyl methyl dodecyl Br butyl butyl butyl methyl methyl dodecyl C1 octyl 3-iodopropenyl ethyl methyl methyl tetradeeyl I- dodecyl methyl methyl methyl methyl dodecyl Cldodccyl ethyl ethyl ethyl ethyl dodecyl CHJCOO' dodecyl ethylene methyl methyl ethylene dodecyl N0 tetradecyl methyl methyl methyl methyl tetradceyl Cltetradecyl chloromethyl nethyl methyl methyl tetradeeyl b13- tetradecyl hydroxymethyl methyl methyl methyl tetradeeyl C N- tetradeeyl butyl butyl hutyl butyl tetmdeeyl 11804- hexadeeyl methyl methyl methyl methyl hexadecyl (/i" octadeeyl methyl methyl methyl methyl octadecyl Cloetadeeyl 3-hydroxypropenyl methyl methyl methyl hexadecyl Cloleyl methyl methyl methyl methyl oleyl Cl- Where the valence of the anion is greater than 1, a number of cations equal to this Valence are present in each salt molecule.
As previously stated, the above-described phosphiniminophosphonium salts are especially useful as emulsifying agents. These salts ordinarily can be used to produce oil-in-water emulsions that are stable for more than one hour, the weight ratio of emulsifier to oil phase generally ranging from about 1:1000 to about 3:1. For example, these salts provide stable water emulsions of dry cleaning solvents, such as tetrachloroethylene, and of other organic solvents, such as carbon tetrachloride. Moreover, these salts provide stable water emulsions of glyceride oils, such as cottonseed oil or soybean oil. In the preparation of such emulsions the phosphiniminophosphoniu1n salt is preferably first dispersed in the oil phase to be emulsified, and the oil-emulsifier combination is then mixed with the water phase. This is because these phosphiniminophosphonium salts tend to cause the formation of viscous solutions or gels when added by themselves to the water phase thereby making it difficult to emulsify oil phase which is added to the water phase thereafter.
Moreover, these phosphiniminophosphonium salts are especially useful as textile softening agents. First of all, they effectively soften textiles, for example, towels, thereby reducing or eliminating harsh feel. Moreover, they are durable softening agents and after application to textiles resist removal and provide softening effect even after five to ten washings of such textiles. Thus, these salts are suitably used as active ingredients in textile softener compositions, as softening agents in industrial textile treatment where durable softening effect is desirable or necessary, and as additives to detergent compositions.
The textile softener compositions referred to above can be in the form of liquids, granular products, tablets, and in other forms.
For example, a liquid textile softener composition can comprise from about 1% to about 15% by weight phosphiniminophosphonium salt and from about 85% to about 99% water. Such compositions also contain preferably from about 1% to about 50%, and more preferably from about 1% to about by weight of an alcohol containing from 1 to about 4 carbon atoms, such as, for example, ethanol or isopropanol, in place of an equal weight of water. This alcoholic component reduces the viscosity of the softener composition thereby causing it to be more readily pourable and also reduces the tendency of the composition to become a gel. This alcoholic ingredient also desirably acts as a freeze point depressant thereby reducing the possibility of the composition freezing during shipping whereby the compositions container is possibly ruptured. Thus, a preferred liquid textile softener composition herein consists essentially by weight of from about 1% to about phosphiniminophosphonium salt, from about 1% to about 50% alcohol, and from about 35% to about 98% water while an especially preferred liquid textile softener composition herein consists essentially by weight of from about 1% to about 15% phosphiniminophosphonium salt, from about 1% to about 10% alcohol and from about 75% to about 98% water. Optional ingredients for the present liquid textile softener compositions include, for example, perfume,
coloring agent, and up to about 1% or more of a nonionic detergent such as, for example, nonyl phenoxy polyoxyethylene ethanol, containing 5 to 25 moles of ethylene oxide per mole of phenol, to help stabilize the composition.
A granular textile softener composition can be prepared simply by mixing urea with the present phosphiniminophosphonium salts. These compositions can comprise, for example, from about 5% to about 50% phosphiniminophosphonium salt and from about 50% to about urea.
These granular compositions can be compressed into tablets.
These softener compositions are applied, for example, by the housewife to textiles during laundering. The housewife can cause the application of such a softener composition simply by adding it, for example, by pouring, into the rinse water which is present during the rinse cycle of washing machine operation. For effective and durable softening the textile softener composition is added to the rinse water in amount sufiicient to provide a concentration of phosphiniminophosphonium salt in the rinse water ranging from about 10 ppm. to about 500 ppm. and preferably from about 25 ppm. to about ppm.
Turning now to industrial applications, the present phosphiniminophosphonium salts are advantageously employed in many industrial textile treating operations where durable softening effect is desired. For example, the above described textile softener composition can be applied to yard goods by passing such yard goods through a pad containing this composition. Or yard goods can be treated with the present phosphiniminophosphonium salts at the same time they are treated with wash wear resins, for example, cyclic ethylene urea, to provide softer feel since treatment with wash wear resins alone usually produces textiles having harsh feed.
As explained above, these phosphiniminophosphonium salts can be employed as durable softening agent additives to various detergent compositions, and ordinarily comprise from about 1% to about 15 by weight of such detergent compositions. The detergent active in these detergent compositions is any detergent which is compatible with the phosphiniminophosphonium salt additive. This detergent active is preferably a nonionic synthetic detergent or a zwitterionic synthetic detergent since the phosphiniminophosphonium salt being cationic is compatible with these detergents while such salt may not be compatible with soap and with anionic synthetic detergents. The phosphiniminophosphonium salt additive can also be used in combination with cationic detergents or with ampholytic or amphoteric detergents with the pH of the system adjusted so that such detergents are cationic detergents. The detergent active ordinarily comprises from about 5% to about 95% by weight of these detergent compositions.
