US20200216368A9 - Use of a cation source to prevent decomposition of (thio)phosphoric acid triamide urease inhibitors when a phosphorus-containing fertilizer is present - Google Patents
Use of a cation source to prevent decomposition of (thio)phosphoric acid triamide urease inhibitors when a phosphorus-containing fertilizer is present Download PDFInfo
- Publication number
- US20200216368A9 US20200216368A9 US16/088,920 US201716088920A US2020216368A9 US 20200216368 A9 US20200216368 A9 US 20200216368A9 US 201716088920 A US201716088920 A US 201716088920A US 2020216368 A9 US2020216368 A9 US 2020216368A9
- Authority
- US
- United States
- Prior art keywords
- fertilizer
- thio
- alkyl
- phosphoric acid
- acid triamide
- 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.)
- Pending
Links
- 239000003337 fertilizer Substances 0.000 title claims abstract description 476
- JLYVRXJEQTZZBE-UHFFFAOYSA-N ctk1c6083 Chemical group NP(N)(N)=S JLYVRXJEQTZZBE-UHFFFAOYSA-N 0.000 title claims abstract description 306
- 150000001768 cations Chemical class 0.000 title claims abstract description 230
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 60
- 239000002601 urease inhibitor Substances 0.000 title description 26
- 229910052698 phosphorus Inorganic materials 0.000 title description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title description 3
- 239000011574 phosphorus Substances 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 245
- 239000008187 granular material Substances 0.000 claims abstract description 176
- 238000000034 method Methods 0.000 claims abstract description 62
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 309
- 150000001412 amines Chemical class 0.000 claims description 239
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 218
- 239000004202 carbamide Substances 0.000 claims description 160
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 150
- -1 C3-C20-cycloalkyl Chemical group 0.000 claims description 127
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 122
- 239000005696 Diammonium phosphate Substances 0.000 claims description 121
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 121
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 121
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 103
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 93
- 239000001110 calcium chloride Substances 0.000 claims description 89
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 89
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 76
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 75
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 75
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 75
- 239000011592 zinc chloride Substances 0.000 claims description 75
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 75
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 75
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 74
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 74
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 74
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 74
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 74
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 74
- 239000006012 monoammonium phosphate Substances 0.000 claims description 74
- 239000011686 zinc sulphate Substances 0.000 claims description 74
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 73
- 150000003839 salts Chemical class 0.000 claims description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims description 46
- 229910052760 oxygen Inorganic materials 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 35
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 35
- 229910052717 sulfur Inorganic materials 0.000 claims description 35
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 31
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 29
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 28
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 claims description 28
- 229920006395 saturated elastomer Polymers 0.000 claims description 24
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 claims description 23
- 239000002426 superphosphate Substances 0.000 claims description 23
- HEPPIYNOUFWEPP-UHFFFAOYSA-N n-diaminophosphinothioylbutan-1-amine Chemical group CCCCNP(N)(N)=S HEPPIYNOUFWEPP-UHFFFAOYSA-N 0.000 claims description 22
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 19
- 125000005842 heteroatom Chemical group 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 12
- MPOFVZMCKSOGHZ-UHFFFAOYSA-N n-diaminophosphinothioylpropan-1-amine Chemical compound CCCNP(N)(N)=S MPOFVZMCKSOGHZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 10
- 239000002367 phosphate rock Substances 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000001506 calcium phosphate Substances 0.000 claims description 8
- 235000011010 calcium phosphates Nutrition 0.000 claims description 7
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 6
- 229910052925 anhydrite Inorganic materials 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 description 150
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 70
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 69
- 239000013256 coordination polymer Substances 0.000 description 65
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 60
- 239000004480 active ingredient Substances 0.000 description 53
- 125000003277 amino group Chemical group 0.000 description 41
- 125000006539 C12 alkyl 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 33
- 229910021529 ammonia Inorganic materials 0.000 description 26
- 0 [1*]N([2*])P(=C)(N([3*])[4*])N([5*])[6*] Chemical compound [1*]N([2*])P(=C)(N([3*])[4*])N([5*])[6*] 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 24
- 238000003860 storage Methods 0.000 description 24
- 150000001721 carbon Chemical group 0.000 description 22
- 239000002689 soil Substances 0.000 description 22
- 125000003545 alkoxy group Chemical group 0.000 description 20
- 125000000217 alkyl group Chemical group 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 108010046334 Urease Proteins 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 229920002873 Polyethylenimine Polymers 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 16
- 150000001414 amino alcohols Chemical class 0.000 description 15
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 15
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- 125000000623 heterocyclic group Chemical group 0.000 description 14
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 229960003390 magnesium sulfate Drugs 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 101001043818 Mus musculus Interleukin-31 receptor subunit alpha Proteins 0.000 description 10
- 229940090496 Urease inhibitor Drugs 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 125000002091 cationic group Chemical group 0.000 description 10
- 230000002401 inhibitory effect Effects 0.000 description 10
- 235000021317 phosphate Nutrition 0.000 description 10
- 229920000768 polyamine Polymers 0.000 description 10
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 10
- 150000003871 sulfonates Chemical class 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 9
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 9
- 235000015097 nutrients Nutrition 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 239000003381 stabilizer Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- FZQMJOOSLXFQSU-UHFFFAOYSA-N 3-[3,5-bis[3-(dimethylamino)propyl]-1,3,5-triazinan-1-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCN1CN(CCCN(C)C)CN(CCCN(C)C)C1 FZQMJOOSLXFQSU-UHFFFAOYSA-N 0.000 description 8
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 8
- 239000003086 colorant Substances 0.000 description 8
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 7
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000000087 stabilizing effect Effects 0.000 description 7
- 150000003512 tertiary amines Chemical class 0.000 description 7
- SSOBBNSVCWLYPH-UHFFFAOYSA-N 2-propylheptan-1-amine Chemical compound CCCCCC(CN)CCC SSOBBNSVCWLYPH-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- 239000003957 anion exchange resin Substances 0.000 description 6
- 229940043276 diisopropanolamine Drugs 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 150000003141 primary amines Chemical class 0.000 description 6
- 150000003335 secondary amines Chemical class 0.000 description 6
- 125000000547 substituted alkyl group Chemical group 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000002671 adjuvant Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 235000012054 meals Nutrition 0.000 description 5
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- 125000004430 oxygen atom Chemical group O* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000006413 ring segment Chemical group 0.000 description 5
- 125000006569 (C5-C6) heterocyclic group Chemical group 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- LSYBWANTZYUTGJ-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl-methylamino]ethanol Chemical compound CN(C)CCN(C)CCO LSYBWANTZYUTGJ-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- ZFMSMUAANRJZFM-UHFFFAOYSA-N Estragole Chemical compound COC1=CC=C(CC=C)C=C1 ZFMSMUAANRJZFM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
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- 238000009835 boiling Methods 0.000 description 4
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- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 4
- 230000000368 destabilizing effect Effects 0.000 description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 4
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- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 4
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 4
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- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 230000000050 nutritive effect Effects 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 3
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 3
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 3
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 239000011731 tocotrienol Substances 0.000 description 1
- 235000019148 tocotrienols Nutrition 0.000 description 1
- RUVINXPYWBROJD-ONEGZZNKSA-N trans-anethole Chemical compound COC1=CC=C(\C=C\C)C=C1 RUVINXPYWBROJD-ONEGZZNKSA-N 0.000 description 1
- 239000001393 triammonium citrate Substances 0.000 description 1
- 235000011046 triammonium citrate Nutrition 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- MCVUKOYZUCWLQQ-UHFFFAOYSA-N tridecylbenzene Chemical class CCCCCCCCCCCCCC1=CC=CC=C1 MCVUKOYZUCWLQQ-UHFFFAOYSA-N 0.000 description 1
- ICKIMNNCJKMGAT-UHFFFAOYSA-M trimethyl(3-oxopent-4-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCC(=O)C=C ICKIMNNCJKMGAT-UHFFFAOYSA-M 0.000 description 1
- UZNHKBFIBYXPDV-UHFFFAOYSA-N trimethyl-[3-(2-methylprop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)NCCC[N+](C)(C)C UZNHKBFIBYXPDV-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 229940040064 ubiquinol Drugs 0.000 description 1
- QNTNKSLOFHEFPK-UPTCCGCDSA-N ubiquinol-10 Chemical compound COC1=C(O)C(C)=C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)C(O)=C1OC QNTNKSLOFHEFPK-UPTCCGCDSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000004108 vegetable carbon Substances 0.000 description 1
- 235000012712 vegetable carbon Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000019235 yellow 2G Nutrition 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 description 1
- USDOQCCMRDNVAH-KKUMJFAQSA-N β-cadinene Chemical compound C1C=C(C)C[C@H]2[C@H](C(C)C)CC=C(C)[C@@H]21 USDOQCCMRDNVAH-KKUMJFAQSA-N 0.000 description 1
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 0.000 description 1
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- 239000002446 δ-tocopherol Substances 0.000 description 1
Classifications
-
- C05G3/08—
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- C05G3/0041—
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
Definitions
- the present invention relates to the use of a cation source (1) to prevent decomposition of a (thio)phosphoric acid triamide (2); to a method for preventing decomposition of a (thio)phosphoric acid triamide (2) by adding a cation source (1); to a mixture M comprising a cation source (1) and a (thio)phosphoric acid triamide (2); to a granule G comprising a fertilizer (3a) and/or a P-containing fertilizer (3b), wherein the granule is coated with a cation source (1); and to a composition B comprising a (thio)phosphoric acid triamide (2), a fertilizer mixture (3), and a cation source (1), wherein the composition B is obtainable by specific processes.
- Urea itself, however, is a form of nitrogen which is absorbed very little if at all, being hydrolyzed relatively rapidly by the enzyme urease, which is present ubiquitously in the soil, to form ammonia and carbon dioxide. In this process, in certain circumstances, gaseous ammonia is emitted to the atmosphere, and is then no longer available in the soil for the plants, thereby lowering the efficiency of fertilization.
- N-alkylthiophosphoric acid triamides N-alkylphosphoric acid triamides, which are described in EP 0 119 487, for example.
- N-alkylthiophosphoric acid triamides such as N-(n-butyl)thiophosphoric acid triamide (NBPT) and N-(n-propyl)thiophosphoric acid triamide (NPPT) can be used.
- NBPT N-(n-butyl)thiophosphoric acid triamide
- NPPT N-(n-propyl)thiophosphoric acid triamide
- the urease inhibitor may be incorporated in the urea by, for example, dissolving it into the melt prior to urea granulation or prilling. A process of this kind is described in U.S. Pat. No. 5,352,265, for example. A further option is to apply the urease inhibitor to the urea granules or prills, in the form of a solution, for example. Corresponding processes for application, and suitable solvents, are described in US 2010/218575 A1, for example.
- the storage life of the urease inhibitor is limited in the presence of urea-containing fertilizers. The higher the temperature, the shorter is the storage life. If, for example, urea is stored under tropical conditions, a major part of the urease inhibitor has undergone decomposition, generally, after about four weeks of storage.
- WO 2015/062667 discloses a composition comprising a (thio)phosphoric acid triamide urease inhibitor in combination with a functionalized amine to increase the stability and storage life of the (thio)phosphoric acid triamides urease inhibitors in the presence of urea-containing fertilizers.
- US 2011/0154874 A1 discloses amine-based additives selected from methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, N,N′,N′′-tris(dimethylaminopropyl)hexahydrotriazine, and 2,2′-dimorpholinyldiethyl ether.
- PCT/IB2015/059864 discloses further amine compounds as additives or coating materials for urea-containing fertilizers.
- urea granules which have been treated with a formulation comprising the urease inhibitors N-n-butylthiophosphoric acid triamide (NBPT) and N-n-propylthiophosphoric acid triamide (NPPT)
- NBPT N-n-butylthiophosphoric acid triamide
- NPPT N-n-propylthiophosphoric acid triamide
- TSP triple super phosphate
- an additional P-containing fertilizer which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer.
- the additional P-containing fertilizer which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer
- a stabilizing agent which is toxicologically unobjectionable, which does not adversely affect the urease inhibiting effect and/or the activity of the (thio)phosphoric acid, which can be easily and safely packaged, transported and shipped, even in large quantities, and which can be easily and safely handled and applied for soil treatment, even in large quantities.
- the present invention relates to the use of a cation source (1) comprising a cation C m+ , wherein
- the present invention relates to a method for preventing decomposition of a (thio)phosphoric acid triamide (2) according to general formula (I)
- the P-containing fertilizer (3b) typically causes a decomposition of the (thio)phosphoric acid triamide (2) of at least 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide within 15 days at a temperature of from 20° C. to 25° C., if no cation source (1) is present, the situation is completely different if a cation source (1) is present.
- the decomposition, which is caused by the P-containing fertilizer (3b) can be reduced as such that less than 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 15 days at a temperature of 20° C. to 25° C., if a cation source (1) is present.
- the decomposition, which is caused by the P-containing fertilizer (3b) can be reduced as such that less than 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 1 month at a temperature of 20° C. to 25° C., if a cation source (1) is present.
- compositions comprising a (thio)phosphoric acid triamide (2) and a fertilizer mixture (3) as defined above is highly advantageous from the commercial perspective, as the (thio)phosphoric acid triamide (2) may be applied to the fertilizer mixture (3) at an early stage, and the resulting composition can be stored until the time of its spreading to the soil. Accordingly, it is not required to store the (thio)phosphoric acid triamide (2) and a fertilizer mixture (3) separately and to apply the (thio)phosphoric acid triamide (2) to the fertilizer mixture (3) only shortly before the application to the soil, which would complicate the handling for the user.
- the application rates of the compositions comprising the (thio)phosphoric acid triamide (2) and the fertilizer mixture (3) can be reduced, as the stability of the (thio)phosphoric acid triamide (2) is improved during storage, so that more (thio)phosphoric acid triamide (2) is available at the time of applying the composition to the soil resulting in a long urease inhibition.
- the present invention further relates to a mixture M comprising
- the mixture M according to the invention may advantageously be used for treating a fertilizer mixture (3).
- the (thio)phosphoric acid triamide (2) in combination with the cation source (1), the (thio)phosphoric acid triamide (2) is directly provided in combination with a stabilizing agent, so that when being combined with the fertilizer mixture (3), the cation source (1) will exhibit its advantageous effect on the stability of the (thio)phosphoric acid triamide (2) as described in detail above.
- the present invention relates to a granule G comprising a urea-containing fertilizer (3a) and/or a P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer, wherein the granule is coated with a cation source (1) comprising a cation C m+ , wherein
- the granule G according to the invention is advantageous because the fertilizer (3a) and/or (3b) can be provided in combination with the stabilizing agent, i.e. the cation source (1), so that, when the (thio)phosphoric acid triamide (2) is added as urease inhibitor, the cation source (1) will exhibit its advantageous effect on the stability of the (thio)phosphoric acid triamide (2) as described in detail above.
- the stabilizing agent i.e. the cation source (1)
- composition B comprising
- composition B comprises the (thio)phosphoric acid triamide (2), the fertilizer mixture (3), and the cation source (1) as stabilizing agent. Accordingly, the composition B exhibits the advantageous properties in terms of the stability as outlined in detail above.
- composition B is specified in terms of processes for combining the different components of the composition B.
- the processes result in advantageous structural features of the composition B, which may enhance the stabilizing effect of the cation source (1).
- fertilizer mixture (3) also refers to granules, capsules, compartments or other units in which both the urea-containing fertilizer (3a) and the P-containing fertilizer (3b) are contained in one granule, capsule, compartment or unit.
- At least one means one or more, preferably one or two, and thus typically refers to individual compounds or mixtures/combinations.
- wt.-% or wt.-% stands for “percent by weight”.
- cation source preferably refers to a compound or composition, which comprises a cation C m+ , wherein C m+ is Ca 2+ , Mg 2+ , Li + , Fe 2+ , Fe 3+ , Al 3+ , Ag + , Cu 2+ , Zn 2+ , Hg 2+ , Pb 2+ , Ba 2+ , or a quaternary ammonium group comprising at least three groups selected from C 1 -C 2 -alkyl and C 1 -C 2 -hydroxyalkyl.
- the cation source (1) is a salt or an ion exchange material.
- the cation source (1) is a salt, for example a salt of the formula (C m+ ) n (A n ⁇ ) m , wherein C m+ represents a cation as defined above with m being 1, 2, or 3, and A n ⁇ represents an anion with n being 1, 2, or 3.
- the cation of the salt is essential.
- Preferred cations C m+ include Ca 2+ , Mg 2+ , Li + , Fe 2+ , Fe 3+ , Al 3+ , Ag + , Cu 2+ , Zn 2+ , Hg 2+ , Pb 2+ , or Ba 2+ .
- the cation source (1) is therefore a salt, which comprises a cation C m+ include Ca 2+ , Mg 2+ , Li + , Fe 2+ , Fe 3+ , Al 3+ , Ag + , Cu 2+ , Zn 2+ , Hg 2+ , Pb 2+ , or Ba 2+ .
- a particularly preferred cation C m+ is Mg 2+ or Ca 2+ .
- the cation source is therefore a salt, which further comprises a cation C m+ , wherein C m+ is Mg 2+ or Ca 2+ .
- C m+ is Ca 2+ .
- C m+ is Mg 2+ .
- Suitable anions A n ⁇ include F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , SO 4 2 ⁇ , NO 3 ⁇ , or CH 3 CO 2 ⁇ .
- the cation source is therefore a salt, which further comprises an anion A n ⁇ , wherein A n ⁇ is F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , SO 4 2 ⁇ , NO 3 ⁇ , or CH 3 CO 2 ⁇ .
- the cation source (1) is a salt, which comprises an anion A n ⁇ , wherein A n ⁇ is Cl ⁇ or SO 4 2 ⁇ .
- a n ⁇ is Cl ⁇ .
- a n ⁇ is SO 4 2 ⁇ .
- Preferred salts include Al 2 (SO 4 ) 3 , Fe(SO 4 ), Fe 2 (SO 4 ) 3 , ZnSO 4 , CuSO 4 , CaSO 4 , AlCl 3 , FeCl 2 , FeCl 3 , ZnCl 2 , CuCl 2 , Mg(NO 3 ) 2 , Ca(NO 3 ) 2 , CaCl 2 , and MgSO 4 . More preferably, the salt is CaCl 2 or MgSO 4 .
- the cation source (1) is a therefore a salt, which is selected from the group consisting of Al 2 (SO 4 ) 3 , Fe(SO 4 ), Fe 2 (SO 4 ) 3 , ZnSO 4 , CuSO 4 , CaSO 4 , AlCl 3 , FeCl 2 , FeCl 3 , ZnCl 2 , CuCl 2 , Mg(NO 3 ) 2 , Ca(NO 3 ) 2 , CaCl 2 , and MgSO 4 , and is preferably CaCl 2 or MgSO 4 .
- the salt is CaCl 2 .
- the salt is MgSO 4 .
- salts may be provided in anhydrous form or in the form of hydrates.
- Hydrates are salts containing water molecules combined in a definite ratio as an integral part of the crystal that are either bound to a metal center or that have crystallized with the metal complex. Such hydrates are also said to contain water of crystallization or water of hydration.
- the “n” is usually a low integer in the range of from 1 to 12, and is for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and it is possible that fraction numbers occur. For example, in a monohydrate n is one, and in a hexahydrate n is 6, and in a heptahydrate n is 7.
- magnesium sulfate monohydrate magnesium sulfate heptahydrate, or a mixture thereof can be preferably used, wherein the magnesium sulfate monohydrate is most preferred.
- salts as used herein may also be double salts, i.e. salts comprising two or more cations and/or two or more anions. They can be obtained by combination of two different salts, which are crystallized in the same regular ionic lattice.
- double salts examples include alums (with the general formula C a C b [SO 4 ] 2 ⁇ 12H 2 O), wherein C a and C b represent different cations of which C a is C a + and C b is C b + , or Tutton's salts (with the general formula [C d ] 2 C d [SO 4 ] 2 ⁇ 6H 2 O), wherein C c and C d represent different cations of which C c is C c + and C d is C d 2+ .
- double salts include ammonium iron(II) sulfate ((NH 4 ) 2 Fe(SO 4 ) 2 ⁇ 6H 2 O) and bromlite (BaCa(CO 3 ) 2 ).
- the cation source (1) is a salt, which has a solubility of at least 33 g/L in water at a temperature of from 15° C. to 25° C.
- the solubility is at least 100 g/L in water at a temperature of from 15° C. to 25° C. It is to be understood that the solubility is measured in deionized or distilled water.
- a certain solubility of the salt is advantageous in view of the fact that the salt can easily dissolve, and the cations thus be released from the crystal lattice.
- the cation source (1) is an ion exchange material.
- Suitable ion exchange materials include zeolites and ion exchange resins.
- Zeolites are aluminosilicates, which have a porous structure that can accommodate a wide variety of cations, such as Ca 2+ , Mg 2+ and others. These positive ions are rather loosely held and can readily be exchanged for others in a contact solution.
- Some of the more common mineral zeolites are analcime, chabazite, clinoptilolite, heulandite, natrolite, phillipsite, and stilbite.
- An example mineral formula is: Na 2 Al 2 Si 3 O 10 ⁇ 2H 2 O, the formula for natrolite.
- cations such as Ca 2+ or Mg 2+ can be released from zeolites, zeolites exhibit a stabilizing effect in the context of the present invention.
- the cation source (1) is therefore zeolite, which comprises a cation C m+ , wherein C m+ is Ca 2+ or Mg 2+ .
- Ion exchange resins comprise an insoluble matrix (or support structure) normally in the form of small (0.3-1 mm diameter) beads, fabricated from an organic polymer substrate.
- the beads are typically porous, providing a high surface area.
- the pore size is typically below 5 nm, preferably below 4 nm. The trapping of ions occurs with the accompanying releasing of other ions.
- anion exchange resins may be used, which are capable of adsorbing anions such as PO 4 3 ⁇ , NO 3 ⁇ , or SO 4 2 ⁇ , in particular PO 4 3 ⁇ .
- the skeleton of such anion exchange resins may be formed by copolymerization of styrene and divinylbenzene (DVB).
- the DVB links the linear styrene chains together and yields an insoluble three-dimensional polymer.
- the DVB may for example be used in an amount of from 1 to 10 wt.-% based on the total weight of the polymer.
- the functional group of the resins is cationic and preferably comprises a quaternary ammonium group.
- an anion exchange resin is therefore to be understood as falling within the term “cation source (1) comprising a cation C m+ ”, wherein C m+ is a quaternary ammonium group comprising at least three groups selected from C 1 -C 2 -alkyl and C 1 -C 2 -hydroxyalkyl.
- the groups on the nitrogen atom of the ammonium group are methyl groups and/or ethanol groups. Particularly preferred are trimethylammonium groups as functional groups.
- the cation source (1) is therefore an anion exchange resin, which comprises a cation C m+ , wherein C m+ is a quaternary ammonium group comprising at least three groups selected from C 1 -C 2 -alkyl and C 1 -C 2 -hydroxyalkyl, and is preferably a quaternary ammonium group comprising three methyl groups or two methyl groups and one hydroxyethyl group.
- the cationic groups of the anion exchange resins can exhibit a stabilizing effect in the context of the present invention.
- the ion exchange resin may alternatively be a cation exchange resin. Accordingly, the ion exchange resin may comprise and release cations, such as Ca 2+ , Mg 2+ and others.
- the skeleton of the resin is also typically based on styrene and DVB as outlined in the context of anion exchange resin.
- the functional group of the cation exchange resins is typically anionic and preferably comprises a sulfonic acid group or a carboxylic acid group. As cations, such as Ca 2+ or Mg 2+ can be released from cation exchange resins, such resins can exhibit a stabilizing effect in the context of the present invention.
- the cation source (1) is therefore a cation exchange resin, which comprises a cation C m+ , wherein C m+ is Ca 2+ or Mg 2+ .
- the term “(thio)phosphoric acid triamide” in each case covers thiophosphoric acid triamides and phosphoric acid triamides.
- the prefix “(thio)” as used herein in each case indicates that a group P ⁇ S or a group P ⁇ O is covered. However, if the prefix “thio” is used without brackets, this indicates that a group P ⁇ S is present.
- (thio)phosphoric acid triamides may be represented by the following general formula (I)
- the organic moieties mentioned in the above definitions of the variables are collective terms for individual listings of the individual group members.
- the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
- alkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, e.g. 3 or 4 carbon atoms.
- alkyl groups are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di methyl propyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methyl pentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl
- Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, n-heptyl, n-octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, and isodecyl.
- cycloalkyl denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 20 carbon atoms, preferably from 3 to 10 carbon atoms, more preferably from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
- aryl includes mono-, bi- or tricyclic aromatic radicals having usually from 6 to 14, preferably 6, 10, or 14 carbon atoms.
- exemplary aryl groups include phenyl, naphthyl and anthracenyl. Phenyl is preferred as aryl group.
- heterocycle or “heterocyclyl” includes 5- or 6-membered monocyclic heterocyclic non-aromatic radicals.
- the heterocyclic non-aromatic radicals usually comprise 1 or 2 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO 2 .
- Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, oxathiola
- (di)alkylaminocarbonyl refers to a (di)alkylamino group, i.e. an amino group comprising 1 or 2 alkyl substituents, which is bonded to the remainder of the molecule via the carbon atom of a carbonyl group (C ⁇ O).
- (thio)phosphoric acid triamide stereoisomers are present, if the compounds contain one or more centers of chirality. In this case, the compounds will be present in the form of different enantiomers or diastereomers, if more than one center of chirality is present.
- the term “(thio)phosphoric acid triamide” preferably covers every possible stereoisomer, i.e. single enantiomers or diastereomers, as well as mixtures thereof.
- Tautomers include, e.g., keto-enol tautomers.
- N-oxides may be formed under oxidative conditions, if tertiary amino groups are present.
- Salts may be formed, e.g., with the basic amino groups of the (thio)phosphoric acid triamides.
- Anions, which stem from an acid, with which the (thio)phosphoric acid amide may have been reacted, are e.g.
- chloride bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate.
- the (thio)phosphoric acid triamide (2) may be represented by the following general formula (I)
- the (thio)phosphoric acid triamide (2) may be represented by the above formula (I), wherein
- (thio)phosphoric acid triamide (2) may also cover combinations of (thio)phosphoric acid triamides (2) according to formula (I) as defined above.
- the (thio)phosphoric acid triamide (2) is selected from the group consisting of
- the (thio)phosphoric acid triamide (2) is N-n-butylthiophosphoric acid triamide (NBPT), N-n-propylthiophosphoric acid triamide (NPPT), or a combination thereof.
- the (thio)phosphoric acid triamide (2) is N-n-propylthiophosphoric acid triamide (NPPT) having the following chemical formula:
- the (thio)phosphoric acid triamide (2) is N-n-butylthiophosphoric acid triamide (NBPT) having the following chemical formula:
- the (thio)phosphoric acid triamide (2) is a combination of N-n-butylthiophosphoric acid triamide (NBPT) and N-n-propylthiophosphoric acid triamide (NPPT). It is particularly preferred that the (thio)phosphoric acid triamide (2) is a combination of NBPT and NPPT, which comprises NBPT in amounts of from 40 to 95 wt.-%, more preferably from 60 to 85 wt.-%, particularly preferably from 72 to 80 wt.-%, in each case based on the total weight of the combination.
- the fertilizer mixture (3) as defined herein comprises a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer.
- fertilizer covers any chemical compound that improves the levels of available plant nutrients and/or the chemical and physical properties of soil, thereby directly or indirectly promoting plant growth, yield, and quality. Fertilizers are typically applied either through the soil (for uptake by plant roots) or by foliar feeding (for uptake through leaves).
- the term “fertilizer” can be subdivided into two major categories: a) organic fertilizers (composed of decayed plant/animal matter) and b) inorganic fertilizers (composed of chemicals and minerals).
- Organic fertilizers include manure, slurry, worm castings, peat, seaweed, sewage, and guano. Green manure crops are also regularly grown to add nutrients (especially nitrogen) to the soil.
- Manufactured organic fertilizers include compost, blood meal, bone meal and seaweed extracts. Further examples are enzymatically digested proteins, fish meal, and feather meal. The decomposing crop residue from prior years is another source of fertility.
- naturally occurring minerals such as mine rock phosphate, sulfate of potash and limestone are also considered inorganic fertilizers.
- Inorganic fertilizers are usually manufactured through chemical processes (such as the Haber-Bosch process), also using naturally occurring deposits, while chemically altering them (e.g. concentrated triple superphosphate).
- Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mine rock phosphate, and limestone.
- a “urea-containing fertilizer (3a)” is defined as a fertilizer comprising at least one component selected from the group consisting of urea, urea ammonium nitrate (UAN), isobutylidene diurea (IBDU), crotonylidene diurea (CDU) and urea formaldehyde (UF), urea-acetaldehyde, and ureaglyoxal condensates.
- the urea-containing fertilizer (3a) is urea.
- the urea has a purity of at least 90%, and may for example be in crystalline, granulated, compacted, prilled or ground form.
- the “P-containing fertilizer (3b)” is any fertilizer providing any form of the chemical element phosphorus (P) or containing any chemical compounds incorporating the chemical element phosphorus (P), including but not limited to phosphate-containing fertilizers or fertilizers containing P 2 O 5 .
