US3463835A - Aromatic polyphosphonic acids,salts and esters - Google Patents
Aromatic polyphosphonic acids,salts and esters Download PDFInfo
- Publication number
- US3463835A US3463835A US493217A US3463835DA US3463835A US 3463835 A US3463835 A US 3463835A US 493217 A US493217 A US 493217A US 3463835D A US3463835D A US 3463835DA US 3463835 A US3463835 A US 3463835A
- Authority
- US
- United States
- Prior art keywords
- phenyl methane
- triphosphonate
- diphosphonate
- phenyl
- phosphite
- 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
- 150000003839 salts Chemical class 0.000 title description 21
- 239000002253 acid Substances 0.000 title description 15
- 150000007513 acids Chemical class 0.000 title description 12
- 150000002148 esters Chemical class 0.000 title description 10
- 125000003118 aryl group Chemical group 0.000 title description 2
- -1 hydrocarbyl tin Chemical compound 0.000 description 80
- OSDUHWLNMWMLCS-UHFFFAOYSA-N CC1=CC=CC=C1.OP(=O)OP(O)(=O)OP(O)=O Chemical compound CC1=CC=CC=C1.OP(=O)OP(O)(=O)OP(O)=O OSDUHWLNMWMLCS-UHFFFAOYSA-N 0.000 description 23
- UESQVBAMIZTJAU-UHFFFAOYSA-N CC1=CC=CC=C1.OP(=O)OP(O)=O Chemical compound CC1=CC=CC=C1.OP(=O)OP(O)=O UESQVBAMIZTJAU-UHFFFAOYSA-N 0.000 description 15
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QCXXTYPCTOXOHU-UHFFFAOYSA-K [Na+].[Na+].[Na+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O Chemical compound [Na+].[Na+].[Na+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O QCXXTYPCTOXOHU-UHFFFAOYSA-K 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- FRLTXWJJMCIUNT-UHFFFAOYSA-N ru78783 Chemical compound OP(O)(=O)C(P(O)(O)=O)C1=CC=CC=C1 FRLTXWJJMCIUNT-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 description 3
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- XAZBQRBKHHTFRW-UHFFFAOYSA-N [NH4+].[NH4+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O Chemical compound [NH4+].[NH4+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O XAZBQRBKHHTFRW-UHFFFAOYSA-N 0.000 description 3
- OIVJDFIDBDKTFA-UHFFFAOYSA-L [Na+].[Na+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O Chemical compound [Na+].[Na+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O OIVJDFIDBDKTFA-UHFFFAOYSA-L 0.000 description 3
- FKBATKDCPBTRAV-UHFFFAOYSA-H [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O.[O-]P(=O)OP([O-])(=O)OP([O-])=O Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O.[O-]P(=O)OP([O-])(=O)OP([O-])=O FKBATKDCPBTRAV-UHFFFAOYSA-H 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- BVXOPEOQUQWRHQ-UHFFFAOYSA-N dibutyl phosphite Chemical compound CCCCOP([O-])OCCCC BVXOPEOQUQWRHQ-UHFFFAOYSA-N 0.000 description 3
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 3
- 125000003106 haloaryl group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PHNWBNNDLFGHTQ-UHFFFAOYSA-N P(=O)(O)OP(=O)(O)OP(=O)O.C(C)C1C(C(C(C=C1)(C)CC)(CC)CC)(CC)CC Chemical compound P(=O)(O)OP(=O)(O)OP(=O)O.C(C)C1C(C(C(C=C1)(C)CC)(CC)CC)(CC)CC PHNWBNNDLFGHTQ-UHFFFAOYSA-N 0.000 description 2
- YJLGBZVUKGODOT-UHFFFAOYSA-N P(=O)(O)OP(=O)O.C(C)C=1C(=C(C(=C(C1)C)CC)CC)CC Chemical compound P(=O)(O)OP(=O)O.C(C)C=1C(=C(C(=C(C1)C)CC)CC)CC YJLGBZVUKGODOT-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- DBJKGIXKSYDMSD-UHFFFAOYSA-H [K+].[K+].[K+].[K+].[K+].[K+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O.[O-]P(=O)OP([O-])(=O)OP([O-])=O Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O.[O-]P(=O)OP([O-])(=O)OP([O-])=O DBJKGIXKSYDMSD-UHFFFAOYSA-H 0.000 description 2
- OCMLSBKAKOWYEY-UHFFFAOYSA-N [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O.[O-]P(=O)OP([O-])(=O)OP([O-])=O Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O.[O-]P(=O)OP([O-])(=O)OP([O-])=O OCMLSBKAKOWYEY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- OOSPDKSZPPFOBR-UHFFFAOYSA-N butyl dihydrogen phosphite Chemical group CCCCOP(O)O OOSPDKSZPPFOBR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- XMQYIPNJVLNWOE-UHFFFAOYSA-N dioctyl hydrogen phosphite Chemical group CCCCCCCCOP(O)OCCCCCCCC XMQYIPNJVLNWOE-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UFFAFBPZFGAMJJ-UHFFFAOYSA-N (2-methoxy-4,6-dimethylphenyl)boronic acid Chemical compound COC1=CC(C)=CC(C)=C1B(O)O UFFAFBPZFGAMJJ-UHFFFAOYSA-N 0.000 description 1
- IQNYBCIGGNQJDL-UHFFFAOYSA-N (4-methylphenyl) dihydrogen phosphite Chemical compound CC1=CC=C(OP(O)O)C=C1 IQNYBCIGGNQJDL-UHFFFAOYSA-N 0.000 description 1
- ZREORSWVGSDDPP-UHFFFAOYSA-N (4-nonylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=C(OP(O)O)C=C1 ZREORSWVGSDDPP-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- RSKXYCDTGOUAKH-UHFFFAOYSA-N 2-methylpropyl dihydrogen phosphite Chemical compound CC(C)COP(O)O RSKXYCDTGOUAKH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RZOQXXYWWBPPRV-UHFFFAOYSA-L CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O.C=1C=CC=CC=1[Sn+2]C1=CC=CC=C1 Chemical compound CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O.C=1C=CC=CC=1[Sn+2]C1=CC=CC=C1 RZOQXXYWWBPPRV-UHFFFAOYSA-L 0.000 description 1
- QBWHGDWICYQJOT-UHFFFAOYSA-L CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O.CCCCCCCC[Sn+2]CCCCCCCC Chemical compound CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O.CCCCCCCC[Sn+2]CCCCCCCC QBWHGDWICYQJOT-UHFFFAOYSA-L 0.000 description 1
