CY1180A - Corrosion inhibited agricultural compositions - Google Patents
Corrosion inhibited agricultural compositions Download PDFInfo
- Publication number
- CY1180A CY1180A CY1180A CY118078A CY1180A CY 1180 A CY1180 A CY 1180A CY 1180 A CY1180 A CY 1180A CY 118078 A CY118078 A CY 118078A CY 1180 A CY1180 A CY 1180A
- Authority
- CY
- Cyprus
- Prior art keywords
- weight
- phosphonomethylglycine
- thiols
- parts
- thiol
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 92
- 238000005260 corrosion Methods 0.000 title claims description 43
- 230000007797 corrosion Effects 0.000 title claims description 43
- -1 alkane thiols Chemical class 0.000 claims description 89
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 claims description 54
- 239000004094 surface-active agent Substances 0.000 claims description 47
- 238000009472 formulation Methods 0.000 claims description 43
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 35
- 239000004202 carbamide Substances 0.000 claims description 35
- 238000002474 experimental method Methods 0.000 claims description 33
- 150000003573 thiols Chemical class 0.000 claims description 32
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 23
- 230000002363 herbicidal effect Effects 0.000 claims description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000004480 active ingredient Substances 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 150000004662 dithiols Chemical class 0.000 claims description 15
- 230000005764 inhibitory process Effects 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical group [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical class CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 11
- 230000008635 plant growth Effects 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 6
- 230000002401 inhibitory effect Effects 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 239000004606 Fillers/Extenders Substances 0.000 claims description 4
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002671 adjuvant Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 claims description 2
- IVTHSFJXIARUFL-UHFFFAOYSA-N triazanium;thiophosphate Chemical group [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=S IVTHSFJXIARUFL-UHFFFAOYSA-N 0.000 claims description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 230000001105 regulatory effect Effects 0.000 claims 2
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 claims 1
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 claims 1
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 claims 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000003085 diluting agent Substances 0.000 claims 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims 1
- 229910000397 disodium phosphate Inorganic materials 0.000 claims 1
- 235000019800 disodium phosphate Nutrition 0.000 claims 1
- 239000003337 fertilizer Substances 0.000 claims 1
- 235000019837 monoammonium phosphate Nutrition 0.000 claims 1
- 239000006012 monoammonium phosphate Substances 0.000 claims 1
- 231100000208 phytotoxic Toxicity 0.000 claims 1
- 230000000885 phytotoxic effect Effects 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 description 22
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 241000196324 Embryophyta Species 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 10
- 235000008504 concentrate Nutrition 0.000 description 10
- NVUDVUDVVXAWGV-UHFFFAOYSA-N dodecane-1,12-dithiol Chemical compound SCCCCCCCCCCCCS NVUDVUDVVXAWGV-UHFFFAOYSA-N 0.000 description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- XVIWVTWNQQUGQI-UHFFFAOYSA-L disodium;sulfanylidenemethanediolate Chemical compound [Na+].[Na+].[O-]C([O-])=S XVIWVTWNQQUGQI-UHFFFAOYSA-L 0.000 description 6
- AALQBIFJJJPDHJ-UHFFFAOYSA-K trisodium;thiophosphate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=S AALQBIFJJJPDHJ-UHFFFAOYSA-K 0.000 description 6
- 241000508725 Elymus repens Species 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012669 liquid formulation Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 239000004471 Glycine Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000003774 sulfhydryl reagent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000013011 aqueous formulation Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000008233 hard water Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- BDFAOUQQXJIZDG-UHFFFAOYSA-N 2-methylpropane-1-thiol Chemical compound CC(C)CS BDFAOUQQXJIZDG-UHFFFAOYSA-N 0.000 description 2
- NHWJLCJXIBETKO-UHFFFAOYSA-N 3-phenoxybenzene-1,2-disulfonic acid Chemical class OS(=O)(=O)C1=CC=CC(OC=2C=CC=CC=2)=C1S(O)(=O)=O NHWJLCJXIBETKO-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- GIJGXNFNUUFEGH-UHFFFAOYSA-N Isopentyl mercaptan Chemical compound CC(C)CCS GIJGXNFNUUFEGH-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- IASQPYXUGFCXJY-UHFFFAOYSA-L [K+].[K+].P(=O)(O)(O)CNCC(=O)[O-].P(=O)(O)(O)CNCC(=O)[O-] Chemical compound [K+].[K+].P(=O)(O)(O)CNCC(=O)[O-].P(=O)(O)(O)CNCC(=O)[O-] IASQPYXUGFCXJY-UHFFFAOYSA-L 0.000 description 2
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- LOCHFZBWPCLPAN-UHFFFAOYSA-N butane-2-thiol Chemical compound CCC(C)S LOCHFZBWPCLPAN-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [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 2
- SIQGBUJXKSJZAV-UHFFFAOYSA-L disodium;2-(phosphonomethylamino)acetate Chemical compound [Na+].[Na+].OP(O)(=O)CNCC([O-])=O.OP(O)(=O)CNCC([O-])=O SIQGBUJXKSJZAV-UHFFFAOYSA-L 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JWINRUZEIRYEJL-UHFFFAOYSA-N octadecan-1-amine 2-(phosphonomethylamino)acetic acid Chemical compound OC(=O)CNCP(O)(O)=O.CCCCCCCCCCCCCCCCCCN JWINRUZEIRYEJL-UHFFFAOYSA-N 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- YWICANUUQPYHOW-UHFFFAOYSA-M sodium;2-(phosphonomethylamino)acetate Chemical compound [Na+].OP(O)(=O)CNCC([O-])=O YWICANUUQPYHOW-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- WSSAMLJXFBGUJI-UHFFFAOYSA-N 2-(phosphonomethylamino)acetic acid Chemical compound OC(=O)CNCP(O)(O)=O.OC(=O)CNCP(O)(O)=O WSSAMLJXFBGUJI-UHFFFAOYSA-N 0.000 description 1
- JHTKHBPGSTYSBH-UHFFFAOYSA-N 2-(phosphonomethylamino)acetic acid;propan-1-amine Chemical compound CCCN.CCCN.OC(=O)CNCP(O)(O)=O JHTKHBPGSTYSBH-UHFFFAOYSA-N 0.000 description 1
- DQNPFPHZAUMZHD-UHFFFAOYSA-N 2-aminoethanol;2-(phosphonomethylamino)acetic acid Chemical compound NCCO.OC(=O)CNCP(O)(O)=O DQNPFPHZAUMZHD-UHFFFAOYSA-N 0.000 description 1
- NFHONWFCTQWTOM-UHFFFAOYSA-N 2-chloroethanamine;2-(phosphonomethylamino)acetic acid Chemical compound NCCCl.OC(=O)CNCP(O)(O)=O NFHONWFCTQWTOM-UHFFFAOYSA-N 0.000 description 1
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical class COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 description 1
- JQVJHSLHRAOQTD-UHFFFAOYSA-N 2-phenoxyethanamine;2-(phosphonomethylamino)acetic acid Chemical compound NCCOC1=CC=CC=C1.OC(=O)CNCP(O)(O)=O JQVJHSLHRAOQTD-UHFFFAOYSA-N 0.000 description 1
- LTERAWRIKDPXBF-UHFFFAOYSA-N 3-(dodecanoylamino)propyl-trimethylazanium;methyl sulfate Chemical compound COS([O-])(=O)=O.CCCCCCCCCCCC(=O)NCCC[N+](C)(C)C LTERAWRIKDPXBF-UHFFFAOYSA-N 0.000 description 1
- FQHJBVUTSWQWSN-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathietane 2,2-dioxide Chemical compound CC1OS(=O)(=O)O1 FQHJBVUTSWQWSN-UHFFFAOYSA-N 0.000 description 1
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 1
- 244000153158 Ammi visnaga Species 0.000 description 1
- 235000010585 Ammi visnaga Nutrition 0.000 description 1
- GTTOJXOMPHRXTF-UHFFFAOYSA-N C1COCCN1.OC(=O)CNCP(O)(O)=O Chemical compound C1COCCN1.OC(=O)CNCP(O)(O)=O GTTOJXOMPHRXTF-UHFFFAOYSA-N 0.000 description 1