The above mentioned nonionic synthetic detergents may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
For example, a well-known class of nonionic synthetic detergents is made available on the market under the trade name Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule, which, of course, exhibits water insolubility, has a molecular weight of about 1500 to 1800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the products is retained up to the point where polyoxyethylene content is about 50% of the total Weight of the condensation product.
Other suitable nonionic synthetic detergents include:
(1) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl radical containing from about 6 to 12 carbon atoms in either straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.
(2) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene di-amineproducts which may be varied in composition depending upon thebalance between the hydrophobic and hydrophilic elements which is desired. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular structure of about 5000 to about 11,000, resulting from the reaction of ethylene oxide groups with a hydrophobic base, constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2500 to 3000, are satisfactory.
(3) The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.
(4) Trialkyl amine oxides and trialkyl phosphine oxides wherein one alkyl radical contains from about 10 to about 18 carbon atoms, from to about 5 ether linkages, and from 0 to about 2 hydroxy groups and wherein the other two alkyl radicals each contain from 1 to about 3 carbon atoms, from 0 to about 2 ether linkages, and from 0 to about 2 hydroxy groups. Specific examples are dodecyl diethanol amine oxide and tetr-adecyl dimethyl phosphine oxide.
(5) Dialkyl sulfoxide detergents having the formula wherein R is a hydrocarbon group containing from about to about 20 carbon atoms, from 0 to about 5 ether linkages, and from 0 to about 3 hydroxyl groups, there being at least one moiety of R which constitutes a carbon chain containing no ether linkages and containing about 10 to 18 carbon atoms, and wherein R is a short alkyl chain containing from about 1 to about 3 carbon atoms having 0-2 hydroxyl groups attached to said short alkyl chain. Specific examples of such sulfoxides are octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradeeyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3- methoxytridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, 2-hydroxyundecyl methyl sulfoxide, 2-hydroxydecyl methyl sulfoxide, and Z-decoxyethyl-2-hydroxyethyl sulfoxide.
Suitable zwitterionic detergents include detergents such as betaine and betaine-like detergents wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic values. For example, suitable zwitterionic detergents include those having the formula R0 Ra 11fl wherein R contains from about 10 to about 18 carbon atoms and from about 0 to about 5 other linkages, wherein R and R are each selected from the group consisting of alkyl groups containing from 1 to about 3 carbon atoms, wherein R is selected from the group consisting of alkylene and hydroxy substituted alkylene groups containing from 1 to about 4 carbon atoms, and wherein Z is selected from the group consisting of ii -o-o and groups. Specific examples of such compounds are l-(hexadecyldimethylammonio)propane-3-sulfonate, l-(dodecyldimethylammonio)butane 3 sulfonate, and l-(dodecyldimethylammonio) acetate. Some other common examples of these detergents are described in US. Patents 2,082,275; 2,129,264; 2,217,846; 2,255,082; 2,702,279.
The ampholytic and amphoteric detergents mentioned above are represented by detergents such as dodocyl-betaalanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of US. 2,658,072, N-higher alkylaspartic acids such as those produced according to the teaching of US. 2,438,091, and the products sold under the trade name Miranol and described in US. Patent 2,528,378. The detergent compositions herein contain from about 0% to preferably from 10% to 90%, by weight of water-soluble alkaline detergency builder salts, either of the organic or inorganic types, and should provide a washing solution pH of from about 9 to about 12. The ratio of builder salts to organic detergent is preferably from about 1:4 to about 20:1, more preferably from about 0.7:1 to about 9:1. Examples of suitable watersoluble inorganic alkaline detergency builder salts are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Specific examples of such salts are sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, orthophosphates, and hexametaphosphates. Examples of suitable organic alkaline detergency builder salts are: 1) water-soluble aminopolycarboxylates (e.g., sodium and potassium ethylenediamine-tetraacetates, nitro triacetates, and N-(Z-hydroxyethyl)-nitrilo diacetates); (2) water-soluble salts of phytic acid (e.g., sodium and potassium phytatessee US. Patent 2,739,942); (3) watersoluble salts of ethane-l-hydroxy-1,1-diphosphonate (e.g., the trisodium and tripotassium salts-see US. Patent 3,159,581); (4) water-soluble salts of methylene diphosphonic acid (e.g., trisodium and tripotassium methylene diphosphonate and the other salts described in the copending application of Francis L. Diehl, Ser .No. 266,025, filed Mar. 18, 1963, now US. Patent 3,213,030; (5) water-soluble salts of substituted methylene diphosphonic acids (e.g., trisodium and tripotassium ethylidene, isopropylidene, benzylmethylidene, and halomethylidene diphosphonates and the other substituted methylene diphosphonates disclosed in the copending application of Clarence H. Roy, Ser. No. 266,055, filed Mar. 18, 1963, now US. Patent 3,422,021); (6) water-soluble salts of polycarboxylate polymers and copolymers as described in the copending application of Francis L. Diehl, Ser. No. 269,359, filed Apr. 1, 1963, now US. Patent 3,308,067. (Specifically, a polyelectrolyte builder material comprising a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to the acid form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment to the polymer chain of any carboxyl-containing radical being separated by not more than 3 carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical.) Specific examples are polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene, and (7) mixtures thereof.