- CSQJDBAJOMSMEJ-UHFFFAOYSA-L CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O.CCCC[Sn+2]CCCC Chemical compound CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O.CCCC[Sn+2]CCCC CSQJDBAJOMSMEJ-UHFFFAOYSA-L 0.000 description 1
- WVQRXGWDLXLHHN-UHFFFAOYSA-K CCCCC[Sn+3].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O Chemical compound CCCCC[Sn+3].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O WVQRXGWDLXLHHN-UHFFFAOYSA-K 0.000 description 1
- KMHSNUDFYFLIAI-UHFFFAOYSA-H CCCC[Sn+3].CCCC[Sn+3].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O.[O-]P(=O)OP([O-])=O.[O-]P(=O)OP([O-])=O Chemical compound CCCC[Sn+3].CCCC[Sn+3].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O.[O-]P(=O)OP([O-])=O.[O-]P(=O)OP([O-])=O KMHSNUDFYFLIAI-UHFFFAOYSA-H 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920005123 Celcon® Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920004943 Delrin® Polymers 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- BNICJMXMUIDSBD-UHFFFAOYSA-K P(=O)([O-])OP(=O)([O-])OP(=O)[O-].C1(=CC=CC=C1)C.[Na+].[Na+].[Na+].[Na+].[Na+] Chemical compound P(=O)([O-])OP(=O)([O-])OP(=O)[O-].C1(=CC=CC=C1)C.[Na+].[Na+].[Na+].[Na+].[Na+] BNICJMXMUIDSBD-UHFFFAOYSA-K 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- ORHCOHGSRQWDQB-UHFFFAOYSA-L [Ag+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O Chemical compound [Ag+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O ORHCOHGSRQWDQB-UHFFFAOYSA-L 0.000 description 1
- WCSKBKCFJREKLK-UHFFFAOYSA-K [Ag+3].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O Chemical compound [Ag+3].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O WCSKBKCFJREKLK-UHFFFAOYSA-K 0.000 description 1
- LDJYMCMWJRVGOB-UHFFFAOYSA-L [Ba+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O Chemical compound [Ba+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O LDJYMCMWJRVGOB-UHFFFAOYSA-L 0.000 description 1
- FVSHEKPNGQBASE-UHFFFAOYSA-H [Ba+2].[Ba+2].[Ba+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O.[O-]P(=O)OP([O-])(=O)OP([O-])=O Chemical compound [Ba+2].[Ba+2].[Ba+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O.[O-]P(=O)OP([O-])(=O)OP([O-])=O FVSHEKPNGQBASE-UHFFFAOYSA-H 0.000 description 1
- VWBYKSAKORNASQ-UHFFFAOYSA-L [Ca+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O Chemical compound [Ca+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O VWBYKSAKORNASQ-UHFFFAOYSA-L 0.000 description 1
- BIHMPGIOLVEIFS-UHFFFAOYSA-H [Ca+2].[Ca+2].[Ca+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O.[O-]P(=O)OP([O-])(=O)OP([O-])=O Chemical compound [Ca+2].[Ca+2].[Ca+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])(=O)OP([O-])=O.[O-]P(=O)OP([O-])(=O)OP([O-])=O BIHMPGIOLVEIFS-UHFFFAOYSA-H 0.000 description 1
- MXOQGIUGANBNNB-UHFFFAOYSA-L [Cd+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O Chemical compound [Cd+2].CC1=CC=CC=C1.[O-]P(=O)OP([O-])=O MXOQGIUGANBNNB-UHFFFAOYSA-L 0.000 description 1
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- 125000005907 alkyl ester group Chemical group 0.000 description 1
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- LRISCVHNAHPHGP-UHFFFAOYSA-N bis(2-dodecylphenyl) hydrogen phosphite Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OP(O)OC1=CC=CC=C1CCCCCCCCCCCC LRISCVHNAHPHGP-UHFFFAOYSA-N 0.000 description 1
- ZOLLZXLIZDRUPF-UHFFFAOYSA-N bis(4-chlorophenyl) hydrogen phosphite Chemical compound C=1C=C(Cl)C=CC=1OP(O)OC1=CC=C(Cl)C=C1 ZOLLZXLIZDRUPF-UHFFFAOYSA-N 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 159000000006 cesium salts Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- PYFRLDVYGBCYLI-UHFFFAOYSA-N decyl dihydrogen phosphite Chemical compound CCCCCCCCCCOP(O)O PYFRLDVYGBCYLI-UHFFFAOYSA-N 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- HEGXHCKAUFQNPC-UHFFFAOYSA-N dicyclohexyl hydrogen phosphite Chemical group C1CCCCC1OP(O)OC1CCCCC1 HEGXHCKAUFQNPC-UHFFFAOYSA-N 0.000 description 1
- SPBMDAHKYSRJFO-UHFFFAOYSA-N didodecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCOP(O)OCCCCCCCCCCCC SPBMDAHKYSRJFO-UHFFFAOYSA-N 0.000 description 1
- XFUSKHPBJXJFRA-UHFFFAOYSA-N dihexyl hydrogen phosphite Chemical group CCCCCCOP(O)OCCCCCC XFUSKHPBJXJFRA-UHFFFAOYSA-N 0.000 description 1
- BAKDLAFAVHBXHW-UHFFFAOYSA-N dioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP([O-])OCCCCCCCCCCCCCCCCCC BAKDLAFAVHBXHW-UHFFFAOYSA-N 0.000 description 1
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 1
- MGJHACFZFDVYIL-UHFFFAOYSA-N dipentyl hydrogen phosphite Chemical group CCCCCOP(O)OCCCCC MGJHACFZFDVYIL-UHFFFAOYSA-N 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical compound [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical group [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
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- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 description 1
- CPRPKIMXLHBUGA-UHFFFAOYSA-N triethyltin Chemical compound CC[Sn](CC)CC CPRPKIMXLHBUGA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3839—Polyphosphonic acids
- C07F9/3843—Polyphosphonic acids containing no further substituents than -PO3H2 groups
Definitions
- This invention relates to novel polyphosphonic acid salts and esters thereof.
