US3518200A - Organic phosphorus compounds,compositions containing same,and uses thereof - Google Patents
Organic phosphorus compounds,compositions containing same,and uses thereof Download PDFInfo
- Publication number
- US3518200A US3518200A US578500A US3518200DA US3518200A US 3518200 A US3518200 A US 3518200A US 578500 A US578500 A US 578500A US 3518200D A US3518200D A US 3518200DA US 3518200 A US3518200 A US 3518200A
- Authority
- US
- United States
- Prior art keywords
- acid
- groups
- diphosphonate
- ester
- compounds
- 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
- 239000000203 mixture Substances 0.000 title description 57
- 150000002903 organophosphorus compounds Chemical class 0.000 title 1
- -1 hydrogen ions Chemical class 0.000 description 103
- 239000002253 acid Substances 0.000 description 68
- 150000001875 compounds Chemical class 0.000 description 46
- 150000002148 esters Chemical class 0.000 description 41
- 125000004432 carbon atom Chemical group C* 0.000 description 38
- 150000007513 acids Chemical class 0.000 description 37
- 239000003599 detergent Substances 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 30
- DKPHLYCEFBDQKM-UHFFFAOYSA-H hexapotassium;1-phosphonato-n,n-bis(phosphonatomethyl)methanamine Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)CN(CP([O-])([O-])=O)CP([O-])([O-])=O DKPHLYCEFBDQKM-UHFFFAOYSA-H 0.000 description 25
- 150000003839 salts Chemical class 0.000 description 24
- 229940102859 methylene diphosphonate Drugs 0.000 description 21
- 125000000217 alkyl group Chemical group 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 17
- 125000003118 aryl group Chemical group 0.000 description 16
- 125000001183 hydrocarbyl group Chemical group 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000004094 surface-active agent Substances 0.000 description 15
- 159000000000 sodium salts Chemical class 0.000 description 14
- 239000011591 potassium Substances 0.000 description 12
- 229910052700 potassium Inorganic materials 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 125000002877 alkyl aryl group Chemical group 0.000 description 11
- 238000005108 dry cleaning Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- XCXJLWLQQPJVDR-UHFFFAOYSA-N 3-(azepan-2-yl)quinoline Chemical compound C1CCCCNC1C1=CN=C(C=CC=C2)C2=C1 XCXJLWLQQPJVDR-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical class [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 6
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 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 5
- HWZUDASOMGNLSM-UHFFFAOYSA-N O=P1OCOP(=O)O1 Chemical compound O=P1OCOP(=O)O1 HWZUDASOMGNLSM-UHFFFAOYSA-N 0.000 description 5
- 229920000388 Polyphosphate Polymers 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000001205 polyphosphate Substances 0.000 description 5
- 235000011176 polyphosphates Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 150000004760 silicates Chemical class 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 235000019832 sodium triphosphate Nutrition 0.000 description 5
- 230000003381 solubilizing effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000002619 bicyclic group Chemical group 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 150000008282 halocarbons Chemical class 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 230000009919 sequestration Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 125000001118 alkylidene group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical class OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 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
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 2
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000003784 tall oil Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004753 textile Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LKGJFSBVIBNBPW-UHFFFAOYSA-N (2-phenyl-1-phosphonoethyl)phosphonic acid Chemical compound OP(O)(=O)C(P(O)(O)=O)CC1=CC=CC=C1 LKGJFSBVIBNBPW-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- AKCZEKXQVYPQTC-UHFFFAOYSA-N 1,3-xylene;dihydrochloride Chemical compound Cl.Cl.CC1=CC=CC(C)=C1 AKCZEKXQVYPQTC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 1
- LNWXALCHPJANMJ-UHFFFAOYSA-N 1-(bromomethyl)-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(CBr)=C1 LNWXALCHPJANMJ-UHFFFAOYSA-N 0.000 description 1
- LZBOHNCMCCSTJX-UHFFFAOYSA-N 1-(chloromethyl)-3-methylbenzene Chemical compound CC1=CC=CC(CCl)=C1 LZBOHNCMCCSTJX-UHFFFAOYSA-N 0.000 description 1
- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 description 1
- CYAKWEQUWJAHLW-UHFFFAOYSA-N 1-(chloromethyl)-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(CCl)C=C1 CYAKWEQUWJAHLW-UHFFFAOYSA-N 0.000 description 1
- LZSYGJNFCREHMD-UHFFFAOYSA-N 1-bromo-2-(bromomethyl)benzene Chemical compound BrCC1=CC=CC=C1Br LZSYGJNFCREHMD-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- AQLKCZOZKNQXDW-UHFFFAOYSA-N 1-bromo-4-tert-butylcyclohexane Chemical compound CC(C)(C)C1CCC(Br)CC1 AQLKCZOZKNQXDW-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- WSULSMOGMLRGKU-UHFFFAOYSA-N 1-bromooctadecane Chemical compound CCCCCCCCCCCCCCCCCCBr WSULSMOGMLRGKU-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 description 1
- OGYBTPYJHQSBBR-UHFFFAOYSA-N 1-chloro-1-methylcyclohexane Chemical compound CC1(Cl)CCCCC1 OGYBTPYJHQSBBR-UHFFFAOYSA-N 0.000 description 1
- BASMANVIUSSIIM-UHFFFAOYSA-N 1-chloro-2-(chloromethyl)benzene Chemical compound ClCC1=CC=CC=C1Cl BASMANVIUSSIIM-UHFFFAOYSA-N 0.000 description 1
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- XGCKOSFYXBAPQM-UHFFFAOYSA-N 1-chloro-3,3-dimethylbutane Chemical compound CC(C)(C)CCCl XGCKOSFYXBAPQM-UHFFFAOYSA-N 0.000 description 1
- DDGRAFHHXYIQQR-UHFFFAOYSA-N 1-chloro-3-(chloromethyl)benzene Chemical compound ClCC1=CC=CC(Cl)=C1 DDGRAFHHXYIQQR-UHFFFAOYSA-N 0.000 description 1
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 description 1
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 description 1
- CLWAXFZCVYJLLM-UHFFFAOYSA-N 1-chlorohexadecane Chemical compound CCCCCCCCCCCCCCCCCl CLWAXFZCVYJLLM-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- ZHKKNUKCXPWZOP-UHFFFAOYSA-N 1-chloroundecane Chemical compound CCCCCCCCCCCCl ZHKKNUKCXPWZOP-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- OWWOMIFQTFZNGK-UHFFFAOYSA-N 1-phosphonobutylphosphonic acid Chemical compound CCCC(P(O)(O)=O)P(O)(O)=O OWWOMIFQTFZNGK-UHFFFAOYSA-N 0.000 description 1
- ROKLPPRTPHAGFK-UHFFFAOYSA-N 1-phosphonooctylphosphonic acid Chemical compound CCCCCCCC(P(O)(O)=O)P(O)(O)=O ROKLPPRTPHAGFK-UHFFFAOYSA-N 0.000 description 1
- IRYOZLKMXHUGKP-UHFFFAOYSA-N 1-phosphonopentylphosphonic acid Chemical compound CCCCC(P(O)(O)=O)P(O)(O)=O IRYOZLKMXHUGKP-UHFFFAOYSA-N 0.000 description 1
- DZQCAOQMXPROIJ-UHFFFAOYSA-N 1-phosphonopropan-2-ylphosphonic acid Chemical compound OP(=O)(O)C(C)CP(O)(O)=O DZQCAOQMXPROIJ-UHFFFAOYSA-N 0.000 description 1
- MYSJYDYZEABHHG-UHFFFAOYSA-N 1-phosphonotridecylphosphonic acid Chemical compound CCCCCCCCCCCCC(P(O)(O)=O)P(O)(O)=O MYSJYDYZEABHHG-UHFFFAOYSA-N 0.000 description 1
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 1
- NCKMMSIFQUPKCK-UHFFFAOYSA-N 2-benzyl-4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1CC1=CC=CC=C1 NCKMMSIFQUPKCK-UHFFFAOYSA-N 0.000 description 1
- JFNPFFAEYZRVJS-UHFFFAOYSA-N 2-bromocycloheptan-1-one Chemical compound BrC1CCCCCC1=O JFNPFFAEYZRVJS-UHFFFAOYSA-N 0.000 description 1
- HZTPKMIMXLTOSK-UHFFFAOYSA-N 2-bromohexanoic acid Chemical compound CCCCC(Br)C(O)=O HZTPKMIMXLTOSK-UHFFFAOYSA-N 0.000 description 1
- JVIGKRUGGYKFSL-UHFFFAOYSA-N 2-chloro-1-methyl-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(C)C(Cl)=C1 JVIGKRUGGYKFSL-UHFFFAOYSA-N 0.000 description 1
- IFMWWVGVDOTBNN-UHFFFAOYSA-N 2-chloro-2,3,3-trimethylbutane Chemical compound CC(C)(C)C(C)(C)Cl IFMWWVGVDOTBNN-UHFFFAOYSA-N 0.000 description 1
- NXXHAWKBICGUCK-UHFFFAOYSA-N 2-chloro-2-methylpentane Chemical compound CCCC(C)(C)Cl NXXHAWKBICGUCK-UHFFFAOYSA-N 0.000 description 1
- FALBWDMCXSULQC-UHFFFAOYSA-N 2-chloro-4-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C(Cl)=C1 FALBWDMCXSULQC-UHFFFAOYSA-N 0.000 description 1
- HJBUWTLHZIRBIM-UHFFFAOYSA-N 2-chloro-4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C(Cl)=C1 HJBUWTLHZIRBIM-UHFFFAOYSA-N 0.000 description 1
- WLHBVLZZOJGNGQ-UHFFFAOYSA-N 2-chloro-4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C(Cl)=C1 WLHBVLZZOJGNGQ-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
- ROPQINLWRARCTM-UHFFFAOYSA-N 2-phosphonopropan-2-ylphosphonic acid Chemical compound OP(=O)(O)C(C)(C)P(O)(O)=O ROPQINLWRARCTM-UHFFFAOYSA-N 0.000 description 1
- AJKDUJRRWLQXHM-UHFFFAOYSA-N 3-bromocyclohexene Chemical compound BrC1CCCC=C1 AJKDUJRRWLQXHM-UHFFFAOYSA-N 0.000 description 1
- COVFMDKBWYLRSV-UHFFFAOYSA-N 3-chloro-2,2-dimethylbutane Chemical compound CC(Cl)C(C)(C)C COVFMDKBWYLRSV-UHFFFAOYSA-N 0.000 description 1
- NMWSKOLWZZWHPL-UHFFFAOYSA-N 3-chlorobiphenyl Chemical group ClC1=CC=CC(C=2C=CC=CC=2)=C1 NMWSKOLWZZWHPL-UHFFFAOYSA-N 0.000 description 1
- LNGQLHZIYFQUIR-UHFFFAOYSA-N 3-chlorocyclohexene Chemical compound ClC1CCCC=C1 LNGQLHZIYFQUIR-UHFFFAOYSA-N 0.000 description 1
- BXSMMAVTEURRGG-UHFFFAOYSA-N 3-chlorohexane Chemical compound CCCC(Cl)CC BXSMMAVTEURRGG-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- OREQWMWYRYXCDF-UHFFFAOYSA-N 4-(4-chlorophenyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(Cl)C=C1 OREQWMWYRYXCDF-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- BMKFFLPVJHCPDD-UHFFFAOYSA-N 5-chloro-5-ethenylcyclohexa-1,3-diene Chemical compound C=CC1(Cl)CC=CC=C1 BMKFFLPVJHCPDD-UHFFFAOYSA-N 0.000 description 1
- QRKINCQKOGXVEO-UHFFFAOYSA-N 5-phosphonopentylphosphonic acid Chemical compound OP(O)(=O)CCCCCP(O)(O)=O QRKINCQKOGXVEO-UHFFFAOYSA-N 0.000 description 1
- WDYVUKGVKRZQNM-UHFFFAOYSA-N 6-phosphonohexylphosphonic acid Chemical compound OP(O)(=O)CCCCCCP(O)(O)=O WDYVUKGVKRZQNM-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BQRBXHGQLWRXIV-UHFFFAOYSA-N C(CCCCCCC)C1=C(C=CC=C1)CCCCCCCC.[Na] Chemical compound C(CCCCCCC)C1=C(C=CC=C1)CCCCCCCC.[Na] BQRBXHGQLWRXIV-UHFFFAOYSA-N 0.000 description 1
- VERCCDBWPZFKFE-UHFFFAOYSA-N C1C=CC=C1.Br.Br Chemical compound C1C=CC=C1.Br.Br VERCCDBWPZFKFE-UHFFFAOYSA-N 0.000 description 1
- PFOIMGLWXPMGFH-UHFFFAOYSA-N C=1(C(=CC=C2C=CC=CC12)S(=O)(=O)OC(C)C)S(=O)(=O)OC(C)C.[Na].[Na] Chemical compound C=1(C(=CC=C2C=CC=CC12)S(=O)(=O)OC(C)C)S(=O)(=O)OC(C)C.[Na].[Na] PFOIMGLWXPMGFH-UHFFFAOYSA-N 0.000 description 1
- ZKSJIKYGQJQMAJ-UHFFFAOYSA-N CC1OP(=O)OP(=O)O1 Chemical compound CC1OP(=O)OP(=O)O1 ZKSJIKYGQJQMAJ-UHFFFAOYSA-N 0.000 description 1
- NWNDPNNOARGOIC-UHFFFAOYSA-N CCCCCCCCCCCCOS(CC1=CC=CC=C1)(=O)=O.N Chemical compound CCCCCCCCCCCCOS(CC1=CC=CC=C1)(=O)=O.N NWNDPNNOARGOIC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XCKGXLYFONQJED-UHFFFAOYSA-L [Na+].[Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccccc1S([O-])(=O)=O.CCCCCCCCCCCCOS(=O)(=O)c1ccccc1S([O-])(=O)=O Chemical compound [Na+].[Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccccc1S([O-])(=O)=O.CCCCCCCCCCCCOS(=O)(=O)c1ccccc1S([O-])(=O)=O XCKGXLYFONQJED-UHFFFAOYSA-L 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- HSDAJNMJOMSNEV-UHFFFAOYSA-N benzyl chloroformate Chemical compound ClC(=O)OCC1=CC=CC=C1 HSDAJNMJOMSNEV-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- XAVFZUKFLWOSOS-UHFFFAOYSA-N bis(dimethoxyphosphoryl)methane Chemical compound COP(=O)(OC)CP(=O)(OC)OC XAVFZUKFLWOSOS-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- LOXORFRCPXUORP-UHFFFAOYSA-N bromo-Cycloheptane Chemical compound BrC1CCCCCC1 LOXORFRCPXUORP-UHFFFAOYSA-N 0.000 description 1