- KQTHWILIRXZROE-UHFFFAOYSA-N CSC(OC)=S.[Na] Chemical compound CSC(OC)=S.[Na] KQTHWILIRXZROE-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PDYXIVPKOMYDOK-UHFFFAOYSA-N Glyphosate-monoammonium Chemical compound [NH4+].OC(=O)CNCP(O)([O-])=O PDYXIVPKOMYDOK-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- XIXFGHVXFFTSMA-UHFFFAOYSA-L N(CC(=O)[O-])CC(=O)[O-].[Na+].[Na+].[Na+] Chemical compound N(CC(=O)[O-])CC(=O)[O-].[Na+].[Na+].[Na+] XIXFGHVXFFTSMA-UHFFFAOYSA-L 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical class C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 240000002439 Sorghum halepense Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- KCNGRSQQOKXAKR-UHFFFAOYSA-N [(2-ethoxy-2-oxoethyl)amino]methylphosphonic acid Chemical compound CCOC(=O)CNCP(O)(O)=O KCNGRSQQOKXAKR-UHFFFAOYSA-N 0.000 description 1
- ZGGNVSKWCFLTQB-UHFFFAOYSA-N [(2-octoxy-2-oxoethyl)amino]methylphosphonic acid Chemical compound CCCCCCCCOC(=O)CNCP(O)(O)=O ZGGNVSKWCFLTQB-UHFFFAOYSA-N 0.000 description 1
- WTJXGSWRASYOOV-UHFFFAOYSA-K [K+].[K+].[K+].P(=O)(O)(O)CNCC(=O)[O-].P(=O)(O)(O)CNCC(=O)[O-].P(=O)(O)(O)CNCC(=O)[O-] Chemical compound [K+].[K+].[K+].P(=O)(O)(O)CNCC(=O)[O-].P(=O)(O)(O)CNCC(=O)[O-].P(=O)(O)(O)CNCC(=O)[O-] WTJXGSWRASYOOV-UHFFFAOYSA-K 0.000 description 1
- IZKSYXAOKNLDLT-UHFFFAOYSA-K [K+].[K+].[K+].[O-]P([O-])([O-])=S Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=S IZKSYXAOKNLDLT-UHFFFAOYSA-K 0.000 description 1
- BDIRUEMDTWYHDH-UHFFFAOYSA-L [Li+].[Li+].P(=O)(O)(O)CNCC(=O)[O-].P(=O)(O)(O)CNCC(=O)[O-] Chemical compound [Li+].[Li+].P(=O)(O)(O)CNCC(=O)[O-].P(=O)(O)(O)CNCC(=O)[O-] BDIRUEMDTWYHDH-UHFFFAOYSA-L 0.000 description 1
- LLPIQRJDHHFHTJ-UHFFFAOYSA-N [NH4+].[NH4+].P(=O)(O)(O)CNCC(=O)[O-].P(=O)(O)(O)CNCC(=O)[O-] Chemical compound [NH4+].[NH4+].P(=O)(O)(O)CNCC(=O)[O-].P(=O)(O)(O)CNCC(=O)[O-] LLPIQRJDHHFHTJ-UHFFFAOYSA-N 0.000 description 1
- KUOXWPCYGDJLBQ-UHFFFAOYSA-N acetic acid methylphosphonic acid Chemical compound C(C)(=O)O.CP(O)(O)=O KUOXWPCYGDJLBQ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- SMTOKHQOVJRXLK-UHFFFAOYSA-N butane-1,4-dithiol Chemical compound SCCCCS SMTOKHQOVJRXLK-UHFFFAOYSA-N 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 150000003940 butylamines Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical class NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- TVMUHOAONWHJBV-UHFFFAOYSA-M dehydroglycinate Chemical compound [O-]C(=O)C=N TVMUHOAONWHJBV-UHFFFAOYSA-M 0.000 description 1
- TVMUHOAONWHJBV-UHFFFAOYSA-N dehydroglycine Chemical compound OC(=O)C=N TVMUHOAONWHJBV-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ISPMIQMKDKSQJY-UHFFFAOYSA-N di(propan-2-yl)azanium;2-(phosphonomethylamino)acetate Chemical compound CC(C)NC(C)C.OC(=O)CNCP(O)(O)=O ISPMIQMKDKSQJY-UHFFFAOYSA-N 0.000 description 1
- IKVVOMGOVBKDFG-UHFFFAOYSA-N diazanium;sulfanylidenemethanediolate Chemical compound [NH4+].[NH4+].[O-]C([O-])=S IKVVOMGOVBKDFG-UHFFFAOYSA-N 0.000 description 1
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical class CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical class CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- XEQIERZCOHTONL-UHFFFAOYSA-L dipotassium;2-(carboxylatomethylamino)acetate Chemical compound [K+].[K+].[O-]C(=O)CNCC([O-])=O XEQIERZCOHTONL-UHFFFAOYSA-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
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- NHDJUIZMBBJKJT-UHFFFAOYSA-N ethanamine;2-(phosphonomethylamino)acetic acid Chemical compound CCN.CCN.OC(=O)CNCP(O)(O)=O NHDJUIZMBBJKJT-UHFFFAOYSA-N 0.000 description 1
- JOAUSGBGCLGDEE-UHFFFAOYSA-N ethane-1,2-diamine;2-(phosphonomethylamino)acetic acid Chemical compound NCCN.OC(=O)CNCP(O)(O)=O JOAUSGBGCLGDEE-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical class CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- FCZFPMKLLXTSNP-UHFFFAOYSA-N ethyl 2-iminoacetate Chemical compound CCOC(=O)C=N FCZFPMKLLXTSNP-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- ABNPJVOPTXYSQW-UHFFFAOYSA-N hexane-2-thiol Chemical compound CCCCC(C)S ABNPJVOPTXYSQW-UHFFFAOYSA-N 0.000 description 1
- VOIGMFQJDZTEKW-UHFFFAOYSA-N hexane-3-thiol Chemical compound CCCC(S)CC VOIGMFQJDZTEKW-UHFFFAOYSA-N 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NBBDVXGYHOWUHM-UHFFFAOYSA-N methanamine;2-(phosphonomethylamino)acetic acid Chemical compound NC.NC.OC(=O)CNCP(O)(O)=O NBBDVXGYHOWUHM-UHFFFAOYSA-N 0.000 description 1
- ONHFWHCMZAJCFB-UHFFFAOYSA-N myristamine oxide Chemical compound CCCCCCCCCCCCCC[N+](C)(C)[O-] ONHFWHCMZAJCFB-UHFFFAOYSA-N 0.000 description 1
- ODJROLZGWWEEKS-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;2-(phosphonomethylamino)acetic acid Chemical compound NCCNCCN.OC(=O)CNCP(O)(O)=O ODJROLZGWWEEKS-UHFFFAOYSA-N 0.000 description 1
- WGQXGEHRJAEFPO-UHFFFAOYSA-N n,n-diethylethanamine;2-(phosphonomethylamino)acetic acid Chemical compound CCN(CC)CC.OC(=O)CNCP(O)(O)=O WGQXGEHRJAEFPO-UHFFFAOYSA-N 0.000 description 1
- IBOBFGGLRNWLIL-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine oxide Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)[O-] IBOBFGGLRNWLIL-UHFFFAOYSA-N 0.000 description 1
- KXGGAOPWQWIKSW-UHFFFAOYSA-N n-methylmethanamine;2-(phosphonomethylamino)acetic acid Chemical compound CNC.CNC.OC(=O)CNCP(O)(O)=O KXGGAOPWQWIKSW-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- BZXFEMZFRLXGCY-UHFFFAOYSA-N octane-2-thiol Chemical compound CCCCCCC(C)S BZXFEMZFRLXGCY-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- ONHIJCVRYPHITQ-UHFFFAOYSA-K trisodium;2-(phosphonomethylamino)acetate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CNCC([O-])=O.OP(O)(=O)CNCC([O-])=O.OP(O)(=O)CNCC([O-])=O ONHIJCVRYPHITQ-UHFFFAOYSA-K 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/161—Mercaptans
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Metallurgy (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
lO CD
PATENT SPECIFICATION <") 1 604 526
(21) Application No. 19157/78 (22) Filed 12 May 1978
(31) Convention Application No. 797083
(32) Filed 16 May 1977
(31) Convention Application No. 862691
(32) Filed 27 Dec. 1977 in
(33) United States of America (US)
^ (44) Complete Specification published 9 Dec. 1981
(51) INT CL3 A01N 57/00
(52) Index at acceptance
C1B 3F1
A5E 311 316 504 506 507 G
(54) CORROSION INHIBITED AGRICULTURAL COMPOSITIONS
(71) We, MONSANTO COMPANY, a corporation organised under the laws of the State of Delaware, United States of America, of 800 North Lindbergh Boulevard, St. Louis, Missouri 63166, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the 5 method by which it is to be performed, to be particularly described in and by the 5
following statement:—
This invention relates to the inhibition of metallic corrosion by aqueous agricultural compositions containing as an active agricultural ingredient an aminomethylenephosphonic acid, or an agriculturally acceptable salt or ester 10 derivative thereof. More particularly, this invention relates to the inhibition of 10 corrosion of iron or zinc surfaces contacted by acjueous agricultural compositions wherein the active agricultural ingredient, an aminomethylenephosphonic acid, or salt or ester derivatives thereof in the presence of water and in the absence of an inhibitor is corrosive of such surfaces and evolves hydrogen gas. According to this 15 invention, corrosion of iron or zinc surfaces is inhibited by the inclusion in such 15
agricultural composition of a corrosion inhibiting amount of a thiol compound or salt thereof as hereinafter described.