Mixtures of organic and/or inorganic builders can be used and are generally desirable. Especially preferred are the mixtures of builders disclosed in the copending application of Burton H. Gedge, Ser. No. 398,705, filed Sept. 23, 1964, now US. Patent 3,392,121, e.g., ternary mixtures of sodium tripolyphosphate, sodium nitrilotriactate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
These detergent compositions can optionally contain from about 1% to about 50%, preferably about 1% to about 10%, by weight of an alcohol containing 1 to about 4 carbon atoms such as, for example, isopropanol or ethanol, to reduce the viscosity of the composition thereby causing it to be more readily pourable and also to reduce the tendency of the composition to become a gel.
These detergent compositions can also contain any of the usual adjuvants, diluents and additives, for example, perfumes, anti-tarnishing agents (e.g., sodium and potassium silicates and benzotriazole), anti-redeposition agents (e.g., alkali metal and ammonium salts of carboxymethyl cellulose), bacteriostatic agents, dyes or pigments (including optical brighteners), suds builders, suds depressors,
and the like, without detracting from the advantageous properties of the composition Normally the organic detergent components, the builders the phosphiniminophosphonium salt component, and the minor ingredients are incorporated into the composition prior to conversion into final product form, e.g., detergent granules, flakes, etc., but they can also be added individually in the form of particles or as liquids.
Turning now to processes for preparing the abovedescribed phosphiniminophosphonium salts, these salts can be prepared by any of a number of processes but preferably are prepared according to one of two novel processes described hereinafter. These novel processes can be used to prepare not only the above phosphiniminophosphonium salts which are effective and durable softening agents and effective emulsifying agents, but also other phosphiniminophosphonium salts known in the prior art which do not possess these advantageous softening and emulsifying properties but which are effective antibacterial agents. Accordingly, these processes are described hereinafter with sufiicient breadth to cover not only the preparation of the above novel phosphiniminophosphonium salts but also the preparation of these other phosphiniminophosphonium salts which are known in the prior art and which are effective antibacterial agents.
In one of these novel processes symmetrical phosphiniminophosphonium salts are prepared by heating an aminophosphonium salt having the formula wherein R is a radical selected from the group consisting of aliphatic radicals containing from 1 to 18 carbon atoms, phenyl and substituted phenyl; R and R are radicals selected from the group consisting of aliphatic radicals containing 1 to about 4 carbon atoms, phenyl and substituted phenyl; and Y is an anion selected from the group consisting of halides (such as chloride, bromide and iodide), cyanide, and azide. R R and R can each be of different chain lengths within the same compound. The aliphatic radicals in this formula can be saturated or unsaturated and branched or straight chain. For example, these aliphatic radicals can be alkyl, alkenyl, substituted alkyl, and substituted alkenyl radicals, the terms alkyl and alkenyl being defined as previously.
Suitable aminophosphonium salts are set forth in Table II below wherein R R R and Y are applied in the structural formula set forth above.
TABLE Ii R12 Rn X methyl cyanide azidc iodide bromide chloride uzide chloride chloride chloride chloride bromide chloride chloride chloride chloride chloride methyl ethylene methyl methyl The above aminophosphonium salts are heated in an inert atmosphere, for example under vacuum, at a temperature ranging from about C. to about 300 C. for a period ranging from about 0.5 hour to about 30 hours to provide essentially complete reaction. Reaction temperatures ranging from about C. to 260 C. and reaction times ranging from about 1 hour to about 20 hours are preferred.
It is preferred that no reaction solvent be employed in this process since the use of a reaction solvent lowers the concentration of aminophosphonium salt and can therefore necessitate longer reaction times. If no reaction solvent is employed a reaction temperature at least 20 C. above the melting point of the aminophosphonium Salt reactant is essential. If a reaction solvent is employed, such reaction solvent must be inert with respect to the aminophosphonium salt and any reaction product and is preferably a high boiling point aromatic or aliphatic hydrocarbon, such as, for example, dodecane.
The following equation represents a typical example of the reaction of this process:
The phosphiniminophosphonium product is separated from by-product by any conventional separation technique, for example, by selectively dissolving the product in a solvent, separating the dissolved product from undissolved by-product by filtration, and evaporating the filtrate to yield substantially pure product.
The aminophosphonium salt reactant of this process while not readily available commercially, can be easily prepared. For example, aminophosphonium chlorides are conveniently prepared by reacting the appropriate trisubstituted phosphine in an inert atmosphere and at room temperature with chloramine gas. The preparation of trisubstituted phosphines is described in Hays, Ser. No. 461,669, filed June 7, 1965.
Turning now to the second of the two novel processes described herein for preparing phosphiniminophosphonium salts, this process can be employed to prepare either symmetrical or unsymmetrical phosphiniminophosphonium salts. In this process an N-alkali-metal phosphinimine is reacted with a trisubstituted phosphine dihalide or dipseudohalide.
The N-alkali-metal phosphinimine for use herein is believed to be a novel compound. It has the structural formula wherein R is a radical selected from the group consisting of aliphatic radicals containing from 1 to about 18 carbon atoms, phenyl, and substituted phenyl; R and R are radicals selected from the group consisting of aliphatic radicals containing 1 to about 4 carbon atoms, phenyl, and substituted phenyl; and M is an alkali metal selected from the group consisting of sodium, potassium, and lithium. R R and R can each be of different chain lengths within the same compound and can be saturated or unsaturated and branched or straight chain. For example, these aliphatic radicals can be alkyl, alkenyl, substituted alkyl, and substituted alkenyl radicals, the terms alkyl and alkenyl being defined as hereinbefore.
Suitable N-alkali-metal phosphinimines are set forth in Table III below wherein R R R and M are applied in the structural formula set forth above.