- BRTFVKHPEHKBQF-UHFFFAOYSA-N bromocyclopentane Chemical compound BrC1CCCC1 BRTFVKHPEHKBQF-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KMJSGLZXFNSANB-UHFFFAOYSA-N chlorocycloheptane Chemical compound ClC1CCCCCC1 KMJSGLZXFNSANB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- RVOJTCZRIKWHDX-UHFFFAOYSA-N cyclohexanecarbonyl chloride Chemical compound ClC(=O)C1CCCCC1 RVOJTCZRIKWHDX-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- OGUICUFYVRBKBX-UHFFFAOYSA-L disodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate;hydron Chemical compound [Na+].[Na+].OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC([O-])=O)CC([O-])=O OGUICUFYVRBKBX-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052920 inorganic sulfate Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AAMAZDUTPXBLIX-UHFFFAOYSA-N lithium;pentadecyl benzenesulfonate Chemical compound [Li].CCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 AAMAZDUTPXBLIX-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- OQXSVLMHUIVNRJ-UHFFFAOYSA-L magnesium;2-dodecylbenzenesulfonate Chemical compound [Mg+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OQXSVLMHUIVNRJ-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- OCIDXARMXNJACB-UHFFFAOYSA-N n'-phenylethane-1,2-diamine Chemical compound NCCNC1=CC=CC=C1 OCIDXARMXNJACB-UHFFFAOYSA-N 0.000 description 1
- MSLICLMCQYQNPK-UHFFFAOYSA-N n-(4-bromophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Br)C=C1 MSLICLMCQYQNPK-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- HJZKOAYDRQLPME-UHFFFAOYSA-N oxidronic acid Chemical compound OP(=O)(O)C(O)P(O)(O)=O HJZKOAYDRQLPME-UHFFFAOYSA-N 0.000 description 1
- LRNLJCBZAUJMIS-UHFFFAOYSA-I pentapotassium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [K+].[K+].[K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LRNLJCBZAUJMIS-UHFFFAOYSA-I 0.000 description 1
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- SNRGKEFSTLRHIG-UHFFFAOYSA-M potassium;2-[bis(carboxymethyl)amino]acetate Chemical compound [K+].OC(=O)CN(CC(O)=O)CC([O-])=O SNRGKEFSTLRHIG-UHFFFAOYSA-M 0.000 description 1
- WIBVOBURKHLIQM-UHFFFAOYSA-N potassium;tetradecyl benzenesulfonate Chemical compound [K].CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 WIBVOBURKHLIQM-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- ZAWGLAXBGYSUHN-UHFFFAOYSA-M sodium;2-[bis(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CC([O-])=O ZAWGLAXBGYSUHN-UHFFFAOYSA-M 0.000 description 1
- DUXXGJTXFHUORE-UHFFFAOYSA-M sodium;4-tridecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 DUXXGJTXFHUORE-UHFFFAOYSA-M 0.000 description 1
- 238000010591 solubility diagram Methods 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- MDTMOBMECRUULW-UHFFFAOYSA-J tetrasodium;dioxido-oxo-(phosphonatomethyl)-$l^{5}-phosphane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)CP([O-])([O-])=O MDTMOBMECRUULW-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- MFXHJJWBUBCCSO-UHFFFAOYSA-K trilithium 2-[bis(carboxylatomethyl)amino]acetate Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O MFXHJJWBUBCCSO-UHFFFAOYSA-K 0.000 description 1
- FYZXEMANQYHCFX-UHFFFAOYSA-K tripotassium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [K+].[K+].[K+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O FYZXEMANQYHCFX-UHFFFAOYSA-K 0.000 description 1
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
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
-
- 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
- C11D1/34—Derivatives of acids of phosphorus
- C11D1/342—Phosphonates; Phosphinates or phosphonites
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
- D06L1/04—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives
Definitions
- a detergent composition containing an organo-methylene diphosphonic compound having the formula wherein R is selected from the class consisting of aliphatic hydrocarbyl, alicyclic, aryl, alkaryl, and aralkyl groups of from 5 to carbon atoms and X is selected from the class consisting of hydrogen ions, alkali metal ions, ammonium ions and amine ions; as well as a dry cleaning composition containing an ester of an organo-methylene diphosphonic acid having the formula X0 H- OX wherein R is selected from the class consisting of aliphatic hydrocarbyl, alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is selected from the class consisting of aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atom
- This invention relates to organic compounds of phosphorus, compositions containing said compounds, and uses thereof.
- An object of this invention is to provide new and useful organic compounds of phosphorus containing a group in their molecules.
- a further object of this invention is to provide new and useful organic compounds of phosphorus containing a group in their molecules with the group being a hydrophobic and/or lipophilic group.
- a further object of this invention is to provide new and useful organophosphonic acids, as well as their salts and esters.
- a more specific object of this invention is to provide new and useful organo-methylene diphosphonic acids or the salts thereof which exhibit, among other things, combined surfactancy sequestering and defiocculating properties.
- a more specific object of this invention is to provide new and useful organo-methylene diphosphonate esters which exhibit, among other things, the unique ability of solubilizing water in water immiscible solvents.
- Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonic acids or the salts thereof.
- Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonic acids or the salts thereof which are suitable for use in aqueous systems.
- Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonate esters.
- a still further object of this invention is to provide detergent compositions containing organo-methylene diphosphonate esters which are suitable for use as drycleaning detergents in organic solvents.
- This invention is directed to new and useful organomethylene diphosphonic acid compounds, as well as the salts and esters thereof, said compounds having the general formula Xo ⁇ ( R (fit/0X P P Xo 1'1 OX wherein: R is selected from the class consisting of aliphatic hydrocarbyl, alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is selected from the class consisting of cations selected from the group of hydrogen ions, alkali metal ions, ammonium ions and amine ions, and aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atoms.
- the aliphatic hydrocarbyl group represented by R contains from 7 to 30 carbon atoms.
- R and X represent groups containing carbon chains, such as aliphatic hydrocarbyl groups, or groups containing alkyl moieties, i.e., aralkyl groups, such carbon chains may be of a straight chain structure or branched chain structure.
- R. and X when they represent aliphatic hydrocarbyl groups, such groups may be saturated or unsaturated.
- R can also contain substituents, such as, hydroxyl, halides, i.e., fluoride, chloride, bromide and iodide, alkoxyl groups, ester groups, ether groups, nitro groups sulfonyl groups, amide groups, amino groups, carboxyl groups, nitroso groups, and the like as long as they do not materially interfere with the hydrophilic and/ or lipophilic nature of groups.
- substituents such as, hydroxyl, halides, i.e., fluoride, chloride, bromide and iodide, alkoxyl groups, ester groups, ether groups, nitro groups sulfonyl groups, amide groups, amino groups, carboxyl groups, nitroso groups, and the like as long as they do not materially interfere with the hydrophilic and/ or lipophilic nature of groups.
- the compounds of the instant invention should preferably contain not more than 25 carbon atoms associated with R and X (when X represents
- organo-methylene diphosphonic acids the salts of organo-methylene diphosphonic acids, and the esters of organo-methylene diphosphonic acids.
- the compounds of the invention can be prepared by various methods with the following methods presented as being representative of their preparation.
- the ester of the organo-methylene diphosphonic acids can be prepared by first forming a metallo-derivative of a methylene diphosphonate ester and reacting this metallo-ester derivative with an organo-halide to produce the desired organo-methylene diphosphonate ester.
- metallo-derivatives of the tetra-ester methylene diphosphonate can be prepared in several ways.
- Group IA (alkali metals) ester derivatives and particularly the sodioand potassio-ester derivatives it is usually only necessary to react the alkali metal directly with the ester. The reaction is often exothermic so that, in most cases, it may be necessary to bring the reactants together while cooling, to dilute the mixture with an inert solvent such as xylene, benzene, toluene, ether, dioxane, hexane and the like, or to add the sodium or potassium slowly to the esters in the inert solvent.
- an inert solvent such as xylene, benzene, toluene, ether, dioxane, hexane and the like, or to add the sodium or potassium slowly to the esters in the inert solvent.
- Group I-B metal derivatives and in particular the silver-ester derivative and cuprous-ester derivative; the Group IIB metal derivatives, and in particular the zinc-ester derivative; and Group IV-A metal derivatives, and in particular the leadand tin-ester derivatives by methods which are similar to the foregoing methods. Because of the relative inexpensiveness and the ready availability of sodium and potassium and because of their rather straight forward reaction with the ester it is generally advantageous to form the sodioand potassio-ester derivatives and therefore, sodium and potassium are the preferred metals for use in forming these ester derivatives.
- reaction (2) the reaction of the metallo ester derivatives with an organo halide, i.e., reaction (2), is relatively straight forward. Often times, however, it may be necessary to use temperatures above room temperature, i.e., about 25 C., in order to facilitate the reaction with temperatures of between about 70 C. to about 180 C. usually being sufiicient. In most cases, depending on the temperature used, a definite precipitate forms, i.e., metalhalide, after a period of time of between about 10 minutes and about 4 hours.
- the precipitate may be removed by several Well known methods, such as, filtration, contrifugation and decantation, or by dissolution with water and phase separation, and, if desired, the filtrate can thereafter be distilled to improve the purity of the organomethylene diphosphonate ester.
- organo halides containing substituent groups such as, hydroxyl, carboxylic acid, and halides
- substituent groups such as, hydroxyl, carboxylic acid, and halides
- carboxylic acid groups can be protected by the well-known method of esterification prior to the reaction and hydrolysis of the ester subsequent to the reaction.
- hydroxyl group can usually be protected by the well known method of ether formation using such materials as dihydropyrane, benzyl chloride, tritychloride and the like to form the ethers followed by removal of the protective groups by such methods as hydrolysis with dilute mineral acids, catalytic hydrogenation, or chemical reduction.
- the halide group of polyhalide compounds can usually be protected by conversion into an ether group, a common reactant being sodium alkoxide, and the ether group subsequently cleaved with a hydrogen halide to remove the protective ether groups.
- the organo-methylene diphosphonic acid can be prepared by the hydrolysis of the corresponding esters with a concentrated mineral acid. Generally, by refluxing the ester and a concentrated mineral acid, such as, HCl or HBr, at reflux temperatures for a period of usually about five hours is all that is necessary for the hydrolysis.
- a concentrated mineral acid such as, HCl or HBr
- the salts of the organo-methylene diphosphonic acids can be prepared by neutralization of the acids with a stoichiometric amount of a base or a salt of a volatile acid that contains essentially the desired cation.
- Bases or salts of volatile acids such as those containing an alkali metal, ammonia and amines are especially suited.
- one of organo-methylene diphosphonic acids can be neutralized with a stoichiometric amount of a base containing the sodium cation, such as NaOH, Na CO and the like.
- organo-methylene diphosphonic acid titrates using a pH meter as a tribasic acid can be prepared by neutralization of the acids with a stoichiometric amount of a base and evaporating to dryness.
- the acids are titrated using a pH meter in the presence of a 10% NaCl solution they will titrate as tetra-basic acids.