The aminomethylenephosphonic acids employed in the compositions of this invention are encompassed by the following formula
20 ( hooc - 20
^HOO
wherein y and z are each individually I or 2, and x is 0 or 1, the sum of x, y and z being 3. Also useful in the compositions of this invention are the agriculturally acceptable salts and esters of these acids.
The term "agricultural composition" as herein employed includes within its 25 scope herbicidal and plant growth regulant compositions. While such compositions 25 are frequently formulated as dry powder compositions and used in this form to dust plant foliage, more commonly they are formulated into solutions, emulsions, suspensions or dispersions for wet application to plant foliage. These liquid formulations usually contain water and more water is added thereto at the time of application in 30 order to dilute the concentration of the active ingredient in the formulation to 30
levels enabling the application of predetermined, controlled amounts to plant foliage. Normally, the dry powder formulations are generally non-corrosive of metal surfaces whereas depending on the specific active ingredient in an aqueous liquid formulation and the surface-active agent which may also be present in the 35 formulation, mild to severe corrosion of metal surfaces will occur when contacted 35 by the aqueous agricultural compositions.
The term "active agricultural ingredient" as herein employed is inclusive of any ingredient functioning as a plant phytotoxicant or as a plant growth regulant. The particular function of an active ingredient can be that of a herbicide when
BNSDOCID: <GB 1604526A l_>
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applied to the plant at moderate to high application rates and, on the other hand, function as a plant growth regulant at low to minute application rates. Such dual function capability is exhibited by some of the aminomethylenephosphonic acids and their agriculturally acceptable salts as described in U.S. Patents 3,455,675 and 3,556,762, the former being directed to phytotoxicant use and the latter to plant growth regulation. The herbicidal activity of N-phosphonomethylglycine and its agriculturally acceptable salt and ester derivatives is described in U.S. Patents 3,799,758; 3,868,407; 3,971,648 and 3,977,860. Plant growth regulant utility for N-phospftonamethylglycine and its agriculturally acceptable salt and ester derivatives is described in U.S. Patents 3,853,530 and 3,988,142.
The aqueous formulations of the aminomethylenephosphonic acids, such as N-phosphonomethylglycine or derivatives thereof, and more particularly those formulations water-diluted to application levels are corrosive to iron, steel or galvanized metal surfaces of containers in which the concentrates or mixtures are stored, and to steel or galvanized surfaces of spraying equipment. Hydrogen evolution is one aspect of the corrosion activity and can cause disruptive pressures in closed containers containing the aqueous agricultural compositions as well as constituting a fire hazard and explosion hazard.
It is known that the application of various organic coatings, such as the phenolics, synthetic rubbers, alkyds, vinyls as well as glass linings to metal surfaces is one practical means for protecting or preventing corrosion of metal surfaces but such coatings increase the cost of containers and other equipment used for application of herbicides or plant growth regulants. Moreover, the integrity of such coatings is subject to accidental or abrasive abuse under agricultural application working conditions whereby the coating is mechanically abraded, scraped or otherwise detached from the metal surface. When this occurs, the exposed metal surface is then readily attacked by the agricultural composition, and such corrosion frequently causes detachment or degradation of the protective coating material adjacent to the exposed metal surface thus accelerating the overall corrosion of the equipment.
Trabanelli et al reported on the performance of various organic sulfur compounds for inhibiting corrosion of iron immersed in sulfuric acid and noted that mercaptans were generally poor inhibitors of iron corrosion and in some instances even functioned as corrosion stimulators (Chemical Abstracts, Volume 72, page 206, 58134z).
It was thus most surprising to discover that thiol compounds, e.g. mercaptans, as well as the ammonium and alkali metal thio salts of inorganic polybasic acids and the thio alkali metal salts are effective inhibitors of metal corrosion for aqueous agricultural compositions containing as an active agricultural ingredient an aminomethylenephosphonic acid, such as N-phosphonomethylglycine or the agriculturally acceptable salt or ester derivatives thereof. Obviously, a satisfactory inhibitor of acidic corrosion as measured by H2 evolution and metal corrosion rate for a herbicidal composition or plant growth regulant composition should not deleteriously modify the agricultural activity of the composition. It was found that both retention of agricultural activity and adequate inhibition of acidic corrosion was obtained by the addition to aqueous formulations of an aminomethylenephosphonic acid or the agriculturally acceptable derivatives of relatively small amounts of certain thio compounds, such as the alkane thiols and dithiols, alkali metal salts of the alkane thiols and dithiols, and the ammonium and alkali metal thio salts of polybasic inorganic acids, i.e., sulfuric acid and phosphoric acid. Adequate inhibition of acidic corrosion as measured by H2 evolution can be obtained with a minimum of 0.15 percent, by weight of the thio compound on the weight of N-phosphonomethylglycine. To insure long term corrosion inhibition, it is preferred to use the thio compound in amounts of 0.3 to 3 percent by weight on the weight of the N-phosphonomethylglycine or aminomethylenephosphonic acid or derivatives thereof although the thio compound can be employed in amounts as high as 20 percent by weight based on the N-phosphonomethylglycine. Not too infrequently, aqueous concentrates of the herbicidal or plant growth regulant compositions may be stored in the vendor's metal containers by the farmer for many months before being used and, hence, it is desirable to minimize corrosion of the container to the maximum extent in order to prevent any possible leakage of the concentrate due to rusting of the container's metal walls. Amounts more than 5 percent by weight of the thio compound can be used if desired but no further commensurate advantage with respect to corrosion is usually realized.
In the agricultural formulations of this invention, one can employ anionic,
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cationic or non-ionic surface-active agents. The surfactants which are useful in the compositions of this invention include those of the cationic, anionic, and non-ionic variety and also amine oxide, imidazolines, propoxylated ethoxylated ethylenediamine, quaternary ammonium compounds, betaine derivatives as well as amphoteric surfactants. Examples of the amine oxides are lauryldimethylamine oxide, cetyldimethylamine oxide, myristyldimethylamine oxide, bis(2-hydroxyethyl)cocoamine oxide and the like. Examples of quaternary amine surfactants are cocotrimethylammonium chloride, alkylamidoethyl alkyl imidazolium methyl methosulfate. Examples of cationic surfactants are N,N-bis(2-hydroxyethyl)alkylamines where the alkyl groups are C14—C18 derived from tallow, N,N-bis(a--ethyl-omega-hydroxy)-poly(oxyethylene)alkyiamines having an average of 3 oxyethylene groups, the alkyl being C,4—C18 derived from tallow and (3-lauramidopropyl) trimethylammonium methyl sulfate. Some anionic surface-active agents are the sulfated fatty alcohols and the alkylarylsulfonates. Representative of the sulfated fatty alcohols are the sodium or lower alkanol amine salts of the monoesters of sulfuric acid with N-aliphatic alcohols containing from 8 to 18 carbon atoms. The alkylarylsulfonates are inclusive of the products derived from the alkylation of an aromatic hydrocarbon, e.g., benzene, naphthalene, diphenyl, diphenyl methane and phenoxybenzene, sulfonation of the resulting alkylated aromatic hydrocarbon and neutralization of the sulfonation product with NaOH or KOH, or with a primary or secondary amine.