- the P-containing fertilizer is selected from the group consisting of a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer.
- the P-containing fertilizer is a NPK fertilizer.
- combinations of these fertilizers may be used as additional P-containing fertilizer (3b).
- P fertilizers, K fertilizers, and N fertilizers are straight fertilizers, i.e. fertilizers that contain only one of the nutritive elements P, K, and N. It is to be understood, however, that these fertilizers may additionally comprise at least one additional nutritive element selected from C, H, O, S, Ca, Mg, Fe, Mn, Cu, Zn, Mo, and B.
- Preferred P fertilizers include basic slag (Thomas phosphate), superphosphate, triple superphosphate, partly digested phosphate rock, soft phosphate rock, dicalcium phosphate, thermal (fused) phosphate, aluminum phosphate, and combinations thereof.
- NPK fertilizers, NP fertilizers, and PK fertilizers are multinutrient fertilizers, i.e. fertilizers that comprise combinations of the nutritive elements P, K, and N as indicated by the terms “NPK”, “NP”, and “PK”. It is to be understood, however, that these fertilizers may additionally comprise at least one additional nutritive element selected from C, H, O, S, Ca, Mg, Fe, Mn, Cu, Zn, Mo, and B.
- the NPK fertilizers, NP fertilizers, and PK fertilizers may be provided as complex fertilizers or bulk-blend or blended fertilizers.
- complex fertilizer refers to a compound fertilizer formed by mixing ingredients that react chemically. In bulk-blend or blended fertilizers, two or more granular fertilizers of similar size are mixed to form a compound fertilizer.
- NPK fertilizers must contain at least 3 wt.-% N plus 5 wt.-% P 2 O 5 plus 5 wt.-% K 2 O and at least 20 wt.-% total nutrients, based on the total weight of the NPK fertilizer.
- the most commonly used grades (N—P 2 O 5 —K 2 O, each in wt %) are
- NP fertilizers under the EEC Guidelines is 3 wt.-% N and 5 wt.-% P 2 O 5 and at least 18 wt.-% total nutrients, based on the total weight of the NP fertilizer. Common grades are 20-20, 22-22, 26-14, 11-52, 16-48, and 18-46. These products are appropriate for potassium-rich soils or where potash is supplied as a separate fertilizer.
- PK fertilizers In the group of PK fertilizers, all combinations of the straight P and K fertilizers listed above are possible. In general, the materials are first milled and then mixed and granulated, so that a fairly homogeneous mixture is obtained. Some products are also made by bulk blending.
- the EEC Guidelines set forth a minimum analysis of 5 wt.-% P 2 O 5 , 5 wt.-% K 2 O, and at least 18 wt.-% nutrients, based on the total weight of the PK fertilizer.
- the additional P-containing fertilizer (3b) is therefore a phosphate-containing fertilizer, i.e. a fertilizer selected from the group consisting of a NPK fertilizer, a NP fertilizer, a PK fertilizer, and a P fertilizer as defined above.
- the additional P-containing fertilizer (3b) causes a decomposition of the (thio)phosphoric acid triamide (2) of at least 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide within 15 days at a temperature of from 20° C. to 25° C., if no cation source (1) according to the invention is present.
- the P-containing fertilizer (3b) is selected from the group consisting of monoammonium phosphate (MAP), diammonium phosphate (DAP), calcium phosphate, super phosphate, double super phosphate, triple super phosphate (TSP), phosphate rock, ammonium polyphosphate (APP), and combinations thereof.
- MAP monoammonium phosphate
- DAP diammonium phosphate
- TSP triple super phosphate
- APP ammonium polyphosphate
- the P-containing fertilizer (3b) is monoammonium phosphate (MAP).
- the P-containing fertilizer (3b) is diammonium phosphate (DAP).
- the P-containing fertilizer (3b) is calcium phosphate.
- the P-containing fertilizer (3b) is super phosphate.
- the P-containing fertilizer (3b) is double super phosphate.
- the P-containing fertilizer (3b) is triple super phosphate (TSP).
- the P-containing fertilizer (3b) is phosphate rock.
- the P-containing fertilizer (3b) is ammonium polyphosphate (APP).
- the cation source (1) as defined herein is used in a composition A comprising a (thio)phosphoric acid triamide (2) and a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) to prevent decomposition of the (thio)phosphoric acid triamide (2).
- the present invention relates to a method for preventing decomposition of a (thio)phosphoric acid triamide (2) in a compositions A comprising the (thio)phosphoric acid triamide (2) and a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b).
- the fertilizers (3a) and (3b) as well as the cation source (1) have been described in detail above.
- the (thio)phosphoric acid triamide (2) has been described in detail above.
- the additional P-containing fertilizer (3b) according to the invention typically causes a decomposition of the (thio)phosphoric acid triamide (2) of at least 1 wt.-% based on the total amount of the (thio)phosphoric acid triamide within 15 days at a temperature of from 20° C. to 25° C., if no cation source (1) according to the invention is present.
- an additional P-containing fertilizer (3b) which causes a decomposition of the (thio)phosphoric acid triamide (2) of at least 5 wt.-% based on the total amount of the (thio)phosphoric acid triamide within 15 days at a temperature of from 20° C. to 25° C., if no cation source (1) according to the invention is present.
- an additional P-containing fertilizer (3b) which causes a decomposition of the (thio)phosphoric acid triamide (2) of at least 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide within 15 days at a temperature of from 20° C. to 25° C., if no cation source (1) according to the invention is present.
- the cation source (1) prevents this decomposition due to the stabilizing effect exhibited by the cations C m+ .
- a decomposition of the (thio)phosphoric acid (2) may additionally be caused by the fertilizer (3a).
- the term “to prevent decomposition of the (thio)phosphoric acid triamide (2)” preferably refers to the decomposition, which is caused by the P-containing fertilizer (3b), but not by the fertilizer (3a).
- the present invention focuses on the decomposition problems caused by the P-containing fertilizer (3b) only, and in this context the cation source (1) as defined herein may be beneficially used.
- the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 50 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 15 days at a temperature of 20° C. to 25° C.
- the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 50 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 1 month at a temperature of 20° C. to 25° C.
- the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 50 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 2 months at a temperature of 20° C. to 25° C.
- the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 20 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 15 days at a temperature of 20° C. to 25° C.
- the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 20 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 1 month at a temperature of 20° C. to 25° C.
- the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 20 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 2 months at a temperature of 20° C. to 25° C.
- the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 15 days at a temperature of 20° C. to 25° C.
- the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 1 month at a temperature of 20° C. to 25° C.
- the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 2 months at a temperature of 20° C. to 25° C.
- the amount of the (thio)phosphoric acid triamide in a sample after a certain time period may be detected e.g. by HPLC using method DIN EN 16651.
- the (thio)phosphoric acid triamide (2) may be provided in combination with a stabilizing agent, which prevents decomposition caused by the fertilizer (3a).
- the decomposition caused by the P-containing fertilizer (3b) can be determined.
- the extent to which the cation source (1) prevents decomposition caused by the P-containing fertilizer (3b) can be determined.
- the amount of the (thio)phosphoric acid triamide (2) in a sample after a certain time period may be determined indirectly by determining the urease inhibiting efficacy that is observable.
- the urease-inhibiting efficacy may be determined by the Dräger test as outlined in the Examples.
- the Dräger test is based on the determination of the concentration of ammonia gas that is set free from a soil sample being treated with a urea-containing fertilizer once a day.
- a certain amount of ammonia is typically produced within a certain time period in a soil sample being treated with a urea-containing fertilizer due to the degradation of the urea-containing fertilizer caused by the urease, which is present in the soil.
- the urea-containing fertilizer is provided in combination with a urease inhibitor such as a (thio)phosphoric acid triamide (2), the degradation of the urea-containing fertilizer is slowed down, so that a lower amount of ammonia will be produced in the same time period.
- a urease inhibitor such as a (thio)phosphoric acid triamide (2)
- the degradation of the urea-containing fertilizer is slowed down, so that a lower amount of ammonia will be produced in the same time period.
- the (thio)phosphoric acid triamide (2) has decomposed to a certain extent, e.g. upon storage, the production of ammonia will be reduced only to a lower extent.
- the ammonia concentration measured after a certain time period may thus be correlated with the amount of the (thio)phosphoric acid triamide (2) in a sample.
- the (thio)phosphoric acid triamide (2) may be provided in combination with a stabilizing agent, which prevents decomposition caused by the fertilizer (3a).
- a stabilizing agent which prevents decomposition caused by the fertilizer (3a).
- the cation source (1) as defined herein reduces the decomposition of the (thio)phosphoric acid triamide, which is caused by the P-containing fertilizer (3b), as such that after a storage time of up to 15 days at a temperature of 20° C. to 25° C.,
- the (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1) exhibits at least 50% of the urease inhibiting efficacy of
- a (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer (3a), but no P-containing fertilizer (3b), and no cation source (1),
- urease inhibiting efficacy means that the time until a threshold value of ammonia is reached is reduced by at most 50%.
- the ammonia is produced in a soil sample being treated with the above mentioned compositions and can be measured according to the Dräger test.
- threshold values include 600 ppm, 500 ppm, 400 ppm or 300 ppm. These threshold values may be reached for example after a time of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 days, if the (thio)phosphoric acid triamide (2) is provided in a composition comprising the fertilizer (3a), but no P-containing fertilizer (3b), and no cation source (1).
- the above embodiment is to be understood as such that the threshold value of 600 ppm is reached at the earliest after 5 days, if the (thio)phosphoric acid triamide (2) is provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1).
- the cation source (1) as defined herein reduces the decomposition of the (thio)phosphoric acid triamide, which is caused by the P-containing fertilizer (3b), as such that after a storage time of up to 15 days at a temperature of 20° C. to 25° C.,
- the (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1) exhibits at least 80% of the urease inhibiting efficacy of
- a (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer (3a), but no P-containing fertilizer (3b), and no cation source (1),
- urease inhibiting efficacy means that the time until a threshold value of ammonia is reached is reduced by at most 20%.
- the above embodiment is to be understood as such that the threshold value of 600 ppm is reached at the earliest after 8 days, if the (thio)phosphoric acid triamide (2) is provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1).
- the cation source (1) as defined herein reduces the decomposition of the (thio)phosphoric acid triamide, which is caused by the P-containing fertilizer (3b), as such that after a storage time of up to 15 days at a temperature of 20° C. to 25° C.,
- the (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1) exhibits at least 90% of the urease inhibiting efficacy of
- a (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer (3a), but no P-containing fertilizer (3b), and no cation source (1),
- urease inhibiting efficacy means that the time until a threshold value of ammonia is reached is reduced by at most 10%.
- the above embodiment is to be understood as such that the threshold value of 600 ppm is reached at the earliest after 9 days, if the (thio)phosphoric acid triamide (2) is provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1).
- the storage time is up to 1 month, preferably up to two months or even longer.
- the (thio)phosphoric acid triamide (2) is in each case provided in combination with an amine (4) as defined in detail further below, in order to exclude a destabilizing effect caused by the urea-containing fertilizer (3a), as the amine (4) acts as a stabilizing agent, which prevents decomposition caused by the fertilizer (3a). It is noted, however, that the amine (4) typically does not prevent decomposition caused by the P-containing fertilizer (3b).
- the cation source (1) is used according to the present invention.
- the present invention also relates to a mixture M comprising a cation source (1) and a (thio)phosphoric acid triamide (2).
- a mixture M comprising a cation source (1) and a (thio)phosphoric acid triamide (2).
- the cation source (1) and the (thio)phosphoric acid triamide (2) have been described in detail above.
- the mixture M further comprises a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer.
- a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer.
- the fertilizers (3a) and (3b) have been described in detail above.
- the present invention also relates to a granule G comprising a urea-containing fertilizer (3a) and/or a P-containing fertilizer (3b), wherein the granule is coated with a cation source (1).
- a granule G comprising a urea-containing fertilizer (3a) and/or a P-containing fertilizer (3b), wherein the granule is coated with a cation source (1).
- the fertilizers (3a) and (3b) as well as the cation source (1) have been described in detail above.
- the term “granule” generally refers to particles, which are preferably between two screen sizes usually within the range of 1 to 4 mm.
- the granules may have a spherical or near-spherical form made by solidification of free-falling droplets in air or other fluid medium (e.g. oil).
- the granule may also comprise a substance to prevent caking or to control the dissolution rate or to improve the physical condition of the granule.
- the substance may be incorporated in the granule or applied as a layer surrounding the granule.
- the fertilizer (3a) and the P-containing fertilizer (3b) may either be provided alone or together in granules.
- a skilled person is aware that granules may be manufactured granulation of solids, slurries, or melts according to standard processes known in the art.
- “coated” means that the granule G comprising the fertilizer (3a) and/or (3b) is surface-treated with the cation source (1).
- the treatment may be performed with the cation source (1) in dry, preferably powdery form, as such that the granule is surrounded by a powder coating.
- the treatment may be performed by preparing a solution of the cation source (1) and treating the granule with the solution.
- the solvent of the solution may then be partially or completely evaporated.
- Preferred solvents in this connection comprise dimethyl sulfoxide (DMSO), dimethylformamide (DMF), water, and combinations thereof.
- the treatment with the solution may result at least partly in an incorporation of the cation source (1) into the granule.
- the granule is further treated with a (thio)phosphoric acid triamide (2).
- the (thio)phosphoric acid triamide (2) has been described in detail above.
- “treated with a (thio)phosphoric acid triamide (2)” means that the granules are surface-treated with the (thio)phosphoric acid triamide (2).
- surface-treatment preferably means that a liquid formulation of the (thio)phosphoric acid triamide (2) has been sprayed onto the granule, so that preferably a coating of the (thio)phosphoric acid triamide (2) surrounding the granule is formed.
- the granule G is either obtained by firstly applying the coating with the cation source (1) and then applying the (thio)phosphoric acid triamide (2) coating or vice versa.
- the granule G may also comprise a coating comprising both the cation source (1) and the (thio)phosphoric acid triamide (2), which is preferably obtained by simultaneously applying (1) and (2), e.g. in the form of the mixture M as defined herein.
- the present invention also relates to a composition B, which comprises a cation source (1), a (thio)phosphoric acid triamide (2), and a fertilizer mixture (3), and is inter alia defined by the process by which the composition is obtainable, wherein 7 options are provided.
- the cation source (1), the (thio)phosphoric acid triamide (2), and the fertilizer mixture (3) have been described in detail above.
- composition B is obtainable by
- composition B is obtainable by
- composition B is obtainable by
- composition B is obtainable by
- composition B is obtainable by
- composition B is obtainable by
- composition B is obtainable by
- the term “granule” is to be understood as defined above in connection with the granule G.
- the granules may in addition to the fertilizer (3a) and/or the P-containing fertilizer (3b) comprise the (thio)phosphoric acid triamide (2).
- the (thio)phosphoric acid triamide (2) may be incorporated in the granule or may be present as a layer surrounding the granule.
- “treating granules with the cation source (1)” means that the granules are surface-treated with the cation source (1).
- the treatment may be performed with the cation source (1) in dry, preferably powdery form, as such that the granule is surrounded by a powder coating.
- the treatment may be performed by preparing a solution of the cation source (1) and treating the granule with the solution.
- the solvent of the solution may then be partially or completely evaporated.
- Preferred solvents in this connection comprise dimethyl sulfoxide (DMSO), dimethylformamide (DMF), water, and combinations thereof.
- the treatment with the solution may result at least partly in an incorporation of the cation source (1) into the granule.
- “treating a blend of granules with the cation source (1)” means that the granules of the blend are surface-treated with the cation source (1).
- the treatment may be performed with the cation source (1) in dry, preferably powdery form, as such that the granules are surrounded by a powder coating.
- the treatment may be performed by preparing a solution of the cation source (1) and treating the granules with the solution.
- the solvent of the solution may then be partially or completely evaporated.
- Preferred solvents in this connection comprise dimethyl sulfoxide (DMSO), dimethylformamide (DMF), water, and combinations thereof.
- the treatment with the solution may result at least partly in an incorporation of the cation source (1) into the granules.
- magnesium sulfate is preferably used in a powdery form.
- the average particle size of the cation source (1) is preferably less than 1 mm, more preferably less than 750 ⁇ m, most preferably less than 500 ⁇ m, particularly preferably less than 250 ⁇ m, particularly more preferably less than 150 ⁇ m, particularly most preferably less than 100 ⁇ m, particularly less than 50 ⁇ m.
- the average particle size of the cation source (1) is preferably more than 1 ⁇ m, more preferably more than 5 ⁇ m, most preferably more than 10 ⁇ m, particularly preferably more than 25 ⁇ m, particularly more preferably more than 40 ⁇ m, particularly most preferably more than 60 ⁇ m, particularly more than 90 ⁇ m.
- the average particle size is measured by sieve analysis with different standard set of sieves.
- the average particle size of the cation source (1) is preferably less than 1 mm, more preferably less than 750 ⁇ m, most preferably less than 500 ⁇ m, particularly preferably less than 250 ⁇ m, particularly more preferably less than 150 ⁇ m, particularly most preferably less than 100 ⁇ m, particularly less than 50 ⁇ m.
- the average particle size of the cation source (1) is preferably more than 1 ⁇ m, more preferably more than 5 ⁇ m, most preferably more than 10 ⁇ m, particularly preferably more than 25 ⁇ m, particularly more preferably more than 40 ⁇ m, particularly most preferably more than 60 ⁇ m, particularly more than 90 ⁇ m.
- the average particle size is measured by sieve analysis with different standard set of sieves.
- the adhesion of the cation source (1) on fertilizer granules can be improved by adding a sticker, preferably by adding a sticker selected from the group of stickers described in U.S. Pat. No. 5,656,571A or in WO2012/168210 A1 or a polymer sticker or another sticker used in the state of the art for the adhesion of the agrochemical formulation to the seed.
- a “sticker” is a material or a substance which increases the firmness of attachment of finely-divided solids or other water-soluble or -insoluble materials to a solid surface, and which may be measured in terms of resistance to time or mechanical action.
- stickers are substances such as latex or other adhesives that improve attachment of finely-divided solids to a solid surface.
- “treating granules with the (thio)phosphoric acid triamide (2)” means that the granules are surface-treated with the (thio)phosphoric acid triamide (2).
- surface-treatment preferably means that a liquid formulation of the (thio)phosphoric acid triamide (2) is sprayed onto the granule, so that preferably a coating of the (thio)phosphoric acid triamide (2) surrounding the granule is formed.
- “treating granules with a mixture comprising the (thio)phosphoric acid triamide (2) and the cation source (1)” means that the granules are surface-treated with the corresponding mixture.
- surface-treatment preferably means that a liquid formulation of the (thio)phosphoric acid triamide (2) and the cation source (1) is sprayed onto the granule.
- surface-treatment also means that a solid formulation of the (thio)phosphoric acid triamide (2) and the cation source (1) is sprayed onto the granule.
- the (thio)phosphoric acid triamide (2) is provided in combination with at least one amine (4).
- the amine (4) typically exhibits a stabilizing effect on the (thio)phosphoric acid triamide (2) in terms of a decomposition caused by the urea-containing fertilizer (3a).
- liquid formulations of the (thio)phosphoric acid triamide (2) preferably comprise a (thio)phosphoric acid triamide (2) and an amine (4).
- the amine(s) (4) can be any amine, i.e. any chemical compound having at least one amino group, including (but not limited to)
- the (thio)phosphoric acid triamide (2) is provided in combination with at least one amine (4) selected from the group consisting of
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- (4a) can be any polymeric polyamine, and is preferably a polyalkyleneimine or polyvinylamine, more preferably a polyalkyleneimine, most preferably a polyethyleneimine, polypropyleneimine, or polybutyleneimine, particularly a polyethyleneimine.
- (4a) is preferably any polymeric polyamine comprising ethyleneimine (—CH 2 CH 2 NH—) as monomeric units, including homopolymers and any copolymers of ethyleneimine, and is preferably a homopolymer of ethyleneimine.
- Copolymers can be alternating, periodic, statistical or block copolymers.
- (4a) can be of any polymer structure, for example a linear polymer, a ring polymer, a cross-linked polymer, a branched polymer, a star polymer, a comb polymer, a brush polymer, a dendronized polymer, or a dendrimer etc.
- (4a) is an essentially linear polymer, and is preferably a linear polymer.
- Polyethyleneimines which may be used are polyethyleneimine homopolymers which may be present in uncrosslinked or crosslinked form.
- the polyethyleneimine homopolymers can be prepared by known processes, as described, for example, in Rompps (Chemie Lexikon, 8th edition, 1992, pages 3532-3533), or in Ullmanns Enzyklopadie der Technischen Chemie, 4th edition, 1974, vol. 8, pages 212-213. and the literature stated there. They have a molecular weight in the range from about 200 to 1000 000 g/mol.
- Corresponding commercial products are for example available under the name Lupasol® from BASF SE.
- the polyethyleneimine (4a) is preferably a polyethylenimine having a degree of branching in the range of from 0.1 to 0.95 (also referred to as “highly branched polyethyleneimine”), and more preferably a polyethylenimine having a degree of branching in the range of from 0.25 to 0.90, more preferably a polyethylenimine having a degree of branching in the range of from 0.30 to 0.80, and most preferably a polyethylenimine having a degree of branching in the range of 0.50 to 0.80.
- Highly branched polyethyleneimines are characterized by its high degree of branching, which can be determined for example via 13 C-NMR spectroscopy, preferably in D 2 O, and is defined as follows:
- D dendritic
- L linear
- T terminal
- the polymeric polyamine (4a) can have different weight average molecular weights.
- the weight average molecular weight of (4a) is preferably at least 200, more preferably at least 400, most preferably at least 550, particularly at least 650, for example at least 750.
- the weight average molecular weight of (4a) is preferably not more than 10,000, more preferably not more than 4,000, most preferably not more than 1,900, particularly not more than 1,500, for example not more than 1,350.
- the weight average molecular weight can be determined by standard gel permeation chromatography (GPC) known to the person skilled in the art.
- the amine (4) is a polyethyleneimine, preferably a polyethyleneimine as defined above.
- Another class of polyamines includes polymers obtainable by condensation of at least one compound selected from N-(hydroxyalkyl)amines of formulae(I.a) and/or (I.b),
- A are independently selected from C 1 -C 6 -alkylene
- R 1 , R 1* , R 2 , R 2* , R 3 , R 3* , R 4 , R 4* , R 5 , and R 5* are independently selected of one another selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the at least three mentioned radicals may be optionally substituted;
- R 6 is selected from hydrogen, alkyl, cycloalkyl or aryl, which may be optionally substituted.
- polyethanolamines are preferred, wherein in the condensation product of the compounds of formulae (I.a) and/or (I.b) as defined above, A is C 1 -alkylene, and R 1 , R 1* , R 2 , R 2* , R 3 , R 3* , R 4 , R 4* , R 5 , and R 6* are each H, and R 6 is selected from hydrogen and C 2 -hydroxyalkyl.
- the polyamine is a polyethanolamine, which is commercially available under the trade name Lupasol® EO.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the number of groups R 21 within (4b) is at least 3, preferably 3 to 5, more preferably 3 to 4, and most preferably 3.
- the number of carbon atoms in each group R 21 within (4b) is 2 to 12, preferably 2 to 9, more preferably 2 to 7, most preferably 2 to 5, particularly preferably 2 to 4, particularly 2 to 3, for example 3, wherein said number of carbon atoms does not include carbon atoms in any alkoxy groups or any other substituents of R 21 .
- the groups R 21 within (4b) are alkoxy- or hydroxy-substituted, preferably hydroxy-substituted.
- At least one of the groups R 21 is or are covalently bound to the amino group of the amine (4b).
- (4b) is an amine N(R 21 ) 3 wherein R 21 is a an alkoxy- or hydroxy-substituted—preferably a hydroxyl-substituted—C 2 to C 12 —preferably a C 2 to C 7 , more preferably a C 2 to C 3 -alkyl group and wherein one of the groups R 21 is different to the other group R 21 .
- (4b) is an amine N(R 21 ) 3 wherein
- R 21 is a an alkoxy- or hydroxy-substituted—preferably a hydroxyl-substituted—C 2 to C 12 —preferably a C 2 to C 7 , more preferably a C 2 to C 3 -alkyl group and wherein one of the groups R 21 is different to the other group R 21 and wherein at least one of the groups R 21 bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the number of groups R 22 within (4c) is at least 2, preferably 2 to 5, more preferably 2 to 4, and most preferably 2 to 3, for example 2.
- the number of carbon atoms in each group R 22 within (4c) is 2 to 12, preferably 2 to 9, more preferably 2 to 7, most preferably 2 to 5, particularly preferably 2 to 4, particularly 2 to 3, for example 3, wherein said number of carbon atoms does not include carbon atoms in any alkoxy groups or any other substituents of R 22 .
- the groups R 22 within (4c) are alkoxy- or hydroxy-substituted, preferably hydroxy-substituted.
- At least one of the groups R 22 is different to the other group(s) R 22 , preferably one of the groups R 22 is different to the other group(s) R 22 .
- At least one of the groups R 22 is or are covalently bound to the amino group of the amine (4c).
- At least one of the groups R 22 bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom, particularly at a secondary carbon atom.
- (4c) is an amine R 24 N(R 22 ) 2 wherein
- R 24 is H or a C 1 to C 12 —, preferably a C 1 to C 7 —, more preferably a C 1 to C 3 -alkyl group and
- R 22 is an alkoxy- or hydroxy-substituted-, preferably a hydroxy-substituted-C 2 to C 12 —, preferably C 2 to C 7 —, more preferably C 2 to C 3 -alkyl group and wherein at least one of the groups R 22 bears the hydroxy substituent at a secondary carbon atom and wherein one of the groups R 22 is different to the other group R 22 .
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the number of carbon atoms in each group R 23 within (4d) is 8 to 40, preferably 8 to 32, more preferably 8 to 24, most preferably 8 to 19, particularly preferably 8 to 16.
- the group R 23 within (4d) is saturated or unsaturated, preferably unsaturated.
- (4d) contains at least one alkoxy or hydroxy group, more preferably at least one alkoxy and at least one hydroxy groups, most preferably at least two alkoxy and at least one hydroxyl group, particularly at least four alkoxy and at least one hydroxyl group.
- (4d) is an amine selected from the group consisting of: ethoxylated (2) cocoalkylamine, ethoxylated (5) cocoalkylamine, ethoxylated (15) cocoalkylamine, ethoxylated (2) oleylamine, lauryl-dimethylamine, oleyl-dimethylamine, and 2-propylheptylamine ethoxylate (5 EO), 2-propylheptylamine ethoxylate (10 EO), and 2-propylheptylamine ethoxylate (20 EO).
- the amine (4) is ethoxylated (2) cocoalkylamine.
- the amine (4) is ethoxylated (5) cocoalkylamine.
- the amine (4) is ethoxylated (15) cocoalkylamine.
- the amine (4) is ethoxylated (2) oleylamine.
- the amine (4) is lauryl-dimethylamine.
- the amine (4) is oleyl-dimethylamine.
- the amine (4) is 2-propylheptylamine ethoxylate (5EO).
- the amine (4) is 2-propylheptylamine ethoxylate (10 EO)
- the amine (4) is 2-propylheptylamine ethoxylate (20 EO).
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- heterocyclic amine stands for a heterocyclic compound in which at least one ring atom of the heterocyclic ring is a nitrogen atom.
- the heterocyclic amine (4e) is saturated or unsaturated, preferably saturated.
- the heterocyclic amine (4e) contains preferably a 5-, 6- or 7-membered heterocyclic ring, more preferably a 5- or 6-membered ring, most preferably a 6-membered ring.
- the heterocyclic amine (4e) contains at least one, more preferably 1 to 3, most preferably 1 to 2, particularly one oxygen atom(s) as ring atom(s) of the heterocyclic ring.
- the heterocyclic amine (4e) is preferably a morpholine or morpholine derivative, more preferably
- N-alkyl morpholine most preferably N-methyl, N-ethyl, N-propyl, or N-butyl morpholine, for example N-methyl morpholine.
- the amine (4) is N-methyl morpholine.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- preferred amines (4f) are secondary and/or tertiary amines, for example methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, N,N′,N′′-tris(dimethylaminopropyl)hexahydrotriazine, and 2,2′-dimorpholinyldiethyl ether.
- methyldiethanolamine tetrahydroxypropylethylenediamine
- trimethylaminoethylethanolamine trimethylaminoethylethanolamine
- N,N,N′,N′-tetramethyl-1,6-hexanediamine N,N′,N′′-tris(dimethylaminopropyl)hexahydrotriazine
- 2,2′-dimorpholinyldiethyl ether 2,2′-dimorpholiny
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- amine is preferably to be understood as an organic compounds, in which at least one amino group is bound to a carbon atom.