- EXAMPLE 1 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 65 C. After all of the potassium is used up about 179 grams of n-hcptyl bromide is added dropwise to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated between about C. and C. for about 10 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester as a colorless liquid. Analysis of the P N.M.R.
- EXAMPLE 2 The ester prepared according to Example 1 is hydrolyzed to the acid by refluxing about 386 grams with about 600 ml. concentrated HCl for about 5 hours. Evaporation to dryness yields the acid, octylidene diphosphonic acid, C H CH[PO(OH) The equivalent weight of this product, by titration, is found to be about 98.0 which compares favorable with the calculated value of about 91.3. Elemental analysis yields the following results.
- Trisodium octylidene diphosphonate C H CH[PO(ONa) [PO(ONa) (OH) is prepared by dissolving about 274 grams of free acid obtained as in Example 2 in about 1.2 liters of 10% NaOH solution and evaporating the aqueous solution to dryness at about 140 C. with the anhydrous form of the salt being formed.
- EXAMPLE 4 Into a suitable reaction vessel about 39.1 grams potassiummetal is added slowly to about 288 grams tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 65 C. After all of the potassium is used up about 247 grams of n-dodecylbromide is added dropwise to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated at about 120 C. for about 4 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester as a colorless liquid. Analysis of the P N.M.R. spectra of the ester indicated tetraethyl tridecylidene diphosphonate,
- Tetraethyl tridecylidene diphosphonate is hydrolyzed to the acid by refluxing about 454 grams with about 600 ml. of concentrated HCl for about 2 to 3 hours. Evaporation to dryness yields the acid, tridecylidene diphosphonic acid, C H CH[PO(OH) which is analyzed with the following results.
- Example 5 is prepared by dissolving about 334 grams of the free acid obtained as in Example 5 in about 1% liters of *NH OH solution and evaporating the aqueous solution to dryness at about 120 C. with the anhydrous form of the salt being formed.
- EXAMPLE 7 Into a suitable reaction vessel about 102 grams of 3- c-hloro-3-methyl pentane is added slowly to a potassiobutyl ester derivative reaction mixture prepared as in Example 1. To ensure a satisfactory degree reaction the mixture is heated at about 120 C. for about 6 hours. After filtering the potassium chloride, the reaction product is purified by distillation yielding tetrabutyl fi-diethyl- ,B-methylethylidene diphosphonate,
- Example 2 is prepared by dissolving about 322 grams of the free acid (cyclohexyl methylene diphosphonic acid), prepared generally by procedures used in Example 2, in about 1 liter of 11.5% NaOH solution and evaporating the aqueous solution to dryness at about 120 C. with the anhydrous form of the salt being formed.
- the free acid cyclohexyl methylene diphosphonic acid
- EXAMPLE 9 Tetraethyl benzyl methylene diphosphonate C6H4CH[P(O)-(OC2H5)2]2 prepared generally by the procedures used in Example 1, is hydrolyzed to the acid by refluxing about 347 grams of the ester with about 800 ml. of concentrated HCl for about 4 hours. Evaporation to dryness yields the acid, benzyl methylene diphosphonic acid,
- EXAMPLE l0 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 479 grams tetraphenyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C. After all of the potassium is used up about 233 grams of 2-bromobipheny1 is added slowly 6 to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated at about C. for about 8 hours. After filtering the potassium bromide, the reaction product is distilled yielding the ester, tetraphenyl biphenyl methylene diphosphonate,
- EXAMPLE l1 Tetraethyl dodecylbenzyl methylene diphosphonate, (C H )C H CH[PO(OC H h, prepared generally by procedures used in Example 1, is hydrolyzed to the acid by reuflxing about 425 grams of the ester with about 800 ml. of concentrated HCl for about 4 hours.
- EXAMPLE l4 Into a suit-able reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams of tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C. After all of the potassium is used up about grams of ot-chloropyrrole is added slowly to the reaction mixture. To ensure a satisfactory degree reaction the mixture is heated at about C. to about C. for about 6 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester, tetraethyl pyrryl-l-methylene diphosphonate,
- esters which can be reacted with metallic sources to form the metallo-ester derivatives, such as the potassio-ester derivatives, according to the procedures as illustrated by the foregoing examples include the following esters: tetramethyl methylene diphosphonate, tetra-n-hexyl methylene diphosphonate, tetera-iso-propyl methylene diphosphonate, tetradodecyl methylene diphosphonate, tetrahexadecyl methylene diphosphonate, tetra-toluyl methylene diphosphonate, tetra-xylyl methylene diphosphonate, and the like, as well as mixed esters, such as, diethyl-dibutyl methylene diphosphonate, diethyl-di-n-hexyl methylene diphosphonate, dimethyl-diethyl methylene diphosphonate and the like
- Alicyclic halide compounds include cyclopentyl bromide, cyclohexyl chloride, cycloheptanyl chloride, cycloheptanyl bromide, cyclopentadiene dibromide, cyclohexane carboxylic acid chloride, l-chloro-l-methyl cyclohexane, 3-bromo-cyclohexene, 3-chloro-cyclohexene, 2'- chloro-cyclopentadiene, 2-bromo-cycloheptanone, l-2-dibromo cycloheptane, 1-bromo-4-tert-butyl-cyclohexane, 1 chloro 1 methyl cyclohexane, 1-2-dibromo-cycloheptane, l-chloro-3-methyl cyclohexane, and the like.
- Aryl halide compounds include the mono-cyclic arylhalide compounds, such as, chlorobenzene, 2-ch1oroaniline, 2-amin0-4, 6'dichloro phenol bromobenzene, 4- bromo aniline and the like, as well as the polycyclic aryl halide compounds, such as, 3-chloro-biphenyl, 4-amino- 4'-chloro biphenyl, 2-chloro-1-napthal, 2-chloro-anthraquinone, l-chloro-napthalene, l-bromo'napthalene, 2- bromo biphenyl, and the like.
- Alkaryl halide compounds include benzyl chloride, B-phenyl ethyl chloride, 4-methyl benzyl chloride, 3- methyl benzyl chloride, Z-methyl benzyl chloride, 2- chlorobenzyl chloride, 4-chlorobenzyl chloride, 3-chlorobenzyl chloride, 4-isopropyl benzyl chloride, m-xylene dichloride, wchloro acetophenone, benzyl chloroformate, benzyl bromide, fl-phenyl ethyl bromide, 2-bromo benzyl bromide, 3-nitro benzyl bromide and the like.
- Aralkyl halide compounds include 2-chlorotoluene, 3- chlorotoluene, 4-chlorotoluene, l-chloro-Z-ethyl benzene, 2-chloro-2-vinyl benzene, l-chloro-Z-isopropyl benzene, 2- chloro-4-isopropyl-l-methyl benzene, p-chloro benzoic, acid, 2-chloro-4-octyl phenol, 2-chloro-4-nonyl phenol, 2- chloro-4-dodecyl phenol, 2-benzyl-4-chlorophenol, 2- bromotoluene, l-bromo-4-ethyl benzene, 4-bro-moacetanilide, 4-bromo-acetophenone, phenaryl bromide, 4-bromobenzoic acid and the like.
- bases or salts of volatile acids which can be reacted with the free acids to produce salt compounds of the instant invention according to the procedures as illutrated by the foregoing examples include the inorganic alkali metal and ammonium salts, oxides and hydroxides,
- organo-methylene diphosphonic acids or the salts thereof were found to exhibit not only good deflocculating or dispersing properties and sequestration properties but also good surfactancy properties. It is highly unusual for all of these properties to be effectively exhibited by the same compound.
- such compounds can advantageously be utilized in applications which can use the foregoing properties, such as, detergent compositions.
- detergent applications such as textile cleaning including synthetic textiles and hard surface cleaning
- the higher alkylidene diphosphonic acids or the salts thereof are preferred in applications which use the combined surfactancy, sequestration and defiocculating properties. These compounds are of the following formula:
- R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from 5 to 20 carbon atoms (preferably 7 to 20 carbon atoms) and Z is a cation selected from the group consisting of hydrogen, alkali metal ions, ammonium ions, and amine ions.
- the compounds of the instant invention are preferably formulated with other compounds which may include other surface active compounds (actives) as well as builders such as sodium tripolyphosphate and tetrapotassium pyrophosphate, antiredeposition agents such as carboxymethyl cellulose and the like, brightening agents, perfumes and the like, in amounts between about 5% to 50% by weight of the detergent composition.
- actives surface active compounds
- builders such as sodium tripolyphosphate and tetrapotassium pyrophosphate
- antiredeposition agents such as carboxymethyl cellulose and the like
- brightening agents perfumes and the like
- builders which can be used with the compounds of the instant invention are organic builder materials which include amino polycarboxylic acids, the amino tri(lower alkylidenephosphonic) acids, the alkylene diphosphonic acids, the water soluble salts of the foregoing acids and mixtures thereof.
- Amino polycarboxylic acids are presented by the general structure GHzCOOH N-CHzCOOH where R is a member selected from the group consisting of the radicals CCOOH Rr R2 o-oo0H wherein R is a member selected from the group consistmg of hydrogen, lower alkyl (l4 carbon atoms), hydroxy substituted lower alkyl, phenyl and hydroxy substituted phenyl, and R is a member selected from the group consisting of hydrogen, lower alkyl (1-4 carbon atoms), and hydroxy substituted lower alkyl.
- amino polycarboxylic acids include nitrilo triacetic acid, ethylenediamine tetraacetic acid, diethylenetriamine penta-acetic acid, 1:2:diaminocyclohexane tetra-acetic acid, hydroxyethyl amino diacetic acid, hydroxyethyl ethylene diamine triacetic acid, orthohydroxyl phenyl ethylene diamine triacetic acid, anthanilic-N-N-diacetic acid, tris(hydroxymethyl) diethylene triamine diacetic acid, c-dibutyl-nitrilo triacetic acid and c-cyclohexenyl-nitrilo triacetic acid.
- Amino tri(lower alkylidene phosphonic acids) are represented by the general structure where X and Y are members selected from the group consisting of hydrogen and lower alkyl groups (1-4 carbon atoms).
- amino tri(lower alkylidenephosphonic) acids include amino tri(methylenephosphonic) acids amino tri(ethylidenephosphonic acid), amino tri (isopropylidenephosphonic acid), amino tri (butylidenephosphonic acid), amino tri(propylidenephosphonic acid), amino tri(tert-amylidenephosphonic acid), amino tri(isoamylidenephosphonic acid) and amino tri sec-butylidenephosphonic acid)
- Alkylene phosphonic acids are represented by the general structure HO E X (])/0 i HO Y 11 OH where X is a member selected from the group consisting of hydrogen and lower alkyl group (l-4 carbon atoms), Y is either hydrogen, hydroxyl, a halogen, especially chlorine, bromine and fluorine, or lower alkyl group (1-4 carbon atoms), and rt is an integer from 1 to 6.
- alkylene diphosphonic acids include methylenediphosphonic acid; ethylidenediphosphonic acid; 1 hydroxyl, ethylidenediphosphonic acid; hexamethylenediphosphonic acid; isopropylidenediphosphonic acid, butylidenediphosphonic acid; hydroxylmethylenediphosphonic acid; 1 hydroxyl, propylenediphosphonic acid; amylidenediphosphonic acid; pentamethylenediphosphonic acid; penta(propylidene)diphosphonic acid; tetra(l-hydroxyethylidene)diphosphonic acid.
- sodium salts of the amino tri(lower alkylidenephosphonic acids), alkylenediphosphonic acids, and aminopolycarboxylic acids are preferred, other water soluble salts such as potassium, lithium, and the like, as well as mixtures of the alkali metal salts may be substituted therefor.
- ammonium salts, as well as amine salts may be used to practice this invention.
- Compounds illustrative of these salts include monopotassium nitrilotriacetate; pentasodium diethylenetriamine pentaacetate; diammonium ethylenediaminetetraacetate; dimethylamino diethylenetriaminetetra-acetate; trilithium nitrilotriacetate; disodium diethylenetriamine penta-acetate; tripotassium ethylenediaminetetra-acetate; diethylamino nitrilotriacetate; pentapotassium diethylenetriamine penta-acetate; monosodium nitrilotriacetate; tetrasodium ethylenediaminetetra-acetate; disodium amino tri(methylphosphonate); dipotassium amino tri(methylphosphonate); diammonium amino tri(methylphosphonate); pentasodium amino tri(methylphosphonate); dilithium amino tri(ethylidenephosphonate); diammonium amino
- builders which can be used with the compounds of the instant invention are inorganic builder materials, usually comprised of inorganic phosphates, carbonates, sulfates, silicates or combinations thereof, and, in particular, the alkali metal salts of the foregoing materials.
- the alkali metal salts are preferably the potassium and sodium salts, although ammonium salts may be employed, particularly in combination with the potassium or sodium salts.
- the phosphate compounds are preferably the chain polyphosphates. Such polyphosphates contain more than 1 phosphorus atom per molecule, as distinguished from orthophosphates which contain only one phosphorus atom per molecule.