- Another object is to prepare salts of such acids.
- a further object is to prepare novel esters of such acids.
- R R R R R and R are the same or different and are selected from the group consisting of hydrogen, metal, ammonium, hydrocarbyl, e.g. alkyl and aryl, haloaryl or hydrocarbyl tin.
- esters of Formula I are conveniently prepared by reacting 1 mole of benzal chloride with 2 moles of dialkyl phosphite, a di-a-ryl phosphite or a di(haloaryl) phosphite.
- the esters of Formula II are prepared in a similar fashion by replacing the benzal chloride with benzo trichloride.
- the free acids of Formulae I and II can be readily prepared by hydrolyzing the esters of the same formula.
- the lower alkyl esters are used for such hydrolysis.
- the hydrolysis is preferably carried out with the aid of an acid catalyst, e.g. hydrochloric acid, sulfuric acid or the like.
- the salts of Formulae I and II can be prepared quite readily by placing an aqueous or organic solution of a salt of the appropriate metal in contact with the free acid of Formulae I and II or with an alkali metal salt thereof.
- the starting secondary phosphites there can be used dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di isobutyl phosphite, di tertiary butyl phosphite, di secondary butyl phosphite, diamyl phosphite, dihexyl phosphite, dicyclohexyl phosphite, dioctyl phosphite, diisodecyl phosphite, di decyl phosphite, dioctadecyl phosphite, diphenyl phosphite, di p-cresyl phosphite, d i (p-nonylphenyl) phosphite, di (o-dodecylphenyl) phosphit
- Examples of compounds within the present invention are phenyl methane diphosphonic acid, phenyl methane triphosphonic acid, tetramethyl phenyl methane diphosphonate, tetraethyl phenyl methane diphosphonate, tetrapropyl phenyl methane diphosphonate, tetrabutyl phenyl methane diphosphonate, tetrahex'yl phenyl methane diphosphonate, tetraoctyl phenyl methane diphosphonate, tetra isodecyl phenyl methane diphosphonate, tetra octadecyl phenyl methane diphosphonate, tetraphenyl phenyl methane diphosphonate, tetra (m-cresyl) phenyl methane diphosphonate, tetra (p-butylphenyl)
- salts of the novel acids can be made from any of the metals in the periodic system.
- alkali metal salts such as lithium, sodium, potassium, rubidium and cesium salts, alkaline earth metal salts such as calcium, barium strontium and magnesium, as well as salts of the metals such as zinc, cadmium, mercury, copper, silver, gold, titanium, zirconium, tin, chromium, tungsten, molybdenum, radium, manganese, iron, cobalt, nickel, platinum, palladium, uranium and the rare earths, e.g., hafnium and cerium.
- Ammonium salts can also be prepared. With the exception of the alkali metals and ammonium the salts that are formed are of the chelate type.
- Alkyltin and aryltin salts (e.g., mono, di or trialkyltin salts) can also be made.
- salts are sodium phenyl methane diphosphonate, potassium phenyl methane diphosphonate, rubidium phenyl methane diphosphonate, ammonium phenyl methane diphosphonate, calcium phenyl methane diphosphonate, barium phenyl methane diphosphonate, magnesium phenyl methane diphosphonate, beryllium phenyl methane diphosphonate, zinc phenyl methane diphosphonate, cadmium phenyl methane diphosphonate, mercury phenyl methane diphosphonate, cupric phenyl methane diphosphonate, silver phenyl methane diphosphonate, auric phenyl methane diphosphonate, titanium phenyl methane diphosphonate, zirconium phenyl methane diphosphonate, stannous phenyl methane diphosphonate, stannic phenyl
- esters coming within Formulae I and II supra are all useful as stabilizers for halogen containing vinyl and vinylidene resins, e.g. vinylchloride resins and as stabiliners for monoolefin polymers, e.g. polyethylene, polypropylene and ethylene-propylene copolymer.
- monoolefin polymers e.g. polyethylene, polypropylene and ethylene-propylene copolymer.
- 0.140 parts of the phosphorous containing ester per parts of the polymer 0.140 parts of the phosphorous containing ester per parts of the polymer.
- the esters are also useful in preparing the free acids within Formulae I and II.
- the free acids of Formulae I and II are all useful as curing agents for melamine-formaldehyde and urea-formaldehyde resins. They are also valuable for forming their metal salts and as detergent additives, extractants, sequestering agents, metal complexing agents, corrosion inhibitors, chelating agents, stabilizers and the like.
- the alkali metal and ammonium salts are particularly valuable in detergent compositions as additives and builders. They are superior in such compositions to sodium tripolyphosphate.
- the free acids and alkali metal and ammonium salts are extremely valuable because of their ability to act as sequestering agents to hold polyvalent metal compounds in aqueous solution. They also are useful to prevent the hydrolysis of alkali metal polyphosphates.
- the metal salts are useful in providing a means for isolating the metals in a form in which they can be readily recovered. They are also useful as a soluble source of the metals.
- the hydrocarbyltin salts are useful as stabilizers for halogen containing resins, e.g. vinyl chloride resins.
- phenyl methane diphosphonic acid, phenyl methane triphosphonic acid and their alkali metal salts exhibit very low surface tension and are superior agents for metal extraction e.g. extraction of gold, silver, vanadium, molybdenum, copper, nickel and iron.
- the novel acids of the present invention have four or six acidic hydrogen atoms (Formulae I and II) in making the salts one or more of the acidic hydrogen atoms can be replaced by the metal or ammonium in forming the salts.
- the acidic hydrogen atoms are replaced in making the salt and unless otherwise indicated when reference is made to a salt in the present specification all of the acidic hydrogen atoms are replaced.
- this is not an essential part of the present invention and the invention includes the partial as Well as the complete salts, e.g.
- the compounds of the present invention and in particular the esters are useful as plasticizers.