The trisubstituted phosphine dihalide or dipseudohalide for use herein has the structural formula R18R19R20PY21 wherein R is a radical selected from the group consisting of aliphatic radicals containing from 1 to about 18 carbon atoms, phenyl, and substituted phenyl; R and R are radicals selected from the group consisting of aliphatic radicals containing from 1 to about 4 carbon atoms, phenyl, and substituted phenyl; and Y is selected from the group consisting of (l) halogens, such as chlorine, bromine, and iodine, and (2) pseudohalogens selected from the group consisting of cyanide and azide. R R and R can each be of different chain lengths within the same compound and can be saturated or unsaturated and branched or straight chain. The term aliphatic is de fined as hereinbefore. Each Y can be different in the same compound.
The above N-alkali-metal phosphinimines are reacted with the above trisubstituted phosphine dihalides or dipseudohalides in an inert atmosphere, for example under argon, at a temperature ranging from about 0 C. to about 50 C. for a period ranging from about 0.5 hour to about 30 hours to provide essentially complete reaction. Room temperature is a preferred reaction temperature. Reaction times ranging from about 1 hour to about 20 hours are preferred.
A reaction solvent is employed in this process which is compatible with the above reactants and with the reaction product. This reaction solvent is preferably an aliphatic or aromatic hydrocarbon uch as benzene, hexane, dodecane, and the like.
The following equation represents a typical example of the reaction of the process:
16 hours (0 4Hn) P=N Li C 2Hz5( C Huh]? C12 room temperature The phosphiniminophosphonium salt product is easily separated from by-product since ordinarily the product is dissolved in the reaction solvent while the by-product is not. For example, the product can be isolated by decanting the solvent phase and evaporating this phase to yield substantially pure product.
The reactants in this process are not readily available commercially but can be prepared by a number of methods. For example, N-alkali-metal phosphinimines can be prepared by reacting an aminophosphonium halide or pseudohalide, e.g., chloride, the preparation of which is described hereinbefore, with aliphtic hydrocarbon alkalimetal salt. Two equivalents of aliphatic hydrocarbon alkali-metal, R M, are employed for each equivalent of aminophosphonium halide or pseudohalide,
In these structural formulae R R R and M are defined as previously; R is an aliphatic radical containing from 1 to about 12 carbon atoms, the term aliphatic being defined as previously; and Y is selected from the group consisting of chloride, bromide, iodide, azide, and cyanide. The reaction is conveniently carried out without external heating at a temperature ranging from about 10 C. to about C. in an inert atmosphere, such as argon, with a reaction time ranging from about 0.5 hour to about 10 hours or more. The following equation represents a typical example of the preparation of an N-alkali-metal phosphinimine:
3 hours (ciHmrflNHzci zn-olmLi argon (C4H9) P=NLi 2041110 LiCl The trisubstituted dihalide or dipseudohalide can be conveniently prepared, for example, by reacting trisubstituted phosphines with a halogen or pseudohalogen.
This reaction is carried out with no external heating, for
example in a solvent such as benzene and in an inert atmosphere such as argon. Reaction is substantially complete within about 10 minutes. As previously mentioned, the preparation of trisubstituted phosphines is described in Hays, Ser. No. 461,669, filed June 7, 1965.
It is noted that the reactants in the above two novel processes for the production of phosphinimino-phosphonium salts contain as anion-producing constituents only halogens and the pseudohalogens, azide and cyanide. This limitation in the structure of the reactants is essential for the production of high yields of phosphiniminophosphonium salt since reactants containing oxygen-containing anion-producing constituents for example produce high yields of by-products. Thus, these two novel processes are advantageously used directly only to produce phosphiniminophosphonium halides, azides and cyanides. However, the anions in the phosphiniminophosphonium salt products produced by these novel processes can be converted to other anions by means of conventional techniques, for example, by means of an ion exchange column.
All percentages and parts herein are by weight unless otherwise specified. All aliphatic radicals herein are straight chain unless otherwise specified. In all reactions herein where such reaction is carried out under an inert atmosphere, any inert atmosphere can be employed; for example, these reactions can be carried out in a vacuum or under inert gases such as argon, nitrogen or helium.
The following examples are illustrative of the present invention and are not to be construed in any way as limiting the scope of the invention.
EXAMPLE I Preparation of dimethyldodecylphosphiniminodimethyldodecylphosphonium chloride Dimethyldodecylaminophosphonium chloride,
12 2s 3 2 -NH Cl was prepared as follows: A 500-ml. three-necked roundbottom flask was fittted with a gas inlet tube, a paddle stirrer driven by an electric motor, and a gas outlet tube connected to a mineral oil bubbler. Twelve grams of dimethyldodecylphosphine prepared according to the method of Hays, Ser. No. 461,669, filed June 7, 1965, was added to the flask which previously had been evacuated and filled with argon. Then 300 ml. of dry benzene was added. The gas inlet tube was arranged so as to extend below the surface of the benzene and then was connected to a chloramine gas generator. Two equivalents of chloramine gas were then passed into the phosphine solution causing heat evolution and a white precipitate to form. The mixture was stirred under argon for one hour without external heating to ensure complete reaction. The white solid in the resulting solid-solution mixture was separated from the solution by filtering. The white solid was then extracted twice with 300 ml. portion of acetonitrile at 82 C., and the remaining white solid primarily consisting of ammonium chloride, was discarded. The acetonitrile was evaporated from the combined extracts to yield a white solid. Recrystallization of this white solid from 300 ml. of acetonitrile yielded 12 grams of substantially pure dimethyldodecylaminophosphonium chloride.