- Chain polyphosphates are non-cyclic (and usually linear) phosphates, as distinguished from ring or cyclic phosphates such as trimetaphosphates and tetrametaphosphates. Examples of the more common chain polyphosphates are tetrapotassium. pyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, potassium hexametaphosphate and sodium hexametaphosphate.
- Another builder material which is preferably utilized along with the chain polyphosphates are the water-soluble sodium and potassium silicates.
- dium silicates can vary quite widely in composition, ranging from tetra and disilicates having a mole ratio of Na O:SiO of 1:4 and 1:2, respectively, to the more alkaline silicates, such as the orthosilicate having a mole ratio of Na O:SiO of 2:1.
- silicate compound for use according to the present invention However, other silicates, or mixtures of silicates, having an overall mole ratio of Na O:SiO between about 1:1 and 1:4 can be used.
- the carbonates and sulfates are preferably the sodium and potassium carbonates and sulfates.
- At least about 5 percent of the builder material by weight of the total composition can be used and usually not over about 90 percent with the preferred range being between about 30 and about percent by weight.
- minor amounts, usually less than about 2 percent by weight of the total composition of additives, such as dyes, perfumes, anti-redeposition agents (sodium carboxymethyl cellulose) and the like can be incorporated into the composition.
- the detergent compositions of this invention may comprise an organo-methylene diphosphonic acid or salt thereof and the above-described builder materials and other additives, the compositions may also contain relatively minor amounts, usually less than 15% by weight, preferably 1 to 10% by weight, on a solids basis, of other organic surface active agents such as foaming agents, emulsifiers, detergent surfactants or the like.
- organic surface active agents include anionic surfactants such as sulfated and sulfonated alkyl, aryl, and alkyl aryl hydrocarbons and alkali metal salts thereof, for example, sodium salts of long chain alkyl sulfates, sodium salts of alkyl naphthalene sulfonic acids, sodium salts of sulfonated abietenes, sodium salts of alkyl benzene sulfonic acids particularly those in which the alkyl group contains from 8-24 carbon atoms; sodium salts of sulfonated mineral oils and sodium salts of sulfosuccinic acid esters such as sodium dioctyl sulfos uccinate.
- anionic surfactants such as sulfated and sulfonated alkyl, aryl, and alkyl aryl hydrocarbons and alkali metal salts thereof, for example, sodium salts of long chain alkyl sulfates, sodium salt
- Advantageous anionic surfactants include the higher alkyl aryl sulfonic acids and their alkali metal and alkaline earth metal salts such as for example sodium dodecyl benzene sulfonate, sodium tridecyl benzene sulfonate, magnesium dodecyl benzene sulfonate, potassium tetradecyl benzene sulfonate, ammonium dodecyl toluene sulfonate, lithium pentadecyl benzene sulfonate, sodium dioctyl benzene sulfonate, disodium dodecyl benzene disulfonate, disodium di-isopropyl naphthalene disulfonate and the like as Well as the alkali metal salts of fatty alcohol esters of sulfuric and sulfonic acids, the alkali metal salts of alkyl aryl (sulf
- Preferred anionic organic surface active agents are, as noted hereinbefore, sodium salts of alkyl benzene sulfonic acids and particularly preferred sodium salts of alkyl benzene sulfonic acids are those in which the alkyl group or radical contains to 18 carbon atoms in a straight (i.e. unbranched) chain.
- nonionic surfactants include products formed by condensing one or more alkylene oxides of 2 to 4 carbon atoms, such as ethylene oxide or propylene oxide, preferably ethylene oxide alone or with other alkylene oxides, with a relatively hydrophobic compound such as a fatty alcohol, fatty acid, sterol, a fatty glyceride, a fatty amine, an aryl amine, a fatty mercapian, tall oil, etc.
- alkylene oxides of 2 to 4 carbon atoms such as ethylene oxide or propylene oxide, preferably ethylene oxide alone or with other alkylene oxides
- a relatively hydrophobic compound such as a fatty alcohol, fatty acid, sterol, a fatty glyceride, a fatty amine, an aryl amine, a fatty mercapian, tall oil, etc.
- Nonionic surface active agents also include those products produced by condensing one or more relatively lower alkyl alcohol amines (such as methanolamine, ethanolamine, propanolamine, etc.) with a fatty acid such as lauric acid, cetyl acid, tall oil fatty acid, abietic acid, etc. to produce the corresponding amide.
- relatively lower alkyl alcohol amines such as methanolamine, ethanolamine, propanolamine, etc.
- a fatty acid such as lauric acid, cetyl acid, tall oil fatty acid, abietic acid, etc.
- Particularly advantageous nonionic surface active agents are condensation products of a hydrophobic compound having at least 1 active hydrogen atom and a lower alkylene oxide (for example the condensation product of an aliphatic alcohol containing from about 8 to about 18 carbon atoms) and from about 3 to about mols of ethylene oxide per mol of the alcohol, or the condensation product of an alkyl phenol containing from about 8 to about 18 carbon atoms in the alkyl group and from about 3 to about 30 mols of ethylene oxide per mol of alkyl phenol.
- Other advantageous nonionic detergents include condensation products of ethylene oxide with a hydrophobic compound formed by condensing propylene oxide with propylene glycol.
- the detergent composition of the present invention is not to be limited to any particular method of mixing the ingredients used in the compositions.
- the organo-methylene diphosphonic acids or salts may be mechanically mixed in, crutched in the detergent composition in the form of a slurry, or dissolved in a solution of the detergent composition.
- the organo-methylene diphosphonic acids or salts may be admixed with other ingredients in any of the forms in which the detergent composition is manufactured in, as well as being added simultaneously or separately to an aqueous solution.
- the organo-methylene diphosphonic acids or salts are intended to be used with the other ingredients at the time of application as a cleansing agent.
- esters of organo-methylene diphosphonic acids were found not only to be substantially miscible with water but also highly soluble in organic solvents, such as hydrocarbon solvent, i.e. hexane and pentane, carbon tetra chloride, haloethylene solvents (perchloroethylene), ethers, alcohols, and the like.
- organic solvents such as hydrocarbon solvent, i.e. hexane and pentane, carbon tetra chloride, haloethylene solvents (perchloroethylene), ethers, alcohols, and the like.
- the esters were found to impart a solubilizing action to water in water-immiscible solvents, such as many of the previously mentioned solvents. This totally unexpected property renders them high- 1y useful as gasoline de-icer additives and along with their surfactancy properties renders them useful as dry cleaning detergents.
- the unique ability to impart a solubilizing action to Water in waterimmiscible solvents can be utilized in many
- esters of higher alkylidene diphosphonic acids are preferred in applications which use the combined surfactancy and/or water solubilizing properties. These compounds are of the following formula:
- R is selected from the class consisting of satu rated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from 5 to 20 carbon atoms (preferably 7 to 20 carbon atoms) and R R R and R are selected from the class consisting of alkyl groups of from 1 to 20 carbon atoms, aryl hydrocarbyl groups and alkaryl groups with the lower alkyl groups being especially preferred.
- ester compounds of the instant invention can be used as either the primary surfactant or in conjunction with other surfactants.
- the primary surfactant When used as substantially the primary surfactant with many of the common organic solvents, such as, Stoddards solvent (petroleum distillate) and perchloroethylene, amounts within the range of .05 to 10% by weight are usually sufficient with amounts of from about 1% to about 2% by weight being preferred.
- a detergent composition consisting essentially of an amount of at least about 5% by weight of said composition of an organo-methylene diphosphonic compound having the formula wherein R is selected from the class consisting of (a) aliphatic hydrocarbyl groups containing from 7 to 30 carbon atoms, (b) alicyclic hydrocarbyl groups containing from 5 to 7 carbon atoms, (c) aryl groups selected from the group consisting of monocyclic, dicyclic, or tricyclic hydrocarbon groups containing from 6 to 18 carbon atoms, (d) amino-substituted aryl groups wherein the aryl portion is the same as that defined in item (c), (e) alkaryl groups wherein the aryl portion of said group is the same as that defined in item (c) and the alkyl portion of said group contains from 1 to 12 carbon atoms, and (f) all of the groups defined in items (a), (b), (c), (d) and (e) containing a halogen substituent, and X is selected from
- a detergent composition according to claim 2, wherein said compound is a sodium salt of tridecylidene diphosphonate.
- a detergent composition according to claim 2, wherein said compound is a sodium salt of octylidene diphosphonate.
- a dry cleaning composition consisting essentially of an amount of at least about 0.05% by weight ofvsaid composition of an ester of an organo-methylene diphosphonic acid, said ester having the formula t I X H 0X wherein R is selected from the class consisting of (a) aliphatic hydrocarbyl groups containing from 7 to 30 carbon atoms, (b) alicyclic hydrocarbyl groups containing from to 7 carbon atoms, (c) aryl groups selected from the group consisting of monocyclic, dicyclic, or tricyclic hydrocarbon groups containing from 6 to 18 carbon atoms, (d) amino-substituted aryl groups wherein the aryl portion is the same as that defined in item (c), (e) alkaryl groups wherein the alkyl portion of said group is the same as that defined in item (c) and the alkyl portion of said group contains from 1 to 12 carbon atoms, and (f) all of the groups defined in items (a), (b), (c),
- X is selected from the class consisting of (a) aliphatic hydrocarbyl groups containing from 7 to 30 carbon atoms, (b) aryl groups selected from the group consisting of monocyclic, dicyclic or tricyclic hydrocarbon groups containing from 6 to 18 carbons atoms, (c) alkaryl groups wherein the aryl portion of said group is the same as that defined in item (b) and the alkyl portion of said group contains from 1 to 12 carbon atoms, and an elfective amount of a dry cleaning organic solvent.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
Description
nited States Patent Ofice 3,518,200 Patented June 30, 1970 12 Claims ABSTRACT OF THE DISCLOSURE A detergent composition is described containing an organo-methylene diphosphonic compound having the formula wherein R is selected from the class consisting of aliphatic hydrocarbyl, alicyclic, aryl, alkaryl, and aralkyl groups of from 5 to carbon atoms and X is selected from the class consisting of hydrogen ions, alkali metal ions, ammonium ions and amine ions; as well as a dry cleaning composition containing an ester of an organo-methylene diphosphonic acid having the formula X0 H- OX wherein R is selected from the class consisting of aliphatic hydrocarbyl, alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is selected from the class consisting of aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atoms.
This application is a continuation-in-part of application Ser. No. 271,607, filed Apr. 9,1963, now US. Pat. No. 3,299,123.
This invention relates to organic compounds of phosphorus, compositions containing said compounds, and uses thereof.
An object of this invention is to provide new and useful organic compounds of phosphorus containing a group in their molecules.
A further object of this invention is to provide new and useful organic compounds of phosphorus containing a group in their molecules with the group being a hydrophobic and/or lipophilic group.
A further object of this invention is to provide new and useful organophosphonic acids, as well as their salts and esters.
A more specific object of this invention is to provide new and useful organo-methylene diphosphonic acids or the salts thereof which exhibit, among other things, combined surfactancy sequestering and defiocculating properties.
A more specific object of this invention is to provide new and useful organo-methylene diphosphonate esters which exhibit, among other things, the unique ability of solubilizing water in water immiscible solvents.
Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonic acids or the salts thereof.
Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonic acids or the salts thereof which are suitable for use in aqueous systems.
Another object of this invention is to provide detergent compositions containing organo-methylene diphosphonate esters.
A still further object of this invention is to provide detergent compositions containing organo-methylene diphosphonate esters which are suitable for use as drycleaning detergents in organic solvents.
Other objects of this invention will appear from the description hereinafter.
This invention is directed to new and useful organomethylene diphosphonic acid compounds, as well as the salts and esters thereof, said compounds having the general formula Xo\( R (fit/0X P P Xo 1'1 OX wherein: R is selected from the class consisting of aliphatic hydrocarbyl, alicyclic, aryl, alkaryl, aralkyl groups of from 5 to 30 carbon atoms and X is selected from the class consisting of cations selected from the group of hydrogen ions, alkali metal ions, ammonium ions and amine ions, and aliphatic hydrocarbyl, aryl, alkaryl and aralkyl groups of from 1 to 30 carbon atoms. Preferably, the aliphatic hydrocarbyl group represented by R contains from 7 to 30 carbon atoms. when the symbols R and X represent groups containing carbon chains, such as aliphatic hydrocarbyl groups, or groups containing alkyl moieties, i.e., aralkyl groups, such carbon chains may be of a straight chain structure or branched chain structure. For the symbols R. and X when they represent aliphatic hydrocarbyl groups, such groups may be saturated or unsaturated. The above mentioned groups which are represented by R can also contain substituents, such as, hydroxyl, halides, i.e., fluoride, chloride, bromide and iodide, alkoxyl groups, ester groups, ether groups, nitro groups sulfonyl groups, amide groups, amino groups, carboxyl groups, nitroso groups, and the like as long as they do not materially interfere with the hydrophilic and/ or lipophilic nature of groups. For most end use applications the compounds of the instant invention should preferably contain not more than 25 carbon atoms associated with R and X (when X represents ester groups), and there are few, if any, end uses, in which the foregoing groups contain more than a total of 50 carbon atoms.