Some non-ionic surface-active agents are the ethoxylated monoamines having the structure yCH2CH20)mH RN
\
(CH2CH20)mH
wherein R is alkyl containing from about 8 to 16 carbon atoms and m is an integer from 2 to 25. Preferred anionic surface-active agents are the aliphatic amine salts of monoalkyl (Ca—C1B) phenoxybenzene disulfonic acids.
All of the alkane thiols and dithiols containing from 2 to 16 carbon atoms in the alkane moiety which have been examined for corrosion inhibition were found effective in substantially eliminating hydrogen evolution under the test conditions herein described. The alkane thiols particularly those containing 8 or less carbon atoms in the alkane moiety have a pronounced disagreeable odor. It is, therefore, preferable to employ alkane thiols having greater than 8 carbon atoms in the alkane moiety. The higher alkane thiols are less odorous and, hence, are preferred in the interests of minimizing worker and user discomfort. The terms "alkane thiol" and "alkane dithiol" are intended to include the normal, secondary and tertiary isomers of these compounds. Representative thiols and dithiols useful in the practice of this invention include 1,2-ethanedithiol, ethanedithiol, 1,3-propanedithiol, 1-propanethiol, 2-propanethiol, 2-methyl-2-propanethiol, 1,4-butanedithiol, 1-butanethiol, 3-methyl-l-butanethiol, 1-hexanethiol, 2-hexanethiol, 3-hexanethiol, 1-octanethiol, 2-octanethiol, 1-decanethiol, 1-dodecanethiol and 1-hexadecanethiol. Representative of the alkali metal salts of the alkane thiols and dithiols are the sodium and potassium salts of 1-ethanethiol, 1-butancthiol, 1-hexanethiol and 1-dodecanethiol. Representative of the ammonium and alkali metal thio salts of inorganic polybasic acids are ammonium thiosulfate, ammonium thiophosphate, ammonium thiocarbonate, sodium thiophosphate, potassium thiophosphate, sodium dimethyldithiocarbonate and sodium thiocarbonate, which unlike the alkane thiols do not contain in their structure an —SH group but nevertheless do inhibit hydrogen evolution to a major extent from steel and zinc surfaces. One can also add compounds such as sodium sulfite to the thiosulfate-containing compositions. Although no improvement in the corrosion inhibition is obtained, this prevents dissociation of the ammonium thiosulfate in this composition.
The corrosion inhibited agricultural compositions of this invention, including concentrates requiring dilution with water prior to plant application, contain from 5 to 95 parts by weight of an agriculturally active agent, from 5 to 95 parts by weight of an adjuvant comprising from 0.25 to 25 parts by weight of a non-ionic or anionic surface-active agent, from 0 to 25 parts by weight of a dispersant and from about 4.5 to about 95 parts by weight of inert liquid extender, e.g., water and from 0.15 to
4
1,604,526
4
2 parts, by weight of a suitable thio compound. The compositions are prepared by mixing the active ingredient, the thio compound, the surface-active agent and the liquid extender to provide liquid compositions in the form of solutions, suspensions, dispersions or emulsions. These liquid compositions immediately prior 5 to application to plants are diluted with water as required to obtain the desired 5
effects (herbicidal or plant growth regulation).
For determining hydrogen evolution, concentrated liquid formulations were prepared according to the following formula, all parts being by weight:
Monoisopropylamine salt of N-phosphonomethylglycine 41 parts
10 Surfactant 15 parts 10
Inhibitor 1 part
Water 43 parts
The liquid concentrates were then diluted with water to actual spray use concentrations, i.e., 5 parts concentrate to 95 parts water and the diluted 15 formulations were tested for hydrogen evolution and corrosion characteristics. The 15 diluted concentrates are normally more corrosive to metals than the concentrates.
Hydrogen evolution was measured according to the following procedure. A metal coupon (mild steel or zinc) was horizontally supported within the mouth of an inverted plastic funnel, the support being toothpicks fastened to the rim of the 20 funnel. The dimensions of the steel coupon were 3.2 cmxl.4 cmx0.6 cm; the zinc 20 coupons were 3.2 cmxl.4 cmx0.2 cm. The funnel assembly with the supported metal coupon was placed into a 250 ml beaker, and enough dilute liquid agricultural formulation was poured into the beaker to completely submerge the funnel. A 100 ml conical graduated glass centrifuge test tube was filled with the 25 formulation, the end of the tube was then finger sealed, inverted and placed over 25
the neck of the funnel. Hydrogen gas evolving from attack on the metal coupon by the formulation ascends upwardly within the conical section of the funnel, then into the funnel neck and finally into the test tube where it collects and displaces the liquid formulation. The amount of collected gas is read directly off the graduations 30 on the test tube. The beaker and its contents are maintained at room temperature 30 during the 24-hour test period.
The corrosion rate of the coupons was determined by immersing degreased mild steel and zinc coupons in a given formulation at room temperature for 96 hours and then measuring weight loss or gain of the coupon and extrapolating the 35 result to an annual rate of corrosion. 35
Water-diluted concentrates prepared as described supra and containing the monoisopropylamine salt of N-phosphonomethylglycine as the active agricultural ingredient were modified by the inclusion of various thiol compounds and surfactants as stated in subsequent Table I. Test data reported in Table I was 40 obtained at room temperature. 40
Weight %
Experiment Inhibitor in
# Surfactant* "Concentrate"
1 A no inhibitor
2 B no inhibitor
3 C no inhibitor
4 A +1%
5 B +1%
6 C +1%
7 C +1%
8 C +1%
9 C + 1%
10 C +1%
11 C +1%
12 C +1%
13 C +1%
14 C +1%
15 C +1%
16 A +2%
17 B +2%
18 C +2%
TABLE I
Inhibitor
Solution PH
H2 Evolution cc During Initial 24 Hours per sq/ft Metal Surface (929 sq/cm) Steel Zinc
Corrosion
Rate (mm/year) Steel Zinc
4.5
15.0
2.3
0.080
0.037
4.3
12.4
2.3
0.091
0.049
4.3
18.0
1.4
0.218
0.068
1 -dodecanethiol
4.5
0
0
0.011
0.026
I-dodecanethiol
4.3
0
0
0.013
0.006
I-dodecanethiol
4.3
0
0
0.017
0.008
1-hexadecylthiol
0
0
0.011
0.025
1-octanethiol
0
0
0.017
0.030
1,12-dodecanedithiol
0
0
0.006
0.013
sodium salt of dodecanethiol
0
0
0.010
0.027
dodecanethiol &
0
0
0.020
0.045
oxalic acid equal to
weight of isopropyl-
amine salt of N-
phosphonomethylglycine
0.035
0.040
dodecanesulfide
0.6
0
dodecanedisulfide
1.9
0
0.033
0.053
octanesulflde
1.1
0
0.022
0.045
octanedisulfide
0.1
0
0.035
0.093
ammonium thiosulfate
0
0
0.040
0.033
ammonium thiosulfate
0.3
0.3
0.111
0.119
ammonium thiosulfate
0.3
0.3
0.155
0.058
Weight %
Experiment Inhibitor in
# Surfactant* "Concentrate"
19 C +1%
20 C +1%
21 C +1%
22 C +1%
23 C +1%
24 A +1%
25 B +1%
26 C +1%
27 A +1%
28 B +1%
29 C +1%
30 A +1%
31 B +1%
32 C +1%
33 Distilled water (no inhibitor)
H2 Evolution cc
During Initial 24
Hours per sq/ft
Corrosion
Metal Surface
Rate
Inhibitor
Solution
(929 sq/cm)
(mm/year)
pH
Steel
Zinc
Steel
Zinc furanomethylthiol
0
3.6
0.058
0.10**
alpha mercaptotoiuene
0
4.1
0.043
0.075**
p-thiocresol
0
0
0.033
0.048
1 -methyl-1 -propanethiol
0
0.6
0.040
0.033
2-methyl- 1-propanethiol
0
9.8
0.038
0.040
sodium thiophosphate
0
6.6
0.022
0.205
sodium thiophosphate
0.7
5.1
0.071
0.231
sodium thiophosphate dimethyldithiocarbamic
3.4
5.8
0.081
0.152
0
1.8
0.020
0.099
acid sodium salt
dimethyldithiocarbamic acid
0
5.1
0.022
0.104
sodium salt
dimethyldithocarbamic acid
0
3.4
0.043
0.093
sodium salt
sodium thiocarbonate
0
0.5
0.022
0.086
sodium thiocarbonate
0.7
2.9
0.055
0.071
sodium thiocarbonate
0.7
1.1
0.068
0.096
0.4
0.3
0.043
0.022
5
10
15
20
25
30
35
40
45
50
55
7
5
10
15
20
25
30
35
40
45
50
1,604,526
♦Surfactant "A" is a non-ionic type surfactant comprising an ethoxylated tailow amine having the structure
^(CH2CH20)mH
RN
\
(CH2CH20)mH
wherein m has an average value of between 15 and 20 and R is alkyl having an average number of carbon atoms of about 17—18.