In a heavy-walled glass pyrolysis tube was placed 2.622 grams (9.3 mmoles) of the above prepared dimethyldodecylaminophosphonium chloride. The tube with its contents was then evacuated to 0.1 mm. Hg, sealed at this pressure, and placed in an oil bath that had been preheated to 195 C. Heating was maintained at this temperature for 16 hours. After cooling to room temperature, the tube was opened to the air and the crystalline rnass partially dissolved in 40 ml. of benzene at 80 C. The insoluble solid was removed by filtration and shown to be ammonium chloride by infrared analysis. The benzene filtrate was evaporated in vacuo to yield a white solid which was recrystallized from 40 ml. of 50/50 by volume benzene-hexane mixture to yield 1.352 grams of dimethyldodecylphosphiniminodimethyldodecylphosphonium chloride.
EXAMPLE II Preparation of dimethyltetradecylphosphiniminodimethyltetradecylphosphonium chloride In a heavy-walled glass pyrolysis tube was placed 5.071 grams (16.4 mmoles) dimethyltetradecylaminophosphonium chloride,
synthesized in a manner similar to the dimethyldodecylaminophosphonium chloride of Example I. The tube with its contents was then evacuated to 0.1 mm. Hg, sealed at this pressure and placed in an oil bath that had been preheated to 180 C. Heating was continued for 16 hours at this temperature. After cooling to room temperature, the crystalline mass was partially dissolved in 80 ml. of acetonitrile at 82 C. The insoluble solid was removed by filtration and shown to be ammonium chloride by infrared analysis. The filtrate was evaporated to give a white solid which was recrystallized from acetonitrile to yield 1.46 grams of substantially pure dimethyltetradecylphosphiniminodimethyltetradecylphosphonium chloride.
EXAMPLE III Preparation of dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride In a heavy-walled glass pyrolysis tube was placed 5.150 grams (15.25 mmoles) of dimethylhexadecylaminophosphonium chloride,
synthesized in a manner similar to the dimethyl dodecylaminophosphonium chloride of Example I. The tube with its contents was then evacuated to 0.1 mm. Hg, sealed at this pressure, and placed in an oil bath that had been preheated to 200 C. Heating was continued at this temperature for 16 hours. After cooling to room temperature the crystalline mass was partially dissolved in ml. of acetonitrile at 82 C. The insoluble solid was removed by filtration and was shown to be ammonium chloride by infrared analysis. The filtrate was cooled to deposit white crystals which were recrystallized from acetonitrile to yield 2.96 grams of substantially pure dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride.
EXAMPLE IV Preparation of triphenylphosphinimino triphenylphosphonium chloride In a heavy-walled glass pyrolysis tube was placed 10.29 grams (32.8 moles) of triphenylaminophosphonium chloride, PNH Cl synthesized in a manner similar to the dimethyldodecylaminophosphonium chloride of Example I. The tube with its contents was then evacuated to 0.1 mm. Hg, sealed at this pressure, and placed in an oil bath that had been preheated to 255 C. Heating was maintained at this temperature for 20 hours during which time the contents of the tube turned black. After cooling to room temperature, the entire crystalline mass which resulted was dissolved in 150 ml. of water at C., treated with charcoal to remove color and filtered to separate the resulting colorless solution and the charcoal. The colorless filtered was cooled to deposit white crystals. The crystals were separated from the remaining solution by decanting. The crystals were allowed to dry to provide 7.80 grams of substantially pure triphenylphosphiniminotriphenylphosphonium chloride.
Other symmetrical phosphiniminophosphonium salts are prepared if molar equivalents of other aminophosphonium salts are substituted for the aminophosphonium salts in the above examples. For example, trimethylphosphiniminotrimethylphosphonium bromide is prepared if trimethylaminophosphonium bromide is substituted for the dimethyldodecylaminophosphonium chloride of Example I; dibutylundecylphosphiniminodibutylundecylphosphonium iodide is prepared if dibutylundecylaminophosphonium iodide is substituted for the dimethyltetradecylaminophosphonium chloride of Example II; dimethyloleylphosphiniminodimethyloleylphosphonium azide is prepared if dimethyloleylaminophosphonium azide is substituted for the dimethylhexadecylaminophosphonium chlo ride in Example III; and dimethyl-p-methylphenylphos- EXAMPLE V Preparation of dimethyldodecylphosphiniminotributylphosphonium chloride N-lithiotributylphosphinimine, (nC H P=NLi, was prepared as follows: In a 100 ml. one-necked round-bot tomed flask was placed 11.57 grams (45.7 moles) of trin-butylaminophosphonium chloride, (n-C H P NH C1 and 30 ml. of benzene under an atmosphere of argon. A solution of tri-n-ibutylaminophosphonium chloride in benzene was then formed by means of vigorous stirring with a magnetic stirrer. To this solution at room temperature was added 57.4 ml. of 1.59 normal solution of n-butyl lithium-hexane solution (91.2 mmoles of n-butyl lithium or about 2 equivalents), and vigorous heat and gas evolution occurred. The resulting yellow solution was stirred for three hours under argon without addition of external heat. The resulting solution containing N-lithiotributylphosphini mine was used hereinafter without isolation or purification of the formed intermediate. The above tri-n-butylaminophosphonium chloride was synthesized in a manner similar to the dimethyldodecylaminophosphonium chloride of Example I.
Dimethyldodecylphosphine dichloride was then prepared as follows: In a one-necked 100 ml. round-bottom flask equipped with a rubber cap and filled with argon was placed 7.05 grams (30.7 mmoles) of dimethyldodecylphosphine, and 50 ml. of dry benzene. The formed solution was vigorously stirred while 772 ml. of chlorine gas was injected into the capped flask. The reaction mixture was then stirred for one hour at room temperature. The resulting solution containing dimethyldodecylphosphine dichloride was used hereinafter without isolation or purification of the formed intermediate. The above dimethyldodecylphosphine was prepared by the method of Hays, previously referred to.