- the compounds of the present invention are useful as stabilizers for alkyl phenols, 6. g. nonyl phenol, 0ctyl phenol, dodecyl phenol to prevent discoloration. All of the compounds of the present invention are useful as flame proofing agents in making polyurethanes.
- the free acids are useful as catalysts in polymerizing formaldehyde to make materials such as Delrin or Celcon.
- Example 1 There were charged into the reaction vessel 23.0 grams (1.0 mole) of sodium metal along with 90 cc. of xylene and 80 cc. of tetrahydrofurane. The vessel was placed under a nitrogen blanket and 138.10 grams -(1.0 mole) of diethyl phosphite added over a 35 minute period. An exothermic reaction ensued which was maintained at 62 C. by external cooling. After addition was complete the mixture was heated to 100 C. and held there until all of the sodium metal was gone. The mixture was cooled to 60 to 70 C. and 80.5 grams (0.5 mole) of benzal chloride were added gradually over a 25 minute period. An exothermic reaction ensued which was maintained at 60 to 70 C. by external cooling.
- the mixture was then heated for 4 hours at 70 to 75 C., cooled to 60 C.
- the liquid material was separated from the solid and the solid boiled 8 times with 100cc. of benzene to extract the organic material.
- the eluate product was then distilled, terminal conditions being a pot temperature of 201 C., distillate temperature 125 C. and pressure 6 mm.
- the solid residue of 70 grams was tetraethyl phenyl methane diphosphonate.
- Example 2 0.9 mole of tetra ethyl phenyl methane diphosphonate was refluxed with 5.4 moles of concentrated hydrochloric acid for 24 hours. Excess acid was removed by stripping under vacuum. 200 ml. of water were added and removed in vacuo, then finally 200 ml. of benzene were added and the water removed and separated by means of a Dean and Stark trap and the benzene was distilled over under reduced pressure yielding phenyl methane diphosphonic acid.
- Example 3 There were mixed together 23.0 grams (1.0 mole) of sodium metal along with 90 cc. of xylene and 80 cc. of tetrahydrofurane and the mixture placed under a nitrogen atmosphere. There were then added over a 35 minute period 138.10 grams (1.0 mole) of diethyl phosphite using external cooling to control the reaction exotherm and maintain the temperature at 60 to 65 C. After addition was complete the mixture was heated to 100 C. and maintained there for about 1 hour until there was no more sodium. The mixture was cooled to 60 C. and there was started the addition of 64.5 grams (0.33 mole) of benzotrichloride (a,a,a-trichlorotoluene).
- benzotrichloride a,a,a-trichlorotoluene
- the exo thermic reaction was cooled to maintain the temperature at 60 to 65 C. during the 25 minute addition period.
- the mixture was heated at 70 to 75 C. for 7 hours and the sodium chloride filtered off.
- the product in the pot was then subjected to distillation, terminal conditions being a pot temperature of 205 C., distillate temperature 125 C. and pressure 4 mm.
- the solid residue in the pot was hexaethyl phenyl methane triphosphonate.
- This product was hydrolyzed and the hydrolysis product purified as in Example 2 to obtain phenyl methane triphosphonic acid.
- Example 4 The procedure of Example 1 was repeated replacing the diethyl phosphite by an equimolar amount of dimethyl phosphite to obtain as the product tetramethyl phenyl methane diphosphonate.
- Example 5 The procedure of Example 1 was repeated replacing the diethyl phosphite by an equimolar amount of dibutyl phosphite to obtain as the product tetrabutyl phenyl methane diphosphonate.
- Example 6 The procedure of Example 1 was repeated replacing the diethyl phosphite by an equimolar amount of diisodecyl phosphite to obtain as the product tetraisodecyl phenyl methane diphosphonate.
- Example 7 The procedure of Example 1 was repeated replacing the diethyl phosphite by an equimolar amount of diphenyl phosphite to obtain as the product :tetraphenyl phenyl methane diphosphonate.
- Example 8 The procedure of Example 3 was repeated replacing the diethyl phosphite by an equimolar amount of dibutyl phosphite to obtain as a product hexabutyl phenyl methane triphosphonate.
- Example 10 The procedure of Example 3 was repeated replacing the diethyl phosphite by an equimolar amount of dioctyl phosphite to obtain as a product hexaoctyl phenyl methane triphosphonate.
- Example 11 The procedure of Example 3 was repeated replacing the diethyl phosphite by an equimolar amount of diphenyl phosphite to obtain as a product hexaphenyl phenyl methane triphosphonate.
- Example 12 The procedure of Example 3 was repeated replacing the diethyl phosphite by an equimolar amount of di (dodecyl) phosphite to obtain as a product hexa (dodecyl) phenyl methane triphosphonate.
- Example 13 The procedure of Example 3 was repeated replacing the diethyl phosphite by an equimolar amount of di (ptolyl) phosphite to obtain as a product hexa (p-tolyl) phenyl methane triphosphonate.
- Example 14 To 1 mole of phenyl methane diphosphonic acid there were added 4 moles of 10% aqueous sodium hydroxide and the mixture was evaporated to dryness to produce tetrasodium phenyl methane diphosphonate.
- Example 15 To 1 mole of phenyl methane triphosphonic acid there were added 6 moles of 10% aqueous sodium hydroxide and the mixture was evaporated to dryness to produce hexasodium phenyl methane triphosphonate.
- Example 16 1 mole of phenyl methane triphosphonic acid was dissolved in 6 moles of 10% aqueous ammonium hydroxide to produce hexa ammonium phenyl methane triphosphonate, in solution. The salt was recovered by evaporating to dryness.
- Example 17 1 mole of phenyl methane triphosphonic acid was dissolved in 4 moles of 10% aqueous sodium hydroxide and the mixture evaporated to yield tetra sodium phenyl methane triphosphonate.
- Example 18 An aqueous lead acetate solution was mixed with an aqueous solution of hexasodium phenyl methane triphosphonate to form the chelated lead phenyl methane triphosphonate.
- Example 19 The procedure of Example 1 was repeated replacing the diethyl phosphite with an equimolar amount of di (2,4,6-trichlorophenyl) phosphite to obtain as the product tetra (2,4,6-trichlorophenyl) phenyl methane diphosphonate.