These compounds can be characterized quite generally as having a PCP linkage in their molecules and are generically described in this specification by the general terms organo-methylene diphosphonic acids, the salts of organo-methylene diphosphonic acids, and the esters of organo-methylene diphosphonic acids.
The compounds of the invention can be prepared by various methods with the following methods presented as being representative of their preparation.
The ester of the organo-methylene diphosphonic acids can be prepared by first forming a metallo-derivative of a methylene diphosphonate ester and reacting this metallo-ester derivative with an organo-halide to produce the desired organo-methylene diphosphonate ester. The
reaction of the metallo-ester derivative with the organohalide is believed represented by the following equation:
(2) MCH PO (ester) +hal-R- RCH [PO (ester 2 +Mhal wherein R represents the same groups as in the foregoing general Formula 1.
In general, metallo-derivatives of the tetra-ester methylene diphosphonate can be prepared in several ways. When preparing the Group IA (alkali metals) ester derivatives and particularly the sodioand potassio-ester derivatives it is usually only necessary to react the alkali metal directly with the ester. The reaction is often exothermic so that, in most cases, it may be necessary to bring the reactants together while cooling, to dilute the mixture with an inert solvent such as xylene, benzene, toluene, ether, dioxane, hexane and the like, or to add the sodium or potassium slowly to the esters in the inert solvent. In some cases it may be necesary to employ all of the immediately foregoing procedures. It is usually advantageous to heat the reaction mixture for the last few minutes of the reaction, however, in order to facilitate the reaction. The Group IIA (alkaline earth metals) and in particular the calcium and magnesium metals can, in most cases, be reacted with the tetra-ester of the methylene diphosphonate in the presence of pyridine with the higher esters requiring in most cases moderate heating for completion of the reaction. In some cases, it is also possible to prepare the Group I-B metal derivatives, and in particular the silver-ester derivative and cuprous-ester derivative; the Group IIB metal derivatives, and in particular the zinc-ester derivative; and Group IV-A metal derivatives, and in particular the leadand tin-ester derivatives by methods which are similar to the foregoing methods. Because of the relative inexpensiveness and the ready availability of sodium and potassium and because of their rather straight forward reaction with the ester it is generally advantageous to form the sodioand potassio-ester derivatives and therefore, sodium and potassium are the preferred metals for use in forming these ester derivatives.
In general, the reaction of the metallo ester derivatives with an organo halide, i.e., reaction (2), is relatively straight forward. Often times, however, it may be necessary to use temperatures above room temperature, i.e., about 25 C., in order to facilitate the reaction with temperatures of between about 70 C. to about 180 C. usually being sufiicient. In most cases, depending on the temperature used, a definite precipitate forms, i.e., metalhalide, after a period of time of between about 10 minutes and about 4 hours. The precipitate may be removed by several Well known methods, such as, filtration, contrifugation and decantation, or by dissolution with water and phase separation, and, if desired, the filtrate can thereafter be distilled to improve the purity of the organomethylene diphosphonate ester.
It may be necessary, however, when using organo halides containing substituent groups, such as, hydroxyl, carboxylic acid, and halides, to protect these groups during the reaction. Usually the carboxylic acid groups can be protected by the well-known method of esterification prior to the reaction and hydrolysis of the ester subsequent to the reaction. Also the hydroxyl group can usually be protected by the well known method of ether formation using such materials as dihydropyrane, benzyl chloride, tritychloride and the like to form the ethers followed by removal of the protective groups by such methods as hydrolysis with dilute mineral acids, catalytic hydrogenation, or chemical reduction. In addition, by using well-known methods the halide group of polyhalide compounds can usually be protected by conversion into an ether group, a common reactant being sodium alkoxide, and the ether group subsequently cleaved with a hydrogen halide to remove the protective ether groups.
The organo-methylene diphosphonic acid can be prepared by the hydrolysis of the corresponding esters with a concentrated mineral acid. Generally, by refluxing the ester and a concentrated mineral acid, such as, HCl or HBr, at reflux temperatures for a period of usually about five hours is all that is necessary for the hydrolysis.
The salts of the organo-methylene diphosphonic acids can be prepared by neutralization of the acids with a stoichiometric amount of a base or a salt of a volatile acid that contains essentially the desired cation. Bases or salts of volatile acids such as those containing an alkali metal, ammonia and amines are especially suited. For example, to make a sodium salt, one of organo-methylene diphosphonic acids can be neutralized with a stoichiometric amount of a base containing the sodium cation, such as NaOH, Na CO and the like. It should be noted that organo-methylene diphosphonic acid titrates using a pH meter as a tribasic acid, however, the tetra salts can be prepared by neutralization of the acids with a stoichiometric amount of a base and evaporating to dryness. In addition, it has been found if the acids are titrated using a pH meter in the presence of a 10% NaCl solution they will titrate as tetra-basic acids.
The following examples are presented to illustrate the invention, with parts by weight being used in the examples unless otherwise indicated.
EXAMPLE 1 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 65 C. After all of the potassium is used up about 179 grams of n-hcptyl bromide is added dropwise to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated between about C. and C. for about 10 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester as a colorless liquid. Analysis of the P N.M.R. spectra of the ester indicates tetraethyl octylidene diphosphonate, C'1H15CH[PO(OC2H5)2]2 with a small amount of impurity 5%) of tetraethyl methylene diphosphonate. Elemental analysis yields the following results.
Calculated (percent): C, 49.80; H, 9.39. Found (percent): C, 46.82; H, 9.51.
EXAMPLE 2 The ester prepared according to Example 1 is hydrolyzed to the acid by refluxing about 386 grams with about 600 ml. concentrated HCl for about 5 hours. Evaporation to dryness yields the acid, octylidene diphosphonic acid, C H CH[PO(OH) The equivalent weight of this product, by titration, is found to be about 98.0 which compares favorable with the calculated value of about 91.3. Elemental analysis yields the following results.
Calculated (percent): C, 35.00; H, 7.29. Found (percent): C, 33.l7; H, 6.89.
EXAMPLE 3 Trisodium octylidene diphosphonate C H CH[PO(ONa) [PO(ONa) (OH) is prepared by dissolving about 274 grams of free acid obtained as in Example 2 in about 1.2 liters of 10% NaOH solution and evaporating the aqueous solution to dryness at about 140 C. with the anhydrous form of the salt being formed.
EXAMPLE 4 Into a suitable reaction vessel about 39.1 grams potassiummetal is added slowly to about 288 grams tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 65 C. After all of the potassium is used up about 247 grams of n-dodecylbromide is added dropwise to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated at about 120 C. for about 4 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester as a colorless liquid. Analysis of the P N.M.R. spectra of the ester indicated tetraethyl tridecylidene diphosphonate,
Elemental analysis of this product yields the following results.
Calculated (percent): C, 55.3; H, 10.2; P, 13.6. Found (percent): C, 54.28; H, 10.58; P, 12.97.
EXAMPLE 5 Tetraethyl tridecylidene diphosphonate is hydrolyzed to the acid by refluxing about 454 grams with about 600 ml. of concentrated HCl for about 2 to 3 hours. Evaporation to dryness yields the acid, tridecylidene diphosphonic acid, C H CH[PO(OH) which is analyzed with the following results.
Calculated (percent): C, 43.4; H, 8.78; P, 17.99. Found (percent): C, 44.86; H, 8.71; P, 17.90.
EXAMPLE 6 Tri-ammonium tridecylidene diphosphonate,
is prepared by dissolving about 334 grams of the free acid obtained as in Example 5 in about 1% liters of *NH OH solution and evaporating the aqueous solution to dryness at about 120 C. with the anhydrous form of the salt being formed.
EXAMPLE 7 Into a suitable reaction vessel about 102 grams of 3- c-hloro-3-methyl pentane is added slowly to a potassiobutyl ester derivative reaction mixture prepared as in Example 1. To ensure a satisfactory degree reaction the mixture is heated at about 120 C. for about 6 hours. After filtering the potassium chloride, the reaction product is purified by distillation yielding tetrabutyl fi-diethyl- ,B-methylethylidene diphosphonate,
7 EXAMPLE 8 Disodium cyclohexyl methylene diphosphonate,
is prepared by dissolving about 322 grams of the free acid (cyclohexyl methylene diphosphonic acid), prepared generally by procedures used in Example 2, in about 1 liter of 11.5% NaOH solution and evaporating the aqueous solution to dryness at about 120 C. with the anhydrous form of the salt being formed.
EXAMPLE 9 Tetraethyl benzyl methylene diphosphonate C6H4CH[P(O)-(OC2H5)2]2 prepared generally by the procedures used in Example 1, is hydrolyzed to the acid by refluxing about 347 grams of the ester with about 800 ml. of concentrated HCl for about 4 hours. Evaporation to dryness yields the acid, benzyl methylene diphosphonic acid,
EXAMPLE l0 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 479 grams tetraphenyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C. After all of the potassium is used up about 233 grams of 2-bromobipheny1 is added slowly 6 to the reaction mixture. To ensure a satisfactory degree of reaction the mixture is heated at about C. for about 8 hours. After filtering the potassium bromide, the reaction product is distilled yielding the ester, tetraphenyl biphenyl methylene diphosphonate,
EXAMPLE l1 Tetraethyl dodecylbenzyl methylene diphosphonate, (C H )C H CH[PO(OC H h, prepared generally by procedures used in Example 1, is hydrolyzed to the acid by reuflxing about 425 grams of the ester with about 800 ml. of concentrated HCl for about 4 hours. Evaporation to dryness yields the acid, dodecylbenzyl methylene diphosphonic aCid, (C12H25)C6H4CH[PO(OH)2]2- I EXAMPLE 12 Tetraethyl acetophenone methylene diphosphonate CH C(O)C H -CH[PO(OC H prepared generally by procedures used in Example 1, is hydrolyzed to the acid by refluxing about 405 grams of the ester with about 800 ml. of concentrated HCl for about 3 hours. Evaporation to dryness yields the acid, acetophenone methylene diphosphonic acid, CH C (O C H CH [PO (OH) EXAMPLE l3 Into a suitable reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams of tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C. After all of the potassium is used up about 333 grams of octadecylbromide is added slowly to the reaction mixture. To ensure a satisfactory degree reaction the mixture is heated at about 120 C. to 140 C. for about 10 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester, tetraethyl nonadecylidene diphosphonate,
Elemental analysis of the product gives the following result.
Calculated (percent): C, 60.5; H, 11.73. Found (percent): C, 63.07; H, 11.49.
Nuclear magnetic resonance analysis gives a P shift in p.p.m. of -23.9.
EXAMPLE l4 Into a suit-able reaction vessel about 39.1 grams of potassium metal is added slowly to about 288 grams of tetraethyl methylene diphosphonate in about 2.5 liters of xylene. The temperature of the reaction vessel is maintained at about 70 C. After all of the potassium is used up about grams of ot-chloropyrrole is added slowly to the reaction mixture. To ensure a satisfactory degree reaction the mixture is heated at about C. to about C. for about 6 hours. After filtering the potassium bromide the reaction product is distilled yielding the ester, tetraethyl pyrryl-l-methylene diphosphonate,
Other methylene diphosphonate esters which can be reacted with metallic sources to form the metallo-ester derivatives, such as the potassio-ester derivatives, according to the procedures as illustrated by the foregoing examples include the following esters: tetramethyl methylene diphosphonate, tetra-n-hexyl methylene diphosphonate, tetera-iso-propyl methylene diphosphonate, tetradodecyl methylene diphosphonate, tetrahexadecyl methylene diphosphonate, tetra-toluyl methylene diphosphonate, tetra-xylyl methylene diphosphonate, and the like, as well as mixed esters, such as, diethyl-dibutyl methylene diphosphonate, diethyl-di-n-hexyl methylene diphosphonate, dimethyl-diethyl methylene diphosphonate and the like.
Other halide compounds which can be reacted with the metallo-ester derivatives, such as the potassio-ester deriva tives, according to procedures as illustrated by the foregoing example to form compounds of the instant invention include aliphatic hydrocarbyl halide compounds, such as, 3-chloro-2-methyl bntene-l; 3-chloro-2-methyl butene- 2; 2 chloro 2-methyl pentane; 3-chloro-2,2-dimethyl butane; 4-chloro-2,2-dimethyl butane; 3-chloro-2,2,3-tri methyl butane; 3-chlorohexane; n-hexyl chloride; n-undecyl chloride; n-hexadecyl chloride; n-hexyl bromide; n-octyl bromide; n-dodecyl bromide; n-tetradecyl bromide; l-bromo-n-caproic acid; 2-bromo hexanoic acid and the like.