At this point the above-formed N-lithiotributylphosphinimine solution was added to the above-formed dimethyldodecylphosphine dichloride solution. This addition was effected with all compounds under argon. The mixture was stirred for 16 hours with no external heating to provide an insoluble white solid and a clear supernatant. The clear supernatant was decanted to separate it from the solid. Evaporation of solvent from the supernatant liquid gave a yellow oil. This oil was dissolved in 50 ml, of carbon tetrachloride at 76 C. After cooling to C., a white solid was deposited. Recrystallization of this solid from carbon tetrachloride yielded 14.58 grams of dimethyldodecylphosphiniminotributylphosphonium chloride.
Other phosphiniminophosphonium salts are prepared by the method of this example if molar equivalent of other N-alkali-metal phosphinimines are substituted for the N-lithiphosphinimine above and/ or molar equivalents of other trisubstituted phosphine dihalides or dipseudohalides are substituted for the dimethyldodecylphosphine dichloride above. For example, N-sodiodimethylpalmitoleylphosphinimine is reacted with dimethylpalmitoleylphosphine diazide to produce dimethylpalmitoleylphosphiniminodimethylpalmitoleylphosphonium azide; N-potassiotributylphosphinimine is reacted with trimethylphosphine dibromide to produce tributylphosphiniminotrimethylph osphonium bromide; and N-lithiodimethyl-p-ethylphosphinimine is reacted with tributylphosphinemonoiodidemonacyanide to form a mixture of dimethyl-p-ethylphenylphosphiniminotributylphosphonium iodide and cyanide.
The halide and pseudohalide anions of the phosphiniminophosphonium salts formed in Examples I-V above can be converted to other anions by conventional ion exchange techniques. For example, the dimethyldodecylphosphiniminotributylphosphonium chloride formed above can be converted to dimethyldodecylphosphinirninotributylphosphonium nitrate in this manner.
EXAMPLE VI Emulsions of carbon tetrachloride One-fourth gram of dimethyldodecylphosphiniminotributylphosphonium chloride prepared in Example V was mixed with 4 ml. of carbon tetrachloride. This mixture was mixed with 4 ml. of water to provide a carbon tetrachloride/water emulsion which is stable for more than twelve hours.
EXAMPLE VII Tetrachloroethylene emulsions A composition containing the new phosphiniminophosphonium salts suitable for use in the dry cleaning of textiles contains:
Percent Dimethyldodecylphosphinirninotributylphosphonium chloride 2.0 Water 0.5 Tetrachloroethylene 97.5
For application to textiles this composition can be diluted to contain as much as 50% Water. After being mixed, this diluted composition is an emulsion which is stable for at least 1 hour, and as such is suitable for application to textiles for dry cleaning purposes.
Other new phosphiniminophosphonium salts, for example, the compounds prepared in Examples I, II, and III can replace the dimethyldodecylphosphiniminotributylphosphonium chloride in the above example to provide stable emulsions upon dilution of the composition.
Ordinarily, useful dry cleaning compositions consist essentially of from about 0.5% to about 5% phosphiniminophosphonium salt, from about 0.5% to about 50% water and from about 45% to about 99% tetrachloroethylene.
The following two examples illustrate textile softener compositions containing the new phosphiniminophosphonium salts. These compositions are applied to textiles as water solutions containing 50 p.p.m. posphiniminophos phoniu-m salt. When so applied these compositions provide effective and durable softening. The softening efi'ect remains even after five washings of the treated textile.
15 EXAMPLE VIII A suitable liquid textile softener composition contains:
Percent Demethylhexaldecylphosphiniminodimethylhexadecylphosphonium chloride Isopropanol 2 3,4,4'-trichlorocarbanilide 1 The condensation product of 9 moles of ethylene oxide with 1 mole of nonylphenol 1 Color 0.003 Perfume 0.25 Water Balance EXAMPLE IX A suitable granular textile softener composition contains:
Percent Urea 75 Dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride 25 Other new phosphiniminophosphonium salts, for example any of the compounds listed in Table I can be substituted for the dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride in above Examples VIII and IX to provide compositions which provide effective and durable softening. The triphenylphosphiniminotriphenylphosphonium chloride prepared in Example IV is not an etfective softening agent and is, therefore, not advantageously substituted in the above softener formulations.
EXAMPLE X In the manufacture of sheeting, 80 x 80 cotton sheeting is pass through a pad containing a water solution of dimethyloctadecylphosphiniminodimethyloctadecylphosphonium chloride. The water solution contains 75 p.p.m. of the phosphiniminophosphonium salt. The sheeting is effectively softened and retain this softened effect even after the consumer has washed it five times with no application of textile softener.
Other new phosphiniminophosphonium salts, e.g., the compounds prepared in Examples I, 11, III and V, can be used in this example in place of the dimethyloctadecyl salt with similar results.
The following Examples XI-XVII illustrate heavy-duty laundry detergent compositions which contain as a softening agent the new phosphiniminophosphonium salts of this invention. These detergent compositions can be used to clean and soften textiles such as sheets and towels.