Surfactant "B" is an anionic type surfactant comprising a mixture which averages about 80 percent or more by weight of a monoisopropylamine salt of a C10 alkyl phenoxybenzene disulfonic acid and up to about 20 percent by weight of dialkylated products of phenoxybenzene disulfonic acid.
Surfactant "C" is also an anionic surfactant and is the triethanolamine salt of a (C8_10) alcohol sulfate; (C8_10) 0S020N(CH2CH20H)3.
H
♦♦Weight gain.
Inspection of the data presented in Table I shows that all the tested alkane thiols and dithiols (Experiments 4—9) and the alkali metal salt of an alkane thiol (Experiment 10) were 100 percent effective in preventing evolution of hydrogen on test coupons of steel and zinc. Additionally, they exhibited the lowest corrosion rates of steel and zinc of all the tested inhibitors being less corrosive than even distilled water per se (Experiment 33).
Almost as effective as the thiol and dithiols and alkali metal salts of the thiols in reducing H, evolution was ammonium thiosulfate (Experments 16, 17 and 18), sodium thiophosphate (Experiments 24, 25 and 26), sodium thiocarbonate (Experiments 30, 31 and 32) and sodium dimethyldithiocarbamate (Experiments 27, 28 and 29). Inhibition of corrosion, however, was only fair. The inhibition of H2 evolution is adequate for safe storage of the ammonium thiosulfate, the sodium thiophosphate and the sodium thiocarbonate inhibited formulations in metal cans, tanks and other metal equipment.
Experiment 11 involved a herbicidal formulation containing in addition to the dodecanethiol inhibitor, the copresence of oxalic acid in an amount equal to the weight of the isopropylamine salt of N-phosphonomethylglycine. The use of oxalic acid in herbicidal formulations containing N-phosphonomethylglycine or its derivatives is disclosed in "Research Disclosure" publication number RDI5334, published January, 1977 by Industrial Opportunities Ltd., Homewell-Havant-Hampshire P09 1EF, United Kingdom. According to said publication, when herbicidal formulations containing N-phosphonomethylglycine or its derivatives are diluted for application purposes with hard water, i.e. water containing calcium or magnesium ions in the range of from 100 to 2000 or more parts by weight per million parts by weight of water, the diluted formulations have diminished herbicidal activity as compared to the same formulations diluted with deionized water. The publication teaches the use of oxalic acid in hard water diluted herbicidal formulations to restore the herbicidal activity and recommends the amount of oxalic acid be at least equivalent to 50 percent of the calcium or magnesium ion to as much as 200 percent or more of such ions present in the diluting hard water. The weight ratio of the N-phosphonomethylglycme compound to oxalic acid ranges from 1 to 10 parts by weight of the glycine compound per I to 10 parts by weight of oxalic acid. Oxalic acid is known to be corrosive of iron surfaces. As demonstrated by the data in Table I for Experiment 11, the normal corrosive action of oxalic acid on iron surfaces is satisfactorily inhibited when a thiol compound is present in the herbicidal formulation.
That the use of thio compounds as inhibitors of metal corrosion in herbicidal compositions containing an amine salt of N-phosphonomethylglycine does not significantly diminish post-emergent herbicidal activity of the composition is quite evident from the data presented in Table II on the post-emergence killing of quackgrass using formulations described in Table I, being Experiments 1 to 6 and 16 to 18. The experimental formulations were suitably diluted with water and applied to quackgrass plants established from vegetative propagules at a rate of 187 liters per hectare. Plants treated with the experimental formulations were placed in
8
1,604,526
8
a greenhouse and observed and recorded 12 days after treatment with the herbicidal formulation.
TABLE II
5
Experiment Number
Surfactant
Inhibitor
Rate (kg/h)*
% Inhibition Plant Response (% Quackgrass 12 Days After Treatment)
5
1
A
None
1.12
95
10
0.56
95
10
0.28
40
2
B
None
1.12
99
0.56
99
0.28
50
15
3
C
None
1.12
99
15
0.56
99
0.28
60
4
A
Dodecanethiol
1.12
98
0.56
98
20
0.28
45
20
5
B
Dodecanethiol
1.12
99
0.56
98
0.28
70
6
C
Dodecanethiol
1.12
99
25
0.56
99
25
0.28
55
16
A
Ammonium thiosulfate
1.12
99
0.56
98
0.28
60
30
17
B
Ammonium thiosulfate
1.12
99
30
0.56
90
0.28
60
18
C
Ammonium thiosulfate
1.12
99
0.56
99
35
0.28
40
35
40
45
50
55
60
♦Amount of monoisopropylamine salt of N-phosphonomethylglycine applied per hectare.
In order to determine what effect on post-emergence herbicidal activity would result when the quantity of thiol inhibitor in a herbicidal formulation containing the monoisopropylamine salt of N-phosphonomethylglycine as the active ingredient was increased many fold beyond that required for adequate inhibition of hydrogen evolution and metal corrosion, two control formulations were prepared, one containing previously described surfactant "A" and the other surfactant "C" according to the following formula, all parts being by weight:
Monoisopropylamine glycine Surfactant Water salt of N-phosphonomethyl-
41 parts 15 parts 44 parts
The formulations were then diluted with water and sufficient additional surfactant added to the diluted formulations for the surfactant to constitute in each instance 1 percent by weight of the diluted formulation. The amount of water used to prepare the diluted formulations was so adjusted that each diluted formulation could be spray applied to the plants at a common rate of 187 liters per hectare, even though the amount of active ingredient in each diluted formulation was maintained at different levels. The amount of thiol inhibitor in each diluted formulation was also adjusted to maintain a constant application of 4.48 kilograms per hectare when the diluted formulation was spray applied at 187 liters per hectare. The diluted formulations (with and without inhibitor) were sprayed on 3 week old greenhouse grown Johnson grass and quackgrass and the observations as to herbicidal effectiveness reported in Table III were made 28 days later.