Alicyclic halide compounds include cyclopentyl bromide, cyclohexyl chloride, cycloheptanyl chloride, cycloheptanyl bromide, cyclopentadiene dibromide, cyclohexane carboxylic acid chloride, l-chloro-l-methyl cyclohexane, 3-bromo-cyclohexene, 3-chloro-cyclohexene, 2'- chloro-cyclopentadiene, 2-bromo-cycloheptanone, l-2-dibromo cycloheptane, 1-bromo-4-tert-butyl-cyclohexane, 1 chloro 1 methyl cyclohexane, 1-2-dibromo-cycloheptane, l-chloro-3-methyl cyclohexane, and the like.
Aryl halide compounds include the mono-cyclic arylhalide compounds, such as, chlorobenzene, 2-ch1oroaniline, 2-amin0-4, 6'dichloro phenol bromobenzene, 4- bromo aniline and the like, as well as the polycyclic aryl halide compounds, such as, 3-chloro-biphenyl, 4-amino- 4'-chloro biphenyl, 2-chloro-1-napthal, 2-chloro-anthraquinone, l-chloro-napthalene, l-bromo'napthalene, 2- bromo biphenyl, and the like.
Alkaryl halide compounds include benzyl chloride, B-phenyl ethyl chloride, 4-methyl benzyl chloride, 3- methyl benzyl chloride, Z-methyl benzyl chloride, 2- chlorobenzyl chloride, 4-chlorobenzyl chloride, 3-chlorobenzyl chloride, 4-isopropyl benzyl chloride, m-xylene dichloride, wchloro acetophenone, benzyl chloroformate, benzyl bromide, fl-phenyl ethyl bromide, 2-bromo benzyl bromide, 3-nitro benzyl bromide and the like.
Aralkyl halide compounds include 2-chlorotoluene, 3- chlorotoluene, 4-chlorotoluene, l-chloro-Z-ethyl benzene, 2-chloro-2-vinyl benzene, l-chloro-Z-isopropyl benzene, 2- chloro-4-isopropyl-l-methyl benzene, p-chloro benzoic, acid, 2-chloro-4-octyl phenol, 2-chloro-4-nonyl phenol, 2- chloro-4-dodecyl phenol, 2-benzyl-4-chlorophenol, 2- bromotoluene, l-bromo-4-ethyl benzene, 4-bro-moacetanilide, 4-bromo-acetophenone, phenaryl bromide, 4-bromobenzoic acid and the like.
Other bases or salts of volatile acids which can be reacted with the free acids to produce salt compounds of the instant invention according to the procedures as illutrated by the foregoing examples include the inorganic alkali metal and ammonium salts, oxides and hydroxides,
' such as NaCl, NaNO Na O, Na CO KOH, K 0, KCl,
K CO KNO LiOH, LiCl, LiNO Li CO CsOH, CsCl, CSNOg, (252003, NH4C1, NH4NO3, (].-II'I4)2CD()3, NHOH, and amines, such as, ethyl amine, diethylamine, propyl amine, propylene diamine, diethylene triamine, hexyl amine, Z-ethylhexyl amine and the like.
Quite unexpectedly organo-methylene diphosphonic acids or the salts thereof were found to exhibit not only good deflocculating or dispersing properties and sequestration properties but also good surfactancy properties. It is highly unusual for all of these properties to be effectively exhibited by the same compound. As can be appreciated, such compounds can advantageously be utilized in applications which can use the foregoing properties, such as, detergent compositions. In many detergent applications such as textile cleaning including synthetic textiles and hard surface cleaning, the ability of the detergent composition to remove the soil, keep the soil suspended in the washing medium, as well as, exerting a water softening effect in the washing medium by sequestration of calcium and magnesium ions, is of paramount importance.
The higher alkylidene diphosphonic acids or the salts thereof are preferred in applications which use the combined surfactancy, sequestration and defiocculating properties. These compounds are of the following formula:
wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from 5 to 20 carbon atoms (preferably 7 to 20 carbon atoms) and Z is a cation selected from the group consisting of hydrogen, alkali metal ions, ammonium ions, and amine ions.
As used in detergent compositions, the compounds of the instant invention are preferably formulated with other compounds which may include other surface active compounds (actives) as well as builders such as sodium tripolyphosphate and tetrapotassium pyrophosphate, antiredeposition agents such as carboxymethyl cellulose and the like, brightening agents, perfumes and the like, in amounts between about 5% to 50% by weight of the detergent composition. The resulting detergent composition is generally effective when used in aqueous systems in conventional amounts such as is normally used with detergent compositions and which is generally about 5% concentration or below.
As being illustrative of builders which can be used with the compounds of the instant invention are organic builder materials which include amino polycarboxylic acids, the amino tri(lower alkylidenephosphonic) acids, the alkylene diphosphonic acids, the water soluble salts of the foregoing acids and mixtures thereof.
Amino polycarboxylic acids are presented by the general structure GHzCOOH N-CHzCOOH where R is a member selected from the group consisting of the radicals CCOOH Rr R2 o-oo0H wherein R is a member selected from the group consistmg of hydrogen, lower alkyl (l4 carbon atoms), hydroxy substituted lower alkyl, phenyl and hydroxy substituted phenyl, and R is a member selected from the group consisting of hydrogen, lower alkyl (1-4 carbon atoms), and hydroxy substituted lower alkyl.
Compounds illustrative of the amino polycarboxylic acids include nitrilo triacetic acid, ethylenediamine tetraacetic acid, diethylenetriamine penta-acetic acid, 1:2:diaminocyclohexane tetra-acetic acid, hydroxyethyl amino diacetic acid, hydroxyethyl ethylene diamine triacetic acid, orthohydroxyl phenyl ethylene diamine triacetic acid, anthanilic-N-N-diacetic acid, tris(hydroxymethyl) diethylene triamine diacetic acid, c-dibutyl-nitrilo triacetic acid and c-cyclohexenyl-nitrilo triacetic acid.
Amino tri(lower alkylidene phosphonic acids) are represented by the general structure where X and Y are members selected from the group consisting of hydrogen and lower alkyl groups (1-4 carbon atoms).
Compounds illustrative of amino tri(lower alkylidenephosphonic) acids include amino tri(methylenephosphonic) acids amino tri(ethylidenephosphonic acid), amino tri (isopropylidenephosphonic acid), amino tri (butylidenephosphonic acid), amino tri(propylidenephosphonic acid), amino tri(tert-amylidenephosphonic acid), amino tri(isoamylidenephosphonic acid) and amino tri sec-butylidenephosphonic acid) Alkylene phosphonic acids are represented by the general structure HO E X (])/0 i HO Y 11 OH where X is a member selected from the group consisting of hydrogen and lower alkyl group (l-4 carbon atoms), Y is either hydrogen, hydroxyl, a halogen, especially chlorine, bromine and fluorine, or lower alkyl group (1-4 carbon atoms), and rt is an integer from 1 to 6.
Compounds illustrative of alkylene diphosphonic acids include methylenediphosphonic acid; ethylidenediphosphonic acid; 1 hydroxyl, ethylidenediphosphonic acid; hexamethylenediphosphonic acid; isopropylidenediphosphonic acid, butylidenediphosphonic acid; hydroxylmethylenediphosphonic acid; 1 hydroxyl, propylenediphosphonic acid; amylidenediphosphonic acid; pentamethylenediphosphonic acid; penta(propylidene)diphosphonic acid; tetra(l-hydroxyethylidene)diphosphonic acid.
It is to be understood that although the sodium salts of the amino tri(lower alkylidenephosphonic acids), alkylenediphosphonic acids, and aminopolycarboxylic acids are preferred, other water soluble salts such as potassium, lithium, and the like, as well as mixtures of the alkali metal salts may be substituted therefor. In addition, the ammonium salts, as well as amine salts, may be used to practice this invention.
Compounds illustrative of these salts include monopotassium nitrilotriacetate; pentasodium diethylenetriamine pentaacetate; diammonium ethylenediaminetetraacetate; dimethylamino diethylenetriaminetetra-acetate; trilithium nitrilotriacetate; disodium diethylenetriamine penta-acetate; tripotassium ethylenediaminetetra-acetate; diethylamino nitrilotriacetate; pentapotassium diethylenetriamine penta-acetate; monosodium nitrilotriacetate; tetrasodium ethylenediaminetetra-acetate; disodium amino tri(methylphosphonate); dipotassium amino tri(methylphosphonate); diammonium amino tri(methylphosphonate); pentasodium amino tri(methylphosphonate); dilithium amino tri(ethylidenephosphonate); diammonium amino tri(ethylidenephosphonate); pentasodium amino tri (isopropylidenephosphonate); pentapotassium amino tri (butylidenephosphonate); diammonium amino tri(isopropylidenephosphonate) disodium amino tri(butylidenephosphonate); diethylamine amino tri(methylphosphonate; dimethylamine amino tri(ethylidenephosphonate); monolithium methylenediphosphonate; dipotassium methylenediphosphonate; diethylamine methylenediphosphonate; triammonium methylenediphosphonate; tetrasodium methylenediphosphonate; trisodium l-hydroxy ethylidenediphosphonate; trisodium tri(2-hydroxy, 3 amylidene) diphosphonate; monopotassium ethylidenediphosphonate; dimethylamine ethylenediphosphonate; tripotassium amylidenediphosphonate; tetrasodium butylidenediphosphonate; diammonium isopropylidenephosphonate; monosodium amylidenediphosphonate; and tripotassium ethylidenediphosphonate.
As being further illustrative of builders which can be used with the compounds of the instant invention are inorganic builder materials, usually comprised of inorganic phosphates, carbonates, sulfates, silicates or combinations thereof, and, in particular, the alkali metal salts of the foregoing materials. The alkali metal salts are preferably the potassium and sodium salts, although ammonium salts may be employed, particularly in combination with the potassium or sodium salts. The phosphate compounds are preferably the chain polyphosphates. Such polyphosphates contain more than 1 phosphorus atom per molecule, as distinguished from orthophosphates which contain only one phosphorus atom per molecule. Chain polyphosphates are non-cyclic (and usually linear) phosphates, as distinguished from ring or cyclic phosphates such as trimetaphosphates and tetrametaphosphates. Examples of the more common chain polyphosphates are tetrapotassium. pyrophosphate, tetrasodium pyrophosphate, sodium tripolyphosphate, potassium hexametaphosphate and sodium hexametaphosphate.
Another builder material which is preferably utilized along with the chain polyphosphates are the water-soluble sodium and potassium silicates. As is well-known, so dium silicates can vary quite widely in composition, ranging from tetra and disilicates having a mole ratio of Na O:SiO of 1:4 and 1:2, respectively, to the more alkaline silicates, such as the orthosilicate having a mole ratio of Na O:SiO of 2:1. In general, sodium silicate (Na O:SiO =1 :2) is the preferred. silicate compound for use according to the present invention. However, other silicates, or mixtures of silicates, having an overall mole ratio of Na O:SiO between about 1:1 and 1:4 can be used. The carbonates and sulfates are preferably the sodium and potassium carbonates and sulfates.
Ordinarily at least about 5 percent of the builder material by weight of the total composition can be used and usually not over about 90 percent with the preferred range being between about 30 and about percent by weight. Additionally, minor amounts, usually less than about 2 percent by weight of the total composition, of additives, such as dyes, perfumes, anti-redeposition agents (sodium carboxymethyl cellulose) and the like can be incorporated into the composition.
Although the detergent compositions of this invention may comprise an organo-methylene diphosphonic acid or salt thereof and the above-described builder materials and other additives, the compositions may also contain relatively minor amounts, usually less than 15% by weight, preferably 1 to 10% by weight, on a solids basis, of other organic surface active agents such as foaming agents, emulsifiers, detergent surfactants or the like. Examples of organic surface active agents include anionic surfactants such as sulfated and sulfonated alkyl, aryl, and alkyl aryl hydrocarbons and alkali metal salts thereof, for example, sodium salts of long chain alkyl sulfates, sodium salts of alkyl naphthalene sulfonic acids, sodium salts of sulfonated abietenes, sodium salts of alkyl benzene sulfonic acids particularly those in which the alkyl group contains from 8-24 carbon atoms; sodium salts of sulfonated mineral oils and sodium salts of sulfosuccinic acid esters such as sodium dioctyl sulfos uccinate.
Advantageous anionic surfactants include the higher alkyl aryl sulfonic acids and their alkali metal and alkaline earth metal salts such as for example sodium dodecyl benzene sulfonate, sodium tridecyl benzene sulfonate, magnesium dodecyl benzene sulfonate, potassium tetradecyl benzene sulfonate, ammonium dodecyl toluene sulfonate, lithium pentadecyl benzene sulfonate, sodium dioctyl benzene sulfonate, disodium dodecyl benzene disulfonate, disodium di-isopropyl naphthalene disulfonate and the like as Well as the alkali metal salts of fatty alcohol esters of sulfuric and sulfonic acids, the alkali metal salts of alkyl aryl (sulfothioic acid) ethers and the alkyl thiosulfuric acid, etc. Preferred anionic organic surface active agents are, as noted hereinbefore, sodium salts of alkyl benzene sulfonic acids and particularly preferred sodium salts of alkyl benzene sulfonic acids are those in which the alkyl group or radical contains to 18 carbon atoms in a straight (i.e. unbranched) chain.