EXAMPLE XI Percent Dimethyldodecylphosphiniminotributylphosphonium 16 EXAMPLE IV Methylethylpropylphosphiniminodimethyldodecylphosphonium bromide 12 Pluronic L-68 l5 Trisodium methylene diphosphonate 50 Sodium sulfate 23 EXAMPLE XV Percent Dimethylhexadecylphosphinimotrimethylphosphonium borate 8 Dimethyldodecylamine oxide l5 Tetrapotassium pyrophosphate 30 Sodium toluene sulfonate 8 Ethanol 10 Water 29 EXAMPLE XVI Percent Dimethyltetradecylphosphiniminodimethyltetradecylphosphonium acetate 5 Dimethyldodecylphosphine oxide 15 Sodium tripolyphosphate 60 Sodium sulfate 20 EXAMPLE XVII Percent Diethylpentadecyphosphiniminotrimethylphosphonium iodide 5 Dimethylcoconut (2%C 66%C 23 %-C 9%- C alkylammonio hydroxypropane sulfonate 20 Trisodium ethylidene diphosphonate 30 Sodium sulfate 45 The following Examples XVIII and XIX illustrate lightduty liquid detergent compositions containing as a softening agent the new phosphiniminophosphonium salts of this invention. These detergent compositions are suitable for cleaning and softening delicate clothing such as sweaters or underwear.
EXAMPLE XVIII Percent Dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride 10 Component A, described below 35 Ethanol 10 Water 45 EXAMPLE XIV Percent Dimethyldodecylphosphiniminodimethyldodecylphosphonium chloride 10 Component A, described below 32 Ethanol 10 Water 48 In the above examples component A is a tertiary amine oxide having a long alkyl chain derived from middle cut coconut alcohol (containing 2%-C 66%-C 23%- C and 9%C and two methyl groups.
Other phosphiniminophosphonium salts can be substituted for the phosphiniminophosphonium salts of Examples XI-XIX to provide laundry detergents. For example, dimethyltetradecyphosphiniminodimethyltetradecylphosphonium chloride can be substituted for the dimethyldodecylphosphiniminodimethyldodecylphosphonium chloride of Example XIX to provide a lightduty liquid detergent having softening properties. Moreover, various other detergent actives can be substituted for the detergent actives in Examples XI-XIX above. For example, various ampholytic detergents, e.g., dodecylbeta-alanine, the sodium salt of N-dodecyl taurine, or disodium N-dodecyl asparate, can replace component A in Examples XVIII and XIX above to provide light-duty liquid detergents, having softening properties.
The previously described novel phosphiniminophos' phonium salts also have utility as antibacterial agents,
wetting agents, detergents, solubilizing agents, waterproofing agents, and gelling or thickening agents. These salts also are very soluble and thus are very advantageously used in various compositions such as softener compositions and detergent compositions; this is because they remain in solution even though the composition containing them freezes and later thaws. On the other hand, additives which are suspended in such compositions tend to separate from the rest of the composition under these same freezing-thawing circumstances.
EXAMPLE XX N-lithiodimethyldodecylphosphinimine was prepared by reacting dimethyldodecylaminophosphonium chloride with n-butyl lithium according to the method for preparing N-lithiotributylphosphinimine in Example V. This prepared compound is a reactive intermediate and can be used in the preparation of the novel phosphiniminophosphonium salts of this invention according to the second of the two novel processes described herein. For example, this N-lithiodimethyldodecylphosphinimine can be reacted with tn'butylphosphine dichloride to produce dimethyldodecylphosphiniminotributylphosphonium chloride.
The foregoing description has been presented describing certain operable and preferred embodiments of this invention. Other variations will be apparent to those skilled in the art.
What is claimed is:
1. A phosphiniminophosphonium salt having the structural formula wherein R is selected from the group consisting of alkyl radicals containing from 1 to about 18 carbon atoms; R R R and R are selected from the group consisting of alkyl radicals having from 1 to about 4 carbon atoms; R is selected from the group consisting of alkyl radicals containing from about 12 to about 18 carbon atoms; and X is an anion which permits solubility and hydrolytic stability of the salt.
2. The phosphiniminophosphonium salt according to claim 1 wherein R, R R R R and R are alkyl radicals and X is an anion selected from the group consisting of halides and pseudohalides.
3. The phosphiniminophosphonium salt according to claim 2 wherein X is an anion selected from the group consisting of chloride, bromide, iodide, azide, and cyanide.
4. Dimethyldodecylphosphiniminodimethyldodecylphosphonium chloride.
5. Dimethyltetradecylphosphiniminodimethyltetradecylphosphonium chloride.
6. Dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride.
7. Dimethyldodecylphosphiniminotributylphosphonium chloride.
8. A process for preparing a phosphiniminophosphonium salt, said process comprising the step of reacting in an inert atmosphere, in the presence of an inert solvent, and at a temperature ranging from about 0 C. to about 50 C., (1) an N-alkali-metal phosphinimine having the formula R R R P=NM wherein R is a radical selected from the group consisting of alkyl radicals containing from 1 to about 18 carbon atoms; R and R are radicals selected from the group consisting of alkyl radicals containing from 1 to about 4 carbon atoms; and M is an alkali metal selected from the group consisting of sodium, potassium and lithium; with (2) a compound having the formula 18 R18R19R20PY21 wherein R is a radical selected from the group consisting of alkyl radicals containing from 1 to about 18 carbon atoms; R and R are radicals selected from the group consisting of alkyl radicals containing from 1 to about 4 carbon atoms; and Y is selected from the group consisting of halogens, azide, and cyanide.