40
45
50
55
60
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5
10
15
20
25
30
35
40
45
50
55
60
9
5
10
15
20
25
30
35
40
45
50
55
60
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TABLE III
% Inhibition
Formulation
Rate
Johnson
Surfactant
Inhibitor
(kg/h)*
Grass
Quackgrass
A
None
0.28
100
100
A
None
0.14
65
98
A
None
0.07
35
25
A
None
0.035
0
20
C
None
0.28
95
100
C
None
0.14
60
95
c
None
0.07
30
35
c
None
0.035
0
20
A
Octanethiol
0.28
85
100
A
Octanethiol
0.14
55
65
A
Octanethiol
0.07
30
15
A
Octanethiol
0.035
0
0
C
Octanethiol
0.28
85
75
c
Octanethiol
0.14
35
45
c
Octanethiol
0.07
20
30
c
Octanethiol
0.035
0
0
A
1,12-Dodecanedithiol
0.28
90
100
A
1,12-dodecanedithiol
0.14
60
90
A
1,12-dodecanedithiol
0.07
15
25
A
1,12-dodecanedithiol
0.035
0
15
C
1,12-dodecanedithiol
0.28
85
100
c
1,12-dodecanedithiol
0.14
35
70
c
1,12-dodecanedithiol
0.07
20
40
c
1,12-dodecanedithiol
0.035
0
20
♦Amount of monoisopropylamine salt of N-phosphonomethylglycine applied per hectare.
Although the amount of thiol inhibitor to active ingredient of the formulations described in Table III ranged from 164:1 at the 0.28 kg/h rate to a high of 1312:1 at the 0.035 kg/h rate of active ingredient, only a slight diminution of herbicidal effectiveness was observed and this occurred principally at ratios of thiol inhibitor to active ingredient or more than 164:1.
Although the inhibitor efficacy of various thio compounds was exemplified with the monoisopropylamine salt of N-phosphonomethylglycine in Table I, substantially similar corrosion inhibition can be expected when a thio compound as herein disclosed is admixed with other salts and esters of N-phosphonomethylglycine such as the alkali metal salts as are disclosed in U.S. Patent No. 3,977,860. Such salts and esters include but are not limited to the following:
monocyclohexylamine salt of N-phosphonomethylglycine di(methylamine) salt of N-phosphonomethylglycine di(dimethylamine) salt of N-phosphonomethylglycine di(ethylamine) salt of N-phosphonomethylglycine di(n-propylamine) salt of N-phosphonomethylglycine di(morpnoline) salt of N-phosphonomethylglycine mono(stearylamine) salt of N-phosphonomethylglycine mono(tallowamine) salt of N-phosphonomethylglycine mono(methylbutyl) salt of N-phosphonomethylglycinc mono(butylamine) salt of N-phosphonomethylglycine)
n-dibutylamine salt of N-phosphonomethylglycine n-octadecylamine salt of N-phosphonomethylglycine »
methoxyethylamine salt of N-phosphonomethylglycine ethylenediamine salt of N-phosphonomethylglycine dipropanolamine salt of N-phosphonomethylglycine chloroethylamine salt of N-phosphonomethylglycine phenoxyethylamine salt of N-phosphonomethylglycine mono(triethylamine) salt of N-phosphonomethylglycine mono(diethylenetriamine) salt of N-phosphonomethylglycine
10
1,604,526
10
monoisopropylamine salt of N-phosphonomethylglycine monomorpholine salt of N-phosphonomethylglycme monoaniiine salt of N-phosphonomethylglycine monoethanolamine salt of N-phosphonomethylglycine 5 jnonodiethanolamine salt of N-phosphonomethylglycine monoammonium salt of N-phosphonomethylglycine monosodium salt of N-phosphonomethylglycine disodium salt of N-phosphonomethylglycine trisodium salt of N-phosphonomethylglycine 10 monopotassium salt of N-phosphonomethylglycine dipotassium salt of N-phosphonomethylglycine tripotassium salt of N-phosphonomethylglycine dilithium salt of N-phosphonomethylglycine monosodium salt of ethyl N-phosphonomethylglycinate 15 monosodium salt of chloroetnyl N-phosphonomethylglycinate methyl N-phosphonomethylglycinate dimethyl N-phosphonomethylglycinate ethyl N-phosphonomethylglycmate 2-chIoroethyl N-phosphonomethylglycinate 20 n-propyl N-phosphonomethylglycinate n-butyl N-phosphonomethylglycinate n-hexyl N-phosphonomethylglycinate cyclohexyl N-pnosphonomethylglycinate n-octyl N-phosphonomethylglycinate 25 n-decyl N-phosphonomethylglycinate n-dodecyl N-phosphonomethylglycinate
Representative but not inclusive of the aminophosphonates described in U.S. Patent No. 3,556,762 and which in aqueous fonnulations cause corrosion of metal surfaces are the following compounds:
30 nitrilodi (acetic acid) (methylphosphonic acid)
tris(dimethylammonium)iminoacetate N-methylphosphonate trisodium iminodiacetate N-methylphosphonate tetra(dimethylammonium)aminoacetate N,N-bis-methylphosphonate 2,2'-bisphosphonomethyliminoacetic acid 35 dipotassium iminodiacetate N-methyl-O-potassium-O-ethylphosphonate
Data on hydrogen evolution and corrosion inhibition by dodecanethiol for several agricultural formulations containing as an active ingredient N-phosphonomethylglycine or salt or ester derivative thereof or an aminophosphonate compound are tabulated in Table IV. The formulations used in 40 Table IV were of two types, liquid and dry powder. Experiments 34 and 35 were conducted on liquid formulations of the following compositions, all parts being by weight:
Experiment 34
Di-(moniosopropylamine) salt of N-phosphonomethyl-
45 glycine 41
Surfactant "C" 15
Water 44
Experiment 35
Di-(monoisopropylamine) salt of N-phosphonomethyl-
50 glycine 41
Surfactant "C" 15
Dodecanethiol 1
Water 43
The dry powder formulations. Experiments 36 to 47 had the following 55 compositions, all parts being by weight:
Experiment 36
Disodium salt of N-phosphonomethylglycine 78
Surfactant "D" 2
Urea 20
5
10
15
20
25
30
35
40
45
50
55
BNSDOCID: <GB 1604526A_I_>
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10
15
20
25
30
35
40
45
50
55
11
5
10
15
20
25
30
35
40
45
50
55
1,604,526
Experiment 37
Disodium salt of N-phosphonomethylglycine 78
Surfactant "D" 2
Dodecanethiol — 9.2 Urea Complex (2.1 parts thiol)
(7.1 parts urea)
Urea 10.9
Experiment 38
Diammonium salt of N-phosphonomethylglycine 74.6
Surfactant "D" 2
Urea 23.4
Experiment 39
Diammonium salt of N-phosphonomethylglycine 74.6
Surfactant "D" 2
Dodecanethiol — 9.2 Urea Complex (2.1 parts thiol)
Urea Complex (7.1 parts urea)
Urea 14.3
Experiment 40
Dipotassium salt of N-phosphonomethylglycine 89.7
Surfactant "D" 2
Urea 8.3
Experiment 41
Dipotassium salt of N-phosphonomethylglycine 87.7
Surfactant "D" 2
Dodecanethiol — 9.2 Urea complex (2.1 parts thiol)
(7.1 parts urea)
Urea 1.2
Experiment 42
N-phosphonomethylglycine 64.4
Surfactant "D" 2
Urea 33.6
Experiment 43
N-phosphonomethylglycine 64.4
Surfactant "D" 2
Dodecanethiol — 9.2 Urea Complex (2.1 parts thiol)
(7.1 parts urea)
Urea 22.4
Experiment 44
2,2'-bisphosphonomethyliminoacetic acid 51
Surfactant "D" 2
Urea 47
Experiment 45
2,2'-bisphosphonomethyliminoacetic acid 52
Surfactant "D" 2
Dodecanethiol — 9.2 Urea Complex (2.1 parts thiol)
(7.1 parts urea)
Urea 37.9
Experiment 46
Monoethyl ester of N-phosphonomethylglycine 86.3
Surfactant "D" 2
Urea 11-7
12 1,604,526 12
Experiment 47
Monoethyl ester of N-phosphonomethylglycine 86.3
Dodecanethiol — 9.2
Urea Complex (2.1 parts thiol)
5 (7.1 parts urea) 5
Urea 2.5
Surfactant "C" is as previously described.
Surfactant "D", an anionic surfactant, is a complex of sodium dioctyl-sulfosuccinate.