- an NH 2 group is bound to a carbon atom
- an NR A H group is bound to a carbon atom
- an NR A R B group is bound to a carbon atom
- R A and R B may each individually be selected from C 1 -C 20 -alkyl, di(C 1 -C 4 -alkyl)amino-C 1 -C 20 -alkyl, and a C 1 -C 4 -alkylene chain, which is bound to the carbon atom to which the NR A H or NR A R B group is bound so that a heterocyclic ring is formed, or R A and R B may together with the nitrogen atom to which they are bound form a 5- to 10-membered
- the carbon atom to which the NH 2 , NR A H, or NR A R B group is bound is not part of a heterocyclic ring, which is formed with R A or R B it is preferably part of a C 1 -C 20 -alkyl group or a di(C 1 -C 4 -alkyl)amino-C 1 -C 20 -alkyl group, so that the amino group may be represented by the formula C 1 -C 20 -alkyl-NH 2 , C 1 -C 20 -alkyl-NR A H, or C 1 -C 20 -alkyl-NR A R B or by the formula di(C 1 -C 4 -alkyl)amino-C 1 -C 20 -alkyl-NH 2 , di(C 1 -C 4 -alkyl)amino-C 1 -C 20 -alkyl-NR A H, or di(C 1 -C 4 -alkyl)amino-C 1
- the amine (4) is a tertiary amine, wherein 2 tertiary amino groups are present, and which may be represented by the formula R a R b N—(C 1 -C 10 alkylene)-NR c R d , wherein R a , R b , R c , and R d are independently of each other selected from C 1 -C 10 -alkyl, or R a and R b and/or R c and R d may together with the nitrogen atom to which they are bound form a 5- to 10-membered, preferably 5- to 6-membered heterocyclic ring, wherein the heterocycle may comprise 1, 2, or 3 additional heteroatoms selected from N, O, and S, wherein the N atom if present is further substituted by C 1 -C 4 -alkyl.
- R a , R b , R c , and R d are independently of each other selected from C 1 -C 4 -
- the amine (4) is selected from N,N,N′,N′-tetramethyl-1,6-hexanediamine, N,N,N′,N′-tetramethyl-1,3-propanediamine, N,N′,N′′-tris(dimethylaminopropyl)hexahydrotriazine, and triethylendiamine (DABCO).
- the amine (4) is N,N,N′,N′-tetramethyl-1,6-hexanediamine (CAS [111-18-2]).
- the amine (4) is N,N,N′,N′-tetramethyl-1,3-propanediamine (CAS [110-95-2]).
- the amine (4) is N,N′,N′′-tris(dimethylaminopropyl)hexahydrotriazine.
- the amine (4) is triethylendiamine (DABCO, available as Lupragen® N201 from BASF).
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the amine (4) may in one embodiment be an amino alcohol.
- Amino alcohols may also be referred to as alkanol amines and are characterized in that they comprise at least one hydroxyl group and at least one amino group.
- amino alcohols may be represented by the formula (H) a N(C 1 -C 10 -hydroxyalkyl) b , preferably by the formula (H) a N(C 1 -C 8 -hydroxyalkyl) b , wherein a is 0 or 1, and b is 2 when a is 1 and 3 when a is 0.
- hydroxyalkyl defines an alkyl group, which comprises at least one, preferably 1, 2, or 3 hydroxyl groups, especially preferably one hydroxyl group.
- Exemplary hydroxyalkyl groups include hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl.
- the amino alcohol comprises not more than one amino group and at least three hydroxyl substituted C 2 -C 8 —, preferably C 2 —O 5 -alkyl groups, wherein at least one of these hydroxyl substituted alkyl groups is different from the other hydroxyl substituted alkyl groups.
- the amino alcohol comprises not more than one amino group and at least three hydroxyl-substituted C 2 -C 3 -alkyl groups, which are covalently bound to the amino group, wherein at least one of these hydroxyl substituted alkyl groups is different from the other hydroxyl substituted alkyl groups.
- amino alcohols may be represented by the generic formula A (H) x N((CH 2 ) m —OH) n , wherein m is 1, 2, or 3, x is 0 or 1, and n is 2 when x is 1 and 3 when x is 0, or by generic formula B (H) y N((CH 2 )—CHOH—CH 3 ) z , such that the length of the carbon chain where the secondary hydroxyl group is located is 3, y is 0 or 1, and z is 2 when y is 1 and 3 when y is 0.
- amino alcohols may be represented by the formula (C 1 -C 4 -alkyl) 2 N—(C 1 -C 4 -alkylene)-N(C 1 -C 4 -alkyl)(C 1 -C 4 -hydroxyalkyl).
- An exemplary amino alcohol in this connection is N,N,N′-trimethylaminoethylethanolamine.
- Preferred amino alcohols according to the invention may be selected from the group consisting of ethanolamine, diethanolamine, methyl diethanolamine, butyl diethanolamine, monoisopropanolamine, diisopropanolamine, methyl diisopropanolamine, triethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N-bis(2-hydroxyethyl)isopropanolamine, N,N,N′-trimethylaminoethylethanolamine, and N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine.
- Preferred amino alcohols according to the invention include ethanolamine, diethanolamine, methyl diethanolamine, butyl diethanolamine, monoisopropanolamine, diisopropanolamine, methyl diisopropanolamine, triethanolamine, tetrahydroxypropylethylenediamine, and trimethylaminoethylethanolamine.
- a preferred amino alcohol is triethanolamine.
- Another preferred amino alcohol is N,N-bis(2-hydroxyethyl)isopropanolamine, also known as diethanolisopropanolamine (DEIPA).
- DEIPA diethanolisopropanolamine
- Another preferred amino alcohol is N,N,N′-trimethylaminoethylethanolamine (CAS [2212-32-0], available as Lupragen® N400 from BASF).
- Another preferred amino alcohol is N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine (CAS [102-60-3]).
- the amine (4) may in another embodiment be an ether amine.
- Ether amines are characterized in that they comprise at least one ether group and at least one amino group.
- the ether amines may be represented by the generic formula NR a R b —(CH 2 ) n [O—(CH 2 ) m ] p —NR c R d , wherein n is 1, 2, 3, 4, or 5, m is 1, 2, 3, 4, or 5, p is 1, 2, 3, 4, or 5, and R a , R b , R c , and R d are independently of each other selected from H and C 1 -C 4 -alkyl, or R a and R b and/or R c and R d may together with the nitrogen atom to which they are bound form a 5- to 10-membered, preferably 5- to 6-membered heterocyclic ring, wherein the heterocycle may comprise 1, 2, or 3 additional heteroatoms selected from N, O, and S, wherein the N atom if present is further substituted by H or C 1 -C 4 -alkyl.
- n is 1 or 2
- m is 1 or 2
- p is 1 or 2
- R a , R b , R c , and R d are each independently selected from C 1 -C 2 -alkyl, or R a and R b and R c and R d each together with the nitrogen atom to which they are bound form a 5- or 6-membered heterocyclic ring, wherein the heterocycle may comprise 1 additional heteroatom selected from N, O, and S, wherein the N-atom if present is further substituted by a C 1 -C 2 -alkyl group.
- the ether amines are heterocyclic 5- to 10-membered, preferably 5- or 6-membered rings comprising an oxygen atom and a nitrogen atom to form the required amino and ether groups, and wherein the nitrogen atom is further substituted by H, C 1 -C 10 -alkyl, C 1 -C 10 -haloalkyl, C( ⁇ O)H, or C( ⁇ O)C 1 -C 10 -alkyl.
- morpholine compounds wherein the nitrogen atom is substituted by C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C( ⁇ O)H, or C( ⁇ O)C 1 -C 4 -alkyl, preferably by C 1 -C 4 -alkyl, C( ⁇ O)H, or C( ⁇ O)CH 3 .
- Preferred ether amines include dimorpholinodiethylether, bis(2-dimethyl-aminoethyl)ether, N-acetylmorpholine, and N-formylmorpholine.
- the amine (4) is dimorpholinodiethylether (available as Lupragen® N106 from BASF).
- the amine (4) is bis(2-dimethyl-aminoethyl)ether (CAS [3033-62-3], available as Lupragen® N205 from BASF).
- the amine (4) is a morpholine compound selected from N-acetylmorpholine and N-formylmorpholine.
- the amines (4l) or (4m) are preferably
- the amine (4) is (L217) triethanolamine.
- the amine (4) is (L218) tripropanolamine.
- the amine (4) is (L219) diisopropanolamine.
- the amine (4) is (L220) triisopropanolamine.
- the amine (4) is (L221) diethanolamine.
- the amine (4) is (L222) methyldipropanolamine.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- an amine selected from the group consisting of methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, N,N′,N′′-tris(dimethylaminopropyl)hexahydrotriazine, and 2,2′-dimorpholinyldiethyl ether.
- the amine (4) is methyldiethanolamine.
- the amine (4) is tetrahydroxypropylethylenediamine.
- the amine (4) is trimethylaminoethylethanolamine.
- the amine (4) is N,N,N′,N′-tetramethyl-1,6-hexanediamine.
- the amine (4) is N,N′,N′′-tris(dimethylaminopropyl)hexahydrotriazine.
- the amine (4) is 2,2′-dimorpholinyldiethyl ether.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- an amine selected from the group consisting of (L10), (L11), (L12), (L13), (L14), (L15), (L16), (L17), (L18), (L19), (L20), (L21), (L22), (L23), (L24) and (L29) as disclosed in the PCT application PCT/IB2015/059864.
- the amine (4) is (L10) an aliphatic alkylenediamine according to the general formula (IA)
- R1 and R2 are simultaneously or each independently hydrogen, linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl, C 3 - to C 8 -cycloalkyl or C 3 - to C 8 -cycloalkyl in which optionally—preferably mandatorily—one or more CH 2 groups have been replaced by O, NH or NR10; or
- R1 and R2 jointly represents a linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl, C 3 - to C 8 -cycloalkyl or C 3 - to C 8 -cycloalkyl in which optionally—preferably mandatorily—one or more CH 2 groups have been replaced by O, NH or NR10; and
- R3 x and R4 are simultaneously or each independently hydrogen, linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl, C 3 - to C 8 -cycloalkyl or C 3 - to C 8 -cycloalkyl in which optionally—preferably mandatorily—one or more CH 2 groups have been replaced by 0, NH or NR10; and
- R10 is linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl or C 3 - to C 8 -cycloalkyl;
- z is a value from 2 to 20, preferably from 2 to 12;
- x is an index which can assume all values from 1 to z.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- R1, R2 and R5 are simultaneously or each independently hydrogen, linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl, C 3 - to C 8 -cycloalkyl or C 3 - to C 8 -cycloalkyl in which optionally—preferably mandatorily—one or more CH 2 groups have been replaced by 0, NH or NR10; or
- two of the three radicals R1, R2 and R5 are covalently bonded to each other to form a linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl, C 3 - to C 8 -cycloalkyl or C 3 - to C 8 -cycloalkyl in which optionally—preferably mandatorily—one or more CH 2 groups have been replaced by O, NH or NR10, and the remaining one of the three radicals R1, R2 and R5 is hydrogen, linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl, C 3 - to C 8 -cycloalkyl or C 3 - to C 8 -cycloalkyl in which optionally—preferably mandatorily—one or more CH 2 groups have been replaced by 0, NH or NR10; and
- R3 y and R4 y are simultaneously or each independently hydrogen, linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl, C 3 - to C 8 -cycloalkyl or C 3 - to C 8 -cycloalkyl in which optionally—preferably mandatorily—one or more CH 2 groups have been replaced by 0, NH or NR10;
- R10 is linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl or C 3 - to C 8 -cycloalkyl;
- a is a value of 2 to 5;
- b is a value of 2 to 12;
- y is an index which can assume all values between 1 and b.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- R1 and R2 are simultaneously or each independently hydrogen, linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl, C 3 - to C 8 -cycloalkyl or C 3 - to C 8 -cycloalkyl in which optionally—preferably mandatorily—one or more CH 2 groups have been replaced by 0, NH or NR10;
- R1 and R2 jointly represents a linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl, C 3 - to C 8 -cycloalkyl or C 3 - to C 8 -cycloalkyl in which optionally—preferably mandatorily—one or more CH 2 groups have been replaced by 0, NH or NR10; and
- R3, R4 and R5 are simultaneously or each independently hydrogen, linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl, C 3 - to C 8 -cycloalkyl or C 3 - to C 8 -cycloalkyl in which optionally—preferably mandatorily—one or more CH 2 groups have been replaced by 0, NH or NR10;
- R10 is linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl or C 3 - to C 8 -cycloalkyl;
- x, y and z are each independently a value from 0 to 100 and the sum of x, y and z are at least 2.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- R 1 to R 6 are—independently from each other—hydrogen, linear or branched C 1 - to C 20 -alkyl, -alkoxy, -polyoxyalkylene, -polyoxyethylene, -hydroxyalkyl, -(alkyl)carboxy, -phosphonoalkyl, -alkylamino radicals, C 2 - to C 20 -alkenyl radicals or C 6 - to C 20 -aryl, -aryloxy, -hydroxyaryl, -arylcarboxy or -arylamino radicals which are optionally further substituted, and
- R 2 , R 3 and R 5 may—independently from each other—optionally be each additionally further polyethyleneimine polymer chains, and
- R 1 may optionally be an NR 3 R 4 or an NH 2 radical
- x, y and z are—independently from each other—0 or an integer, wherein the sum of x, y and z must be chosen in such a way that the average molar mass is within the specified range.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- (L15) a polyethyleneimine according to the general formula (V) wherein at least one of the radicals R 2 to R 6 is a polyoxyalkylene radical.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- L16a condensation of at least one compound selected from N-(hydroxyalkyl)amines of formulae (I.a) and/or (I.b),
- A are independently selected from C 1 -C 6 -alkylene
- R 1 , R 1* , R 2 , R 2* , R 3 , R 3* , R 4 , R 4* , R 5 and R 5* are independently of one another selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted;
- R 6 is selected from hydrogen, alkyl, cycloalkyl or aryl, which may be optionally substituted.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- L17a condensation of at least one compound selected from N-(hydroxyalkyl)amines of formulae (I.a) and/or (I.b),
- A are independently selected from C 1 -C 6 -alkylene
- R 1 , R 1* , R 2 , R 2* , R 3 , R 3* , R 4 , R 4* , R 5 and R 5* are independently of one another selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted;
- R 6 is selected from hydrogen, alkyl, cycloalkyl or aryl, which may be optionally substituted;
- step L17b) reacting at least a part of the remaining hydroxy groups and/or, if present, at least a part of the secondary amino groups of the polyether provided in step L17a) with at least one alkylene oxide.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- (L18) a derivative obtainable by quaternization, protonation, sulphation and/or phosphation of the polymer (L16) or (L17).
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- (L20) a bicyclic, tricyclic or higher polycyclic polyamine.
- the amine (4) is (L21) an amine containing not more than one amino group and two alkoxy- or hydroxy-substituted C 2 to C 12 alkyl groups R21a and one C 1 to C 10 alkyl group R21b, wherein the R21a group bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom and wherein the two groups R21a are identical.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- (L22) an amine containing not more than one amino group and one alkoxy- or hydroxy-substituted C 2 to C 12 alkyl group R 22a and two C 1 to C 10 alkyl groups R 22b , wherein the two groups R 22b are identical.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- (L23) an imidazolidinone N-substituted on one or two of its nitrogen atoms with alkyl groups R 23 wherein R 23 may optionally be substituted with OH groups.
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- the amine (4) is N-(2-aminoethyl)-2-aminoethyl amine (4)
- Preferred combinations of the cation source (1) and the (thio)phosphoric acid triamide (2) are defined in the following Table A.
- Preferred combinations of the cation source (1) and the fertilizer (3a) are defined in the following Table B.
- Preferred combinations of the cation source (1) and the P-containing fertilizer (3b) are defined in the following Table C.
- Preferred combinations of the cation source (1) and the fertilizers (3a) and (3b) are defined in the following Table D.
- the (thio)phosphoric acid triamide (2) i.e. NBPT, NPPT or NBPT+NPPT, may preferably be provided in combination with an amine (4) as defined above.
- the cation source (1) is provided in certain minimum amount based on the fertilizer mixture (3) or the P-containing fertilizer (3b) in order to exhibit the stabilizing effect.
- the cation source (1) is used in an amount of at least 0.25 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 0.5 wt.-% based on the total weight of the P-containing fertilizer (3b).
- the cation source (1) is used in an amount of at least 0.375 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 0.75 wt.-% based on the total weight of the P-containing fertilizer (3b).
- the cation source (1) is used in an amount of at least 0.5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 1 wt.-% based on the total weight of the P-containing fertilizer (3b).
- the cation source (1) is used in an amount of at least 1 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 2 wt.-% based on the total weight of the P-containing fertilizer (3b).
- the cation source (1) is used in an amount of at most 20 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at most 40 wt.-% based on the total weight of the P-containing fertilizer (3b)
- the cation source (1) is used in an amount of at most 10 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at most 20 wt.-% based on the total weight of the P-containing fertilizer (3b).
- the cation source (1) is used in an amount of at most 5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 10 wt.-% based on the total weight of the P-containing fertilizer (3b).
- the cation source (1) is used in an amount of at most 2.5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 5 wt.-% based on the total weight of the P-containing fertilizer (3b).
- the cation source (1) is used in such an amount that it does not exhibit any urease inhibiting effect by itself.
- the (thio)phosphoric acid triamide (2) is used in an amount of at least 0.005 wt.-% based on the total weight of the fertilizer (3a).
- the (thio)phosphoric acid triamide (2) is used in an amount of at least 0.01 wt.-% based on the total weight of the fertilizer (3a).
- the (thio)phosphoric acid triamide (2) is used in an amount of at least 0.05 wt.-% based on the total weight of the fertilizer (3a).
- the (thio)phosphoric acid triamide (2) is used in an amount of at most 20 wt.-% based on the total weight of the fertilizer (3a).
- the (thio)phosphoric acid triamide (2) is used in an amount of at most 10 wt.-% based on the total weight of the fertilizer (3a).
- the amine (4) is used in an amount of at least 0.005 wt.-% based on the total weight of the fertilizer (3a).
- the amine (4) is used in an amount of at least 0.01 wt.-% based on the total weight of the fertilizer (3a).
- the amine (4) is used in an amount of at least 0.05 wt.-% based on the total weight of the fertilizer (3a).
- the amine (4) is used in an amount of at most 20 wt.-% based on the total weight of the fertilizer (3a).
- the amine (4) is used in an amount of at most 10 wt.-% based on the total weight of the fertilizer (3a).
- compositions A and B, the mixture M, and the granule G may further comprise auxiliaries such as solvents, solid carriers, surfactants, adjuvants, thickeners, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers, binders, preservatives, antioxidants, and odorants.
- auxiliaries such as solvents, solid carriers, surfactants, adjuvants, thickeners, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers, binders, preservatives, antioxidants, and odorants.
- Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
- Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
- mineral oil fractions of medium to high boiling point e.g. kerosene, diesel oil
- oils of vegetable or animal origin oils of vegetable or animal origin
- aliphatic, cyclic and aromatic hydrocarbons e.g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes
- lactates carbonates, fatty acid esters, gammabutyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
- Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
- mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
- polysaccharides e.g. cellulose, starch
- fertilizers
- Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
- Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
- sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
- Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkyl phenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
- Examples of phosphates are phosphate esters.
- Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
- Suitable non ionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
- alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, aryl phenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
- Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
- N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
- esters are fatty acid esters, glycerol esters or monoglycerides.
- sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
- polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
- Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
- Suitable amphoteric surfactants are alkylbetains and imidazolines.
- Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide or of the A-B—C type comprising alkanol, polyethylene oxide and polypropylene oxide.
- Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or poly-ethyleneamines.
- Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports OS256, T&F Informa UK, 2006, chapter 5.
- Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
- Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
- Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
- Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
- Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples are
- Preferred colorants are metal-complex dyes, more preferably chromium-complex dyes, for example Orasol Yellow 141.
- Suitable tackifiers or binders are polyvinylpyrrolidones, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
- Suitable preservatives include e.g. sodium benzoate, benzoic acid, sorbic acid, and derivatives thereof.
- Suitable antioxidants include sulfites, ascorbic acid, tocopherol, tocopherol acetate, tocotrienol, melatonin, carotene, beta-carotene, ubiquinol, and derivatives thereof. Tocophercol acetate is preferred as antioxidant.
- Suitable odorants include perfume materials which are for example mentioned in U.S. Pat. No. 7,182,537, including allo-ocimene, Allyl cyclohexanepropionate, Allyl heptanoate, trans-Anethole, benzylbutyrate, Camphene, Cadinene, Carvacrol, cis-3-Hexenyl tiglate, Citronellol, Citronellyl acetate, Citronellyl nitrile, Citronellyl propionate, Cyclohexylethyl acetate, Decyl Aldehyde (Capraldehyde), Dihydromyrcenol, Dihydromyrcenyl acetate, 3,7-Dimethyl-1-octanol, Diphenyloxide, Fenchyl Acetate (1,3,3-Trimethyl-2-norbornanyl acetate), Geranyl acetate, Geranyl formate, Geranyl nitrile
- Urease inhibitor “U1” was obtained from BASF SE. Composition:
- DAP Diammonium phosphate
- TSP Triple super phosphate
- Zinc chloride Zinc chloride (ZnCl 2 )
- Aluminium sulfate Al 2 (SO 4 ) 3
- urea treated with U1 3 kg were added to an ERWEKA mixer (dimensions mix drum: 50 cm diameter, 20 cm high). The mixer is turned on (27 RPM) and U1 formulation is sprayed on the urea using a syringe. Afterwards, the fertilizer/U1 mixture is mixed for 3 minutes
- Active ingredient content on urea was analyzed by HPLC (high-pressure liquid chromatography) using method DIN EN 16651. In case of bulk blends, the urea granules were separated from the other fertilizers before dissolving in water for HPLC analysis.
- urea treated with a urease inhibitor and 10 g of the other fertilizer are added to a small jar. After closing the jar, the fertilizers are mixed by vigorously shaking the jar. The closed jar is then stored at room temperature in a dark place. At the end of the storage time, urea granules are removed and tested using the Dräger test.
- Urea granules treated with 0.04 wt.-% U1 active ingredient were mixed with TSP (Triple Super Phosphate) fertilizer granules. After mixing, the samples were stored in closed containers at room temperature. After 1 day of storage, the urea granules were separated from the TSP granules and the active ingredient (a.i.) concentration on the urea was analyzed by HPLC. Table 1 shows that when U1 treated urea granules are mixed with TSP granules, 50-90% of the a.i.
- Urea treated with U1 (0.04 wt.-% active on urea) was mixed with different phosphate fertilizers in a 1:1 wt.-% ratio. These mixtures were stored in closed containers at room temperature for 8 days. Afterwards, the urea granules were separated out and tested in the Dräger test. The following samples were tested:
- Urea was treated with different NBPT based urease inhibitors (0.04 wt.-% active ingredient on urea).
- a 16-8-22 wetblend fertilizer was treated with a solution of CaCl 2 dissolved in DMSO.
- CaCl 2 solution 8 g CaCl 2 was dissolved in 100 g DMSO.
- 50 grams of fertilizer was treated with 8.4 grams of CaCl 2 solution.
- the fertilizer was allowed to dry for 2 days at room temperature. Afterwards the fertilizer was treated with U1 to obtain a U1 active ingredient concentration on the fertilizer of 0.04 wt.-%. After 1 month storage in a closed jar at room temperature in a dark place, the fertilizer was tested with the Dräger test. The following samples were tested:
- CaCl 2 is able to prevent the degradation of U1 active ingredient on wetblend fertilizers.
- a mixture M comprising
- composition M according to Embodiment 3, wherein the composition further comprises
- a granule G comprising a urea-containing fertilizer (3a) and/or a P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer, wherein the granule is coated with a cation source (1) comprising a cation C m+ , wherein
- composition B comprising
- Embodiment 1 The use according to Embodiment 1, the method according to Embodiment 2, the mixture M according to any one of Embodiments 3 or 4, or the composition B according to any one of Embodiments 5 or 6, wherein the cation source (1) is a salt, which comprises a cation C m+ , wherein
- the cation source (1) is a salt, which is selected from the group consisting of Al 2 (SO 4 ) 3 , Fe(SO 4 ), Fe 2 (SO 4 ) 3 , ZnSO 4 , CuSO 4 , CaSO 4 , AlCl 3 , FeCl 2 , FeCl 3 , ZnCl 2 , CuCl 2 , Mg(NO 3 ) 2 , Ca(NO 3 ) 2 , CaCl 2 , and MgSO 4 , and is preferably CaCl 2 or MgSO 4 .
- Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16 The use according to any one of Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the method according to any one of Embodiments 2, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the mixture M according to any one of Embodiments 3, 4, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the granule G according to any one of Embodiments 5, 6, 8, 9, 10, 11, 12, 13, 14, 15 or 16, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, wherein the cation source (1) is used in an amount of at least 0.25 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 0.5 wt.-% based on the total weight of the P-containing fertilizer (3b).
- Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16 The use according to any one of Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the method according to any one of Embodiments 2, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the mixture M according to any one of Embodiments 3, 4, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the granule G according to any one of Embodiments 5, 6, 8, 9, 10, 11, 12, 13, 14, 15 or 16, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, wherein the cation source (1) is used in an amount of at most 5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at most 10 wt.-% based on the total weight of the P-containing fertilizer (3b).
- Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16 The use according to any one of Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the method according to any one of Embodiments 2, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the mixture M according to any one of Embodiments 3, 4, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the granule G according to any one of Embodiments 5, 6, 8, 9, 10, 11, 12, 13, 14, 15 or 16, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, wherein the cation source (1) is used in an amount of at least 0.5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 1 wt.-% based on the total weight of the P-containing fertilizer (3b).
- Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16 The use according to any one of Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the method according to any one of Embodiments 2, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the mixture M according to any one of Embodiments 3, 4, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the granule G according to any one of Embodiments 5, 6, 8, 9, 10, 11, 12, 13, 14, 15 or 16, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, wherein the cation source (1) is used in an amount of at most 2.5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at most 5 wt.-% based on the total weight of the P-containing fertilizer (3b).
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Abstract
Description
- The present invention relates to the use of a cation source (1) to prevent decomposition of a (thio)phosphoric acid triamide (2); to a method for preventing decomposition of a (thio)phosphoric acid triamide (2) by adding a cation source (1); to a mixture M comprising a cation source (1) and a (thio)phosphoric acid triamide (2); to a granule G comprising a fertilizer (3a) and/or a P-containing fertilizer (3b), wherein the granule is coated with a cation source (1); and to a composition B comprising a (thio)phosphoric acid triamide (2), a fertilizer mixture (3), and a cation source (1), wherein the composition B is obtainable by specific processes.
- Worldwide, the predominant and further-increasing amount of the nitrogen used for fertilizing is employed in the form of urea or urea-containing fertilizers. Urea itself, however, is a form of nitrogen which is absorbed very little if at all, being hydrolyzed relatively rapidly by the enzyme urease, which is present ubiquitously in the soil, to form ammonia and carbon dioxide. In this process, in certain circumstances, gaseous ammonia is emitted to the atmosphere, and is then no longer available in the soil for the plants, thereby lowering the efficiency of fertilization.
- It is known that the degree of utilization of the nitrogen when using urea-containing fertilizers can be improved by spreading urea-containing fertilizers together with substances which are able to inhibit or decrease the enzymatic cleavage of urea (for a general review, see Kiss, S. Simihaian, M. (2002) Improving Efficiency of Urea Fertilizers by Inhibition of Soil Urease Activity, ISBN 1-4020-0493-1, Kluwer Academic Publishers, Dordrecht, The Netherlands).
- Among the most potent known urease inhibitors are N-alkylthiophosphoric acid triamides and N-alkylphosphoric acid triamides, which are described in EP 0 119 487, for example.
- Additionally, mixtures of N-alkylthiophosphoric acid triamides such as N-(n-butyl)thiophosphoric acid triamide (NBPT) and N-(n-propyl)thiophosphoric acid triamide (NPPT) can be used. The mixtures and their preparation are described in US 2010/218575 A1, for example.
- These urease inhibitors are described in U.S. Pat. No. 4,530,714, for example. In order for this class of compound to be able to act as a urease inhibitor, there must first be a conversion to the corresponding oxo form. That form reacts subsequently with the urease, causing its inhibition.
- It is advisable to apply the urease inhibitors together with the urea onto or into the soil, since this ensures that the inhibitor comes into contact, together with the fertilizer, with the soil. The urease inhibitor may be incorporated in the urea by, for example, dissolving it into the melt prior to urea granulation or prilling. A process of this kind is described in U.S. Pat. No. 5,352,265, for example. A further option is to apply the urease inhibitor to the urea granules or prills, in the form of a solution, for example. Corresponding processes for application, and suitable solvents, are described in US 2010/218575 A1, for example.
- It is known in the art that the storage life of the urease inhibitor is limited in the presence of urea-containing fertilizers. The higher the temperature, the shorter is the storage life. If, for example, urea is stored under tropical conditions, a major part of the urease inhibitor has undergone decomposition, generally, after about four weeks of storage.
- In order to address this problem, WO 2015/062667 discloses a composition comprising a (thio)phosphoric acid triamide urease inhibitor in combination with a functionalized amine to increase the stability and storage life of the (thio)phosphoric acid triamides urease inhibitors in the presence of urea-containing fertilizers.