Examples of nonionic surfactants include products formed by condensing one or more alkylene oxides of 2 to 4 carbon atoms, such as ethylene oxide or propylene oxide, preferably ethylene oxide alone or with other alkylene oxides, with a relatively hydrophobic compound such as a fatty alcohol, fatty acid, sterol, a fatty glyceride, a fatty amine, an aryl amine, a fatty mercapian, tall oil, etc. Nonionic surface active agents also include those products produced by condensing one or more relatively lower alkyl alcohol amines (such as methanolamine, ethanolamine, propanolamine, etc.) with a fatty acid such as lauric acid, cetyl acid, tall oil fatty acid, abietic acid, etc. to produce the corresponding amide.
Particularly advantageous nonionic surface active agents are condensation products of a hydrophobic compound having at least 1 active hydrogen atom and a lower alkylene oxide (for example the condensation product of an aliphatic alcohol containing from about 8 to about 18 carbon atoms) and from about 3 to about mols of ethylene oxide per mol of the alcohol, or the condensation product of an alkyl phenol containing from about 8 to about 18 carbon atoms in the alkyl group and from about 3 to about 30 mols of ethylene oxide per mol of alkyl phenol. Other advantageous nonionic detergents include condensation products of ethylene oxide with a hydrophobic compound formed by condensing propylene oxide with propylene glycol.
Other typical examples of these catagories of the anionic and nonionic surface active agents are described in Schwartz and Perry, Surface Active Agents, Interscience Publishers, New York (1949) and the Journal of water at room temperature. The compounds tested were at concentrations believed representative of detergent concentrations used in actual applications. The results of the test are tabulated below.
TAB LE 1 Surface tension (dyne/cm.) at indicated molar concentrations As can be observed from the above table, compounds illustrative of the invention, i.e., (2) and (3), exhibit the ability to lower the surface tension of water (4). Compounds (2) and (3) compared very favorably with sodium dodecylbenzene sulfonate (5), a widely used surfactant, when used in molar concentrations of 5x10 and 10- It should be noted that compound (1) exhibited no appreciably surfactancy ability since a compound exhibiting a surface tension above about at molar concentrations of 5 1O and 10* is not usually regarded as a surfactant. As can be appreciated, therefore, by reason of their surfactancy, compounds of this invention are particularly Well suited for use in detergent compositions.
Compounds illustrative of the invention were tested for deflocculating properties in a carefully controlled kaolin slurry. The kaolin used in the evaluation was essentially free of impurities and was placed in an aqueous slurry with a solids content about 68%. The slurry throughout the evaluation was maintained at a pH of about 7 with NaOH or HCl. The apparent viscosity was determined with a Stormer viscometer at 300 rpm. The results of the tests are tabulated below.
TABLE 2 Apparent viscosity in centipoises at 300 r.p.m. Stormer at indicated weight percent of deflocculating agent on a dry clay basis American Oil Chemists Society, vol. 34, No. 4, pp. 170- 216 (April 1957).
The detergent composition of the present invention is not to be limited to any particular method of mixing the ingredients used in the compositions. The organo-methylene diphosphonic acids or salts may be mechanically mixed in, crutched in the detergent composition in the form of a slurry, or dissolved in a solution of the detergent composition. In addition, the organo-methylene diphosphonic acids or salts may be admixed with other ingredients in any of the forms in which the detergent composition is manufactured in, as well as being added simultaneously or separately to an aqueous solution. In any event, the organo-methylene diphosphonic acids or salts are intended to be used with the other ingredients at the time of application as a cleansing agent.
Compounds illustrative of the invention were tested for surfactancy properties by determining surface tension measurements with a Du Nuoy tensiometer in distilled As can be observed from the above table, minor amounts of the compounds illustrative of the invention, i.e., (2) and (3) deflocculated a plastic slurry into a flowable slurry. In addition, compounds (2) and (3) compared Wery favorably with sodium tripolyphosphate (4), a widely used deflocculant, and compound (1) when used in amounts of about .1 and .15 weight based on a dry clay basis.
Compounds illustrative of the invention were tested for sequestration properties. The conditions of the test were to dissolve .25 gm. of the tetrasodium salt of the compound of the instant invention and .25 gm. of Na C- O in 250 ml. of water and adjust the pH to 12 with NaOH. To the solution is added 0.1 M Ca(NO until a cloudy endpoint, i.e., the precipitation of CaC O- is achieved. In order to calculate the pounds of calcium sequestered by pounds of material tested, the volume of 0.1 M Ca(NO used, in cc. units, is multiplied by 1.6. The results of the test are tabulated below.
13 TABLE 3 Lbs. calcium/ 100 lbs. Compound: of compound (1) Tetrasodium octylidene diphosphonate C H CH[PO(ONa) 4-8 (2) Tetrasodium tridecylidene diphosphonate C1gH25CH[PO(ONa)2] 1.0
As can be observed from the above table, compounds illustrative of the instant invention, i.e. (1) and (2) exhibited the ability to sequester calcium, thus indicating their beneficial use in aqueous systems containing such 1011s.
The following detergent formulations in which the percentages are by weight are presented as being illustrative of the present invention:
Percent Tetrasodium tridecylidene diphosphonate 20 Sodium tripolyphosphate 50 Sodium carboxymethyl cellulose 1 Sodium silicate 10 Sodium sulfate 19 Tetrasodium octylidene diphosphonate 20 Trisodium l-hydroxy, ethylidene diphosphonate 30- Sodium carboxymethyl cellulose 1 Sodium silicate 10 Sodium sulfate 19 Sodium tripolyphosphate 20 Trisodium pentadecylidene diphosphonate 20 Trisodium nitrilo triacetate 30 Sodium silicate 10 Sodium carbonate 40 Tetrapotassium tridecylidene diphosphonate 5 Tetrasodium octylidene diphosphonate 5 Sodium dodecyl benzene sulfonate Pentasodium amino tri(methylphosphonate) 30 Sodium carboxymethyl cellulose 1 Sodium sulfate 49 Percent Tetrasodium octadecylene diphosphonate 20 Nonionic condensate (dodecyl alcohol-ethylene oxide on a 1:10 molar ratio basis) 10 Tetrapotassium pyrophosphate 30 Sodium silicate 39 Sodium carboxymethyl cellulose 1 All of the foregoing detergent formulations are effective for cleaning textiles, hard surfaces such as dishes, walls and the like when used in concentrations of about 0.2% in water.
The esters of organo-methylene diphosphonic acids were found not only to be substantially miscible with water but also highly soluble in organic solvents, such as hydrocarbon solvent, i.e. hexane and pentane, carbon tetra chloride, haloethylene solvents (perchloroethylene), ethers, alcohols, and the like. Also, the esters were found to impart a solubilizing action to water in water-immiscible solvents, such as many of the previously mentioned solvents. This totally unexpected property renders them high- 1y useful as gasoline de-icer additives and along with their surfactancy properties renders them useful as dry cleaning detergents. As can be appreciated, however, the unique ability to impart a solubilizing action to Water in waterimmiscible solvents can be utilized in many and varied applications and, therefore, the foregoing mentioned applications are merely indicative of their use.
The esters of higher alkylidene diphosphonic acids are preferred in applications which use the combined surfactancy and/or water solubilizing properties. These compounds are of the following formula:
wherein R is selected from the class consisting of satu rated and ethylenically unsaturated aliphatic hydrocarbyl radicals containing from 5 to 20 carbon atoms (preferably 7 to 20 carbon atoms) and R R R and R are selected from the class consisting of alkyl groups of from 1 to 20 carbon atoms, aryl hydrocarbyl groups and alkaryl groups with the lower alkyl groups being especially preferred.
Because of the complexity of the ternary solubility diagram of the esters of the instant inventionwaterwater-immiscible solvents the following is set forth for example purposes only.
A solution of 10 cc. of hexane and 5 cc. of the following esters of the higher alkylidene diphosphonic acids dissolves the amounts of water at room temperature indicated in Table 4. The water Was added dropwise until permanent cloudiness or phase separation was observed. The tabulated results are presented. in the following table.
TABLE 4 Compound: H 0 added (cc.)
(1) Tetra ethyl octylidene diphosphonate C H CH[P0(OC H .5 (2) Tetra ethyl tridecylidene diphosphonate C H CH[PO(OC H 2.5
It should be noted that the foregoing example solutions exhibited no phase separation at the end of a one week period of standing nor was there a phase separation after the solutions had been centrifuged at 5,000 rpm. for one hour indicating that the water was completely dissolved in the water-immiscible solvent. It should further be noted that tetraethyl methylene diphosphonate, CH [PO(OC H did not impart a solubilizing action to Water in a Water-immiscible solvent.
As dry cleaning additives the ester compounds of the instant invention can be used as either the primary surfactant or in conjunction with other surfactants. When used as substantially the primary surfactant with many of the common organic solvents, such as, Stoddards solvent (petroleum distillate) and perchloroethylene, amounts within the range of .05 to 10% by weight are usually sufficient with amounts of from about 1% to about 2% by weight being preferred.
What is claimed is:
1. A detergent composition consisting essentially of an amount of at least about 5% by weight of said composition of an organo-methylene diphosphonic compound having the formula wherein R is selected from the class consisting of (a) aliphatic hydrocarbyl groups containing from 7 to 30 carbon atoms, (b) alicyclic hydrocarbyl groups containing from 5 to 7 carbon atoms, (c) aryl groups selected from the group consisting of monocyclic, dicyclic, or tricyclic hydrocarbon groups containing from 6 to 18 carbon atoms, (d) amino-substituted aryl groups wherein the aryl portion is the same as that defined in item (c), (e) alkaryl groups wherein the aryl portion of said group is the same as that defined in item (c) and the alkyl portion of said group contains from 1 to 12 carbon atoms, and (f) all of the groups defined in items (a), (b), (c), (d) and (e) containing a halogen substituent, and X is selected from the class consisting of hydrogen ions, alkali metal ions, ammonium ions and amine ions,
1 5 and a builder material in an amount of at least about 5% by weight of said composition.
2. A detergent composition according to claim 1, wherein said compound has the following formula wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl groups containing from 7 to 20 carbon atoms and X is selected from the class consisting of hydrogen ions, alkali metal ions, ammonium ions and amine ions.
3. A detergent composition according to claim 2, wherein said compound is a sodium salt of tridecylidene diphosphonate.
4. A detergent composition according to claim 2, wherein said compound is a sodium salt of octylidene diphosphonate.
5. A detergent composition according to claim 2, wherein said compound is present in amounts of from about 5% to 50% by weight of said composition.
6. A detergent composition according to claim 2, wherein there is present a builder material in amounts of from about 5% to 90% by weight of said composition.
7. A detergent composition according to claim 2, wherein there is present an organic surface active agent selected from the group consisting of anionic and nonionic surface active agents in amounts less than about 15% by weight of said composition.
8. A dry cleaning composition consisting essentially of an amount of at least about 0.05% by weight ofvsaid composition of an ester of an organo-methylene diphosphonic acid, said ester having the formula t I X H 0X wherein R is selected from the class consisting of (a) aliphatic hydrocarbyl groups containing from 7 to 30 carbon atoms, (b) alicyclic hydrocarbyl groups containing from to 7 carbon atoms, (c) aryl groups selected from the group consisting of monocyclic, dicyclic, or tricyclic hydrocarbon groups containing from 6 to 18 carbon atoms, (d) amino-substituted aryl groups wherein the aryl portion is the same as that defined in item (c), (e) alkaryl groups wherein the alkyl portion of said group is the same as that defined in item (c) and the alkyl portion of said group contains from 1 to 12 carbon atoms, and (f) all of the groups defined in items (a), (b), (c),
(d) and (e) containing a halogen substituent, and X is selected from the class consisting of (a) aliphatic hydrocarbyl groups containing from 7 to 30 carbon atoms, (b) aryl groups selected from the group consisting of monocyclic, dicyclic or tricyclic hydrocarbon groups containing from 6 to 18 carbons atoms, (c) alkaryl groups wherein the aryl portion of said group is the same as that defined in item (b) and the alkyl portion of said group contains from 1 to 12 carbon atoms, and an elfective amount of a dry cleaning organic solvent.