10 Experiments 34, 36, 38, 40, 42 and 44 were control experiments containing no 10
inhibitor. Experiments 37, 39,41, 43 and 45 were dry solid formulations containing a complex of urea and dodecanethiol. Alkane thiols such as dodecanethiol are substantially water insoluble and although a surfactant is an aid in effecting dispersion of the thiol in an aqueous formulation, it has been found that a solid 15 complex of urea and a straight chain alkane thiol when mixed with a dry mixture of 15 the active ingredient and surfactant enhances dispersibility of the thiol in aqueous agricultural formulations and minimizes separation of the thiol component. The complex dissolves readily in water to reform the urea and the thiol with the thiol being finely dispersed and remaining in suspension. The urea-thiol complex is 20 prepared by dissolving the alkane thiol in a solvent such as isoctane and mixing the 20 solution at room temperature with sufficient urea prewetted with methanol until the urea increases in volume; the reaction is slightly exothermic. The molar ratio of urea to alkane thiol used to form the complex is proportional to the thiol's chain length being at least 6; 1 for alkane thiols containing 6 carbon atoms, 10:1 moles for 25 dodecanethiol and about 16:1 for thiols of 16 carbon atoms. The solvents used in 25 the reaction are removed by washing and drying. The corrosion experiments reported in Table IV were all conducted with the liquid as well as the solid type formulations having been diluted with water in amount corresponding to normal application dilutions, namely a dilution that would apply per hectare 2.24 kilograms 30 of active ingredient (calculated as N-phosphonomethylglycine or 2,2'- 30 bisphosphonomethyliminoacetic acid) at a spraying rate of 187 liters per hectare.
Diisopropylamine salt of
N-phosphonomethylglycine Diisopropylamine salt of
N-phosphonomethylglycine Disodium salt of N-pnosphono-
methylglycine Disodium salt of N-phosphonomethylglycine Diammonium salt of N-phosphono methylglycine Diammonium salt of N-phosphono methylglycine Dipotassium salt of N-phosphonomethylglycine Dipotassium salt of N-phos-
phonomethylglycine N-phosphonomethylglycine N-phosphonomethylglycine 2,2'-bis-phosphonomethyl-
iminoacetic acid 2,2'-bis-phosphonomethyl-
iminoacetic acid Monoethyl ester of N-phos-
phonomethylglycine Monoethyl ester of N-phosphonomethylglycine
TABLE IV
Inhibitor pH
H2 Evolution cc/sq.ft. from Steel from Zinc 0—24 Hours 0—24 Hours
Corrosion Rate (mm/hr) Steel Zinc
None 7.17 5.3
Dodecanethiol 7.10 0
None 6.54 4.99
Dodecanethiol 6.79 0
None 6.56 5.20
Dodecanethiol 6.60 0
None 6.70 6.19
Dodecanethiol 6.79 0
None 2.17 4.3
Dodecanethiol 2.14 0
None — 233
Dodecanethiol — 0
None — 0.6
Dodecanethiol — 0
1.8 0 0 0
0.60 0
0.8 0
89.9
0.8
720
2.9 0.5 0
0.266
0.012
0.172
0.017
0.132
0.010
0.0812
0.007
0.010 0.003 6.45
0.030
0.040
0.020
0.320
0.005
0.055
0.017
0.045
0.010
0.035
0.002
2.029 0.187 23.3
0.038
0.063
0.030
Claims (14)
14
1,604,526
14
Thiols other than the alkane thiols have also been found effective in inhibiting corrosion by aqueous agricultural compositions as herein contemplated. Such thiols include the aromatic and cycloaliphatic thiols. For example, 2% inhibiting amounts of p-chlorothiophenol, 2-aminothiophenol, 2-furanomethanethiol, 5 toluenethiol, 2-benzoxazolthioI and mercaptobenzothiazole enable a dry disodium 5
salt of N-phosphonomethylglycine formulation corresponding to Experiment 36 when diluted with water reduces the hydrogen evolution and the metal corrosion rate. Similar corrosion inhibition was obtained when fertilizer diluent ingredients other than urea were included in the agricultural formulations, as, for example, 10 monoammonium phosphate and disodium phosphate. 10
WHAT WE CLAIM IS:—
1. An agricultural composition comprising as an agricultural active ingredient from 5 to 95 parts by weight of an aminomethylenephosphonic acid of the formula
HOOC - - P(OH)2\
40
^ooc
15 wherein y and z are each individually 1 or 2, and x is 0 or 1, the sum of x, y and z 15 being 3, or an agriculturally acceptable salt or ester thereof, from 5 to 95 parts by weight of an adjuvant comprising from 0.25 to 25 parts by weight of a non-ionic or anionic surface active agent, from 0 to 25 parts of a dispersant, and from 4.5 to 95 parts by weight of an inert liquid extender, and from 0.15 to 3% by weight of said
20 aminomethylenephosphonic acid of a thio compound selected from the alkane 20 thiols and dithiols having from 2 to 16 carbon atoms in the alkane moiety, aromatic thiols, cycloaliphatic thiols, the alkali metal salt of said thiols and dithiols and the ammonium and alkali metal thio salts of polybasic inorganic acids for all combinations of x, y and z excepting the combination x=y=z=l representative of N-
25 phospETonomethylglycine wherein said thio compound comprises from 0.15 to 20% 25 by weight of the said N-phosphonomethylglycine.
2. An agricultural composition according to Claim 1 wherein the alkane thiol is 1-dodecanethiol.
3. An agricultural composition according to Claim 1 wherein the alkane thiol is
30 l-octanethiol. 30
4. An agricultural composition according to Claim 1 wherein the alkane thiol is 1-hexadecylthiol.
5. An agricultural composition according to Claim 1 wherein the ammonium thio salt is ammonium thiosulfate.
35
6. An agricultural composition according to Claim 1 wherein the ammonium 35
thio salt is ammonium thiophosphate.
7. An agricultural composition according to Claim 1 containing between 1 and 10 parts by weight of oxalic acid per 1 to 10 parts by weight of an amine salt of N-phosphonomethylglycine.
8. A dry agricultural composition according to Claim 1 wherein the thiol is a 40 straight chain alkane thiol and complexed with urea, the molar ratio of the thiol to
' urea being proportional to the carbon atom chain in the alkane thiol being at least
1:6 for a six carbon thiol and at least 1:16 for a sixteen carbon thiol.
9. An agricultural composition according to Claim I wherein the active
45 ingredient is 2,2'-bisphosphomethyliminoacetic acid. 45
10. An agricultural composition according to Claim 1 wherein the active ingredient is the monoisopropylamine salt of N-phosphonomethylglycine.
11. A method for inhibiting corrosion of iron and zinc metal surfaces in contact with an aqueous agricultural composition comprising from 5 to 95 parts by
50 weight water, from 0 to 25 parts by weight of a surfactant and an active ingredient 50 selected from the aminomethylenephosphonic acids of the formula
H.
r r " ^
(HOOC - CE-4 N—tCH_ - P (OH) A
^ j~k x
BNSDOCID: <GB 1604526A_L>
15
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15
wherein y and z are each individually 1 or 2, and x is 0 or 1, the sum of x, y and z being 3, and the agriculturally acceptable salts and esters thereof which comprises adding to the composition from 0.15 to 3% by weight of said aminomethylenephosphonic acid of a thio compound selected from alkane thiols 5 and dithiols having from 2 to 16 carbon atoms in the alkane moiety, aromatic thiols, 5
cycloaliphatic thiols, the alkali metal salts of said thiols and dithiols and the ammonium and alkali metal thio salts of polybasic inorganic acids for all combinations of x, y and z excepting the combination x=y=z=l representative of N-phosphonomethylglycine wherein said thio compound comprises from 0, 15 to
20 20% by weight of the said N-phosphonomethylglycine. 10
12. A method in accordance with Claim 11 wherein the alkane thiol is a 1-dodecane thiol.
13. A method in accordance with Claim II wherein the alkane thiol is 1-octanethiol.
15
14. A method in accordance with Claim II wherein the alkane thiol is 1- 15
hexadecylthiol.
15. A method in accordance with Claim II wherein the thio compound is ammonium thiosulfate.
16. A method in accordance with Claim 11 wherein the thiol is an alkane thiol
20 complexed with urea and the urea-thiol complex is admixed with a dry mixture of 20 the active ingredient and the surfactant before dispersing in water.