- US 2011/0154874 A1 discloses amine-based additives selected from methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, N,N′,N″-tris(dimethylaminopropyl)hexahydrotriazine, and 2,2′-dimorpholinyldiethyl ether.
- The PCT application PCT/IB2015/059864 discloses further amine compounds as additives or coating materials for urea-containing fertilizers.
- However, it has been observed that further stability problems of the (thio)phosphoric acid triamide urease inhibitors arise, if the urease inhibitors are not only used together with urea-containing fertilizers, but also with an additional P-containing fertilizer which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer. The present invention focuses on this additional destabilizing effect of the additional P-containing fertilizer.
- For example, it has been observed that if urea granules, which have been treated with a formulation comprising the urease inhibitors N-n-butylthiophosphoric acid triamide (NBPT) and N-n-propylthiophosphoric acid triamide (NPPT), are mixed with granules comprising triple super phosphate (TSP) a decomposition of 50 to 90 wt.-% of the urease inhibitors is observed after only one day depending on the amount of TSP in the mixture, while no decomposition is observed after one day in the absence of TSP granules.
- It was therefore an object of the present invention to provide a stabilizing agent, which is suitable for preventing decomposition of (thio)phosphoric acid triamide urease inhibitors, if the urease inhibitors are not only applied together with urea-containing fertilizers, but also with with an additional P-containing fertilizer which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer. In this connection, it was another object to improve the storage life of compositions comprising the (thio)phosphoric acid triamide a fertilizer mixture comprising a urea-containing fertilizer and with an additional P-containing fertilizer which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer.
- In particular, it was an object of the present invention to prevent decomposition of a (thio)phosphoric acid triamide, which is caused by the additional P-containing fertilizer which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer, but not by the urea-containing fertilizer. In this regard, it was desired to reduce the decomposition caused by the additional P-containing fertilizer as such that less than 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide decompose due to the influence of the additional P-containing fertilizer within 15 days at a temperature of 20° C. to 25° C.
- In connection with the above objects, it was further desired to provide a stabilizing agent, which is toxicologically unobjectionable, which does not adversely affect the urease inhibiting effect and/or the activity of the (thio)phosphoric acid, which can be easily and safely packaged, transported and shipped, even in large quantities, and which can be easily and safely handled and applied for soil treatment, even in large quantities.
- In view of the above objects, the present invention relates to the use of a cation source (1) comprising a cation Cm+, wherein
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl;
in a composition A comprising - (i) a (thio)phosphoric acid triamide (2) according to general formula (I)
-
- wherein
- X1 is O or S;
- R1 is C1-C20-alkyl, C3-C2O-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl;
- R2 is H, C1-C20-alkyl, C3-C2O-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl; or
- R1 and R2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of N, O, and S; and
- R3, R4, R5, and R6 are independently of each other selected from the group consisting of H and C1-C4-alkyl;
and
- (ii) a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer;
to prevent decomposition of the (thio)phosphoric acid triamide (2). - Furthermore, the present invention relates to a method for preventing decomposition of a (thio)phosphoric acid triamide (2) according to general formula (I)
-
- wherein
- X1 is O or S;
- R1 is C1-C20-alkyl, C3-C2O-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl;
- R2 is H, C1-C20-alkyl, C3-C2O-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl; or
- R1 and R2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of N, O, and S; and
- R3, R4, R5, and R6 are independently of each other selected from the group consisting of H and C1-C4-alkyl;
in a composition A comprising
- (i) the (thio)phosphoric acid triamide (2);
and - (ii) a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer;
by adding a cation source (1) comprising a cation Cm+ to the composition A, wherein
Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl. - It has surprisingly been found by the inventors of the present invention that decomposition of a (thio)phosphoric acid triamide (2) as defined above in a composition A comprising the (thio)phosphoric acid triamide (2) and a fertilizer mixture (3) as defined above can be prevented by using or adding a cation source (1) comprising a cation Cm+ as defined above.
- In particular, it has been found that, while the P-containing fertilizer (3b) typically causes a decomposition of the (thio)phosphoric acid triamide (2) of at least 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide within 15 days at a temperature of from 20° C. to 25° C., if no cation source (1) is present, the situation is completely different if a cation source (1) is present. In particular, it has been found that the decomposition, which is caused by the P-containing fertilizer (3b), can be reduced as such that less than 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 15 days at a temperature of 20° C. to 25° C., if a cation source (1) is present. Preferably, the decomposition, which is caused by the P-containing fertilizer (3b), can be reduced as such that less than 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 1 month at a temperature of 20° C. to 25° C., if a cation source (1) is present.
- The above described improved storage stability of compositions comprising a (thio)phosphoric acid triamide (2) and a fertilizer mixture (3) as defined above is highly advantageous from the commercial perspective, as the (thio)phosphoric acid triamide (2) may be applied to the fertilizer mixture (3) at an early stage, and the resulting composition can be stored until the time of its spreading to the soil. Accordingly, it is not required to store the (thio)phosphoric acid triamide (2) and a fertilizer mixture (3) separately and to apply the (thio)phosphoric acid triamide (2) to the fertilizer mixture (3) only shortly before the application to the soil, which would complicate the handling for the user. Furthermore, the application rates of the compositions comprising the (thio)phosphoric acid triamide (2) and the fertilizer mixture (3) can be reduced, as the stability of the (thio)phosphoric acid triamide (2) is improved during storage, so that more (thio)phosphoric acid triamide (2) is available at the time of applying the composition to the soil resulting in a long urease inhibition.
- The present invention further relates to a mixture M comprising
- (i) a cation source (1) comprising a cation Cm+, wherein
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl
and
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl
- (ii) a (thio)phosphoric acid triamide (2) according to general formula (I)
-
- wherein
- X1 is O or S;
- R1 is C1-C20-alkyl, C3-C2O-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl;
- R2 is H, C1-C20-alkyl, C3-C2O-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl; or
- R1 and R2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of N, O, and S; and
- R3, R4, R5, and R6 are independently of each other selected from the group consisting of H and C1-C4-alkyl.
- The mixture M according to the invention may advantageously be used for treating a fertilizer mixture (3). By providing the (thio)phosphoric acid triamide (2) in combination with the cation source (1), the (thio)phosphoric acid triamide (2) is directly provided in combination with a stabilizing agent, so that when being combined with the fertilizer mixture (3), the cation source (1) will exhibit its advantageous effect on the stability of the (thio)phosphoric acid triamide (2) as described in detail above.
- Furthermore, the present invention relates to a granule G comprising a urea-containing fertilizer (3a) and/or a P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer, wherein the granule is coated with a cation source (1) comprising a cation Cm+, wherein
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl.
- The granule G according to the invention is advantageous because the fertilizer (3a) and/or (3b) can be provided in combination with the stabilizing agent, i.e. the cation source (1), so that, when the (thio)phosphoric acid triamide (2) is added as urease inhibitor, the cation source (1) will exhibit its advantageous effect on the stability of the (thio)phosphoric acid triamide (2) as described in detail above.
- Moreover, the present invention relates to a composition B comprising
- (i) a (thio)phosphoric acid triamide (2) according to general formula (I)
-
- wherein
- X1 is O or S;
- R1 is C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl;
- R2 is H, C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl; or
- R1 and R2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of N, O, and S; and
- R3, R4, R5, and R6 are independently of each other selected from the group consisting of H and C1-C4-alkyl;
- (ii) a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer; and
- (iii) a cation source (1) comprising a cation Cm+, wherein
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl;
wherein the composition B is obtainable
by a process comprising the steps of
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl;
- (a1) treating granules comprising the urea-containing fertilizer (3a) and the (thio)phosphoric acid triamide (2) with the cation source (1);
- (b1) blending the treated granules of step (a1) with granules comprising the P-containing fertilizer (3b);
or by a process comprising the steps of - (a2) treating granules comprising the P-containing fertilizer (3b) with the cation source (1);
- (b2) blending the treated granules of step (a2) with granules comprising the urea-containing fertilizer (3a) and the (thio)phosphoric acid triamide (2);
or by a process comprising the steps of - (a3) blending granules comprising the urea-containing fertilizer (3a) and the (thio)phosphoric acid triamide (2) with granules comprising the P-containing fertilizer (3b); and
- (b3) treating the blend of step (a3) with the cation source (1);
or by a process comprising the steps of - (a4) treating granules comprising the fertilizer mixture (3) with the (thio)phosphoric acid triamide (2); and
- (b4) treating the treated granules of step (a4) with the cation source (1);
or by a process comprising the steps of - (a5) treating granules comprising the fertilizer mixture (3) with the cation source (1); and
- (b5) treating the treated granules of step (a5) with the (thio)phosphoric acid triamide (2); or by a process comprising the steps of
- (a6) providing granules comprising the fertilizer mixture (3); and
- (b6) treating the granules of step (a6) with a—solid or liquid—mixture comprising the (thio)phosphoric acid triamide (2) and the cation source (3);
or by a process comprising the steps of - (a7) providing granules comprising the fertilizer mixture (3) and the cation source (1); and
- (b7) treating the granules of step (a7) with the (thio)phosphoric acid triamide (2).
- The above defined composition B comprises the (thio)phosphoric acid triamide (2), the fertilizer mixture (3), and the cation source (1) as stabilizing agent. Accordingly, the composition B exhibits the advantageous properties in terms of the stability as outlined in detail above.
- Furthermore, the composition B is specified in terms of processes for combining the different components of the composition B. The processes result in advantageous structural features of the composition B, which may enhance the stabilizing effect of the cation source (1).
- The present invention is described in detail hereinafter. The following definitions and preferred embodiments apply to the use (and the composition A defined in this connection), the method (and the composition A defined in this connection), the mixture M, the granule G, and the composition B as defined herein. It is to be understood that the preferred embodiments are preferred on their own as well as in combination.
- As used in this specification and in the appended claims, the singular forms of “a” and “an” also include the respective plurals unless the context clearly dictates otherwise.
- The term “fertilizer mixture (3)” also refers to granules, capsules, compartments or other units in which both the urea-containing fertilizer (3a) and the P-containing fertilizer (3b) are contained in one granule, capsule, compartment or unit.
- The term “at least one” as used herein means one or more, preferably one or two, and thus typically refers to individual compounds or mixtures/combinations.
- The abbreviation wt.-% or wt.-% stands for “percent by weight”.
- The term “cation source” as used herein preferably refers to a compound or composition, which comprises a cation Cm+, wherein Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl.
- In one embodiment, the cation source (1) is a salt or an ion exchange material.
- In one preferred embodiment, the cation source (1) is a salt, for example a salt of the formula (Cm+)n(An−)m, wherein Cm+ represents a cation as defined above with m being 1, 2, or 3, and An− represents an anion with n being 1, 2, or 3.
- Regarding the selection of a suitable salt, the cation of the salt is essential. Preferred cations Cm+ include Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, or Ba2+. In a preferred embodiment, the cation source (1) is therefore a salt, which comprises a cation Cm+ include Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, or Ba2+. A particularly preferred cation Cm+ is Mg2+ or Ca2+. In a more preferred embodiment, the cation source is therefore a salt, which further comprises a cation Cm+, wherein Cm+ is Mg2+ or Ca2+. In one particularly preferred embodiment Cm+ is Ca2+. In another particularly preferred embodiment, Cm+ is Mg2+.
- Suitable anions An− include F−, Cl−, Br−, I−, SO4 2−, NO3 −, or CH3CO2 −. In a preferred embodiment, the cation source is therefore a salt, which further comprises an anion An−, wherein An− is F−, Cl−, Br−, I−, SO4 2−, NO3 −, or CH3CO2 −. In a more preferred embodiment, the cation source (1) is a salt, which comprises an anion An−, wherein An− is Cl− or SO4 2−. In one particularly preferred embodiment An− is Cl−. In another particularly preferred embodiment, An− is SO4 2−.
- Preferred salts include Al2(SO4)3, Fe(SO4), Fe2(SO4)3, ZnSO4, CuSO4, CaSO4, AlCl3, FeCl2, FeCl3, ZnCl2, CuCl2, Mg(NO3)2, Ca(NO3)2, CaCl2, and MgSO4. More preferably, the salt is CaCl2 or MgSO4. In a preferred embodiment, the cation source (1) is a therefore a salt, which is selected from the group consisting of Al2(SO4)3, Fe(SO4), Fe2(SO4)3, ZnSO4, CuSO4, CaSO4, AlCl3, FeCl2, FeCl3, ZnCl2, CuCl2, Mg(NO3)2, Ca(NO3)2, CaCl2, and MgSO4, and is preferably CaCl2 or MgSO4. In one particularly preferred embodiment, the salt is CaCl2. In another particularly preferred embodiment, the salt is MgSO4.
- It is to be understood that the salts may be provided in anhydrous form or in the form of hydrates.
- Hydrates are salts containing water molecules combined in a definite ratio as an integral part of the crystal that are either bound to a metal center or that have crystallized with the metal complex. Such hydrates are also said to contain water of crystallization or water of hydration. The notation “salt x.nH2O”, where n is the number of water molecules per formula unit of the salt, is commonly used to show that a salt is hydrated. The “n” is usually a low integer in the range of from 1 to 12, and is for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and it is possible that fraction numbers occur. For example, in a monohydrate n is one, and in a hexahydrate n is 6, and in a heptahydrate n is 7. In case the cation source (1) or the salt is MgSO4, anhydrous magnesium sulfate, magnesium sulfate monohydrate, magnesium sulfate heptahydrate, or a mixture thereof can be preferably used, wherein the magnesium sulfate monohydrate is most preferred.
- It is to be understood that the salts as used herein may also be double salts, i.e. salts comprising two or more cations and/or two or more anions. They can be obtained by combination of two different salts, which are crystallized in the same regular ionic lattice. Examples of double salts include alums (with the general formula CaCb[SO4]2×12H2O), wherein Ca and Cb represent different cations of which Ca is Ca + and Cb is Cb +, or Tutton's salts (with the general formula [Cd]2Cd[SO4]2×6H2O), wherein Cc and Cd represent different cations of which Cc is Cc+ and Cd is Cd 2+. Further examples of double salts include ammonium iron(II) sulfate ((NH4)2Fe(SO4)2×6H2O) and bromlite (BaCa(CO3)2).
- In one embodiment, the cation source (1) is a salt, which has a solubility of at least 33 g/L in water at a temperature of from 15° C. to 25° C. Preferably the solubility is at least 100 g/L in water at a temperature of from 15° C. to 25° C. It is to be understood that the solubility is measured in deionized or distilled water. A certain solubility of the salt is advantageous in view of the fact that the salt can easily dissolve, and the cations thus be released from the crystal lattice.
- In another preferred embodiment, the cation source (1) is an ion exchange material.
- Suitable ion exchange materials include zeolites and ion exchange resins.
- Zeolites are aluminosilicates, which have a porous structure that can accommodate a wide variety of cations, such as Ca2+, Mg2+ and others. These positive ions are rather loosely held and can readily be exchanged for others in a contact solution. Some of the more common mineral zeolites are analcime, chabazite, clinoptilolite, heulandite, natrolite, phillipsite, and stilbite. An example mineral formula is: Na2Al2Si3O10×2H2O, the formula for natrolite. As cations, such as Ca2+ or Mg2+ can be released from zeolites, zeolites exhibit a stabilizing effect in the context of the present invention.
- In a preferred embodiment of the invention the cation source (1) is therefore zeolite, which comprises a cation Cm+, wherein Cm+ is Ca2+ or Mg2+.
- Ion exchange resins comprise an insoluble matrix (or support structure) normally in the form of small (0.3-1 mm diameter) beads, fabricated from an organic polymer substrate. The beads are typically porous, providing a high surface area. The pore size is typically below 5 nm, preferably below 4 nm. The trapping of ions occurs with the accompanying releasing of other ions.
- For example, anion exchange resins may be used, which are capable of adsorbing anions such as PO4 3−, NO3 −, or SO4 2−, in particular PO4 3−. The skeleton of such anion exchange resins may be formed by copolymerization of styrene and divinylbenzene (DVB). The DVB links the linear styrene chains together and yields an insoluble three-dimensional polymer. The DVB may for example be used in an amount of from 1 to 10 wt.-% based on the total weight of the polymer. The functional group of the resins is cationic and preferably comprises a quaternary ammonium group. As used herein, an anion exchange resin is therefore to be understood as falling within the term “cation source (1) comprising a cation Cm+”, wherein Cm+ is a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl. Preferably, the groups on the nitrogen atom of the ammonium group are methyl groups and/or ethanol groups. Particularly preferred are trimethylammonium groups as functional groups.
- In a preferred embodiment, the cation source (1) is therefore an anion exchange resin, which comprises a cation Cm+, wherein Cm+ is a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl, and is preferably a quaternary ammonium group comprising three methyl groups or two methyl groups and one hydroxyethyl group.
- The cationic groups of the anion exchange resins can exhibit a stabilizing effect in the context of the present invention.
- The ion exchange resin may alternatively be a cation exchange resin. Accordingly, the ion exchange resin may comprise and release cations, such as Ca2+, Mg2+ and others. The skeleton of the resin is also typically based on styrene and DVB as outlined in the context of anion exchange resin. The functional group of the cation exchange resins is typically anionic and preferably comprises a sulfonic acid group or a carboxylic acid group. As cations, such as Ca2+ or Mg2+ can be released from cation exchange resins, such resins can exhibit a stabilizing effect in the context of the present invention.
- In a preferred embodiment of the invention, the cation source (1) is therefore a cation exchange resin, which comprises a cation Cm+, wherein Cm+ is Ca2+ or Mg2+.
- As used herein, the term “(thio)phosphoric acid triamide” in each case covers thiophosphoric acid triamides and phosphoric acid triamides. Thus, the prefix “(thio)” as used herein in each case indicates that a group P═S or a group P═O is covered. However, if the prefix “thio” is used without brackets, this indicates that a group P═S is present.
- It is noted that the terms “(thio)phosphoric acid triamide” and “(thio)phosphoric triamide” may interchangeably be used.
- As used herein, “(thio)phosphoric acid triamides” may be represented by the following general formula (I)
-
- wherein
- X1 is O or S; R1 is C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl;
- R2 is H, C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl; or
- R1 and R2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of N, O, and S; and
- R3, R4, R5, and R6 are independently of each other selected from the group consisting of H and C1-C4-alkyl.
- The organic moieties mentioned in the above definitions of the variables are collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
- The term “alkyl” as used herein denotes in each case a straight-chain or branched alkyl group having usually from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, e.g. 3 or 4 carbon atoms. Examples of alkyl groups are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di methyl propyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methyl pentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, and 1-ethyl-2-methylpropyl. Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, n-heptyl, n-octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, and isodecyl.
- The term “cycloalkyl” as used herein denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 20 carbon atoms, preferably from 3 to 10 carbon atoms, more preferably from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
- The term “aryl” includes mono-, bi- or tricyclic aromatic radicals having usually from 6 to 14, preferably 6, 10, or 14 carbon atoms. Exemplary aryl groups include phenyl, naphthyl and anthracenyl. Phenyl is preferred as aryl group.
- The term “arylalkyl” refers to aryl as defined above, which is bonded via a C1-C4-alkyl group, in particular a methyl group (=arylmethyl), to the remainder of the molecule, examples including benzyl, 1-phenylethyl, 2-phenylethyl, etc.
- The term “heterocycle” or “heterocyclyl” includes 5- or 6-membered monocyclic heterocyclic non-aromatic radicals. The heterocyclic non-aromatic radicals usually comprise 1 or 2 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2. Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1,3- and 1,4-dioxanyl, thiopyranyl, S-oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihydrothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetrahydrothiopyranyl, S-dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S-dioxothiomorpholinyl, thiazinyl and the like. Preferred examples of heterocyclic radicals are piperazinyl, morpholinyl, pyrrolyl, pyrazolyl, triazolyl, oxazolyl, thiazolyl, and imidazolyl groups.
- The term “(di)alkylaminocarbonyl” refers to a (di)alkylamino group, i.e. an amino group comprising 1 or 2 alkyl substituents, which is bonded to the remainder of the molecule via the carbon atom of a carbonyl group (C═O).
- It is to be understood that, preferably, also stereoisomers, tautomers, N-oxides, and salts of the (thio)phosphoric acid triamides are covered by the term “(thio)phosphoric acid triamide”. Stereoisomers are present, if the compounds contain one or more centers of chirality. In this case, the compounds will be present in the form of different enantiomers or diastereomers, if more than one center of chirality is present. The term “(thio)phosphoric acid triamide” preferably covers every possible stereoisomer, i.e. single enantiomers or diastereomers, as well as mixtures thereof. Tautomers include, e.g., keto-enol tautomers. N-oxides may be formed under oxidative conditions, if tertiary amino groups are present. Salts may be formed, e.g., with the basic amino groups of the (thio)phosphoric acid triamides. Anions, which stem from an acid, with which the (thio)phosphoric acid amide may have been reacted, are e.g. chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
- In a preferred embodiment, the (thio)phosphoric acid triamide (2) may be represented by the following general formula (I)
-
- wherein
- X1 is O or S;
- R1 is C1-C5-alkyl, C5-C6-cycloalkyl, phenyl, or benzyl;
- R2 is H, or C1-C4-alkyl; and
- R3, R4, R5, and R6 are each H.
- Preferably, the (thio)phosphoric acid triamide (2) may be represented by the above formula (I), wherein
-
- X1 is S;
- R1 is C1-C5-alkyl, C5-C6-cycloalkyl, phenyl, or benzyl;
- R2 is H or C1-C4-alkyl; and
- R3, R4, R5, and R6 are each H;
- and wherein even more preferably
- X1 is S;
- R1 is C1-C5-alkyl;
- R2 is H or C1-C4-alkyl; and
- R3, R4, R5, and R6 are each H.
- It is to be understood that the term “(thio)phosphoric acid triamide (2)” may also cover combinations of (thio)phosphoric acid triamides (2) according to formula (I) as defined above.
- In one embodiment of the invention, the (thio)phosphoric acid triamide (2) is selected from the group consisting of
- N-benzyl-N-methylthiophosphoric acid triamide, N,N-diethylthiophosphoric acid triamide, N-(n-butyl)thiophosphoric acid triamide, N-isopropylphosphoric acid triamide, N-(n-hexyl)thiophosphoric acid triamide, N-(sec-butyl)thiophosphoric acid triamide, N,N-diethylphosphoric acid triamide, N-(n-propyl)thiophosphoric acid triamide, N,N-diisopropylthiophosphoric acid triamide, N,N-dimethylthiophosphoric acid triamide, N-(n-octyl)phosphoric acid triamide, N-(n-butyl)phosphoric acid triamide, N-cyclohexylphosphoric acid triamide, N-benzyl-N-methylphosphoric acid triamide, N,N-dimethylphosphoric acid triamide, N-cyclohexylthiophosphoric acid triamide, and combinations thereof.
- In one embodiment of the invention, the (thio)phosphoric acid triamide (2) is N-n-butylthiophosphoric acid triamide (NBPT), N-n-propylthiophosphoric acid triamide (NPPT), or a combination thereof.
- In one preferred embodiment of the invention, the (thio)phosphoric acid triamide (2) is N-n-propylthiophosphoric acid triamide (NPPT) having the following chemical formula:
- In another preferred embodiment of the invention, the (thio)phosphoric acid triamide (2) is N-n-butylthiophosphoric acid triamide (NBPT) having the following chemical formula:
- In yet another preferred embodiment of the invention, the (thio)phosphoric acid triamide (2) is a combination of N-n-butylthiophosphoric acid triamide (NBPT) and N-n-propylthiophosphoric acid triamide (NPPT). It is particularly preferred that the (thio)phosphoric acid triamide (2) is a combination of NBPT and NPPT, which comprises NBPT in amounts of from 40 to 95 wt.-%, more preferably from 60 to 85 wt.-%, particularly preferably from 72 to 80 wt.-%, in each case based on the total weight of the combination.
- The fertilizer mixture (3) as defined herein comprises a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer.
- As used herein, the term “fertilizer” covers any chemical compound that improves the levels of available plant nutrients and/or the chemical and physical properties of soil, thereby directly or indirectly promoting plant growth, yield, and quality. Fertilizers are typically applied either through the soil (for uptake by plant roots) or by foliar feeding (for uptake through leaves). The term “fertilizer” can be subdivided into two major categories: a) organic fertilizers (composed of decayed plant/animal matter) and b) inorganic fertilizers (composed of chemicals and minerals). Organic fertilizers include manure, slurry, worm castings, peat, seaweed, sewage, and guano. Green manure crops are also regularly grown to add nutrients (especially nitrogen) to the soil. Manufactured organic fertilizers include compost, blood meal, bone meal and seaweed extracts. Further examples are enzymatically digested proteins, fish meal, and feather meal. The decomposing crop residue from prior years is another source of fertility. In addition, naturally occurring minerals such as mine rock phosphate, sulfate of potash and limestone are also considered inorganic fertilizers. Inorganic fertilizers are usually manufactured through chemical processes (such as the Haber-Bosch process), also using naturally occurring deposits, while chemically altering them (e.g. concentrated triple superphosphate). Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mine rock phosphate, and limestone.
- As used herein, a “urea-containing fertilizer (3a)” is defined as a fertilizer comprising at least one component selected from the group consisting of urea, urea ammonium nitrate (UAN), isobutylidene diurea (IBDU), crotonylidene diurea (CDU) and urea formaldehyde (UF), urea-acetaldehyde, and ureaglyoxal condensates.
- In a preferred embodiment of the invention, the urea-containing fertilizer (3a) is urea.
- In customary commercial fertilizer quality, the urea has a purity of at least 90%, and may for example be in crystalline, granulated, compacted, prilled or ground form.
- As used herein, the “P-containing fertilizer (3b)” is any fertilizer providing any form of the chemical element phosphorus (P) or containing any chemical compounds incorporating the chemical element phosphorus (P), including but not limited to phosphate-containing fertilizers or fertilizers containing P2O5. Preferably, the P-containing fertilizer is selected from the group consisting of a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer. Most preferably, the P-containing fertilizer is a NPK fertilizer. Of course, also combinations of these fertilizers may be used as additional P-containing fertilizer (3b).
- P fertilizers, K fertilizers, and N fertilizers are straight fertilizers, i.e. fertilizers that contain only one of the nutritive elements P, K, and N. It is to be understood, however, that these fertilizers may additionally comprise at least one additional nutritive element selected from C, H, O, S, Ca, Mg, Fe, Mn, Cu, Zn, Mo, and B.
- Preferred P fertilizers include basic slag (Thomas phosphate), superphosphate, triple superphosphate, partly digested phosphate rock, soft phosphate rock, dicalcium phosphate, thermal (fused) phosphate, aluminum phosphate, and combinations thereof.
- NPK fertilizers, NP fertilizers, and PK fertilizers are multinutrient fertilizers, i.e. fertilizers that comprise combinations of the nutritive elements P, K, and N as indicated by the terms “NPK”, “NP”, and “PK”. It is to be understood, however, that these fertilizers may additionally comprise at least one additional nutritive element selected from C, H, O, S, Ca, Mg, Fe, Mn, Cu, Zn, Mo, and B.
- The NPK fertilizers, NP fertilizers, and PK fertilizers may be provided as complex fertilizers or bulk-blend or blended fertilizers. The term complex fertilizer refers to a compound fertilizer formed by mixing ingredients that react chemically. In bulk-blend or blended fertilizers, two or more granular fertilizers of similar size are mixed to form a compound fertilizer.
- According to the EEC Guidelines, NPK fertilizers must contain at least 3 wt.-% N plus 5 wt.-% P2O5 plus 5 wt.-% K2O and at least 20 wt.-% total nutrients, based on the total weight of the NPK fertilizer. The most commonly used grades (N—P2O5—K2O, each in wt %) are
-
- nutrient ratio 1:1:1:
- 15-15-15, 16-16-16, 17-17-17
-
- nutrient ratios 1:2:3 and 1:1.5:2:
- 5-10-15, 6-12-18, 10-15-20
-
- nutrient ratio 1:1:1.5-1.7:
- 13-13-21, 14-14-20, 12-12-17
-
- nutrient ratios 3:1:1 and 2:1:1:
- 24-8-8, 20-10-10
-
- low-phosphate grades:
- 15-5-20, 15-9-15
- The minimum analysis for NP fertilizers under the EEC Guidelines is 3 wt.-% N and 5 wt.-% P2O5 and at least 18 wt.-% total nutrients, based on the total weight of the NP fertilizer. Common grades are 20-20, 22-22, 26-14, 11-52, 16-48, and 18-46. These products are appropriate for potassium-rich soils or where potash is supplied as a separate fertilizer.
- In the group of PK fertilizers, all combinations of the straight P and K fertilizers listed above are possible. In general, the materials are first milled and then mixed and granulated, so that a fairly homogeneous mixture is obtained. Some products are also made by bulk blending. The EEC Guidelines set forth a minimum analysis of 5 wt.-% P2O5, 5 wt.-% K2O, and at least 18 wt.-% nutrients, based on the total weight of the PK fertilizer.
- It has been found that in particular phosphate-containing fertilizers can cause stability problems of (thio)phosphoric acid triamides (2).