- Example 20 The procedure of Example 3 was repeated replacing the diethyl phosphite with an equimolar amount of di (2,4,6-trichlorophenyl) phosphite to obtain as the product hexa (2,4,6-trichlorophenyl) phenyl methane triphosphonate.
- R R R R R and R are selected from the group consisting of hydrogen, alkyl, phenyl, alkylphenyl,
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Description
United States Patent US. Cl. 260-932 7 Claims ABSTRACT OF THE DISCLOSURE There are prepared compounds having a formula selected from the group consisting of where R R R R R and R are selected from the group consisting of hydrogen, hydrocarbyl, haloaryl, metal, ammonium and hydrocarbyl tin.
This invention relates to novel polyphosphonic acid salts and esters thereof.
The present application is a continuation-in-part of application Ser. No. 485,624, filed on Sept. 7, 1965, entitled Methane Diphosphonic Acid.
It is an object of the present invention to prepare novel polyphosphonic acids.
Another object is to prepare salts of such acids.
A further object is to prepare novel esters of such acids.
Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications Within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
It has now been found that these objects can be obtained by preparing compounds having one of the formulae 3,463,835 Patented Aug. 26, 1969 where R R R R R and R are the same or different and are selected from the group consisting of hydrogen, metal, ammonium, hydrocarbyl, e.g. alkyl and aryl, haloaryl or hydrocarbyl tin.
The esters of Formula I are conveniently prepared by reacting 1 mole of benzal chloride with 2 moles of dialkyl phosphite, a di-a-ryl phosphite or a di(haloaryl) phosphite. The esters of Formula II are prepared in a similar fashion by replacing the benzal chloride with benzo trichloride.
The free acids of Formulae I and II can be readily prepared by hydrolyzing the esters of the same formula. Preferably the lower alkyl esters are used for such hydrolysis. The hydrolysis is preferably carried out with the aid of an acid catalyst, e.g. hydrochloric acid, sulfuric acid or the like.
The salts of Formulae I and II can be prepared quite readily by placing an aqueous or organic solution of a salt of the appropriate metal in contact with the free acid of Formulae I and II or with an alkali metal salt thereof.
As the starting secondary phosphites there can be used dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di isobutyl phosphite, di tertiary butyl phosphite, di secondary butyl phosphite, diamyl phosphite, dihexyl phosphite, dicyclohexyl phosphite, dioctyl phosphite, diisodecyl phosphite, di decyl phosphite, dioctadecyl phosphite, diphenyl phosphite, di p-cresyl phosphite, d i (p-nonylphenyl) phosphite, di (o-dodecylphenyl) phosphite, di (m-octylphenyl) phosphite, di (p-chlorophenyl) phosphite, di (2,4,5-trichlorophenyl) phosphite, di (2,4,5- tribromophenyl) phosphite, di benzyl phosphite.
Examples of compounds Within the present invention are phenyl methane diphosphonic acid, phenyl methane triphosphonic acid, tetramethyl phenyl methane diphosphonate, tetraethyl phenyl methane diphosphonate, tetrapropyl phenyl methane diphosphonate, tetrabutyl phenyl methane diphosphonate, tetrahex'yl phenyl methane diphosphonate, tetraoctyl phenyl methane diphosphonate, tetra isodecyl phenyl methane diphosphonate, tetra octadecyl phenyl methane diphosphonate, tetraphenyl phenyl methane diphosphonate, tetra (m-cresyl) phenyl methane diphosphonate, tetra (p-butylphenyl) phenyl methane diphosphonate, tetra (p-nonylphenyl) phenyl methane diphosphonate, tetra (p-dodecylphenyl) phenyl methane diphosphonate, tetra benzyl phenyl methane diphosphonate, tetra (p-chlorophenyl) phenyl methane diphosphonate, tetra (2,4,6-trichlorophenyl) phenyl methane diphosphonate, tetra (2,4,5-tribromophenyl) phenyl methane diphosphonate, hexamethyl phenyl methane triphosphonate, hexaethyl phenyl methane triphosphonate, hexapropyl phenyl methane triphosphonate, hexaisopropyl phenyl methane triphosphonate, hexabutyl phenyl methane triphosphonate, hexa secondary butyl phenyl methane triphosphonate, hexa tertiary butyl phenyl methane triphosphonate, hexa amyl phenyl methane triphosphonate, hexa hexyl phenyl methane triphosphonate, hexa heptyl phenyl methane triphosphonate, hexa octyl phenyl methane triphosphonate, hexa (decyl) phenyl methane triphosphonate, hexa (isodecyl) phenyl methane triphosphonate, hexa propyl phenyl methane triphosphonate, hexa phenyl phenyl methane triphosphonate, di octyl tetra phenyl phenyl methane triphosphonate, hexa (pcresyl) phenyl methane triphosphonate, hexa (o-butylphenyl) phenyl methane triphosphonate, hexa (p-nonylphenyl) phenyl methane triphosphonate, hexa (p-tetradecylphenyl) phenyl methane triphosphonate, hexa (cyclohexyl) phenyl methane triphosphonate, hexa benzyl phenyl methane triphosphonate, hexa (p-chlorophenyl) phenyl methane triphosphonate, hexa (2,4,6-trichlorophenyl) phenyl methane triphosphonate, hexa (2,4,6-tribromophenyl) phenyl methane triphosphonate.
There are also included within the invention salts of the novel acids. These salts can be made from any of the metals in the periodic system. Thus there can be prepared alkali metal salts such as lithium, sodium, potassium, rubidium and cesium salts, alkaline earth metal salts such as calcium, barium strontium and magnesium, as well as salts of the metals such as zinc, cadmium, mercury, copper, silver, gold, titanium, zirconium, tin, chromium, tungsten, molybdenum, radium, manganese, iron, cobalt, nickel, platinum, palladium, uranium and the rare earths, e.g., hafnium and cerium. Ammonium salts can also be prepared. With the exception of the alkali metals and ammonium the salts that are formed are of the chelate type.
Alkyltin and aryltin salts (e.g., mono, di or trialkyltin salts) can also be made.