9. A dry cleaning composition according to claim 8, wherein said ester is a higher alkylidene diphosphonic acid which functions substantially as a detergent, said ester having the formula R30 0 R 0 OR: may R4O/ 1 1 ORz wherein R is selected from the class consisting of saturated and ethylenically unsaturated aliphatic hydrocarbyl groups containing from 7 to 20 carbon atoms, and R R R and R are selected from the class consisting of alkyl groups of from 1 to 20 carbon atoms, aryl hydrocarbyl groups selected from the group consisting of monocyclic, dicyclic or tricyclic hydrocarbon groups contain ing from 6 to 18 carbon atoms and alkaryl groups wherein the aryl portion of said group is the same as defined above and the alkyl portion of said group contains from 1 to 12 carbon atoms.
10. A dry cleaning composition according to claim 9, wherein said detergent is present in amounts of from about .05 to 10% by weight of said composition.
11. A dry cleaning composition according to claim 10, wherein said detergent is tetraethyl octylidene diphosphonate.
12. A dry cleaning composition according to claim 10, wherein said detergent is tetraethyl tridecylidene diphos phonate.
References Cited UNITED STATES PATENTS 3,299,123 1/1967 Fitch et al. 260-O 3,169,930 2/1965 Gedge 252-137 LEON D. ROSDOL, Primary Examiner D. L. ALBRECHT, Assistant Examiner US. Cl. X.R.
37 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,518 ,200 Dated June so 1970 Steven Josevn Pitch and Riyad R. Irani Inventofl a) It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 9 line H the "C" in the structure should be an O Signed and sealed this 2nd day of May 1972.
(SEAL) Attest:
EDJARD M.FLETCHER, JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US271607A US3299123A (en) | 1963-04-09 | 1963-04-09 | Substituted methylene diphosphonic acids and salts and esters thereof |
US590449A US3414393A (en) | 1963-04-09 | 1966-08-29 | Gasoline compositions containing diphosphonates |
US57850066A | 1966-09-12 | 1966-09-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3518200A true US3518200A (en) | 1970-06-30 |
Family
ID=27402394
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US271607A Expired - Lifetime US3299123A (en) | 1963-04-09 | 1963-04-09 | Substituted methylene diphosphonic acids and salts and esters thereof |
US590449A Expired - Lifetime US3414393A (en) | 1963-04-09 | 1966-08-29 | Gasoline compositions containing diphosphonates |
US578500A Expired - Lifetime US3518200A (en) | 1963-04-09 | 1966-09-12 | Organic phosphorus compounds,compositions containing same,and uses thereof |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US271607A Expired - Lifetime US3299123A (en) | 1963-04-09 | 1963-04-09 | Substituted methylene diphosphonic acids and salts and esters thereof |
US590449A Expired - Lifetime US3414393A (en) | 1963-04-09 | 1966-08-29 | Gasoline compositions containing diphosphonates |
Country Status (2)
Country | Link |
---|---|
US (3) | US3299123A (en) |
DE (2) | DE1302929B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4148603A (en) * | 1974-10-04 | 1979-04-10 | Henkel Kommanditgesellschaft Auf Aktien | Method of washing textiles and composition containing inorganic silicates and polycarboxylates and/or polyphosphonates |
US5332728A (en) * | 1992-11-23 | 1994-07-26 | Bristol-Myers Squibb Company | Method for treating a fungal infection |
US20060191851A1 (en) * | 2005-02-25 | 2006-08-31 | Mizuno William G | Method for treating feedwater, feedwater treatment composition, and apparatus for treating feedwater |
Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1302557B (en) * | 1963-04-09 | 1971-08-26 | ||
DE1496916B1 (en) * | 1964-09-22 | 1969-10-23 | Monsanto Co | Cyanide-free, galvanic bath and process for the deposition of galvanic coatings |
US3463835A (en) * | 1965-10-05 | 1969-08-26 | Plains Chem Dev Co | Aromatic polyphosphonic acids,salts and esters |
US4020091A (en) * | 1965-10-28 | 1977-04-26 | Plains Chemical Development Co. | Chelation |
US3400176A (en) * | 1965-11-15 | 1968-09-03 | Procter & Gamble | Propanepolyphosphonate compounds |
NL149701C (en) * | 1965-12-08 | 1981-05-15 | Procter & Gamble | METHOD FOR PREPARING AN AGENT TOOTHIC CARE, WHICH INCLUDES A PHOSPHONIC ACID DERIVATIVE AS AN ACTIVE INGREDIENT, AND FORMED TOOTHIC CARE. |
USRE29182E (en) * | 1965-12-08 | 1977-04-12 | The Procter & Gamble Company | Oral composition for calculus retardation |
US3475486A (en) * | 1966-09-12 | 1969-10-28 | Monsanto Co | Process for preparing phosphonic acids |
US3609075A (en) * | 1968-06-25 | 1971-09-28 | Procter & Gamble | Cleaning and softening detergent compositions |
US3678154A (en) * | 1968-07-01 | 1972-07-18 | Procter & Gamble | Oral compositions for calculus retardation |
US3624188A (en) * | 1968-10-25 | 1971-11-30 | Procter & Gamble | Hypohalogenation of tetramethyl and tetraethyl methylenediphosphonates and trihydrocarbyl phosphonoacetates |
DE1958123C3 (en) * | 1969-11-19 | 1978-09-28 | Henkel Kgaa, 4000 Duesseldorf | Process for the preparation of 1-aminoalkane-1,1-diphosphonic acids or their salts |
US3940436A (en) * | 1970-04-13 | 1976-02-24 | Monsanto Company | Substituted ethane diphosphonic acids and salts and esters thereof |
US3617576A (en) * | 1970-04-13 | 1971-11-02 | Monsanto Co | Methods of scale inhibition |
US3705191A (en) * | 1970-04-13 | 1972-12-05 | Monsanto Co | Substituted ethane diphosphonic acids and salts and esters thereof |
US4116990A (en) * | 1970-04-30 | 1978-09-26 | Plains Chemical Development Co. | Chelation |
US3683080A (en) * | 1970-08-28 | 1972-08-08 | Procter & Gamble | Compositions for inhibiting anomalous deposition and mobilization of calcium phosphate in animal tissue |
DE2343195C2 (en) * | 1973-08-27 | 1981-11-19 | Henkel KGaA, 4000 Düsseldorf | Cyclic aminophosphonic acids and processes for their preparation |
US3992332A (en) * | 1974-08-22 | 1976-11-16 | Hemson Joseph Zenon | Liquid composition for fabric treatment |
US4163733A (en) * | 1977-10-25 | 1979-08-07 | Buckman Laboratories, Inc. | Synergistic compositions for corrosion and scale control |
US4138431A (en) * | 1978-06-29 | 1979-02-06 | Nalco Chemical Company | Reaction of α-phosphorus containing carboxylic acids with phosphorous acid to prepare scale and corrosion inhibitors |
US4416877A (en) * | 1979-02-13 | 1983-11-22 | Symphar S.A. | Anti-atherosclerotic pharmaceutical compositions containing diphosphonate compounds |
GB2043072B (en) * | 1979-02-13 | 1983-11-23 | Symphar Sa | Diphosphonate compounds |
FR2531088B1 (en) * | 1982-07-29 | 1987-08-28 | Sanofi Sa | ANTI-INFLAMMATORY PRODUCTS DERIVED FROM METHYLENEDIPHOSPHONIC ACID AND THEIR PREPARATION METHOD |
DE3540150A1 (en) * | 1985-11-13 | 1987-05-14 | Boehringer Mannheim Gmbh | NEW DIPHOSPHONIC ACID DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS |
US4818774A (en) * | 1986-03-10 | 1989-04-04 | Occidental Chemical Corporation | Organophosphorus compounds |
CH675422A5 (en) * | 1988-03-31 | 1990-09-28 | Symphar Sa | |
US5233092A (en) * | 1989-11-06 | 1993-08-03 | Xiao Zaosheng | Diphosphonate compounds, their preparation and application |
US5157027A (en) * | 1991-05-13 | 1992-10-20 | E. R. Squibb & Sons, Inc. | Bisphosphonate squalene synthetase inhibitors and method |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3169930A (en) * | 1962-03-20 | 1965-02-16 | Procter & Gamble | Built liquid detergent |
US3299123A (en) * | 1963-04-09 | 1967-01-17 | Monsanto Co | Substituted methylene diphosphonic acids and salts and esters thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2339096A (en) * | 1941-05-22 | 1944-01-11 | Cities Service Oil Co | Solvent composition and method of cleaning lubricated apparatus |
US2651656A (en) * | 1950-04-17 | 1953-09-08 | Us Rubber Co | Process of preparing tetraalkyl esters of 1, 2-ethanediphosphonic acid |
US2634288A (en) * | 1951-01-10 | 1953-04-07 | Virginia Carolina Chem Corp | Tetraalkyl esters of alkane diphosphonic acids |
NL77048C (en) * | 1951-07-06 | |||
US2897071A (en) * | 1953-06-30 | 1959-07-28 | Ethyl Corp | Gasoline fuels |
US2889213A (en) * | 1954-01-06 | 1959-06-02 | Phillips Petroleum Co | Engine fuel containing anti-icing additives |
US2793945A (en) * | 1954-01-11 | 1957-05-28 | Exxon Research Engineering Co | Residual fuels |
US2999739A (en) * | 1956-03-28 | 1961-09-12 | Ethyl Corp | Antiknock fluids |
US3093672A (en) * | 1960-10-03 | 1963-06-11 | Monsanto Chemicals | Diphosphonate alkyl esters |
-
0
- DE DENDAT1302557D patent/DE1302557B/de active Pending
-
1963
- 1963-04-09 US US271607A patent/US3299123A/en not_active Expired - Lifetime
-
1964
- 1964-04-08 DE DE19641302929D patent/DE1302929B/de active Pending
-
1966
- 1966-08-29 US US590449A patent/US3414393A/en not_active Expired - Lifetime
- 1966-09-12 US US578500A patent/US3518200A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3169930A (en) * | 1962-03-20 | 1965-02-16 | Procter & Gamble | Built liquid detergent |
US3299123A (en) * | 1963-04-09 | 1967-01-17 | Monsanto Co | Substituted methylene diphosphonic acids and salts and esters thereof |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4148603A (en) * | 1974-10-04 | 1979-04-10 | Henkel Kommanditgesellschaft Auf Aktien | Method of washing textiles and composition containing inorganic silicates and polycarboxylates and/or polyphosphonates |
US5332728A (en) * | 1992-11-23 | 1994-07-26 | Bristol-Myers Squibb Company | Method for treating a fungal infection |
US20060191851A1 (en) * | 2005-02-25 | 2006-08-31 | Mizuno William G | Method for treating feedwater, feedwater treatment composition, and apparatus for treating feedwater |
US20080223791A1 (en) * | 2005-02-25 | 2008-09-18 | Ecolab Inc. | Method for treating feedwater |
US7537705B2 (en) | 2005-02-25 | 2009-05-26 | Ecolab Inc. | Method for treating feedwater |
Also Published As
Publication number | Publication date |
---|---|
DE1302929B (en) | 1971-12-30 |
DE1302557B (en) | 1971-08-26 |
US3299123A (en) | 1967-01-17 |
US3414393A (en) | 1968-12-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3518200A (en) | Organic phosphorus compounds,compositions containing same,and uses thereof | |
US3344077A (en) | Organic phosphorus compounds | |
US3451937A (en) | Phosphonate compounds | |
US3720621A (en) | Aquenous detergent compositions | |
US3502585A (en) | Detergent compositions containing propanepolyphosphonate compounds | |
US3526592A (en) | New compounds and detergent compositions containing them | |
US3368978A (en) | Builder compositions and detergent compositions using same | |
CA1318209C (en) | Detersive system with an improved hardness ion complexing agent | |
US3586633A (en) | Alkaline cleansing agent | |
US4440646A (en) | Chelation | |
US3304330A (en) | Tertiary phosphine oxide compounds | |
US3459670A (en) | Builders for synthetic detergents | |
US3463734A (en) | Builders for synthetic detergents | |
US4911856A (en) | Low acid, soluble salt containing aqueous-organic softening agents for detersive systems | |
US3629124A (en) | Bleaching sterilizing disinfecting and deterging compositions | |
US3394083A (en) | Effervescent builder compositions and detergent compositions containing the same | |
US3471406A (en) | Detergent compositions containing methane tri and tetra phosphonic acid compounds | |
US3553129A (en) | Emulsifying and textile softening phosphonium compounds, process for preparing the same and other compounds, reactive intermediates | |
US3717589A (en) | Sodium nitrilotriacetate and processes for producing same | |
US3734954A (en) | Polyphosphinic acids and salts thereof | |
US3551339A (en) | Built detergent compositions | |
US3470243A (en) | Tetrakis(dihydrogen phosphono methyl)-ethylene diamine,n,n'-dioxide and related compounds | |
US3391083A (en) | Surface active agents | |
US3383323A (en) | Amino tri-lower alkylidenephosphonic acid builders for synthetic detergents | |
US3639281A (en) | Built detergent compositions containing tris(methyl phosphonic acid) phosphine oxide and its salts |