9. The process of claim 8 wherein Y is selected from the group consisting of chlorine and bromine.
10. The process of claim 8 wherein the reaction time ranges from about 0.5 hour to about 30 hours.
11. The process of claim 8 wherein the reaction time ranges from about 1 hour to about 20 hours.
12. An N-alkali metal phosphinimine having the structural formula R R R P=NM wherein R is a radical selected from the group consisting of alkyl radicals containing from 1 to about 18 carbon atoms; R and R are radicals selected from the group consisting of alkyl radicals containing 1 to about 4 carbon atoms; and M is an alkali metal selected from the group consisting of sodium, potassium, and lithium.
13. N-lithiotributylphosphinimine.
14. A process for preparing an N-alkali-metal phosphinimine of claim 12, said process comprising reacting in an inert atmosphere, in the presence of an inert solvent, and at a temperature ranging from about 10 C. to about C., (1) an aminophosphonium halide or pseudohalide having the formula wherein R is a radical selected from the group consisting of alkyl radicals containing from 1 to about 18 carbon atoms; R and R are radicals selected from the group consisting of alkyl radicals containing 1 to about 4 carbon atoms; and Y is selected from the group consisting of chloride, bromide, iodide, azide, and cyanide; with (2) two equivalents of hydrocarbon alkali-metal salt having the structural formula R M wherein R is a radical selected from the group consisting of alkyl radicals containing from 1 to about 12 carbon atoms; and M is an alkali metal selected from the group consisting of sodium, potassium, and lithium.
15. The process of claim 14 wherein tributylaminophosphonium chloride is reacted with butyl lithium.
16. A process for preparing a symmetrical ph0sphiniminophosphonium salt, said process comprising the step of heating to an elevated temperature and in an inert atmosphere an aminophosphonium salt having the formula wherein R is a radical selected from the group consisting of alkyl radicals containing from 1 to about 18 carbon atoms; R and R are radicals selected from the group consisting of alkyl radicals containing from 1 to about 4 carbon atoms; and wherein Y is an anion selected from the group consisting of halides, azide and cyanide; said elevated temperature being at least 20 C. in excess of the melting point of said aminophosphonium salt.
17. A process for preparing a dimethyldodecylphosphiniminedimethyldodecylphosphonium salt, said process comprising the step of heating at a temperature ranging from about 100 C. to about 300 C. in the presence of an inert solvent and in an inert atmosphere a dimethyldodecylaminophosphonium salt having the formula R R R P NH Y wherein R is dodecyl; R and R each are methyl; and Y is an anion selected from the group consisting of halides, azide and cyanide.
18. The process of claim 17 wherein Y is selected from the group consisting of chloride, iodide, bromide, azide, and cyanide.
19. The process of claim 17 wherein the reaction time ranges from about 0.5 hour to about 30 hours.
19 20 20. The process of claim 19 wherein the reaction time Appel et a1. Chem. Ber., vol. 98, pp. 1355-58 (April, ranges from about 1 hour to about 20 hours and the reac- 1965). tion temperature ranges from about 150 C. to about HENRY R. JILES, Primary Examiner 5 H. I. MOATZ, Assistant Examiner US. Cl. X.R. 252-8.8; 424-320 References Cited Sisler et 21]., J. Am. Chem. Soc., vol. 81, pp. 2982-85 (1959).
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US51582665 US3332874A (en) | 1965-12-23 | 1965-12-23 | Detergent composition |
US51782665A | 1965-12-30 | 1965-12-30 | |
CH328567A CH490488A (en) | 1965-12-23 | 1967-03-07 | Softening and cleaning agents |
US75447868A | 1968-08-21 | 1968-08-21 |
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US3475490A true US3475490A (en) | 1969-10-28 |
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US3475490D Expired - Lifetime US3475490A (en) | 1965-12-23 | 1965-12-30 | Emulsifying and textile softening phosphonium compounds,processes for preparing the same |
US3553129D Expired - Lifetime US3553129A (en) | 1965-12-23 | 1968-08-21 | Emulsifying and textile softening phosphonium compounds, process for preparing the same and other compounds, reactive intermediates |
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US51582665 Expired - Lifetime US3332874A (en) | 1965-12-23 | 1965-12-23 | Detergent composition |
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US3553129D Expired - Lifetime US3553129A (en) | 1965-12-23 | 1968-08-21 | Emulsifying and textile softening phosphonium compounds, process for preparing the same and other compounds, reactive intermediates |
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JP2009227617A (en) * | 2008-03-24 | 2009-10-08 | Koei Chem Co Ltd | Ammonium salt, and antistatic agent using the same |
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US3625910A (en) * | 1968-07-29 | 1971-12-07 | Chevron Res | Hydrogenated olefin sulfonate detergent bars |
US3819538A (en) * | 1972-05-15 | 1974-06-25 | Dow Chemical Co | Environmentally compatible laundry detergent |
US4601844A (en) * | 1984-08-31 | 1986-07-22 | The Procter & Gamble Company | Granular automatic dishwasher detergent with alkyl phosphate and calcium ion source |
GB8900023D0 (en) * | 1989-01-03 | 1989-03-01 | Shell Int Research | Detergent composition |
AU2010341700B2 (en) | 2009-12-22 | 2015-08-20 | Chevron Oronite Company Llc | Isomerized alpha olefin sulfonate and method of making the same |
WO2022106413A1 (en) * | 2020-11-19 | 2022-05-27 | Unilever Ip Holdings B.V. | Hard surface cleaning composition |
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US2061618A (en) * | 1936-11-24 | Sulphonated hydrocarbon | ||
US2061620A (en) * | 1936-11-24 | Sulphonated derivatives of aliphat | ||
US2061617A (en) * | 1936-11-24 | Stllphonic acid derivatives of aii | ||
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CA796280A (en) | 1968-10-08 |
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US3553129A (en) | 1971-01-05 |
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US3332874A (en) | 1967-07-25 |
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