Illustrative examples of salts are sodium phenyl methane diphosphonate, potassium phenyl methane diphosphonate, rubidium phenyl methane diphosphonate, ammonium phenyl methane diphosphonate, calcium phenyl methane diphosphonate, barium phenyl methane diphosphonate, magnesium phenyl methane diphosphonate, beryllium phenyl methane diphosphonate, zinc phenyl methane diphosphonate, cadmium phenyl methane diphosphonate, mercury phenyl methane diphosphonate, cupric phenyl methane diphosphonate, silver phenyl methane diphosphonate, auric phenyl methane diphosphonate, titanium phenyl methane diphosphonate, zirconium phenyl methane diphosphonate, stannous phenyl methane diphosphonate, stannic phenyl methane diphosphonate, chromic phenyl methane diphosphonate, tungsten phenyl methane diphosphonate, molybdenum phenyl methane diphosphonate, manganous phenyl methane diphosphonate, ferrous phenyl methane diphosphonate, ferric phenyl methane diphosphonate, cobaltic phenyl methane diphosphonate, nickelous phenyl methane dit phosphonate, platinum phenyl methane diphosphonate, palladium phenyl methane diphosphonate, uranium phenyl methane diphosphonate, uranyl phenyl methane diphosphonate, plumbous phenyl methane diphosphonate, hafnium phenyl methane diphosphonate, cerium phenyl methane diphosphonate, dibutyltin phenyl methane diphosphonate, monobutyltin phenyl methane diphosphonate, tributyltin phenyl methane diphosphonate, dioctyltin phenyl methane diphosphonate, diphenyltin phenyl methane diphosphonate, sodium phenyl methane triphosphonate, potassium phenyl methane triphosphonate, ammonium phenyl methane triphosphonate, rubidium phenyl methane triphosphonate, cesium phenyl methane triphosphonate, lithium phenyl methane triphosphonate, calcium phenyl methane triphosphonate, magnesium phenyl methane triphosphonate, beryllium phenyl methane triphosphonate, strontium phenyl methane triphosphonate, barium phenyl methane triphosphonate, radium phenyl methane triphosphonate, zinc phenyl meth- -ane triphosphonate, cadmium phenyl methane triphosphonate, mercury phenyl methane triphosphonate, cupric phenyl methane triphosphonate, silver phenyl methane triphosphonate, aurous phenyl methane triphosphonate, titanic phenyl methane triphosphonate, zirconium phenyl methane triphosphonate, plumbous phenyl methane triphosphonate, stannous phenyl methane triphosphonate, stannic phenyl methane triphosphonate, chromic phenyl methane triphosphonate, tungsten phenyl methane triphosphonate, molybdenum phenyl methane triphosphonate, manganous phenyl methane triphosphonate, ferrous phenyl methane triphosphonate, ferric phenyl methane triphosphonate, cobaltic phenyl methane triphosphonate, nickelous phenyl methane triphosphonate, platinum phenyl methane triphosphonate, palladium phenyl methane triphosphonate, uranium phenyl methane triphosphonate, uranyl phenyl methane triphosphonate, cerium phenyl methane triphosphonate, hafnium phenyl methane triphosphonate, dibutyltin phenyl methane triphosphonate, dioctyltin phenyl methane triphosphonate, amyltin phenyl methane triphosphonate, triethyltin phenyl methane triphosphonate, di (o-tolyl) tin phenyl methane triphosphonate.
The esters coming within Formulae I and II supra are all useful as stabilizers for halogen containing vinyl and vinylidene resins, e.g. vinylchloride resins and as stabiliners for monoolefin polymers, e.g. polyethylene, polypropylene and ethylene-propylene copolymer. For such stabilizer uses there is normally employed 0.140 parts of the phosphorous containing ester per parts of the polymer. The esters are also useful in preparing the free acids within Formulae I and II.
The free acids of Formulae I and II are all useful as curing agents for melamine-formaldehyde and urea-formaldehyde resins. They are also valuable for forming their metal salts and as detergent additives, extractants, sequestering agents, metal complexing agents, corrosion inhibitors, chelating agents, stabilizers and the like. The alkali metal and ammonium salts are particularly valuable in detergent compositions as additives and builders. They are superior in such compositions to sodium tripolyphosphate. The free acids and alkali metal and ammonium salts are extremely valuable because of their ability to act as sequestering agents to hold polyvalent metal compounds in aqueous solution. They also are useful to prevent the hydrolysis of alkali metal polyphosphates.
The metal salts (other than the alkali metal salts) are useful in providing a means for isolating the metals in a form in which they can be readily recovered. They are also useful as a soluble source of the metals. The hydrocarbyltin salts are useful as stabilizers for halogen containing resins, e.g. vinyl chloride resins.
The phenyl methane diphosphonic acid, phenyl methane triphosphonic acid and their alkali metal salts exhibit very low surface tension and are superior agents for metal extraction e.g. extraction of gold, silver, vanadium, molybdenum, copper, nickel and iron.
Unless otherwise indicated, all proportions are by weight.
Since the novel acids of the present invention have four or six acidic hydrogen atoms (Formulae I and II) in making the salts one or more of the acidic hydrogen atoms can be replaced by the metal or ammonium in forming the salts. Usually all of the acidic hydrogen atoms are replaced in making the salt and unless otherwise indicated when reference is made to a salt in the present specification all of the acidic hydrogen atoms are replaced. However, it should be understood that this is not an essential part of the present invention and the invention includes the partial as Well as the complete salts, e.g. mono sodium phenyl methane triphosphonate, di sodium phenyl methane triphosphonate, tri sodium phenyl methane triphosphonate, tetra sodium phenyl methane triphosphonate, penta sodium phenyl methane triphosphonate, hexa sodium phenyl methane triphosphonate, di potassium phenyl methane triphosphonate, tetra potassium phenyl methane triphosphonate, hexa potassium phenyl methane triphosphonate, mono ammonium phenyl methane triphosphonate, tri ammonium phenyl methane triphosphonate, hexa ammonium phenyl methane triphosphonate, mono sodium phenyl methane diphosphonate, di sodium phenyl methane diphosphonate, tri sodium phenyl methane diphosphonate, tetra sodium phenyl methane diphosphonate, mono potassium phenyl methane diphosphonate, tetra potassium phenyl methane diphosphonate, di ammonium phenyl methane diphosphonate, tetra ammonium phenyl methane diphosphonate.