17. A method which comprises contacting a plant with a phytotoxic amount of an aqueous herbicidal composition comprising from 5 to 95 parts by weight an amine salt of N-phosphonomethylglycine, from 0 to 25 parts by weight of a
25 surfactant, from 5 to 95 parts by weight water and from 0.15 to 3% by weight of said 25 aminomethylenephosphonic acid of a thio compound selected from alkane thiols and dithiols having from 2 to 16 carbon atoms in the alkane moiety, aromatic thiols, cycloaliphatic thiols, the alkali metal salts of said thiols and dithiols and the ammonium and alkali metal thio salts of polybasic inorganic acids for all
30 combinations of x, y and z excepting the combination x=y=z=l representative of 30 N-phosphonomethylglycine wherein said thio compound comprises from 0.15 to 20% by weight of the said N-phosphonomethylglycine.
18. A method according to Claim 17 wherein the thio compound constitutes between 0.15 and 3 percent by weight of the amine salt of N-
35 phosphonomethylglycine. 35
19. A method according to Claim 17 wherein the amine salt is the monoisopropylamine salt of N-phosphonomethylglycine.
20. A method which comprises contacting a plant with a plant growth regulating amount of an aqueous plant growth regulating composition comprising
40 from 5 to 95 parts by weight of an aminomethylenephosphonic acids having the 40 formula
HOOC -
^hcx:
wherein y and z are each individually 1 or 2, and x is 0 or 1, the sum of x, y and z being 3, and the agriculturally acceptable salts and esters thereof, from 5 to 95 parts 45 by weight of an adjuvant comprising from 0.25 to 25 parts by weight of a non-ionic 45 or anionic surface active agent, from 0 to 25 parts of a dispersant, and from 4.5 to 95 parts by weight of an inert liquid extender, and from 0.15 to 3% by weight of said aminomethylenephosphonic acid of a thio compound selected from the alkane thiols and dithiols having from 2 to 16 carbon atoms in the alkane moiety, aromatic
BNSDOCID: <GB 1604526A_I_>
16
1,604,526
16
thiols, cycloaliphatic thiols, the alkali metal salts of said thiols arid dithiols and the ammonium and alkali metal thio salts of polybasic inorganic acids for all combinations of x, y and z excepting the combination x=y=z= 1 representative of N-phosphonomethylglycine wherein said thio compound comprises from 0, 15 to 5 20% by weight of the said N-phosphonomethylglycine. 5
M. F. CLARKE,
Chartered Patent Agent,
Monsanto House,
10—18 Victoria Street,
London SW1H ONQ
Printed for Her Majesty's Stationery Office, by the Courier Press, Leamington Spa, 1981 Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.
BNSDOCID: <GB 1604526A_I_>
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79708377A | 1977-05-16 | 1977-05-16 | |
| US05/862,691 US4159901A (en) | 1977-05-16 | 1977-12-27 | Corrosion inhibited agricultural compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CY1180A true CY1180A (en) | 1983-10-07 |
Family
ID=27121824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CY1180A CY1180A (en) | 1977-05-16 | 1978-05-12 | Corrosion inhibited agricultural compositions |
Country Status (33)
| Country | Link |
|---|---|
| JP (1) | JPS5417126A (en) |
| AR (1) | AR221337A1 (en) |
| AT (1) | AT362184B (en) |
| AU (1) | AU519686B2 (en) |
| BG (1) | BG29862A3 (en) |
| CA (1) | CA1095281A (en) |
| CS (1) | CS205121B2 (en) |
| CY (1) | CY1180A (en) |
| DD (1) | DD137050A5 (en) |
| DE (1) | DE2820903A1 (en) |
| DK (1) | DK210578A (en) |
| EG (1) | EG13404A (en) |
| ES (1) | ES469651A1 (en) |
| FI (1) | FI62458C (en) |
| FR (1) | FR2390901A1 (en) |
| GB (1) | GB1604526A (en) |
| GR (1) | GR68085B (en) |
| IE (1) | IE46894B1 (en) |
| IL (1) | IL54694A (en) |
| IT (1) | IT1094641B (en) |
| KE (1) | KE3266A (en) |
| LU (1) | LU79649A1 (en) |
| MY (1) | MY8400125A (en) |
| NL (1) | NL7805012A (en) |
| NO (1) | NO781691L (en) |
| NZ (1) | NZ187256A (en) |
| OA (1) | OA05961A (en) |
| PH (1) | PH15128A (en) |
| PL (1) | PL113460B1 (en) |
| PT (1) | PT68043B (en) |
| SE (1) | SE7805461L (en) |
| SG (1) | SG9483G (en) |
| TR (1) | TR20256A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4608978A (en) * | 1983-09-26 | 1986-09-02 | Carol Block Limited | Method and apparatus for photoepiltion |
| KR860008713A (en) * | 1985-05-29 | 1986-12-18 | 죤 알. 페넬 | Solid plant erukseong composition and its manufacturing method |
| BR8605102A (en) * | 1985-10-21 | 1987-07-21 | Stauffer Chemical Co | LIQUID PLANT COMPOSITION AND LIQUID HERBICIDE COMPOSITION |
| CA2031017A1 (en) * | 1989-12-01 | 1991-06-02 | Robert J. Goos | Ammonium thiosulfate as herbicide extender |
| KR102179943B1 (en) | 2020-05-14 | 2020-11-18 | 이수인(주) | Water Outlet With Filter Attached To The Sink Faucet |
-
1978
- 1978-05-10 IL IL54694A patent/IL54694A/en unknown
- 1978-05-10 NL NL7805012A patent/NL7805012A/en not_active Application Discontinuation
- 1978-05-10 EG EG302/78A patent/EG13404A/en active
- 1978-05-10 ES ES469651A patent/ES469651A1/en not_active Expired
- 1978-05-12 FI FI781505A patent/FI62458C/en not_active IP Right Cessation
- 1978-05-12 CS CS783059A patent/CS205121B2/en unknown
- 1978-05-12 LU LU79649A patent/LU79649A1/en unknown
- 1978-05-12 BG BG039748A patent/BG29862A3/en unknown
- 1978-05-12 SE SE7805461A patent/SE7805461L/en unknown
- 1978-05-12 GR GR56226A patent/GR68085B/el unknown
- 1978-05-12 AT AT346578A patent/AT362184B/en not_active IP Right Cessation
- 1978-05-12 OA OA56467A patent/OA05961A/en unknown
- 1978-05-12 DK DK210578A patent/DK210578A/en unknown
- 1978-05-12 GB GB19157/78A patent/GB1604526A/en not_active Expired
- 1978-05-12 IT IT23368/78A patent/IT1094641B/en active
- 1978-05-12 DD DD78205356A patent/DD137050A5/en unknown
- 1978-05-12 AU AU36063/78A patent/AU519686B2/en not_active Expired
- 1978-05-12 IE IE969/78A patent/IE46894B1/en unknown
- 1978-05-12 FR FR7814306A patent/FR2390901A1/en active Pending
- 1978-05-12 AR AR272152A patent/AR221337A1/en active
- 1978-05-12 NO NO78781691A patent/NO781691L/en unknown
- 1978-05-12 NZ NZ187256A patent/NZ187256A/en unknown
- 1978-05-12 PH PH21132A patent/PH15128A/en unknown
- 1978-05-12 CY CY1180A patent/CY1180A/en unknown
- 1978-05-12 TR TR20256A patent/TR20256A/en unknown
- 1978-05-12 DE DE19782820903 patent/DE2820903A1/en not_active Withdrawn
- 1978-05-12 JP JP5707078A patent/JPS5417126A/en active Pending
- 1978-05-12 PL PL1978206727A patent/PL113460B1/en unknown
- 1978-05-15 CA CA303,367A patent/CA1095281A/en not_active Expired
- 1978-05-15 PT PT68043A patent/PT68043B/en unknown
-
1983
- 1983-03-03 SG SG94/83A patent/SG9483G/en unknown
- 1983-03-07 KE KE3266A patent/KE3266A/en unknown
-
1984
- 1984-12-30 MY MY125/84A patent/MY8400125A/en unknown
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