- In one embodiment of the invention, the additional P-containing fertilizer (3b) is therefore a phosphate-containing fertilizer, i.e. a fertilizer selected from the group consisting of a NPK fertilizer, a NP fertilizer, a PK fertilizer, and a P fertilizer as defined above.
- In one embodiment of the invention, the additional P-containing fertilizer (3b) causes a decomposition of the (thio)phosphoric acid triamide (2) of at least 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide within 15 days at a temperature of from 20° C. to 25° C., if no cation source (1) according to the invention is present.
- In a preferred embodiment, the P-containing fertilizer (3b) is selected from the group consisting of monoammonium phosphate (MAP), diammonium phosphate (DAP), calcium phosphate, super phosphate, double super phosphate, triple super phosphate (TSP), phosphate rock, ammonium polyphosphate (APP), and combinations thereof.
- In one particularly preferred embodiment, the P-containing fertilizer (3b) is monoammonium phosphate (MAP).
- In one particularly preferred embodiment, the P-containing fertilizer (3b) is diammonium phosphate (DAP).
- In one particularly preferred embodiment, the P-containing fertilizer (3b) is calcium phosphate.
- In one particularly preferred embodiment, the P-containing fertilizer (3b) is super phosphate.
- In one particularly preferred embodiment, the P-containing fertilizer (3b) is double super phosphate.
- In one particularly preferred embodiment, the P-containing fertilizer (3b) is triple super phosphate (TSP).
- In one particularly preferred embodiment, the P-containing fertilizer (3b) is phosphate rock.
- In one particularly preferred embodiment, the P-containing fertilizer (3b) is ammonium polyphosphate (APP).
- As already indicated above, the cation source (1) as defined herein is used in a composition A comprising a (thio)phosphoric acid triamide (2) and a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) to prevent decomposition of the (thio)phosphoric acid triamide (2). Furthermore, the present invention relates to a method for preventing decomposition of a (thio)phosphoric acid triamide (2) in a compositions A comprising the (thio)phosphoric acid triamide (2) and a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b). The fertilizers (3a) and (3b) as well as the cation source (1) have been described in detail above. Furthermore, the (thio)phosphoric acid triamide (2) has been described in detail above.
- As used herein, the term “to prevent decomposition of the (thio)phosphoric acid triamide (2)” is to be understood as follows.
- The additional P-containing fertilizer (3b) according to the invention typically causes a decomposition of the (thio)phosphoric acid triamide (2) of at least 1 wt.-% based on the total amount of the (thio)phosphoric acid triamide within 15 days at a temperature of from 20° C. to 25° C., if no cation source (1) according to the invention is present.
- In the focus of the invention is an additional P-containing fertilizer (3b), which causes a decomposition of the (thio)phosphoric acid triamide (2) of at least 5 wt.-% based on the total amount of the (thio)phosphoric acid triamide within 15 days at a temperature of from 20° C. to 25° C., if no cation source (1) according to the invention is present.
- Even more in the focus of the invention is an additional P-containing fertilizer (3b), which causes a decomposition of the (thio)phosphoric acid triamide (2) of at least 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide within 15 days at a temperature of from 20° C. to 25° C., if no cation source (1) according to the invention is present.
- The cation source (1) prevents this decomposition due to the stabilizing effect exhibited by the cations Cm+.
- It is to be understood that a decomposition of the (thio)phosphoric acid (2) may additionally be caused by the fertilizer (3a). However, as used in the context of the present invention, the term “to prevent decomposition of the (thio)phosphoric acid triamide (2)” preferably refers to the decomposition, which is caused by the P-containing fertilizer (3b), but not by the fertilizer (3a). Thus, the present invention focuses on the decomposition problems caused by the P-containing fertilizer (3b) only, and in this context the cation source (1) as defined herein may be beneficially used.
- In one embodiment, the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 50 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 15 days at a temperature of 20° C. to 25° C. Preferably, the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 50 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 1 month at a temperature of 20° C. to 25° C. More preferably, the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 50 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 2 months at a temperature of 20° C. to 25° C.
- In another embodiment, the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 20 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 15 days at a temperature of 20° C. to 25° C. Preferably, the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 20 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 1 month at a temperature of 20° C. to 25° C. More preferably, the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 20 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 2 months at a temperature of 20° C. to 25° C.
- In another embodiment, the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 15 days at a temperature of 20° C. to 25° C. Preferably, the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 1 month at a temperature of 20° C. to 25° C. More preferably, the cation source (1) as defined herein reduces the decomposition, which is caused by the P-containing fertilizer (3b), as such that less than 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide (2) decompose due to the influence of the P-containing fertilizer (3b) within 2 months at a temperature of 20° C. to 25° C.
- The amount of the (thio)phosphoric acid triamide in a sample after a certain time period may be detected e.g. by HPLC using method DIN EN 16651. In order to exclude a destabilizing effect caused by the urea-containing fertilizer (3a), the (thio)phosphoric acid triamide (2) may be provided in combination with a stabilizing agent, which prevents decomposition caused by the fertilizer (3a). By comparing the decomposition of the (thio)phosphoric acid triamide (2) in the presence of the fertilizer (3a) only, with the decomposition of the (thio)phosphoric acid triamide (2) in the presence of the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b), the decomposition caused by the P-containing fertilizer (3b) can be determined. By comparing this result with the result in the case that a cation source (1) is present, the extent to which the cation source (1) prevents decomposition caused by the P-containing fertilizer (3b) can be determined.
- Alternatively, the amount of the (thio)phosphoric acid triamide (2) in a sample after a certain time period may be determined indirectly by determining the urease inhibiting efficacy that is observable. The urease-inhibiting efficacy may be determined by the Dräger test as outlined in the Examples. The Dräger test is based on the determination of the concentration of ammonia gas that is set free from a soil sample being treated with a urea-containing fertilizer once a day. In general, a certain amount of ammonia is typically produced within a certain time period in a soil sample being treated with a urea-containing fertilizer due to the degradation of the urea-containing fertilizer caused by the urease, which is present in the soil. If the urea-containing fertilizer is provided in combination with a urease inhibitor such as a (thio)phosphoric acid triamide (2), the degradation of the urea-containing fertilizer is slowed down, so that a lower amount of ammonia will be produced in the same time period. On the other hand, if the (thio)phosphoric acid triamide (2) has decomposed to a certain extent, e.g. upon storage, the production of ammonia will be reduced only to a lower extent. The ammonia concentration measured after a certain time period may thus be correlated with the amount of the (thio)phosphoric acid triamide (2) in a sample. In order to exclude a destabilizing effect caused by the urea-containing fertilizer (3a), the (thio)phosphoric acid triamide (2) may be provided in combination with a stabilizing agent, which prevents decomposition caused by the fertilizer (3a). By comparing the decomposition of the (thio)phosphoric acid triamide (2) in the presence of the fertilizer (3a) only, with the decomposition of the (thio)phosphoric acid triamide (2) in the presence of the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b), the decomposition caused by the P-containing fertilizer (3b) can be determined. By comparing this result with the result in the case that a cation source (1) is present, the extent to which the cation source (1) prevents decomposition caused by the P-containing fertilizer (3b) can be determined.
- In one embodiment, the cation source (1) as defined herein reduces the decomposition of the (thio)phosphoric acid triamide, which is caused by the P-containing fertilizer (3b), as such that after a storage time of up to 15 days at a temperature of 20° C. to 25° C.,
- the (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1) exhibits at least 50% of the urease inhibiting efficacy of
- a (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer (3a), but no P-containing fertilizer (3b), and no cation source (1),
- wherein at least 50% of the urease inhibiting efficacy means that the time until a threshold value of ammonia is reached is reduced by at most 50%.
- As outlined above, the ammonia is produced in a soil sample being treated with the above mentioned compositions and can be measured according to the Dräger test.
- Depending on the soil sample, typical threshold values include 600 ppm, 500 ppm, 400 ppm or 300 ppm. These threshold values may be reached for example after a time of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 days, if the (thio)phosphoric acid triamide (2) is provided in a composition comprising the fertilizer (3a), but no P-containing fertilizer (3b), and no cation source (1).
- For example, in the case that a threshold value of 600 ppm is reached after 10 days, if the (thio)phosphoric acid triamide (2) is provided in a composition comprising the fertilizer (3a), but no P-containing fertilizer (3b), and no cation source (1), the above embodiment is to be understood as such that the threshold value of 600 ppm is reached at the earliest after 5 days, if the (thio)phosphoric acid triamide (2) is provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1).
- In a preferred embodiment, the cation source (1) as defined herein reduces the decomposition of the (thio)phosphoric acid triamide, which is caused by the P-containing fertilizer (3b), as such that after a storage time of up to 15 days at a temperature of 20° C. to 25° C.,
- the (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1) exhibits at least 80% of the urease inhibiting efficacy of
- a (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer (3a), but no P-containing fertilizer (3b), and no cation source (1),
- wherein at least 80% of the urease inhibiting efficacy means that the time until a threshold value of ammonia is reached is reduced by at most 20%.
- For example, in the case that a threshold value of 600 ppm is reached after 10 days, if the (thio)phosphoric acid triamide (2) is provided in a composition comprising the fertilizer (3a), but no P-containing fertilizer (3b), and no cation source (1), the above embodiment is to be understood as such that the threshold value of 600 ppm is reached at the earliest after 8 days, if the (thio)phosphoric acid triamide (2) is provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1).
- In an even more preferred embodiment, the cation source (1) as defined herein reduces the decomposition of the (thio)phosphoric acid triamide, which is caused by the P-containing fertilizer (3b), as such that after a storage time of up to 15 days at a temperature of 20° C. to 25° C.,
- the (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1) exhibits at least 90% of the urease inhibiting efficacy of
- a (thio)phosphoric acid triamide (2) being provided in a composition comprising the fertilizer (3a), but no P-containing fertilizer (3b), and no cation source (1),
- wherein at least 90% of the urease inhibiting efficacy means that the time until a threshold value of ammonia is reached is reduced by at most 10%.
- For example, in the case that a threshold value of 600 ppm is reached after 10 days, if the (thio)phosphoric acid triamide (2) is provided in a composition comprising the fertilizer (3a), but no P-containing fertilizer (3b), and no cation source (1), the above embodiment is to be understood as such that the threshold value of 600 ppm is reached at the earliest after 9 days, if the (thio)phosphoric acid triamide (2) is provided in a composition comprising the fertilizer mixture (3) comprising the fertilizer (3a) and the P-containing fertilizer (3b) and the cation source (1).
- In connection with the above embodiments, it is preferred that the storage time is up to 1 month, preferably up to two months or even longer.
- Furthermore, it is preferred in connection with the above embodiments that the (thio)phosphoric acid triamide (2) is in each case provided in combination with an amine (4) as defined in detail further below, in order to exclude a destabilizing effect caused by the urea-containing fertilizer (3a), as the amine (4) acts as a stabilizing agent, which prevents decomposition caused by the fertilizer (3a). It is noted, however, that the amine (4) typically does not prevent decomposition caused by the P-containing fertilizer (3b). For this purpose, the cation source (1) is used according to the present invention.
- The present invention also relates to a mixture M comprising a cation source (1) and a (thio)phosphoric acid triamide (2). The cation source (1) and the (thio)phosphoric acid triamide (2) have been described in detail above.
- In a preferred embodiment, the mixture M further comprises a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer. The fertilizers (3a) and (3b) have been described in detail above.
- The present invention also relates to a granule G comprising a urea-containing fertilizer (3a) and/or a P-containing fertilizer (3b), wherein the granule is coated with a cation source (1). The fertilizers (3a) and (3b) as well as the cation source (1) have been described in detail above.
- As used herein, the term “granule” generally refers to particles, which are preferably between two screen sizes usually within the range of 1 to 4 mm. The granules may have a spherical or near-spherical form made by solidification of free-falling droplets in air or other fluid medium (e.g. oil). Apart from the fertilizer, the granule may also comprise a substance to prevent caking or to control the dissolution rate or to improve the physical condition of the granule. The substance may be incorporated in the granule or applied as a layer surrounding the granule. It is to be understood that the fertilizer (3a) and the P-containing fertilizer (3b) may either be provided alone or together in granules. A skilled person is aware that granules may be manufactured granulation of solids, slurries, or melts according to standard processes known in the art.
- As used herein, “coated” means that the granule G comprising the fertilizer (3a) and/or (3b) is surface-treated with the cation source (1). The treatment may be performed with the cation source (1) in dry, preferably powdery form, as such that the granule is surrounded by a powder coating. Alternatively, the treatment may be performed by preparing a solution of the cation source (1) and treating the granule with the solution. The solvent of the solution may then be partially or completely evaporated. Preferred solvents in this connection comprise dimethyl sulfoxide (DMSO), dimethylformamide (DMF), water, and combinations thereof. The treatment with the solution may result at least partly in an incorporation of the cation source (1) into the granule.
- In a preferred embodiment, the granule is further treated with a (thio)phosphoric acid triamide (2). The (thio)phosphoric acid triamide (2) has been described in detail above.
- As used in the context of the granule G, “treated with a (thio)phosphoric acid triamide (2)” means that the granules are surface-treated with the (thio)phosphoric acid triamide (2). In this connection, surface-treatment preferably means that a liquid formulation of the (thio)phosphoric acid triamide (2) has been sprayed onto the granule, so that preferably a coating of the (thio)phosphoric acid triamide (2) surrounding the granule is formed.
- It is to be understood that the granule G is either obtained by firstly applying the coating with the cation source (1) and then applying the (thio)phosphoric acid triamide (2) coating or vice versa. The granule G may also comprise a coating comprising both the cation source (1) and the (thio)phosphoric acid triamide (2), which is preferably obtained by simultaneously applying (1) and (2), e.g. in the form of the mixture M as defined herein.
- The present invention also relates to a composition B, which comprises a cation source (1), a (thio)phosphoric acid triamide (2), and a fertilizer mixture (3), and is inter alia defined by the process by which the composition is obtainable, wherein 7 options are provided. The cation source (1), the (thio)phosphoric acid triamide (2), and the fertilizer mixture (3) have been described in detail above.
- In one embodiment, the composition B is obtainable by
- (a1) treating granules comprising the urea-containing fertilizer (3a) and the (thio)phosphoric acid triamide (2) with the cation source (1);
- (b1) blending the treated granules of step (a1) with granules comprising the P-containing fertilizer (3b).
- In another embodiment, the composition B is obtainable by
- (a2) treating granules comprising the P-containing fertilizer (3b) with the cation source (1);
- (b2) blending the treated granules of step (a2) with granules comprising the urea-containing fertilizer (3a) and the (thio)phosphoric acid triamide (2).
- In another embodiment, the composition B is obtainable by
- (a3) blending granules comprising the urea-containing fertilizer (3a) and the (thio)phosphoric acid triamide (2) with granules comprising the P-containing fertilizer (3b); and
- (b3) treating the blend of step (a3) with the cation source (1).
- In another embodiment, the composition B is obtainable by
- (a4) treating granules comprising the fertilizer mixture (3) with the (thio)phosphoric acid triamide (2); and
- (b4) treating the treated granules of step (a4) with the cation source (1).
- In another embodiment, the composition B is obtainable by
- (a5) treating granules comprising the fertilizer mixture (3) with the cation source (1); and
- (b5) treating the treated granules of step (a5) with the (thio)phosphoric acid triamide (2).
- In another embodiment, the composition B is obtainable by
- (a6) providing granules comprising the fertilizer mixture (3); and
- (b6) treating the granules of step (a6) with a—solid or liquid—mixture comprising the (thio)phosphoric acid triamide (2) and the cation source (1).
- In another embodiment, the composition B is obtainable by
- (a7) providing granules comprising the fertilizer mixture (3) and the cation source (1); and
- (b7) treating the granules of step (a7) with the (thio)phosphoric acid triamide (2).
- Unless otherwise indicated, the term “granule” is to be understood as defined above in connection with the granule G. Where indicated, the granules may in addition to the fertilizer (3a) and/or the P-containing fertilizer (3b) comprise the (thio)phosphoric acid triamide (2). In this case, unless otherwise indicated, the (thio)phosphoric acid triamide (2) may be incorporated in the granule or may be present as a layer surrounding the granule.
- As used in the context of the processes by which the composition B is obtainable, “treating granules with the cation source (1)” means that the granules are surface-treated with the cation source (1). The treatment may be performed with the cation source (1) in dry, preferably powdery form, as such that the granule is surrounded by a powder coating. Alternatively, the treatment may be performed by preparing a solution of the cation source (1) and treating the granule with the solution. The solvent of the solution may then be partially or completely evaporated. Preferred solvents in this connection comprise dimethyl sulfoxide (DMSO), dimethylformamide (DMF), water, and combinations thereof. The treatment with the solution may result at least partly in an incorporation of the cation source (1) into the granule.
- Similarly, “treating a blend of granules with the cation source (1)” means that the granules of the blend are surface-treated with the cation source (1). The treatment may be performed with the cation source (1) in dry, preferably powdery form, as such that the granules are surrounded by a powder coating. Alternatively, the treatment may be performed by preparing a solution of the cation source (1) and treating the granules with the solution. The solvent of the solution may then be partially or completely evaporated. Preferred solvents in this connection comprise dimethyl sulfoxide (DMSO), dimethylformamide (DMF), water, and combinations thereof. The treatment with the solution may result at least partly in an incorporation of the cation source (1) into the granules.
- In case the cation source (1) is MgSO4 when a blend of granules is treated with the cation source (1), magnesium sulfate is preferably used in a powdery form.
- In case the cation source (1) is used in a powdery form when a blend of granules is treated with the cation source (1), the average particle size of the cation source (1) is preferably less than 1 mm, more preferably less than 750 μm, most preferably less than 500 μm, particularly preferably less than 250 μm, particularly more preferably less than 150 μm, particularly most preferably less than 100 μm, particularly less than 50 μm. In case the cation source (1) is used in a powdery form when a blend of granules is treated with the cation source (1), the average particle size of the cation source (1) is preferably more than 1 μm, more preferably more than 5 μm, most preferably more than 10 μm, particularly preferably more than 25 μm, particularly more preferably more than 40 μm, particularly most preferably more than 60 μm, particularly more than 90 μm. The average particle size is measured by sieve analysis with different standard set of sieves.
- In case the cation source (1) is MgSO4 and used in a powdery form when a blend of granules is treated with the cation source (1), the average particle size of the cation source (1) is preferably less than 1 mm, more preferably less than 750 μm, most preferably less than 500 μm, particularly preferably less than 250 μm, particularly more preferably less than 150 μm, particularly most preferably less than 100 μm, particularly less than 50 μm. In case the cation source (1) is used in a powdery form when a blend of granules is treated with the cation source (1), the average particle size of the cation source (1) is preferably more than 1 μm, more preferably more than 5 μm, most preferably more than 10 μm, particularly preferably more than 25 μm, particularly more preferably more than 40 μm, particularly most preferably more than 60 μm, particularly more than 90 μm. The average particle size is measured by sieve analysis with different standard set of sieves.
- In case the cation source (1), particularly MgSO4, is used in a powdery form when a blend of granules is treated with the cation source (1), the adhesion of the cation source (1) on fertilizer granules (particularly granules of urea-containing fertilizer (3a) and/or granules of fertilizer (3b) selected from the group consisting of a NPK fertilizer, a NP fertilizer, a NK fertilizer, a PK fertilizer, a P fertilizer, a K fertilizer, and a N fertilizer) can be improved by adding a sticker, preferably by adding a sticker selected from the group of stickers described in U.S. Pat. No. 5,656,571A or in WO2012/168210 A1 or a polymer sticker or another sticker used in the state of the art for the adhesion of the agrochemical formulation to the seed.
- In the context of this invention, a “sticker” is a material or a substance which increases the firmness of attachment of finely-divided solids or other water-soluble or -insoluble materials to a solid surface, and which may be measured in terms of resistance to time or mechanical action. Typically, stickers are substances such as latex or other adhesives that improve attachment of finely-divided solids to a solid surface.
- As used in the context of the processes by which the composition B is obtainable, “treating granules with the (thio)phosphoric acid triamide (2)” means that the granules are surface-treated with the (thio)phosphoric acid triamide (2). In this connection, surface-treatment preferably means that a liquid formulation of the (thio)phosphoric acid triamide (2) is sprayed onto the granule, so that preferably a coating of the (thio)phosphoric acid triamide (2) surrounding the granule is formed.
- As used in the context of the processes by which the composition B is obtainable, “treating granules with a mixture comprising the (thio)phosphoric acid triamide (2) and the cation source (1)” means that the granules are surface-treated with the corresponding mixture. In this connection, surface-treatment preferably means that a liquid formulation of the (thio)phosphoric acid triamide (2) and the cation source (1) is sprayed onto the granule. In an alternative embodiment, surface-treatment also means that a solid formulation of the (thio)phosphoric acid triamide (2) and the cation source (1) is sprayed onto the granule.
- In connection with the above defined use (and the composition A defined in this connection), the method (and the composition A defined in this connection), the mixture M, the granule G, and the composition B according to the invention, it is generally preferred that the (thio)phosphoric acid triamide (2) is provided in combination with at least one amine (4). The amine (4) typically exhibits a stabilizing effect on the (thio)phosphoric acid triamide (2) in terms of a decomposition caused by the urea-containing fertilizer (3a).
- Thus, liquid formulations of the (thio)phosphoric acid triamide (2) preferably comprise a (thio)phosphoric acid triamide (2) and an amine (4).
- In general, the amine(s) (4) can be any amine, i.e. any chemical compound having at least one amino group, including (but not limited to)
-
- primary, secondary, and tertiary amines,
- linear, branched, and cyclic amines,
- aliphatic and aromatic amines,
- monomeric, oligomeric and polymeric amines,
- biogenic and non-biogenic amines.
- In a preferred embodiment of the invention, the (thio)phosphoric acid triamide (2) is provided in combination with at least one amine (4) selected from the group consisting of
- (4a) a polymeric polyamine; and
- (4b) an amine containing not more than one amino group and at least three alkoxy or hydroxy-substituted C2 to C12 alkyl groups R21, wherein at least one of the groups R21 is different to the other groups R21; and
- (4c) an amine containing not more than one amino group and at least two alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R22, wherein at least one of the groups R22 bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom and wherein at least one of the groups R22 is different to the other group(s) R22; and
- (4d) an amine containing at least one saturated or unsaturated C8 to C40 alkyl group R23; and
- (4e) a saturated or unsaturated heterocyclic amine which contains at least one oxygen atom as ring atom and which does not contain a further alkoxy group; and
- (4f) an amine having a boiling point of more than 100° C., preferably more than 150° C., more preferably more than 200° C. at ambient pressure (1 bar), and
- (4g) a primary amine, and
- (4h) a secondary amine, and
- (4i) a tertiary amine,
- (4j) an amine containing not more than one amino group and at least two alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R22,
- (4k) an amine containing not more than one amino group and at least three alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R22,
- (4l) an amine containing not more than one amino group and at least three alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R41, wherein all groups R41 within said amine are identical, and
- (4m) an amine containing not more than one amino group and at least two alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R42, wherein at least one of the groups R42 bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom and wherein all groups R42 with said amine are identical, and
- (4n) an amine selected from the group consisting of methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, N,N′,N″-tris(dimethylaminopropyl)hexahydrotriazine, and 2,2′-dimorpholinyldiethyl ether, and
- (4o) an amine selected from the group consisting of (L10), (L11), (L12), (L13), (L14), (L15),
- (L16), (L17), (L18), (L19), (L20), (L21), (L22), (L23), (L24) and (L29) as disclosed in the PCT application PCT/IB2015/059864.
- According to one embodiment, the amine (4) is
- (4a) a polymeric polyamine.
- Generally, (4a) can be any polymeric polyamine, and is preferably a polyalkyleneimine or polyvinylamine, more preferably a polyalkyleneimine, most preferably a polyethyleneimine, polypropyleneimine, or polybutyleneimine, particularly a polyethyleneimine.
- According to one embodiment, (4a) is preferably any polymeric polyamine comprising ethyleneimine (—CH2CH2NH—) as monomeric units, including homopolymers and any copolymers of ethyleneimine, and is preferably a homopolymer of ethyleneimine. Copolymers can be alternating, periodic, statistical or block copolymers.
- Generally, (4a) can be of any polymer structure, for example a linear polymer, a ring polymer, a cross-linked polymer, a branched polymer, a star polymer, a comb polymer, a brush polymer, a dendronized polymer, or a dendrimer etc. According to one embodiment, (4a) is an essentially linear polymer, and is preferably a linear polymer.
- Polyethyleneimines which may be used are polyethyleneimine homopolymers which may be present in uncrosslinked or crosslinked form. The polyethyleneimine homopolymers can be prepared by known processes, as described, for example, in Rompps (Chemie Lexikon, 8th edition, 1992, pages 3532-3533), or in Ullmanns Enzyklopadie der Technischen Chemie, 4th edition, 1974, vol. 8, pages 212-213. and the literature stated there. They have a molecular weight in the range from about 200 to 1000 000 g/mol. Corresponding commercial products are for example available under the name Lupasol® from BASF SE.
- According to one embodiment of the invention, the polyethyleneimine (4a) is preferably a polyethylenimine having a degree of branching in the range of from 0.1 to 0.95 (also referred to as “highly branched polyethyleneimine”), and more preferably a polyethylenimine having a degree of branching in the range of from 0.25 to 0.90, more preferably a polyethylenimine having a degree of branching in the range of from 0.30 to 0.80, and most preferably a polyethylenimine having a degree of branching in the range of 0.50 to 0.80.
- Highly branched polyethyleneimines are characterized by its high degree of branching, which can be determined for example via 13C-NMR spectroscopy, preferably in D2O, and is defined as follows:
-
Degree of branching=D+T/D+T+L - D (dendritic) equals the percentage of tertiary amino groups, L (linear) equals the percentage of secondary amino groups, and T (terminal) equals the percentage of primary amino groups.
- Generally, the polymeric polyamine (4a) can have different weight average molecular weights. The weight average molecular weight of (4a) is preferably at least 200, more preferably at least 400, most preferably at least 550, particularly at least 650, for example at least 750. The weight average molecular weight of (4a) is preferably not more than 10,000, more preferably not more than 4,000, most preferably not more than 1,900, particularly not more than 1,500, for example not more than 1,350. The weight average molecular weight can be determined by standard gel permeation chromatography (GPC) known to the person skilled in the art.
- In one embodiment, the amine (4) is a polyethyleneimine, preferably a polyethyleneimine as defined above.
- Another class of polyamines includes polymers obtainable by condensation of at least one compound selected from N-(hydroxyalkyl)amines of formulae(I.a) and/or (I.b),
- wherein
- A are independently selected from C1-C6-alkylene;
- R1, R1*, R2, R2*, R3, R3*, R4, R4*, R5, and R5* are independently selected of one another selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the at least three mentioned radicals may be optionally substituted; and
- R6 is selected from hydrogen, alkyl, cycloalkyl or aryl, which may be optionally substituted.
- Preferred are polyethanolamines. In this connection, polyethanolamines are preferred, wherein in the condensation product of the compounds of formulae (I.a) and/or (I.b) as defined above, A is C1-alkylene, and R1, R1*, R2, R2*, R3, R3*, R4, R4*, R5, and R6* are each H, and R6 is selected from hydrogen and C2-hydroxyalkyl.
- In one preferred embodiment, the polyamine is a polyethanolamine, which is commercially available under the trade name Lupasol® EO.
- According to another embodiment, the amine (4) is
- (4b) an amine containing not more than one amino group and at least three alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R21, wherein at least one of the groups R21 is different to the other groups R21.
- The number of groups R21 within (4b) is at least 3, preferably 3 to 5, more preferably 3 to 4, and most preferably 3.
- The number of carbon atoms in each group R21 within (4b) is 2 to 12, preferably 2 to 9, more preferably 2 to 7, most preferably 2 to 5, particularly preferably 2 to 4, particularly 2 to 3, for example 3, wherein said number of carbon atoms does not include carbon atoms in any alkoxy groups or any other substituents of R21.
- The groups R21 within (4b) are alkoxy- or hydroxy-substituted, preferably hydroxy-substituted. For one amine (4b), among the at least three groups R21, at least one of the groups R21 is different to the other groups R21, preferably one of the groups R21 is different to the other groups R21.
- Preferably at least one of the groups R21, more preferably at least two of the groups R21, most preferably at least three of the groups R21, particularly all groups R21 is or are covalently bound to the amino group of the amine (4b).
- According to another preferred embodiment, (4b)
-
- is an amine containing not more than one amino group and at least three hydroxy-substituted C2 to C8—or preferably C2 to C5—alkyl groups R21, wherein at least one of the groups R21 is different to the other groups R21,
- is preferably an amine containing not more than one amino group and at least three hydroxy-substituted C2 to C3 alkyl groups R21, wherein at least one of the groups R21 is different to the other groups R21,
- is more preferably an amine containing not more than one amino group and three hydroxy-substituted C2 to C3 alkyl groups R21 which are covalently bound to the amino group, wherein one of the groups R21 is different to the other groups R21, and
- is for example an amine selected from the group consisting of Bis(hydroxyethyl)-isopropanolamine (DEIPA), and 1,1′-((2-Hydroxyethyl)imino)dipropan-2-ol.