The compounds of the present invention, and in particular the esters are useful as plasticizers.
The compounds of the present invention, particularly the free acids, alkali metal and ammonium salts, are useful as stabilizers for alkyl phenols, 6. g. nonyl phenol, 0ctyl phenol, dodecyl phenol to prevent discoloration. All of the compounds of the present invention are useful as flame proofing agents in making polyurethanes. The free acids are useful as catalysts in polymerizing formaldehyde to make materials such as Delrin or Celcon.
Example 1 There were charged into the reaction vessel 23.0 grams (1.0 mole) of sodium metal along with 90 cc. of xylene and 80 cc. of tetrahydrofurane. The vessel was placed under a nitrogen blanket and 138.10 grams -(1.0 mole) of diethyl phosphite added over a 35 minute period. An exothermic reaction ensued which was maintained at 62 C. by external cooling. After addition was complete the mixture was heated to 100 C. and held there until all of the sodium metal was gone. The mixture was cooled to 60 to 70 C. and 80.5 grams (0.5 mole) of benzal chloride were added gradually over a 25 minute period. An exothermic reaction ensued which was maintained at 60 to 70 C. by external cooling. The mixture was then heated for 4 hours at 70 to 75 C., cooled to 60 C. The liquid material was separated from the solid and the solid boiled 8 times with 100cc. of benzene to extract the organic material. The eluate product was then distilled, terminal conditions being a pot temperature of 201 C., distillate temperature 125 C. and pressure 6 mm. The solid residue of 70 grams was tetraethyl phenyl methane diphosphonate.
Example 2 0.9 mole of tetra ethyl phenyl methane diphosphonate was refluxed with 5.4 moles of concentrated hydrochloric acid for 24 hours. Excess acid was removed by stripping under vacuum. 200 ml. of water were added and removed in vacuo, then finally 200 ml. of benzene were added and the water removed and separated by means of a Dean and Stark trap and the benzene was distilled over under reduced pressure yielding phenyl methane diphosphonic acid.
Example 3 There were mixed together 23.0 grams (1.0 mole) of sodium metal along with 90 cc. of xylene and 80 cc. of tetrahydrofurane and the mixture placed under a nitrogen atmosphere. There were then added over a 35 minute period 138.10 grams (1.0 mole) of diethyl phosphite using external cooling to control the reaction exotherm and maintain the temperature at 60 to 65 C. After addition was complete the mixture was heated to 100 C. and maintained there for about 1 hour until there was no more sodium. The mixture was cooled to 60 C. and there was started the addition of 64.5 grams (0.33 mole) of benzotrichloride (a,a,a-trichlorotoluene). The exo thermic reaction was cooled to maintain the temperature at 60 to 65 C. during the 25 minute addition period. The mixture was heated at 70 to 75 C. for 7 hours and the sodium chloride filtered off. The product in the pot was then subjected to distillation, terminal conditions being a pot temperature of 205 C., distillate temperature 125 C. and pressure 4 mm. The solid residue in the pot was hexaethyl phenyl methane triphosphonate. This product was hydrolyzed and the hydrolysis product purified as in Example 2 to obtain phenyl methane triphosphonic acid.
Example 4 The procedure of Example 1 was repeated replacing the diethyl phosphite by an equimolar amount of dimethyl phosphite to obtain as the product tetramethyl phenyl methane diphosphonate.
Example 5 The procedure of Example 1 was repeated replacing the diethyl phosphite by an equimolar amount of dibutyl phosphite to obtain as the product tetrabutyl phenyl methane diphosphonate.
Example 6 The procedure of Example 1 was repeated replacing the diethyl phosphite by an equimolar amount of diisodecyl phosphite to obtain as the product tetraisodecyl phenyl methane diphosphonate.
Example 7 The procedure of Example 1 was repeated replacing the diethyl phosphite by an equimolar amount of diphenyl phosphite to obtain as the product :tetraphenyl phenyl methane diphosphonate.
Example 8 Example 9 The procedure of Example 3 was repeated replacing the diethyl phosphite by an equimolar amount of dibutyl phosphite to obtain as a product hexabutyl phenyl methane triphosphonate.
Example 10 The procedure of Example 3 was repeated replacing the diethyl phosphite by an equimolar amount of dioctyl phosphite to obtain as a product hexaoctyl phenyl methane triphosphonate.
Example 11 The procedure of Example 3 was repeated replacing the diethyl phosphite by an equimolar amount of diphenyl phosphite to obtain as a product hexaphenyl phenyl methane triphosphonate.
Example 12 The procedure of Example 3 was repeated replacing the diethyl phosphite by an equimolar amount of di (dodecyl) phosphite to obtain as a product hexa (dodecyl) phenyl methane triphosphonate.
Example 13 The procedure of Example 3 was repeated replacing the diethyl phosphite by an equimolar amount of di (ptolyl) phosphite to obtain as a product hexa (p-tolyl) phenyl methane triphosphonate.
Example 14 To 1 mole of phenyl methane diphosphonic acid there were added 4 moles of 10% aqueous sodium hydroxide and the mixture was evaporated to dryness to produce tetrasodium phenyl methane diphosphonate.
Example 15 To 1 mole of phenyl methane triphosphonic acid there were added 6 moles of 10% aqueous sodium hydroxide and the mixture was evaporated to dryness to produce hexasodium phenyl methane triphosphonate.
7 Example 16 1 mole of phenyl methane triphosphonic acid was dissolved in 6 moles of 10% aqueous ammonium hydroxide to produce hexa ammonium phenyl methane triphosphonate, in solution. The salt was recovered by evaporating to dryness.
Example 17 1 mole of phenyl methane triphosphonic acid was dissolved in 4 moles of 10% aqueous sodium hydroxide and the mixture evaporated to yield tetra sodium phenyl methane triphosphonate.
Example 18 An aqueous lead acetate solution was mixed with an aqueous solution of hexasodium phenyl methane triphosphonate to form the chelated lead phenyl methane triphosphonate.
In similar fashion an aqueous ferric chloride solution was mixed with an aqueous solution of hexa potassium phenyl methane triphosphonate to form the chelated ferric phenyl methane triphosphonate.
Example 19 The procedure of Example 1 was repeated replacing the diethyl phosphite with an equimolar amount of di (2,4,6-trichlorophenyl) phosphite to obtain as the product tetra (2,4,6-trichlorophenyl) phenyl methane diphosphonate.
Example 20 The procedure of Example 3 was repeated replacing the diethyl phosphite with an equimolar amount of di (2,4,6-trichlorophenyl) phosphite to obtain as the product hexa (2,4,6-trichlorophenyl) phenyl methane triphosphonate.
Iclaim:
1. A compound having the formula where R R R R R and R are selected from the group consisting of hydrogen, alkyl, phenyl, alkylphenyl,
chlorophenyl, bromophenyl, benzyl, metal and ammonium.
2. A compound according to claim 1 wherein R R References Cited UNITED STATES PATENTS 3,299,123 1/1967 Fitch et a1. 260-932 CHARLES B. PARKER, Primary Examiner ANTON H. SUTTO, Assistant Examiner US. or. X.R.
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US (1) | US3463835A (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3549677A (en) * | 1966-12-29 | 1970-12-22 | Procter & Gamble | Stannous salts of polyphosphonic acids |
US3678154A (en) * | 1968-07-01 | 1972-07-18 | Procter & Gamble | Oral compositions for calculus retardation |
US3793199A (en) * | 1970-06-08 | 1974-02-19 | Texaco Inc | Friction reducing agent for lubricants |
US3894986A (en) * | 1972-10-25 | 1975-07-15 | Hoechst Ag | Flame resistant thermoplastic polyesters |
US3900444A (en) * | 1972-10-25 | 1975-08-19 | Hoechst Ag | Flame resistant thermoplastic polyesters |
US4116990A (en) * | 1970-04-30 | 1978-09-26 | Plains Chemical Development Co. | Chelation |
US4133823A (en) * | 1975-02-28 | 1979-01-09 | Monsanto Company | Reaction products of metal oxides and salts with phosphorus compounds |
US4188234A (en) * | 1965-08-24 | 1980-02-12 | Plains Chemical Development Co. | Chelation |
EP0015370A1 (en) * | 1979-02-13 | 1980-09-17 | Symphar S.A. | Diphosphonate or phosphate-phosphonate derivatives and pharmaceutical compositions containing them |
US4232146A (en) * | 1978-09-26 | 1980-11-04 | Occidental Research Corporation | Process for preparing layered organophosphorus inorganic polymers |
US4256872A (en) * | 1978-09-26 | 1981-03-17 | Occidental Research Corporation | Process for preparing layered organophosphorus inorganic polymers |
US4416877A (en) * | 1979-02-13 | 1983-11-22 | Symphar S.A. | Anti-atherosclerotic pharmaceutical compositions containing diphosphonate compounds |
US4910240A (en) * | 1986-03-14 | 1990-03-20 | Akzo America Inc. | Thermally stable diphosphonate-type flame retardant additive for plastics |
US20110008634A1 (en) * | 2008-08-11 | 2011-01-13 | Autonetworks Technologies, Ltd. | Rust inhibitor and surface treatment metal material |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3299123A (en) * | 1963-04-09 | 1967-01-17 | Monsanto Co | Substituted methylene diphosphonic acids and salts and esters thereof |
-
1965
- 1965-10-05 US US493217A patent/US3463835A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3299123A (en) * | 1963-04-09 | 1967-01-17 | Monsanto Co | Substituted methylene diphosphonic acids and salts and esters thereof |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4188234A (en) * | 1965-08-24 | 1980-02-12 | Plains Chemical Development Co. | Chelation |
US3549677A (en) * | 1966-12-29 | 1970-12-22 | Procter & Gamble | Stannous salts of polyphosphonic acids |
US3678154A (en) * | 1968-07-01 | 1972-07-18 | Procter & Gamble | Oral compositions for calculus retardation |
US4116990A (en) * | 1970-04-30 | 1978-09-26 | Plains Chemical Development Co. | Chelation |
US3793199A (en) * | 1970-06-08 | 1974-02-19 | Texaco Inc | Friction reducing agent for lubricants |
US3894986A (en) * | 1972-10-25 | 1975-07-15 | Hoechst Ag | Flame resistant thermoplastic polyesters |
US3900444A (en) * | 1972-10-25 | 1975-08-19 | Hoechst Ag | Flame resistant thermoplastic polyesters |
US4133823A (en) * | 1975-02-28 | 1979-01-09 | Monsanto Company | Reaction products of metal oxides and salts with phosphorus compounds |
US4256872A (en) * | 1978-09-26 | 1981-03-17 | Occidental Research Corporation | Process for preparing layered organophosphorus inorganic polymers |
US4232146A (en) * | 1978-09-26 | 1980-11-04 | Occidental Research Corporation | Process for preparing layered organophosphorus inorganic polymers |
EP0015370A1 (en) * | 1979-02-13 | 1980-09-17 | Symphar S.A. | Diphosphonate or phosphate-phosphonate derivatives and pharmaceutical compositions containing them |
US4309364A (en) * | 1979-02-13 | 1982-01-05 | Symphar S.A. | Diphosphonates |
US4416877A (en) * | 1979-02-13 | 1983-11-22 | Symphar S.A. | Anti-atherosclerotic pharmaceutical compositions containing diphosphonate compounds |
US4910240A (en) * | 1986-03-14 | 1990-03-20 | Akzo America Inc. | Thermally stable diphosphonate-type flame retardant additive for plastics |
US20110008634A1 (en) * | 2008-08-11 | 2011-01-13 | Autonetworks Technologies, Ltd. | Rust inhibitor and surface treatment metal material |
EP2333135A1 (en) * | 2008-08-11 | 2011-06-15 | AutoNetworks Technologies, Ltd. | Rust inhibitor and surface-treated metal material |
EP2333135A4 (en) * | 2008-08-11 | 2014-06-04 | Autonetworks Technologies Ltd | Rust inhibitor and surface-treated metal material |
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