- According to another preferred embodiment, (4b) is an amine N(R21)3 wherein R21 is a an alkoxy- or hydroxy-substituted—preferably a hydroxyl-substituted—C2 to C12—preferably a C2 to C7, more preferably a C2 to C3-alkyl group and wherein one of the groups R21 is different to the other group R21.
- According to another preferred embodiment, (4b) is an amine N(R21)3 wherein
- R21 is a an alkoxy- or hydroxy-substituted—preferably a hydroxyl-substituted—C2 to C12—preferably a C2 to C7, more preferably a C2 to C3-alkyl group and wherein one of the groups R21 is different to the other group R21 and wherein at least one of the groups R21 bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom.
- According to another embodiment, the amine (4) is
- (4c) an amine containing not more than one amino group and at least two alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R22, wherein at least one of the groups R22 bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom and wherein at least one of the groups R22 is different to the other group(s) R22.
- The number of groups R22 within (4c) is at least 2, preferably 2 to 5, more preferably 2 to 4, and most preferably 2 to 3, for example 2.
- The number of carbon atoms in each group R22 within (4c) is 2 to 12, preferably 2 to 9, more preferably 2 to 7, most preferably 2 to 5, particularly preferably 2 to 4, particularly 2 to 3, for example 3, wherein said number of carbon atoms does not include carbon atoms in any alkoxy groups or any other substituents of R22.
- The groups R22 within (4c) are alkoxy- or hydroxy-substituted, preferably hydroxy-substituted.
- For one amine (4c), among the at least two groups R22, at least one of the groups R22 is different to the other group(s) R22, preferably one of the groups R22 is different to the other group(s) R22.
- Preferably at least one of the groups R22, more preferably at least two of the groups R22, most preferably all groups R22 is or are covalently bound to the amino group of the amine (4c).
- Preferably at least one of the groups R22, more preferably one of the groups R22 bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom, particularly at a secondary carbon atom.
- According to another preferred embodiment, (4c)
-
- is an amine containing not more than one amino group and at least two hydroxy-substituted C2 to C7 alkyl groups R22, wherein at least one of the groups R22 bears the hydroxy substituent at a secondary or tertiary carbon atom and wherein at least one of the groups R22 is different to the other group(s) R22,
- is more preferably an amine containing not more than one amino group and at least two hydroxy-substituted C2 to C4 alkyl groups R22, wherein at least one of the groups R22 bears the hydroxy substituent at a secondary carbon atom and wherein at least one of the groups R22 is different to the other group(s) R22,
- is most preferably an amine containing not more than one amino group and two hydroxy-substituted C2 to C3 alkyl groups R22 which are covalently bound to the amino group of the amine (4c), wherein at least one of the groups R22 bears the hydroxy substituent at a secondary carbon atom and wherein one of the groups R22 is different to the other group R22,
- is for example an amine selected from the group consisting of 1-((2-hydroxyethyl)amino)propan-2-ol, and N-Methyl-N-hydroxyethyl-isopropanolamine.
- According to another preferred embodiment, (4c) is an amine R24N(R22)2 wherein
- R24 is H or a C1 to C12—, preferably a C1 to C7—, more preferably a C1 to C3-alkyl group and
- R22 is an alkoxy- or hydroxy-substituted-, preferably a hydroxy-substituted-C2 to C12—, preferably C2 to C7—, more preferably C2 to C3-alkyl group and wherein at least one of the groups R22 bears the hydroxy substituent at a secondary carbon atom and wherein one of the groups R22 is different to the other group R22.
- According to another embodiment, the amine (4) is
- (4d) an amine containing at least one saturated or unsaturated C8 to C40 alkyl group R23.
- The number of carbon atoms in each group R23 within (4d) is 8 to 40, preferably 8 to 32, more preferably 8 to 24, most preferably 8 to 19, particularly preferably 8 to 16.
- The group R23 within (4d) is saturated or unsaturated, preferably unsaturated.
- According to another preferred embodiment, (4d) contains at least one alkoxy or hydroxy group, more preferably at least one alkoxy and at least one hydroxy groups, most preferably at least two alkoxy and at least one hydroxyl group, particularly at least four alkoxy and at least one hydroxyl group.
- For example, (4d) is an amine selected from the group consisting of: ethoxylated (2) cocoalkylamine, ethoxylated (5) cocoalkylamine, ethoxylated (15) cocoalkylamine, ethoxylated (2) oleylamine, lauryl-dimethylamine, oleyl-dimethylamine, and 2-propylheptylamine ethoxylate (5 EO), 2-propylheptylamine ethoxylate (10 EO), and 2-propylheptylamine ethoxylate (20 EO).
- In one preferred embodiment, the amine (4) is ethoxylated (2) cocoalkylamine.
- In one preferred embodiment, the amine (4) is ethoxylated (5) cocoalkylamine.
- In one preferred embodiment, the amine (4) is ethoxylated (15) cocoalkylamine.
- In one preferred embodiment, the amine (4) is ethoxylated (2) oleylamine.
- In one preferred embodiment, the amine (4) is lauryl-dimethylamine.
- In one preferred embodiment, the amine (4) is oleyl-dimethylamine.
- In one preferred embodiment, the amine (4) is 2-propylheptylamine ethoxylate (5EO).
- In one preferred embodiment, the amine (4) is 2-propylheptylamine ethoxylate (10 EO)
- In one preferred embodiment, the amine (4) is 2-propylheptylamine ethoxylate (20 EO).
- According to another embodiment, the amine (4) is
- (4e) a saturated or unsaturated heterocyclic amine which contains at least one oxygen atom as ring atom and which does not contain a further alkoxy group.
- The term “heterocyclic amine” stands for a heterocyclic compound in which at least one ring atom of the heterocyclic ring is a nitrogen atom.
- The heterocyclic amine (4e) is saturated or unsaturated, preferably saturated.
- The heterocyclic amine (4e) contains preferably a 5-, 6- or 7-membered heterocyclic ring, more preferably a 5- or 6-membered ring, most preferably a 6-membered ring.
- The heterocyclic amine (4e) contains at least one, more preferably 1 to 3, most preferably 1 to 2, particularly one oxygen atom(s) as ring atom(s) of the heterocyclic ring.
- The heterocyclic amine (4e) is preferably a morpholine or morpholine derivative, more preferably
- N-alkyl morpholine, most preferably N-methyl, N-ethyl, N-propyl, or N-butyl morpholine, for example N-methyl morpholine.
- In one preferred embodiment, the amine (4) is N-methyl morpholine.
- According to another embodiment, the amine (4) is
- (4f) an amine having a boiling point of more than 100° C., preferably more than 150° C., more preferably more than 200° C. at ambient pressure (1 bar).
- Such amines are described in US 2011/0154874 A1. Accordingly, preferred amines (4f) are secondary and/or tertiary amines, for example methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, N,N′,N″-tris(dimethylaminopropyl)hexahydrotriazine, and 2,2′-dimorpholinyldiethyl ether.
- According to another embodiment, the amine (4) is
- (4g) a primary amine.
- According to another embodiment, the amine (4) is
- (4h) a secondary amine.
- According to another embodiment, the amine (4) is
- (4i) a tertiary amine.
- In connection with the above embodiments relating to (4g), (4h) and (4i), the term “amine” is preferably to be understood as an organic compounds, in which at least one amino group is bound to a carbon atom. In a primary amine, an NH2 group is bound to a carbon atom, in a secondary amine an NRAH group is bound to a carbon atom, and in a tertiary amine an NRARB group is bound to a carbon atom, wherein RA and RB may each individually be selected from C1-C20-alkyl, di(C1-C4-alkyl)amino-C1-C20-alkyl, and a C1-C4-alkylene chain, which is bound to the carbon atom to which the NRAH or NRARB group is bound so that a heterocyclic ring is formed, or RA and RB may together with the nitrogen atom to which they are bound form a 5- to 10-membered, preferably 5- to 6-membered heterocyclic ring, wherein the heterocycle may comprise 1, 2, or 3 additional nitrogen atoms, and wherein the N atoms if present are each individually further substituted by H, C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, or by a C1-C4-alkylene chain, which is bound to the carbon atom to which the NRARB group is bound, so that a further heterocyclic ring is formed. If the carbon atom to which the NH2, NRAH, or NRARB group is bound is not part of a heterocyclic ring, which is formed with RA or RB it is preferably part of a C1-C20-alkyl group or a di(C1-C4-alkyl)amino-C1-C20-alkyl group, so that the amino group may be represented by the formula C1-C20-alkyl-NH2, C1-C20-alkyl-NRAH, or C1-C20-alkyl-NRARB or by the formula di(C1-C4-alkyl)amino-C1-C20-alkyl-NH2, di(C1-C4-alkyl)amino-C1-C20-alkyl-NRAH, or di(C1-C4-alkyl)amino-C1-C20-alkyl-NRARB, wherein RA and RB may each individually be selected from C1-C20-alkyl, and di(C1-C4-alkyl)amino-C1-C20-alkyl, or RA and RB may together with the nitrogen atom to which they are bound form a 5- to 10-membered, preferably 5- to 6-membered heterocyclic ring, wherein the heterocycle may comprise 1, 2, or 3 additional heteroatoms nitrogen atoms, and wherein the N atoms if present are each individually further substituted by H, C1-C4-alkyl, or di(C1-C4-alkyl)amino-C1-C4-alkyl.
- In one preferred embodiment of the invention, the amine (4) is a tertiary amine, wherein 2 tertiary amino groups are present, and which may be represented by the formula RaRbN—(C1-C10alkylene)-NRcRd, wherein Ra, Rb, Rc, and Rd are independently of each other selected from C1-C10-alkyl, or Ra and Rb and/or Rc and Rd may together with the nitrogen atom to which they are bound form a 5- to 10-membered, preferably 5- to 6-membered heterocyclic ring, wherein the heterocycle may comprise 1, 2, or 3 additional heteroatoms selected from N, O, and S, wherein the N atom if present is further substituted by C1-C4-alkyl. Preferably, Ra, Rb, Rc, and Rd are independently of each other selected from C1-C4-alkyl.
- In one embodiment of the invention, the amine (4) is selected from N,N,N′,N′-tetramethyl-1,6-hexanediamine, N,N,N′,N′-tetramethyl-1,3-propanediamine, N,N′,N″-tris(dimethylaminopropyl)hexahydrotriazine, and triethylendiamine (DABCO).
- In one preferred embodiment of the invention, the amine (4) is N,N,N′,N′-tetramethyl-1,6-hexanediamine (CAS [111-18-2]).
- In one preferred embodiment of the invention, the amine (4) is N,N,N′,N′-tetramethyl-1,3-propanediamine (CAS [110-95-2]).
- In one preferred embodiment of the invention, the amine (4) is N,N′,N″-tris(dimethylaminopropyl)hexahydrotriazine.
- In one preferred embodiment of the invention, the amine (4) is triethylendiamine (DABCO, available as Lupragen® N201 from BASF).
- According to another embodiment, the amine (4) is
- (4j) an amine containing not more than one amino group and at least two alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R22.
- According to another embodiment, the amine (4) is
- (4k) an amine containing not more than one amino group and at least three alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R22.
- According to another embodiment, the amine (4) is
- (4l) an amine containing not more than one amino group and at least three alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R41, wherein all groups R41 within said amine are identical.
- According to another embodiment, the amine (4) is
- (4m) an amine containing not more than one amino group and at least two alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R42, wherein at least one of the groups R42 bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom and wherein all groups R42 with said amine are identical.
- In the context of the above embodiments (4j) to (4m), the amine (4) may in one embodiment be an amino alcohol.
- Amino alcohols may also be referred to as alkanol amines and are characterized in that they comprise at least one hydroxyl group and at least one amino group.
- In one embodiment, amino alcohols may be represented by the formula (H)aN(C1-C10-hydroxyalkyl)b, preferably by the formula (H)aN(C1-C8-hydroxyalkyl)b, wherein a is 0 or 1, and b is 2 when a is 1 and 3 when a is 0. In this connection, it is to be understood that the term “hydroxyalkyl” defines an alkyl group, which comprises at least one, preferably 1, 2, or 3 hydroxyl groups, especially preferably one hydroxyl group. Exemplary hydroxyalkyl groups include hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl.
- In one embodiment, it is preferred that the amino alcohol comprises not more than one amino group and at least three hydroxyl substituted C2-C8—, preferably C2—O5-alkyl groups, wherein at least one of these hydroxyl substituted alkyl groups is different from the other hydroxyl substituted alkyl groups.
- It is even more preferred that the amino alcohol comprises not more than one amino group and at least three hydroxyl substituted C2-C3-alkyl groups, wherein at least one of these hydroxyl substituted alkyl groups is different from the other hydroxyl substituted alkyl groups.
- It is even more preferred that the amino alcohol comprises not more than one amino group and at least three hydroxyl-substituted C2-C3-alkyl groups, which are covalently bound to the amino group, wherein at least one of these hydroxyl substituted alkyl groups is different from the other hydroxyl substituted alkyl groups.
- In other embodiments of the invention, amino alcohols may be represented by the generic formula A (H)xN((CH2)m—OH)n, wherein m is 1, 2, or 3, x is 0 or 1, and n is 2 when x is 1 and 3 when x is 0, or by generic formula B (H)yN((CH2)—CHOH—CH3)z, such that the length of the carbon chain where the secondary hydroxyl group is located is 3, y is 0 or 1, and z is 2 when y is 1 and 3 when y is 0.
- In another embodiment of the invention, amino alcohols may be represented by the formula (C1-C4-alkyl)2N—(C1-C4-alkylene)-N(C1-C4-alkyl)(C1-C4-hydroxyalkyl). An exemplary amino alcohol in this connection is N,N,N′-trimethylaminoethylethanolamine.
- Preferred amino alcohols according to the invention may be selected from the group consisting of ethanolamine, diethanolamine, methyl diethanolamine, butyl diethanolamine, monoisopropanolamine, diisopropanolamine, methyl diisopropanolamine, triethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N-bis(2-hydroxyethyl)isopropanolamine, N,N,N′-trimethylaminoethylethanolamine, and N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine.
- Preferred amino alcohols according to the invention include ethanolamine, diethanolamine, methyl diethanolamine, butyl diethanolamine, monoisopropanolamine, diisopropanolamine, methyl diisopropanolamine, triethanolamine, tetrahydroxypropylethylenediamine, and trimethylaminoethylethanolamine.
- A preferred amino alcohol is triethanolamine.
- Another preferred amino alcohol is N,N-bis(2-hydroxyethyl)isopropanolamine, also known as diethanolisopropanolamine (DEIPA).
- Another preferred amino alcohol is N,N,N′-trimethylaminoethylethanolamine (CAS [2212-32-0], available as Lupragen® N400 from BASF).
- Another preferred amino alcohol is N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine (CAS [102-60-3]).
- In the context of the above embodiments (4j) to (4m), the amine (4) may in another embodiment be an ether amine.
- Ether amines are characterized in that they comprise at least one ether group and at least one amino group.
- In one embodiment of the invention, the ether amines may be represented by the generic formula NRaRb—(CH2)n[O—(CH2)m]p—NRcRd, wherein n is 1, 2, 3, 4, or 5, m is 1, 2, 3, 4, or 5, p is 1, 2, 3, 4, or 5, and Ra, Rb, Rc, and Rd are independently of each other selected from H and C1-C4-alkyl, or Ra and Rb and/or Rc and Rd may together with the nitrogen atom to which they are bound form a 5- to 10-membered, preferably 5- to 6-membered heterocyclic ring, wherein the heterocycle may comprise 1, 2, or 3 additional heteroatoms selected from N, O, and S, wherein the N atom if present is further substituted by H or C1-C4-alkyl. Preferably n is 1 or 2, m is 1 or 2, p is 1 or 2, Ra, Rb, Rc, and Rd are each independently selected from C1-C2-alkyl, or Ra and Rb and Rc and Rd each together with the nitrogen atom to which they are bound form a 5- or 6-membered heterocyclic ring, wherein the heterocycle may comprise 1 additional heteroatom selected from N, O, and S, wherein the N-atom if present is further substituted by a C1-C2-alkyl group.
- In one embodiment of the invention, the ether amines are heterocyclic 5- to 10-membered, preferably 5- or 6-membered rings comprising an oxygen atom and a nitrogen atom to form the required amino and ether groups, and wherein the nitrogen atom is further substituted by H, C1-C10-alkyl, C1-C10-haloalkyl, C(═O)H, or C(═O)C1-C10-alkyl. Particularly preferred are morpholine compounds, wherein the nitrogen atom is substituted by C1-C4-alkyl, C1-C4-haloalkyl, C(═O)H, or C(═O)C1-C4-alkyl, preferably by C1-C4-alkyl, C(═O)H, or C(═O)CH3.
- Preferred ether amines include dimorpholinodiethylether, bis(2-dimethyl-aminoethyl)ether, N-acetylmorpholine, and N-formylmorpholine.
- In one preferred embodiment of the invention, the amine (4) is dimorpholinodiethylether (available as Lupragen® N106 from BASF).
- In one preferred embodiment of the invention, the amine (4) is bis(2-dimethyl-aminoethyl)ether (CAS [3033-62-3], available as Lupragen® N205 from BASF).
- In one preferred embodiment of the invention, the amine (4) is a morpholine compound selected from N-acetylmorpholine and N-formylmorpholine.
- The amines (4l) or (4m) are preferably
- (L217) triethanolamine,
- (L218) tripropanolamine,
- (L219) diisopropanolamine,
- (L220) triisopropanolamine,
- (L221) diethanolamine, or
- (L222) methyldipropanolamine.
- In one preferred embodiment, the amine (4) is (L217) triethanolamine.
- In another preferred embodiment, the amine (4) is (L218) tripropanolamine.
- In another preferred embodiment, the amine (4) is (L219) diisopropanolamine.
- In another preferred embodiment, the amine (4) is (L220) triisopropanolamine.
- In another preferred embodiment, the amine (4) is (L221) diethanolamine.
- In another preferred embodiment, the amine (4) is (L222) methyldipropanolamine.
- According to another embodiment, the amine (4) is
- (4n) an amine selected from the group consisting of methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, N,N′,N″-tris(dimethylaminopropyl)hexahydrotriazine, and 2,2′-dimorpholinyldiethyl ether.
- In one embodiment, the amine (4) is methyldiethanolamine.
- In one embodiment, the amine (4) is tetrahydroxypropylethylenediamine.
- In one embodiment, the amine (4) is trimethylaminoethylethanolamine.
- In one embodiment, the amine (4) is N,N,N′,N′-tetramethyl-1,6-hexanediamine.
- In one embodiment, the amine (4) is N,N′,N″-tris(dimethylaminopropyl)hexahydrotriazine.
- In one embodiment, the amine (4) is 2,2′-dimorpholinyldiethyl ether.
- According to another embodiment, the amine (4) is
- (4o) an amine selected from the group consisting of (L10), (L11), (L12), (L13), (L14), (L15), (L16), (L17), (L18), (L19), (L20), (L21), (L22), (L23), (L24) and (L29) as disclosed in the PCT application PCT/IB2015/059864.
- In one preferred embodiment, the amine (4) is (L10) an aliphatic alkylenediamine according to the general formula (IA)
- wherein the radicals are defined as follows:
- R1 and R2 are simultaneously or each independently hydrogen, linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl, C3- to C8-cycloalkyl or C3- to C8-cycloalkyl in which optionally—preferably mandatorily—one or more CH2 groups have been replaced by O, NH or NR10; or
- alternatively R1 and R2 jointly represents a linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl, C3- to C8-cycloalkyl or C3- to C8-cycloalkyl in which optionally—preferably mandatorily—one or more CH2 groups have been replaced by O, NH or NR10; and
- R3x and R4, are simultaneously or each independently hydrogen, linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl, C3- to C8-cycloalkyl or C3- to C8-cycloalkyl in which optionally—preferably mandatorily—one or more CH2 groups have been replaced by 0, NH or NR10; and
- R10 is linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl or C3- to C8-cycloalkyl; and
- z is a value from 2 to 20, preferably from 2 to 12; and
- x is an index which can assume all values from 1 to z.
- In one preferred embodiment, the amine (4) is
- (L11) an oligomeric polyalkyleneamine according to the general formula (II)
- wherein the radicals are each defined as follows:
- R1, R2 and R5 are simultaneously or each independently hydrogen, linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl, C3- to C8-cycloalkyl or C3- to C8-cycloalkyl in which optionally—preferably mandatorily—one or more CH2 groups have been replaced by 0, NH or NR10; or
- two of the three radicals R1, R2 and R5 are covalently bonded to each other to form a linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl, C3- to C8-cycloalkyl or C3- to C8-cycloalkyl in which optionally—preferably mandatorily—one or more CH2 groups have been replaced by O, NH or NR10, and the remaining one of the three radicals R1, R2 and R5 is hydrogen, linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl, C3- to C8-cycloalkyl or C3- to C8-cycloalkyl in which optionally—preferably mandatorily—one or more CH2 groups have been replaced by 0, NH or NR10; and
- R3y and R4y are simultaneously or each independently hydrogen, linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl, C3- to C8-cycloalkyl or C3- to C8-cycloalkyl in which optionally—preferably mandatorily—one or more CH2 groups have been replaced by 0, NH or NR10;
- R10 is linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl or C3- to C8-cycloalkyl;
- a is a value of 2 to 5;
- b is a value of 2 to 12;
- and y is an index which can assume all values between 1 and b.
- In one preferred embodiment, the amine (4) is
- (L12) a polyetheramine according to general formula (III):
- wherein the radicals are each defined as follows:
- R1 and R2 are simultaneously or each independently hydrogen, linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl, C3- to C8-cycloalkyl or C3- to C8-cycloalkyl in which optionally—preferably mandatorily—one or more CH2 groups have been replaced by 0, NH or NR10;
- alternatively R1 and R2 jointly represents a linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl, C3- to C8-cycloalkyl or C3- to C8-cycloalkyl in which optionally—preferably mandatorily—one or more CH2 groups have been replaced by 0, NH or NR10; and
- R3, R4 and R5 are simultaneously or each independently hydrogen, linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl, C3- to C8-cycloalkyl or C3- to C8-cycloalkyl in which optionally—preferably mandatorily—one or more CH2 groups have been replaced by 0, NH or NR10;
- R10 is linear or branched C1- to C12-alkyl, C7- to C12-aralkyl, C6- to C10-aryl or C3- to C8-cycloalkyl;
- x, y and z are each independently a value from 0 to 100 and the sum of x, y and z are at least 2.
- In one preferred embodiment, the amine (4) is
- (L13) a polyvinylamine-related polymer selected from the group consisting of
- (L501) polyvinylamine,
- (L502) a polyvinylamine according to the general formula (IV)
- which has an average molar mass (Mw) of from 200 to 2,000,000 g/mol and wherein R7 to R11 are independently from each other
- hydrogen, linear or branched C1- to C20-alkyl, -alkoxy, -polyoxyethylene, -hydroxyalkyl, -(alkyl)carboxy, -phosphonoalkyl, -alkylamino radicals, formamidyl, pyrrolidonyl-, imidazolyl radicats, C2- to C20-alkenyl radicals or C6- to C20-aryl, -aryloxy, o-Hydroxybenzoyl, Phthalimidoyl, o-Carboxamidobenzoyl, o-(C1- to C8-Alkoxycarbonyl)benzoyl, o-Aminobenzoyl, o-(Mono-C1- to C8-alkylamino)benzoyl, o-(Di-C1- to C8-alkylamino)benzoyl, 2-Cyano-3,3-diphenylacryloyl, or mBenzimidazolyl-p-hydroxybenzoyl radicals which may be optionally further substituted, wherein s is an integer, t is 0 or an integer, wherein the sum of s and t must be chosen in such a way that the average molar mass is within the specified range,
- (L503) polyallylamine,
- (L504) poly(diallyldimethylammonium chloride),
- (L505) cationic polyvinylformamide,
- (L506) cationic polyvinylpyrrolidone,
- (L507) cationic polyvinylacetamide,
- (L508) cationic polyvinylmethylformamide,
- (L509) cationic polyvinyl methylacetamide,
- (L510) poly(dimethylaminopropylmethacrylamide),
- (L511) poly(dimethylaminoethyl acrylate),
- (L512) poly(diethylaminoethyl acrylate),
- (L513) poly(acryloylethyltrimethylammonium chloride),
- (L514) poly(acrylamido propyltrimethylammonium chloride),
- (L515) poly(methacrylamidotripropyltrimethyla-mmonium chloride),
- (L516) cationic polyacrylamide,
- (L517) poly(vinylpyridine),
- (L518) hexadimethrine bromide,
- (L519) poly(dimethylamine-co-epichlorohydrin),
- (L520) poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine),
- (L521) poly(amidoamine-epichlorohydrin),
- (L522) linear, branched or hyperbranched polyamidoamines, or
- (L523) polyamidoamines having an average molar mass (MW) of from 1,000 to 200,000 g/mol, and
- (L524) cationic starch, or copolymers which contain N-vinylformamide, allylamine, diallyldimethylammonium chloride, N-vinylacetamide, N-vinylpyrrolidone, N-methyl-N-vinylformamide, N-methyl-N-vinylacetamide, dimethylaminopropylmethacrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acryloylethyltrimethylammonium chloride or methacrylamidopropyltrimethylammonium chloride in the form of polymerized units and, if desired, in cleaved form, and the salts thereof when the polymers are basic polymers.
- In one preferred embodiment, the amine (4) is
- (L14) a polyethyleneimine according to the general formula (V)
- which has an average molar mass (MW) of from 200 to 1,000,000 g/mol and in which
- R1 to R6 are—independently from each other—hydrogen, linear or branched C1- to C20-alkyl, -alkoxy, -polyoxyalkylene, -polyoxyethylene, -hydroxyalkyl, -(alkyl)carboxy, -phosphonoalkyl, -alkylamino radicals, C2- to C20-alkenyl radicals or C6- to C20-aryl, -aryloxy, -hydroxyaryl, -arylcarboxy or -arylamino radicals which are optionally further substituted, and
- R2, R3 and R5 may—independently from each other—optionally be each additionally further polyethyleneimine polymer chains, and
- R1 may optionally be an NR3R4 or an NH2 radical, and
- x, y and z are—independently from each other—0 or an integer, wherein the sum of x, y and z must be chosen in such a way that the average molar mass is within the specified range.
- In one preferred embodiment, the amine (4) is
- (L15) a polyethyleneimine according to the general formula (V) wherein at least one of the radicals R2 to R6 is a polyoxyalkylene radical.
- In one preferred embodiment, the amine (4) is
- a polymer obtainable by the process (L16P) comprising the step L16a)
- L16a) condensation of at least one compound selected from N-(hydroxyalkyl)amines of formulae (I.a) and/or (I.b),
- wherein
- A are independently selected from C1-C6-alkylene;
- R1, R1*, R2, R2*, R3, R3*, R4, R4*, R5 and R5* are independently of one another selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted; and
- R6 is selected from hydrogen, alkyl, cycloalkyl or aryl, which may be optionally substituted.
- In one preferred embodiment, the amine (4) is
- (L17) a polymer obtainable by the process (L17P) comprising the two steps L17a) and L17b)
- L17a) condensation of at least one compound selected from N-(hydroxyalkyl)amines of formulae (I.a) and/or (I.b),
- wherein
- A are independently selected from C1-C6-alkylene;
- R1, R1*, R2, R2*, R3, R3*, R4, R4*, R5 and R5* are independently of one another selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted; and
- R6 is selected from hydrogen, alkyl, cycloalkyl or aryl, which may be optionally substituted; and
- L17b) reacting at least a part of the remaining hydroxy groups and/or, if present, at least a part of the secondary amino groups of the polyether provided in step L17a) with at least one alkylene oxide.
- In one preferred embodiment, the amine (4) is
- (L18) a derivative obtainable by quaternization, protonation, sulphation and/or phosphation of the polymer (L16) or (L17).
- In one preferred embodiment, the amine (4) is
- (L19) dendritic polyamines or their precursors selected from
- (L554) N,N,N′,N′-tetraaminopropylalkylenediamine,
- (L555) dendritic amines obtainable from N,N,N′,N′-tetraaminopropylalkylenediamine by amino-n-propylation (for example known as N14-, N30-, N62- and N128-amine according to the number of their nitrogen atoms),
- (L556) N,N,N′,N′-tetraaminopropylethylenediamine,
- (L557) dendritic amines obtainable from N,N,N′,N′-tetraaminopropylethylenediamine by amino-n-propylation (for example known as N14-, N30-, N62- and N128-amine according to the number of their nitrogen atoms),
- (L558) N,N,N′,N′-tetraaminopropylpropylenediamine,
- (L559) dendritic amines obtainable from N,N,N′,N′-tetraaminopropylpropylenediamine by amino-n-propylation (for example known as N14-, N30-, N62- and N128-amine according to the number of their nitrogen atoms),
- (L560) N,N,N′,N′-tetraaminopropylbutylenediamine,
- (L561) dendritic amines obtainable from N,N,N′,N′-tetraaminopropylbutylenediamine by amino-n-propylation (for example known as N14-, N30-, N62- and N128-amine according to the number of their nitrogen atoms).
- In one preferred embodiment, the amine (4) is
- (L20) a bicyclic, tricyclic or higher polycyclic polyamine.
- In one preferred embodiment, the amine (4) is (L21) an amine containing not more than one amino group and two alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R21a and one C1 to C10 alkyl group R21b, wherein the R21a group bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom and wherein the two groups R21a are identical.
- In one preferred embodiment, the amine (4) is
- (L22) an amine containing not more than one amino group and one alkoxy- or hydroxy-substituted C2 to C12 alkyl group R22a and two C1 to C10 alkyl groups R22b, wherein the two groups R22b are identical.
- In one preferred embodiment, the amine (4) is
- (L23) an imidazolidinone N-substituted on one or two of its nitrogen atoms with alkyl groups R23 wherein R23 may optionally be substituted with OH groups.
- In one preferred embodiment, the amine (4) is
- (L24) a morpholine N-substituted with alkyl groups R24 wherein R24 may optionally be substituted with OH groups.
- In one preferred embodiment, the amine (4) is
- (L29) a homopolymer of amino acids.
- In connection with the use (and the composition A defined in this connection), the method (and the composition A defined in this connection), the mixture M, the granule G, and the composition B as defined herein, the following combinations of embodiments are particularly preferred according to the present invention.
- Preferred combinations of the cation source (1) and the (thio)phosphoric acid triamide (2) are defined in the following Table A.
-
TABLE A (1) + (2) (1) (2) A-1 CaCl2 NBPT A-2 CaCl2 NPPT A-3 CaCl2 NBPT + NPPT A-4 MgSO4 NBPT A-5 MgSO4 NPPT A-6 MgSO4 NBPT + NPPT A-7 Al2(SO4)3 NBPT A-8 Al2(SO4)3 NPPT A-9 Al2(SO4)3 NBPT + NPPT A-10 FeSO4 NBPT A-11 FeSO4 NPPT A-12 FeSO4 NBPT + NPPT A-13 ZnCl2 NBPT A-14 ZnCl2 NPPT A-15 ZnCl2 NBPT + NPPT A-16 ZnSO4 NBPT A-17 ZnSO4 NPPT A-18 ZnSO4 NBPT + NPPT A-19 CuSO4, NBPT A-20 CuSO4, NPPT A-21 CuSO4, NBPT + NPPT A-22 Ca(NO3)2 NBPT A-23 Ca(NO3)2 NPPT A-24 Ca(NO3)2 NBPT + NPPT - Preferred combinations of the cation source (1) and the fertilizer (3a) are defined in the following Table B.
-
TABLE B (1) + (3a) (1) (3a) B-1 CaCl2 U B-2 MgSO4 U B-3 Al2(SO4)3 U B-4 FeSO4 U B-5 ZnCl2 U B-6 ZnSO4 U B-7 CuSO4, U B-8 Ca(NO3)2 U U = urea - Preferred combinations of the cation source (1) and the P-containing fertilizer (3b) are defined in the following Table C.
-
TABLE C (1) + (3b) (1) (3b) C-1 CaCl2 MAP C-2 CaCl2 DAP C-3 CaCl2 CP C-4 CaCl2 SP C-5 CaCl2 DSP C-6 CaCl2 TSP C-7 CaCl2 PR C-8 CaCl2 APP C-9 MgSO4 MAP C-10 MgSO4 DAP C-11 MgSO4 CP C-12 MgSO4 SP C-13 MgSO4 DSP C-14 MgSO4 TSP C-15 MgSO4 PR C-16 MgSO4 APP C-17 Al2(SO4)3 MAP C-18 Al2(SO4)3 DAP C-19 Al2(SO4)3 CP C-20 Al2(SO4)3 SP C-21 Al2(SO4)3 DSP C-22 Al2(SO4)3 TSP C-23 Al2(SO4)3 PR C-24 Al2(SO4)3 APP C-25 FeSO4 MAP C-26 FeSO4 DAP C-27 FeSO4 CP C-28 FeSO4 SP C-29 FeSO4 DSP C-30 FeSO4 TSP C-31 FeSO4 PR C-32 FeSO4 APP C-33 ZnCl2 MAP C-34 ZnCl2 DAP C-35 ZnCl2 CP C-36 ZnCl2 SP C-37 ZnCl2 DSP C-38 ZnCl2 TSP C-39 ZnCl2 PR C-40 ZnCl2 APP C-41 ZnSO4 MAP C-42 ZnSO4 DAP C-43 ZnSO4 CP C-44 ZnSO4 SP C-45 ZnSO4 DSP C-46 ZnSO4 TSP C-47 ZnSO4 PR C-48 ZnSO4 APP C-49 CuSO4 MAP C-50 CuSO4 DAP C-51 CuSO4 CP C-52 CuSO4 SP C-53 CuSO4 DSP C-54 CuSO4 TSP C-55 CuSO4 PR C-56 CuSO4 APP C-57 Ca(NO3)2 MAP C-58 Ca(NO3)2 DAP C-59 Ca(NO3)2 CP C-60 Ca(NO3)2 SP C-61 Ca(NO3)2 DSP C-62 Ca(NO3)2 TSP C-63 Ca(NO3)2 PR C-64 Ca(NO3)2 APP CP = calcium phosphate SP = super phosphate DSP = double super phosphate PR = phosphate rock - The remaining abbreviations correspond to the abbreviations used before.
- Preferred combinations of the cation source (1) and the fertilizers (3a) and (3b) are defined in the following Table D.
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TABLE D (1) + (3a)/(3b) (1) (3a) (3b) D-1 CaCl2 U MAP D-2 CaCl2 U DAP D-3 CaCl2 U CP D-4 CaCl2 U SP D-5 CaCl2 U DSP D-6 CaCl2 U TSP D-7 CaCl2 U PR D-8 CaCl2 U APP D-9 MgSO4 U MAP D-10 MgSO4 U DAP D-11 MgSO4 U CP D-12 MgSO4 U SP D-13 MgSO4 U DSP D-14 MgSO4 U TSP D-15 MgSO4 U PR D-16 MgSO4 U APP D-17 Al2(SO4)3 U MAP D-18 Al2(SO4)3 U DAP D-19 Al2(SO4)3 U CP D-20 Al2(SO4)3 U SP D-21 Al2(SO4)3 U DSP D-22 Al2(SO4)3 U TSP D-23 Al2(SO4)3 U PR D-24 Al2(SO4)3 U APP D-25 FeSO4 U MAP D-26 FeSO4 U DAP D-27 FeSO4 U CP D-28 FeSO4 U SP D-29 FeSO4 U DSP D-30 FeSO4 U TSP D-31 FeSO4 U PR D-32 FeSO4 U APP D-33 ZnCl2 U MAP D-34 ZnCl2 U DAP D-35 ZnCl2 U CP D-36 ZnCl2 U SP D-37 ZnCl2 U DSP D-38 ZnCl2 U TSP D-39 ZnCl2 U PR D-40 ZnCl2 U APP D-41 ZnSO4 U MAP D-42 ZnSO4 U DAP D-43 ZnSO4 U CP D-44 ZnSO4 U SP D-45 ZnSO4 U DSP D-46 ZnSO4 U TSP D-47 ZnSO4 U PR D-48 ZnSO4 U APP D-49 CuSO4 U MAP D-50 CuSO4 U DAP D-51 CuSO4 U CP D-52 CuSO4 U SP D-53 CuSO4 U DSP D-54 CuSO4 U TSP D-55 CuSO4 U PR D-56 CuSO4 U APP D-57 Ca(NO3)2 U MAP D-58 Ca(NO3)2 U DAP D-59 Ca(NO3)2 U CP D-60 Ca(NO3)2 U SP D-61 Ca(NO3)2 U DSP D-62 Ca(NO3)2 U TSP D-63 Ca(NO3)2 U PR D-64 Ca(NO3)2 U APP - The abbreviations are the same as used in Tables B and C.
- Preferred combinations of the cation source (1), the (thio)phosphoric acid triamide (2), and the fertilizers (3a) and (3b) are defined in the following Table E. In Table E, “NBPT+NPPT” is abbreviated as “NYPT”.
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TABLE E (1) + (2) + (3a)/(3b) (1) (2) (3a) (3b) E-1 CaCl2 NBPT U MAP E-2 CaCl2 NBPT U DAP E-3 CaCl2 NBPT U CP E-4 CaCl2 NBPT U SP E-5 CaCl2 NBPT U DSP E-6 CaCl2 NBPT U TSP E-7 CaCl2 NBPT U PR E-8 CaCl2 NBPT U APP E-9 CaCl2 NBPT U MAP E-10 CaCl2 NBPT U DAP E-11 CaCl2 NBPT U CP E-12 CaCl2 NBPT U SP E-13 CaCl2 NBPT U DSP E-14 CaCl2 NBPT U TSP E-15 CaCl2 NBPT U PR E-16 CaCl2 NBPT U APP E-17 MgSO4 NBPT U MAP E-18 MgSO4 NBPT U DAP E-19 MgSO4 NBPT U CP E-20 MgSO4 NBPT U SP E-21 MgSO4 NBPT U DSP E-22 MgSO4 NBPT U TSP E-23 MgSO4 NBPT U PR E-24 MgSO4 NBPT U APP E-25 MgSO4 NBPT U MAP E-26 MgSO4 NBPT U DAP E-27 MgSO4 NBPT U CP E-28 MgSO4 NBPT U SP E-29 MgSO4 NBPT U DSP E-30 MgSO4 NBPT U TSP E-31 MgSO4 NBPT U PR E-32 MgSO4 NBPT U APP E-33 CaCl2 NPPT U MAP E-34 CaCl2 NPPT U DAP E-35 CaCl2 NPPT U CP E-36 CaCl2 NPPT U SP E-37 CaCl2 NPPT U DSP E-38 CaCl2 NPPT U TSP E-39 CaCl2 NPPT U PR E-40 CaCl2 NPPT U APP E-41 CaCl2 NPPT U MAP E-42 CaCl2 NPPT U DAP E-43 CaCl2 NPPT U CP E-44 CaCl2 NPPT U SP E-45 CaCl2 NPPT U DSP E-46 CaCl2 NPPT U TSP E-47 CaCl2 NPPT U PR E-48 CaCl2 NPPT U APP E-49 MgSO4 NPPT U MAP E-50 MgSO4 NPPT U DAP E-51 MgSO4 NPPT U CP E-52 MgSO4 NPPT U SP E-53 MgSO4 NPPT U DSP E-54 MgSO4 NPPT U TSP E-55 MgSO4 NPPT U PR E-56 MgSO4 NPPT U APP E-57 MgSO4 NPPT U MAP E-58 MgSO4 NPPT U DAP E-59 MgSO4 NPPT U CP E-60 MgSO4 NPPT U SP E-61 MgSO4 NPPT U DSP E-62 MgSO4 NPPT U TSP E-63 MgSO4 NPPT U PR E-64 MgSO4 NPPT U APP E-65 CaCl2 NYPT U MAP E-66 CaCl2 NYPT U DAP E-67 CaCl2 NYPT U CP E-68 CaCl2 NYPT U SP E-69 CaCl2 NYPT U DSP E-70 CaCl2 NYPT U TSP E-71 CaCl2 NYPT U PR E-72 CaCl2 NYPT U APP E-73 CaCl2 NYPT U MAP E-74 CaCl2 NYPT U DAP E-75 CaCl2 NYPT U CP E-76 CaCl2 NYPT U SP E-77 CaCl2 NYPT U DSP E-78 CaCl2 NYPT U TSP E-79 CaCl2 NYPT U PR E-80 CaCl2 NYPT U APP E-81 MgSO4 NYPT U MAP E-82 MgSO4 NYPT U DAP E-83 MgSO4 NYPT U CP E-84 MgSO4 NYPT U SP E-85 MgSO4 NYPT U DSP E-86 MgSO4 NYPT U TSP E-87 MgSO4 NYPT U PR E-88 MgSO4 NYPT U APP E-89 MgSO4 NYPT U MAP E-90 MgSO4 NYPT U DAP E-91 MgSO4 NYPT U CP E-92 MgSO4 NYPT U SP E-93 MgSO4 NYPT U DSP E-94 MgSO4 NYPT U TSP E-95 MgSO4 NYPT U PR E-96 MgSO4 NYPT U APP E-97 Al2(SO4)3 NBPT U MAP E-98 Al2(SO4)3 NBPT U DAP E-99 Al2(SO4)3 NBPT U CP E-100 Al2(SO4)3 NBPT U SP E-101 Al2(SO4)3 NBPT U DSP E-102 Al2(SO4)3 NBPT U TSP E-103 Al2(SO4)3 NBPT U PR E-104 Al2(SO4)3 NBPT U APP E-105 Al2(SO4)3 NBPT U MAP E-106 Al2(SO4)3 NBPT U DAP E-107 Al2(SO4)3 NBPT U CP E-108 Al2(SO4)3 NBPT U SP E-109 Al2(SO4)3 NBPT U DSP E-110 Al2(SO4)3 NBPT U TSP E-111 Al2(SO4)3 NBPT U PR E-112 Al2(SO4)3 NBPT U APP E-113 FeSO4 NBPT U MAP E-114 FeSO4 NBPT U DAP E-115 FeSO4 NBPT U CP E-116 FeSO4 NBPT U SP E-117 FeSO4 NBPT U DSP E-118 FeSO4 NBPT U TSP E-119 FeSO4 NBPT U PR E-120 FeSO4 NBPT U APP E-121 FeSO4 NBPT U MAP E-122 FeSO4 NBPT U DAP E-123 FeSO4 NBPT U CP E-124 FeSO4 NBPT U SP E-125 FeSO4 NBPT U DSP E-126 FeSO4 NBPT U TSP E-127 FeSO4 NBPT U PR E-128 FeSO4 NBPT U APP E-129 Al2(SO4)3 NPPT U MAP E-130 Al2(SO4)3 NPPT U DAP E-131 Al2(SO4)3 NPPT U CP E-132 Al2(SO4)3 NPPT U SP E-133 Al2(SO4)3 NPPT U DSP E-134 Al2(SO4)3 NPPT U TSP E-135 Al2(SO4)3 NPPT U PR E-136 Al2(SO4)3 NPPT U APP E-137 Al2(SO4)3 NPPT U MAP E-138 Al2(SO4)3 NPPT U DAP E-139 Al2(SO4)3 NPPT U CP E-140 Al2(SO4)3 NPPT U SP E-141 Al2(SO4)3 NPPT U DSP E-142 Al2(SO4)3 NPPT U TSP E-143 Al2(SO4)3 NPPT U PR E-144 Al2(SO4)3 NPPT U APP E-145 FeSO4 NPPT U MAP E-146 FeSO4 NPPT U DAP E-147 FeSO4 NPPT U CP E-148 FeSO4 NPPT U SP E-149 FeSO4 NPPT U DSP E-150 FeSO4 NPPT U TSP E-151 FeSO4 NPPT U PR E-152 FeSO4 NPPT U APP E-153 FeSO4 NPPT U MAP E-154 FeSO4 NPPT U DAP E-155 FeSO4 NPPT U CP E-156 FeSO4 NPPT U SP E-157 FeSO4 NPPT U DSP E-158 FeSO4 NPPT U TSP E-159 FeSO4 NPPT U PR E-160 FeSO4 NPPT U APP E-161 Al2(SO4)3 NYPT U MAP E-162 Al2(SO4)3 NYPT U DAP E-163 Al2(SO4)3 NYPT U CP E-164 Al2(SO4)3 NYPT U SP E-165 Al2(SO4)3 NYPT U DSP E-166 Al2(SO4)3 NYPT U TSP E-167 Al2(SO4)3 NYPT U PR E-168 Al2(SO4)3 NYPT U APP E-169 Al2(SO4)3 NYPT U MAP E-170 Al2(SO4)3 NYPT U DAP E-171 Al2(SO4)3 NYPT U CP E-172 Al2(SO4)3 NYPT U SP E-173 Al2(SO4)3 NYPT U DSP E-174 Al2(SO4)3 NYPT U TSP E-175 Al2(SO4)3 NYPT U PR E-176 Al2(SO4)3 NYPT U APP E-177 FeSO4 NYPT U MAP E-178 FeSO4 NYPT U DAP E-179 FeSO4 NYPT U CP E-180 FeSO4 NYPT U SP E-181 FeSO4 NYPT U DSP E-182 FeSO4 NYPT U TSP E-183 FeSO4 NYPT U PR E-184 FeSO4 NYPT U APP E-185 FeSO4 NYPT U MAP E-186 FeSO4 NYPT U DAP E-187 FeSO4 NYPT U CP E-188 FeSO4 NYPT U SP E-189 FeSO4 NYPT U DSP E-190 FeSO4 NYPT U TSP E-191 FeSO4 NYPT U PR E-192 FeSO4 NYPT U APP E-193 ZnCl2 NBPT U MAP E-194 ZnCl2 NBPT U DAP E-195 ZnCl2 NBPT U CP E-196 ZnCl2 NBPT U SP E-197 ZnCl2 NBPT U DSP E-198 ZnCl2 NBPT U TSP E-199 ZnCl2 NBPT U PR E-200 ZnCl2 NBPT U APP E-201 ZnCl2 NBPT U MAP E-202 ZnCl2 NBPT U DAP E-203 ZnCl2 NBPT U CP E-204 ZnCl2 NBPT U SP E-205 ZnCl2 NBPT U DSP E-206 ZnCl2 NBPT U TSP E-207 ZnCl2 NBPT U PR E-208 ZnCl2 NBPT U APP E-209 ZnSO4 NBPT U MAP E-210 ZnSO4 NBPT U DAP E-211 ZnSO4 NBPT U CP E-212 ZnSO4 NBPT U SP E-213 ZnSO4 NBPT U DSP E-214 ZnSO4 NBPT U TSP E-215 ZnSO4 NBPT U PR E-216 ZnSO4 NBPT U APP E-217 ZnSO4 NBPT U MAP E-218 ZnSO4 NBPT U DAP E-219 ZnSO4 NBPT U CP E-220 ZnSO4 NBPT U SP E-221 ZnSO4 NBPT U DSP E-222 ZnSO4 NBPT U TSP E-223 ZnSO4 NBPT U PR E-224 ZnSO4 NBPT U APP E-225 ZnCl2 NPPT U MAP E-226 ZnCl2 NPPT U DAP E-227 ZnCl2 NPPT U CP E-228 ZnCl2 NPPT U SP E-229 ZnCl2 NPPT U DSP E-230 ZnCl2 NPPT U TSP E-231 ZnCl2 NPPT U PR E-232 ZnCl2 NPPT U APP E-233 ZnCl2 NPPT U MAP E-234 ZnCl2 NPPT U DAP E-235 ZnCl2 NPPT U CP E-236 ZnCl2 NPPT U SP E-237 ZnCl2 NPPT U DSP E-238 ZnCl2 NPPT U TSP E-239 ZnCl2 NPPT U PR E-240 ZnCl2 NPPT U APP E-241 ZnSO4 NPPT U MAP E-242 ZnSO4 NPPT U DAP E-243 ZnSO4 NPPT U CP E-244 ZnSO4 NPPT U SP E-245 ZnSO4 NPPT U DSP E-246 ZnSO4 NPPT U TSP E-247 ZnSO4 NPPT U PR E-248 ZnSO4 NPPT U APP E-249 ZnSO4 NPPT U MAP E-250 ZnSO4 NPPT U DAP E-251 ZnSO4 NPPT U CP E-252 ZnSO4 NPPT U SP E-253 ZnSO4 NPPT U DSP E-254 ZnSO4 NPPT U TSP E-255 ZnSO4 NPPT U PR E-256 ZnSO4 NPPT U APP E-257 ZnCl2 NYPT U MAP E-258 ZnCl2 NYPT U DAP E-259 ZnCl2 NYPT U CP E-260 ZnCl2 NYPT U SP E-261 ZnCl2 NYPT U DSP E-262 ZnCl2 NYPT U TSP E-263 ZnCl2 NYPT U PR E-264 ZnCl2 NYPT U APP E-265 ZnCl2 NYPT U MAP E-266 ZnCl2 NYPT U DAP E-267 ZnCl2 NYPT U CP E-268 ZnCl2 NYPT U SP E-269 ZnCl2 NYPT U DSP E-270 ZnCl2 NYPT U TSP E-271 ZnCl2 NYPT U PR E-272 ZnCl2 NYPT U APP E-273 ZnSO4 NYPT U MAP E-274 ZnSO4 NYPT U DAP E-275 ZnSO4 NYPT U CP E-276 ZnSO4 NYPT U SP E-277 ZnSO4 NYPT U DSP E-278 ZnSO4 NYPT U TSP E-279 ZnSO4 NYPT U PR E-280 ZnSO4 NYPT U APP E-281 ZnSO4 NYPT U MAP E-282 ZnSO4 NYPT U DAP E-283 ZnSO4 NYPT U CP E-284 ZnSO4 NYPT U SP E-285 ZnSO4 NYPT U DSP E-286 ZnSO4 NYPT U TSP E-287 ZnSO4 NYPT U PR E-288 ZnSO4 NYPT U APP E-289 CuSO4 NBPT U MAP E-290 CuSO4 NBPT U DAP E-291 CuSO4 NBPT U CP E-292 CuSO4 NBPT U SP E-293 CuSO4 NBPT U DSP E-294 CuSO4 NBPT U TSP E-295 CuSO4 NBPT U PR E-296 CuSO4 NBPT U APP E-297 CuSO4 NBPT U MAP E-298 CuSO4 NBPT U DAP E-299 CuSO4 NBPT U CP E-300 CuSO4 NBPT U SP E-301 CuSO4 NBPT U DSP E-302 CuSO4 NBPT U TSP E-303 CuSO4 NBPT U PR E-304 CuSO4 NBPT U APP E-305 Ca(NO3)2 NBPT U MAP E-306 Ca(NO3)2 NBPT U DAP E-307 Ca(NO3)2 NBPT U CP E-308 Ca(NO3)2 NBPT U SP E-309 Ca(NO3)2 NBPT U DSP E-310 Ca(NO3)2 NBPT U TSP E-311 Ca(NO3)2 NBPT U PR E-312 Ca(NO3)2 NBPT U APP E-313 Ca(NO3)2 NBPT U MAP E-314 Ca(NO3)2 NBPT U DAP E-315 Ca(NO3)2 NBPT U CP E-316 Ca(NO3)2 NBPT U SP E-317 Ca(NO3)2 NBPT U DSP E-318 Ca(NO3)2 NBPT U TSP E-319 Ca(NO3)2 NBPT U PR E-320 Ca(NO3)2 NBPT U APP E-321 CuSO4 NPPT U MAP E-322 CuSO4 NPPT U DAP E-323 CuSO4 NPPT U CP E-324 CuSO4 NPPT U SP E-325 CuSO4 NPPT U DSP E-326 CuSO4 NPPT U TSP E-327 CuSO4 NPPT U PR E-328 CuSO4 NPPT U APP E-329 CuSO4 NPPT U MAP E-330 CuSO4 NPPT U DAP E-331 CuSO4 NPPT U CP E-332 CuSO4 NPPT U SP E-333 CuSO4 NPPT U DSP E-334 CuSO4 NPPT U TSP E-335 CuSO4 NPPT U PR E-336 CuSO4 NPPT U APP E-337 Ca(NO3)2 NPPT U MAP E-338 Ca(NO3)2 NPPT U DAP E-339 Ca(NO3)2 NPPT U CP E-340 Ca(NO3)2 NPPT U SP E-341 Ca(NO3)2 NPPT U DSP E-342 Ca(NO3)2 NPPT U TSP E-343 Ca(NO3)2 NPPT U PR E-344 Ca(NO3)2 NPPT U APP E-345 Ca(NO3)2 NPPT U MAP E-346 Ca(NO3)2 NPPT U DAP E-347 Ca(NO3)2 NPPT U CP E-348 Ca(NO3)2 NPPT U SP E-349 Ca(NO3)2 NPPT U DSP E-350 Ca(NO3)2 NPPT U TSP E-351 Ca(NO3)2 NPPT U PR E-352 Ca(NO3)2 NPPT U APP E-353 CuSO4 NYPT U MAP E-354 CuSO4 NYPT U DAP E-355 CuSO4 NYPT U CP E-356 CuSO4 NYPT U SP E-357 CuSO4 NYPT U DSP E-358 CuSO4 NYPT U TSP E-359 CuSO4 NYPT U PR E-360 CuSO4 NYPT U APP E-361 CuSO4 NYPT U MAP E-362 CuSO4 NYPT U DAP E-363 CuSO4 NYPT U CP E-364 CuSO4 NYPT U SP E-365 CuSO4 NYPT U DSP E-366 CuSO4 NYPT U TSP E-367 CuSO4 NYPT U PR E-368 CuSO4 NYPT U APP E-369 Ca(NO3)2 NYPT U MAP E-370 Ca(NO3)2 NYPT U DAP E-371 Ca(NO3)2 NYPT U CP E-372 Ca(NO3)2 NYPT U SP E-373 Ca(NO3)2 NYPT U DSP E-374 Ca(NO3)2 NYPT U TSP E-375 Ca(NO3)2 NYPT U PR E-376 Ca(NO3)2 NYPT U APP E-377 Ca(NO3)2 NYPT U MAP E-378 Ca(NO3)2 NYPT U DAP E-379 Ca(NO3)2 NYPT U CP E-380 Ca(NO3)2 NYPT U SP E-381 Ca(NO3)2 NYPT U DSP E-382 Ca(NO3)2 NYPT U TSP E-383 Ca(NO3)2 NYPT U PR E-384 Ca(NO3)2 NYPT U APP - The abbreviations are the same as used in Tables B and C.
- It is to be understood that in each case of the preferred embodiments listed in the above Tables A and E, the (thio)phosphoric acid triamide (2), i.e. NBPT, NPPT or NBPT+NPPT, may preferably be provided in combination with an amine (4) as defined above.
- In connection with the use (and the composition A defined in this connection), the method (and the composition A defined in this connection), the mixture M, the granule G, and the composition B as defined herein, it is preferred that the cation source (1) is provided in certain minimum amount based on the fertilizer mixture (3) or the P-containing fertilizer (3b) in order to exhibit the stabilizing effect.
- In a preferred embodiment, the cation source (1) is used in an amount of at least 0.25 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 0.5 wt.-% based on the total weight of the P-containing fertilizer (3b).
- In a more preferred embodiment, the cation source (1) is used in an amount of at least 0.375 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 0.75 wt.-% based on the total weight of the P-containing fertilizer (3b).
- In an even more preferred embodiment, the cation source (1) is used in an amount of at least 0.5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 1 wt.-% based on the total weight of the P-containing fertilizer (3b).
- In a most preferred embodiment, the cation source (1) is used in an amount of at least 1 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 2 wt.-% based on the total weight of the P-containing fertilizer (3b).
- In another preferred embodiment, the cation source (1) is used in an amount of at most 20 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at most 40 wt.-% based on the total weight of the P-containing fertilizer (3b)
- In a more preferred embodiment, the cation source (1) is used in an amount of at most 10 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at most 20 wt.-% based on the total weight of the P-containing fertilizer (3b).
- In a most preferred embodiment, the cation source (1) is used in an amount of at most 5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 10 wt.-% based on the total weight of the P-containing fertilizer (3b).
- In a particularly preferred embodiment, the cation source (1) is used in an amount of at most 2.5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 5 wt.-% based on the total weight of the P-containing fertilizer (3b).
- Preferably, the cation source (1) is used in such an amount that it does not exhibit any urease inhibiting effect by itself.
- These amounts especially apply to the situation, where the cation source (1) is a salt as defined above.
- A skilled person further knows suitable amounts of the (thio)phosphoric acid triamide (2) and optionally the amine (4) based on the fertilizer (3a).
- In a preferred embodiment, the (thio)phosphoric acid triamide (2) is used in an amount of at least 0.005 wt.-% based on the total weight of the fertilizer (3a).
- In a more preferred embodiment, the (thio)phosphoric acid triamide (2) is used in an amount of at least 0.01 wt.-% based on the total weight of the fertilizer (3a).
- In an even more preferred embodiment, the (thio)phosphoric acid triamide (2) is used in an amount of at least 0.05 wt.-% based on the total weight of the fertilizer (3a).
- In another preferred embodiment, the (thio)phosphoric acid triamide (2) is used in an amount of at most 20 wt.-% based on the total weight of the fertilizer (3a).
- In another preferred embodiment, the (thio)phosphoric acid triamide (2) is used in an amount of at most 10 wt.-% based on the total weight of the fertilizer (3a).
- These amounts apply especially to the situation, where the (thio)phosphoric acid triamide (2) is NBPT or NPPT or the combination of NBPT and NPPT. In connection with the combination of NBPT and NPPT, it is to be understood that the above amounts refer to the combination and not to the individual compounds.
- In another preferred embodiment, the amine (4) is used in an amount of at least 0.005 wt.-% based on the total weight of the fertilizer (3a).
- In a more preferred embodiment, the amine (4) is used in an amount of at least 0.01 wt.-% based on the total weight of the fertilizer (3a).
- In an even more preferred embodiment, the amine (4) is used in an amount of at least 0.05 wt.-% based on the total weight of the fertilizer (3a).
- In another preferred embodiment, the amine (4) is used in an amount of at most 20 wt.-% based on the total weight of the fertilizer (3a).
- In another preferred embodiment, the amine (4) is used in an amount of at most 10 wt.-% based on the total weight of the fertilizer (3a).
- It is to be understood that the compositions A and B, the mixture M, and the granule G may further comprise auxiliaries such as solvents, solid carriers, surfactants, adjuvants, thickeners, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers, binders, preservatives, antioxidants, and odorants.
- Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
- Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gammabutyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
- Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
- Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
- Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkyl phenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
- Suitable non ionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, aryl phenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
- Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide or of the A-B—C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or poly-ethyleneamines.
- Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports OS256, T&F Informa UK, 2006, chapter 5.
- Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
- Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
- Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
- Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
- Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are
-
- inorganic colorants, such as iron oxide, titan oxide, iron hexacyanoferrate,
- metal-complex dyes such as chromium-complex dyes, for example Orasol Yellow 141,
- organic colorants such as alizarin-, azo- and phthalocyanine colorants.
- Preferred colorants are metal-complex dyes, more preferably chromium-complex dyes, for example Orasol Yellow 141.
- Suitable tackifiers or binders are polyvinylpyrrolidones, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
- Suitable preservatives include e.g. sodium benzoate, benzoic acid, sorbic acid, and derivatives thereof.
- Suitable antioxidants include sulfites, ascorbic acid, tocopherol, tocopherol acetate, tocotrienol, melatonin, carotene, beta-carotene, ubiquinol, and derivatives thereof. Tocophercol acetate is preferred as antioxidant.
- Suitable odorants include perfume materials which are for example mentioned in U.S. Pat. No. 7,182,537, including allo-ocimene, Allyl cyclohexanepropionate, Allyl heptanoate, trans-Anethole, benzylbutyrate, Camphene, Cadinene, Carvacrol, cis-3-Hexenyl tiglate, Citronellol, Citronellyl acetate, Citronellyl nitrile, Citronellyl propionate, Cyclohexylethyl acetate, Decyl Aldehyde (Capraldehyde), Dihydromyrcenol, Dihydromyrcenyl acetate, 3,7-Dimethyl-1-octanol, Diphenyloxide, Fenchyl Acetate (1,3,3-Trimethyl-2-norbornanyl acetate), Geranyl acetate, Geranyl formate, Geranyl nitrile, cis-3-Hexenyl isobutyrate, Hexyl Neopentanoate, Hexyl tiglate, alpha-Ionone, Ethyl Vanillin L80, lsoeugenol, Methyl cinnamate, Methyl dihydrojasmonate, Methyl beta-naphthyl ketone, Phenoxy ethyl isobutyrate, Vanillin L28, Isobornyl acetate, Isobutyl benzoate, Isononyl acetate, Isononyl alcohol (3,5,5-Trimethyl-1-hexanol), Isopulegyl acetate, Lauraldehyde, d-Limonene, Linalyl acetate, (−)-L-Menthyl acetate, Methyl Chavicol (Estragole), Methyl n-nonyl acetaldehyde, methyl octyl acetaldehyde, beta-Myrcene, Neryl acetate, Nonyl acetate, Nonaldehyde, p-Cymene, alpha-Pinene, beta-Pinene, alpha-Terpinene, gamma-Terpinene, alpha-Terpinyl acetate, Tetrahydrolinalool, Tetrahydromyrcenol, 2-Undecenal, Verdox (o-t-Butylcyclohexyl acetate), Vertenex (4-tert,Butylcyclohexyl acetate). Citronellyl nitrile is preferred as odorant.
- The present invention is further illustrated by the following examples.
- Materials:
- Urease Inhibitors:
- Urease inhibitor “U1” was obtained from BASF SE. Composition:
-
- 18.75 wt.-% N-butylphosphorothioic triamide (NBPT, CAS-no.: 94317-64-3)
- 6.25 wt.-% N-propylphosphorothioic triamide (NPPT, CAS-no.: 916809-14-8)
- 15-25 wt.-% stabilizer
- 30-40 wt.-% benzyl alcohol (CAS-no.: 100-51-6)
- 10-20 wt.-% Agnique AMD 3 L (CAS-no.: 35123-06-9)
- 0.5-2 wt.-% colorant
- 0.5-2 wt.-% odorant
- Fertilizers:
- Urea (Piagran 46) was obtained from SKW Piesteritz.
- Any one of the following fertilizers was used as additional P-containing fertilizer: Diammonium phosphate (DAP)
- Triple super phosphate (TSP)
- 16-8-22 fertilizer
- Cation source:
- Any one of the following salts was used as cation source:
- Magnesium sulfate anhydrous (MgSO4)
- Magnesium sulfate heptahydrate (MgSO4×7H2O)
- Calcium chloride anhydrous (CaCl2)
- Calcium sulfate dihydrate (CaSO4×2H2O)
- Calcium nitrate (Ca(NO3)2)
- Copper sulfate (CuSO4)
- Iron sulfate (FeSO4)
- Zinc sulfate (ZnSO4)
- Zinc chloride (ZnCl2)
- Aluminium sulfate (Al2(SO4)3)
- General Experimental Details:
- For the preparation of urea treated with U1, 3 kg of urea fertilizer granules were added to an ERWEKA mixer (dimensions mix drum: 50 cm diameter, 20 cm high). The mixer is turned on (27 RPM) and U1 formulation is sprayed on the urea using a syringe. Afterwards, the fertilizer/U1 mixture is mixed for 3 minutes
- For the Dräger test, 150 g Limburgerhof (Germany) soil is added to a 500 mL wide-mouth jar (9 cm diameter). Fertilizer granules are added and distributed evenly over the soil. The amount of fertilizer added corresponds to 115 mg of urea-N. The soil and fertilizer are then wetted with a fine spray of water (1 mL). Afterwards, the jar is closed with a lid. In the middle of the lid a hole is made in which an ammonia gas test tube (Dräger, Ammoniak 20/a-D 8101301, Diffusionsröhrchen) is placed. The urease, naturally present in the soil, hydrolyses urea into carbon dioxide and ammonia. The concentration of ammonia gas is read out once a day from the scale on the Dräger diffusion tube. All tests are performed in duplicate.
- Active ingredient content on urea was analyzed by HPLC (high-pressure liquid chromatography) using method DIN EN 16651. In case of bulk blends, the urea granules were separated from the other fertilizers before dissolving in water for HPLC analysis.
- For the preparation of dry blend fertilizer mixtures, 10 g of urea treated with a urease inhibitor and 10 g of the other fertilizer are added to a small jar. After closing the jar, the fertilizers are mixed by vigorously shaking the jar. The closed jar is then stored at room temperature in a dark place. At the end of the storage time, urea granules are removed and tested using the Dräger test.
- Urea granules treated with 0.04 wt.-% U1 active ingredient were mixed with TSP (Triple Super Phosphate) fertilizer granules. After mixing, the samples were stored in closed containers at room temperature. After 1 day of storage, the urea granules were separated from the TSP granules and the active ingredient (a.i.) concentration on the urea was analyzed by HPLC. Table 1 shows that when U1 treated urea granules are mixed with TSP granules, 50-90% of the a.i.
- degrades within a day, depending on the amount of TSP in the mixture.
-
TABLE 1 A.i. analysis after separating urea from TSP mixtures U1 a.i. (wt.-%) Remaining a.i. (%) Urea 0.037 100 Urea/TSP 2:1 0.017 45.9 Urea/TSP 1:1 0.005 13.5 Urea/TSP 1:2 0.003 8.1 - Urea treated with U1 (0.04 wt.-% active on urea) was mixed with different phosphate fertilizers in a 1:1 wt.-% ratio. These mixtures were stored in closed containers at room temperature for 8 days. Afterwards, the urea granules were separated out and tested in the Dräger test. The following samples were tested:
- Sample 1: Urea
- Sample 2: Urea treated with 0.04 wt.-% U1 active ingredient
- Sample 3: Urea treated with 0.04 wt.-% U1 active ingredient, then mixed with TSP in a 50:50 wt.-% ratio
- Sample 4: Urea treated with 0.04 wt.-% U1 active ingredient, then mixed with DAP in a 50:50 wt.-% ratio
- Each experiment was performed twice (samples a and b). As can be seen in Table 2a, a concentration of 600 ppm NH3 is reached with untreated urea after 2 days. Treatment with 0.04 wt.-% U1 active ingredient effectively inhibits the urease activity and only after 9 days a NH3 concentration of 600 ppm is reached. For the urea granules treated with U1, which were mixed with phosphate fertilizers, a clear reduction in the efficacy of U1 is observed. With TSP the 600 ppm NH3 concentration is reached after 3 days and with DAP after 4 days. Repeating the Dräger test after storing the mixtures for 36 days (Table 2b), shows no urease inhibition for the TSP and DAP samples (>1500 ppm NH3 after 3 days) anymore.
-
TABLE 2a Emission after a 9 day storage period Ammonia emission (ppm) Time Sample 1 Sample 2 Sample 3 Sample 4 (days) a b a b a b a b 0 0 0 0 0 0 0 0 0 1 20 0 0 0 0 0 0 0 2 650 500 20 0 150 100 75 50 3 >1500 >1500 20 20 600 600 250 250 4 50 50 1500 1500 600 600 5 100 100 >1500 >1500 1200 1200 6 200 200 >1500 >1500 7 300 300 10 900 800 -
TABLE 2b Emission after a 36 day storage period Ammonia emission (ppm) Time Sample 1 Sample 2 Sample 3 Sample 4 (days) a b a b a b a b 0 0 0 0 0 0 0 0 0 3 >1500 >1500 50 50 >1500 >1500 >1500 >1500 4 75 75 5 150 125 6 250 250 7 300 400 8 450 500 9 700 800 10 800 950 - 10 g U1 treated urea and 0.5 g magnesium sulfate were added to a jar and mixed by shaking the jar. Afterwards, 10 gram phosphate fertilizer was added and mixed by shaking the jar.
- Sample 1: urea treated with 0.04 wt.-% U1 active ingredient (Comparative Sample)
- Sample 2: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.5 g MgSO4, 10 g TSP
- Sample 3: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.5 g MgSO4, 10 g DAP
- The closed jar was then stored at room temperature in a dark place. After 0.5, 2, 4 and 6 months urea granules were removed from the jar and tested with the Dräger test. As can be seen in tables 3a and 3b, 2.5 wt.-% magnesium sulfate can prevent degradation of U1 in mixtures containing phosphate fertilizers for up to 6 months.
-
TABLE 3a Emission after 0.5 months of storage Ammonia emissions (ppm) Time Sample 1 Sample 2 (days) a b a b Sample 3 0 0 0 0 0 0 0 1 0 0 0 0 0 0 2 20 0 20 50 0 0 3 20 20 100 150 20 20 4 50 50 300 300 50 50 5 100 100 550 600 100 100 6 200 200 1000 1000 200 200 7 300 300 1500 1400 300 400 10 900 800 >1500 >1500 800 1100 -
TABLE 3b Emission after 2, 4, or 6 months of storage Ammonia emission (ppm) 2 months storage of NP mixture 4 months storage of NP mixture 6 months storage of NP mixture Time Sample 1 Sample 3 Sample 1 Sample 3 Sample 1 Sample 3 (days) a b a b a b a b a b a b 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 10 10 20 20 0 0 0 0 3 20 20 20 20 20 20 20 20 0 0 5 5 4 22 22 40 30 na na na na 5 5 20 20 5 35 35 60 50 40 30 50 50 10 10 40 40 6 50 50 100 100 50 50 75 100 30 30 50 60 7 100 100 250 200 100 100 175 200 50 50 75 100 8 190 190 350 280 150 125 250 250 60 60 110 140 9 250 250 500 300 200 200 300 350 80 80 200 200 10 275 275 550 350 225 275 400 475 100 100 250 250 11 300 325 500 600 180 180 320 320 12 450 400 700 800 280 280 450 400 13 320 300 600 500 na: data not available - 10 g U1 treated urea and 0.25 gram magnesium sulfate were added to a jar and mixed by shaking the jar. Afterwards, 10 g phosphate fertilizer was added and mixed by shaking the jar.
- Sample 1: 10 g urea, 0.25 g MgSO4
- Sample 2: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 10 g DAP
- Sample 3: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.25 g MgSO4, 10 g DAP
- The closed jar was then stored at room temperature in a dark place. After 1 month the urea granules were removed from the jar and tested with the Dräger test. As can be seen in Table 4, magnesium sulfate by itself does not inhibit the urease activity, but does prevent the degradation of U1 in fertilizer mixtures containing DAP.
-
TABLE 4 Time ammonia emission (ppm) (days) 1a 1b 2a 2b 3a 3b 0 0 0 0 0 0 0 1 0 0 0 20 0 0 2 800 775 825 750 0 0 3 >1500 >1500 >1500 >1500 20 20 4 30 50 5 50 60 6 100 100 7 200 200 8 300 300 9 350 350 10 450 475 - 10 gram U1 treated urea and 0.5 gram salt were added to a jar and mixed by shaking the jar. Afterwards, 10 gram DAP was added and mixed in by shaking the jar.
- Sample 1: urea
- Sample 2: urea treated with 0.04 wt.-% U1 active ingredient
- Sample 8: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.25 g anhydrous magnesium
- sulfate
- Sample 9: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.25 g anhydrous magnesium sulfate, 10 g DAP
- Sample 10: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.25 magnesium sulfate heptahydrate, 10 g DAP
- Sample 11: 10 g urea treated with 0.04 wt.-% U1 active ingredient 0.25 g calcium sulfate dehydrate, 10 g DAP
- Sample 12: 10 g urea treated with 0.04 wt.-% U1 active ingredient 0.25 g anhydrous calcium chloride, 10 g DAP
- The closed jar was then stored at room temperature in a dark place. After 18 days, the urea granules were removed from the jar and tested with the Dräger test. As shown in Table 5, magnesium sulfate on its own does not inhibit the urease enzyme. Magnesium sulfate heptahydrate does prevent the degradation of U1 as effectively as anhydrous magnesium sulfate, showing that the desiccant properties of magnesium sulfate do not play a role in the prevention of U1 degradation. Also other cation providing salts, like calcium sulfate and calcium chloride are effective in preventing the degradation of U1.
-
TABLE 5 (part 1) Ammonia emission (ppm) Time 1 2 8 (days) a b a b a b 0 0 0 0 0 0 0 3 >1500 >1500 20 20 >1500 >1500 4 25 25 5 50 50 6 75 75 7 125 125 8 200 200 9 300 300 10 400 350 (part 2) Ammonia emission (ppm) Time 9 10 11 12 (days) a b a b a b a b 0 0 0 0 0 0 0 0 0 3 25 20 20 20 25 25 20 15 4 50 30 45 35 50 60 25 20 5 100 50 60 60 150 150 50 50 6 150 100 100 125 300 300 100 75 7 300 300 200 275 500 500 200 125 8 450 300 300 475 800 800 300 275 9 525 350 475 525 1100 1100 450 325 10 700 475 525 800 1400 1300 525 425 - 10 g U1 treated urea and different amounts of magnesium sulfate were added to a jar and mixed by shaking the jar. Afterwards, 10 g DAP was added and mixed by shaking the jar. The closed jar was then stored at room temperature in a dark place. After 5 days, the urea granules were removed from the jar and tested with the Dräger test. The following samples were tested:
-
- Sample 1: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.5 g anhydrous magnesium sulfate, 10 g DAP
- Sample 2: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.25 g anhydrous magnesium sulfate, 10 g DAP
- Sample 3: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.18 g anhydrous magnesium sulfate, 10 g DAP
- Sample 4: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.11 g anhydrous magnesium sulfate, 10 g DAP
- Sample 5: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.05 g anhydrous magnesium sulfate, 10 g DAP
- As can be seen in Table 6, after 5 days storage of the NP mixture as low as 0.25 wt.-% MgSO4 is effective to avoid U1 degradation.
-
TABLE 6 Emission with various concentrations of MgSO4 Time Ammonia emission (ppm) (Days) 1a 1b 2a 2b 3a 3b 4a 4b 5a 5b 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 2 10 15 15 10 15 20 15 15 20 20 3 20 25 30 20 25 30 30 25 30 40 4 30 50 40 40 50 50 50 50 80 90 5 50 75 60 60 90 75 90 90 150 150 6 100 150 125 125 150 125 175 175 250 275 7 200 250 225 250 225 225 275 275 400 400 8 300 350 300 350 350 300 400 350 550 550 9 425 500 425 500 475 425 500 500 800 800 10 680 780 580 780 650 650 800 780 1000 1080 - 10 g urea treated with 0.04 wt.-% U1 active ingredient and 0.25 g magnesium sulfate were added to a jar and mixed by shaking the jar. Afterwards, 10 g DAP was added and mixed by shaking the jar. The closed jar was then stored at room temperature in a dark place. After 5 months the urea granules were removed from the jar and tested with the Dräger test. As can be seen in Table 7, 1.25 wt.-% magnesium sulfate can prevent degradation of U1 in mixtures containing DAP for up to 5 months.
-
- Sample 1: urea
- Sample 2: urea treated with 0.04 wt.-% U1 active ingredient
- Sample 3: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 10 g DAP
- Sample 4: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.25 g anhydrous magnesium sulfate, 10 g DAP
-
TABLE 7 Emission after storage of 5 months with 1.25 wt.-% MgSO4 Time Ammonia emission (ppm) (Days) 1a 1b 2a 2b 3a 3b 4a 4b 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 2 50 80 0 0 70 30 0 0 3 1000 900 0 0 900 800 0 0 4 >1500 >1500 5 10 >1500 >1500 20 20 5 10 20 30 20 6 40 20 50 50 7 50 40 100 100 8 60 50 120 150 9 80 70 200 200 10 150 100 300 300 11 220 180 450 400 12 300 220 600 600 13 380 400 780 780 - Urea was treated with different NBPT based urease inhibitors (0.04 wt.-% active ingredient on urea).
- 10 g of the treated urea and 0.5 g magnesium sulfate were added to a jar and mixed by shaking the jar. Afterwards, 10 g DAP was added and mixed by shaking the jar. The closed jar was then stored at room temperature in a dark place. After 3 weeks the urea granules were removed from the jar and tested with the Dräger test. The following samples were tested:
-
- Sample 1: 10 g urea treated with 0.04 wt.-% U1 active ingredient
- Sample 2: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 10 g DAP
- Sample 3: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.5 g anhydrous, magnesium
- sulfate, 10 g DAP
- Sample 4: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.5 g anhydrous, calcium chloride, 10 g DAP
- Sample 5: 10 g urea treated with 0.04 wt.-% Agrotain Advance active ingredient
- Sample 6: 10 g urea treated with 0.04 wt.-% Agrotain Advance active ingredient, 10 g DAP
- Sample 7: 10 g urea treated with 0.04 wt.-% Agrotain Advance active ingredient, 0.5 g anhydrous magnesium sulfate, 10 g DAP
- Sample 8: 10 g urea treated with 0.04 wt.-% Agrotain Advance active ingredient 0.5 g anhydrous calcium chloride, 10 g DAP
- Sample 9: 10 g urea treated with 0.04 wt.-% Agrotain Ultra active ingredient
- Sample 10: 10 g urea treated with 0.04 wt.-% Agrotain Ultra active ingredient, 10 g DAP
- Sample 11: 10 g urea treated with 0.04 wt.-% Agrotain Ultra active ingredient, 0.5 g anhydrous magnesium sulfate, 10 g DAP
- Sample 12: 10 g urea treated with 0.04 wt.-% Agrotain Ultra active ingredient, 0.5 g anhydrous calcium chloride, 10 g DAP
- As can be seen in Table 8 a, b, and c for all of the tested products active ingredient degradation takes place in the presence of DAP resulting in a significantly reduced efficacy. Addition of MgSO4 or CaCl2 eliminates the influence of DAP on the performance of the tested urease inhibitors in urea/DAP blends.
-
TABLE 8a Emission with U1 Time Ammonia emission (ppm) (Days) 1a 1b 2a 2b 3a 3b 4a 4b 0 0 0 0 0 0 0 0 0 1 0 0 10 10 0 0 0 0 2 10 10 45 30 5 5 5 5 3 20 20 150 100 20 20 20 20 4 30 30 400 400 35 35 35 35 5 50 50 800 800 50 50 50 50 6 100 90 1350 1250 100 100 75 60 7 200 120 >1500 >1500 120 180 100 100 8 250 200 200 250 200 150 9 300 300 300 300 300 200 10 400 400 300 400 350 300 11 500 500 450 500 500 400 -
TABLE 8b Emission with Agrotain Advance Time Ammonia emission (ppm) (Days) 5a 5b 6a 6b 7a 7b 8a 8b 0 0 0 0 0 0 0 0 0 1 0 0 10 10 0 20 0 0 2 5 5 50 40 5 25 5 5 3 20 20 300 200 20 50 20 20 4 35 35 1000 800 35 100 35 35 5 50 50 >1500 >1500 50 100 50 50 6 60 100 100 200 75 75 7 120 180 180 300 120 120 8 200 250 200 350 200 200 9 300 300 300 450 300 280 10 350 400 400 500 350 350 11 500 500 500 700 500 500 -
TABLE 8c Emission with Agrotain Ultra Time Ammonia emission (ppm) (Days) 9a 9b 10a 10b 11a 11b 12a 12b 0 0 0 0 0 0 0 0 0 1 0 0 10 10 0 0 0 0 2 10 10 25 40 10 10 5 10 3 20 20 300 400 20 20 20 20 4 35 35 1300 1500 35 35 35 35 5 50 50 >1500 >1500 50 50 50 50 6 75 60 100 100 100 100 7 150 120 180 180 180 180 8 200 200 250 200 250 250 9 350 300 350 350 350 350 10 500 350 500 500 500 500 11 650 500 600 600 600 600 - A 16-8-22 wetblend fertilizer was treated with a solution of CaCl2 dissolved in DMSO. For the preparation of the CaCl2 solution, 8 g CaCl2 was dissolved in 100 g DMSO. 50 grams of fertilizer was treated with 8.4 grams of CaCl2 solution. The fertilizer was allowed to dry for 2 days at room temperature. Afterwards the fertilizer was treated with U1 to obtain a U1 active ingredient concentration on the fertilizer of 0.04 wt.-%. After 1 month storage in a closed jar at room temperature in a dark place, the fertilizer was tested with the Dräger test. The following samples were tested:
-
- Sample 1: 16-8-22 fertilizer treated with U1 active ingredient
- Sample 2: 16-8-22 fertilizer treated with CaCl2 solution
- Sample 3: 16-8-22 fertilizer treated with CaCl2 solution and U1 active ingredient
- As can be seen in Table 9, CaCl2 is able to prevent the degradation of U1 active ingredient on wetblend fertilizers.
-
TABLE 9 Emission of a NPK wetblend fertilizer treated with a CaCl2 solution Time Ammonia emission (ppm) (Days) 1a 1b 2a 2b 3a 3b 0 0 0 0 0 0 0 1 10 20 2 15 0 0 2 35 50 20 30 20 20 3 100 50 70 150 25 25 4 300 200 450 650 50 50 5 750 550 1500 >1500 75 75 6 1500 1500 >1500 100 100 7 >1500 >1500 200 200 8 350 350 10 650 650 11 900 900 12 1350 1500 13 >1500 >1500 14 - 10 gram U1 treated urea and 0.5 gram salt were added to a jar and mixed by shaking the jar. Afterwards, 10 gram DAP was added and mixed in by shaking the jar.
-
- Sample 10.1: urea
- Sample 10.2: urea treated with 0.04 wt.-% U1 active ingredient
- Sample 10.3: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 10 g DAP
- Sample 10.4: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.5 g Al2(SO4)3, 10 g DAP
- Sample 10.5: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.5 g FeSO4, 10 g DAP
- Sample 10.6: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.5 g ZnCl2, 10 g DAP
- Sample 10.7: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.5 g ZnSO4, 10 g DAP
- Sample 10.8: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.5 g CuSO4, 10 g DAP
- Sample 10.9: 10 g urea treated with 0.04 wt.-% U1 active ingredient, 0.5 g Ca(NO3)2, 10 g DAP
- The closed jar was then stored at room temperature in a dark place. After 14 days, the urea granules were removed from the jar and tested with the Dräger test. As shown in Table 10a and Table 10b, all tested salts reduce the effect of DAP on the degradation of U1 in fertilizer mixtures containing DAP.
-
TABLE 10a Ammonia emission (ppm) Time Sample Sample Sample Sample Sample (Days) 10.1 10.2 10.3 10.4 10.5 0 0 0 0 0 0 1 5 0 0 0 0 2 510 0 20 0 10 3 >1500 20 100 20 20 4 30 400 50 50 5 40 650 100 100 6 50 1150 250 200 7 75 >1500 400 300 8 120 600 550 10 200 825 800 -
TABLE 10b Ammonia emission (ppm) Time Sample Sample Sample Sample (Days) 10.6 10.7 10.8 10.9 0 0 0 0 0 1 0 0 0 0 2 10 10 0 0 3 25 30 50 20 4 50 50 15 50 5 60 80 30 60 6 100 120 50 120 7 200 200 70 270 8 400 350 100 450 10 550 500 200 600 - Particularly preferred embodiments (Embodiments) of the invention are described below:
- Use of a cation source (1) comprising a cation Cm+, wherein
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl;
in a composition A comprising - (i) a (thio)phosphoric acid triamide (2) according to general formula (I)
-
- wherein
- X1 is O or S;
- R1 is C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl;
- R2 is H, C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)akylaminocarbonyl; or
- R1 and R2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of N, O, and S; and
- R3, R4, R5, and R6 are independently of each other selected from the group consisting of H and C1-C4-alkyl;
and
- (ii) a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer;
to prevent decomposition of the (thio)phosphoric acid triamide (2). - A method for preventing decomposition of a (thio)phosphoric acid triamide (2) according to general formula (I)
-
- wherein
- X1 is O or S;
- R1 is C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl;
- R2 is H, C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl; or
- R1 and R2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of N, O, and S; and
- R3, R4, R5, and R6 are independently of each other selected from the group consisting of H and C1-C4-alkyl;
in a composition A comprising
- (i) the (thio)phosphoric acid triamide (2);
and - (ii) a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer;
by adding a cation source (1) comprising a cation Cm+ to the composition A, wherein - Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl.
- A mixture M comprising
- (i) a cation source (1) comprising a cation Cm+, wherein
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl;
and
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl;
- (ii) a (thio)phosphoric acid triamide (2) according to general formula (I)
-
- wherein
- X1 is O or S;
- R1 is C1-C20-alkyl, C3-C2O-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl;
- R2 is H, C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl; or
- R1 and R2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of N, O, and S; and
- R3, R4, R5, and R6 are independently of each other selected from the group consisting of H and C1-C4-alkyl.
- The mixture M according to Embodiment 3, wherein the composition further comprises
- (iii) a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer.
- A granule G comprising a urea-containing fertilizer (3a) and/or a P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer, wherein the granule is coated with a cation source (1) comprising a cation Cm+, wherein
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl;
- The granule G according to Embodiment 5, wherein the granule is further treated with a (thio)phosphoric acid triamide (2) according to general formula (I)
-
- wherein
- X1 is O or S;
- R1 is C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl;
- R2 is H, C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl; or
- R1 and R2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of N, O, and S; and
- R3, R4, R5, and R6 are independently of each other selected from the group consisting of H and C1-C4-alkyl.
- A composition B comprising
- (i) a (thio)phosphoric acid triamide (2) according to general formula (I)
-
- wherein
- X1 is O or S;
- R1 is C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl;
- R2 is H, C1-C20-alkyl, C3-C20-cycloalkyl, C6-C20-aryl, C6-C20-aryl-C1-C4-alkyl, or C1-C6-(di)alkylaminocarbonyl; or
- R1 and R2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of N, O, and S; and
- R3, R4, R5, and R6 are independently of each other selected from the group consisting of H and C1-C4-alkyl;
- (ii) a fertilizer mixture (3) comprising a urea-containing fertilizer (3a) and an additional P-containing fertilizer (3b) which is preferably a NPK fertilizer, a NP fertilizer, a PK fertilizer, or a P fertilizer; and
- (iii) a cation source (1) comprising a cation Cm+, wherein
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl;
wherein the composition B is obtainable
by a process comprising the steps of
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, Ba2+, or a quaternary ammonium group comprising at least three groups selected from C1-C2-alkyl and C1-C2-hydroxyalkyl;
- (a1) treating granules comprising the urea-containing fertilizer (3a) and the (thio)phosphoric acid triamide (2) with the cation source (1);
- (b1) blending the treated granules of step (a1) with granules comprising the P-containing fertilizer (3b);
or by a process comprising the steps of - (a2) treating granules comprising the P-containing fertilizer (3b) with the cation source (1);
- (b2) blending the treated granules of step (a2) with granules comprising the urea-containing fertilizer (3a) and the (thio)phosphoric acid triamide (2);
or by a process comprising the steps of - (a3) blending granules comprising the urea-containing fertilizer (3a) and the (thio)phosphoric acid triamide (2) with granules comprising the P-containing fertilizer (3b); and
- (b3) treating the blend of step (a3) with the cation source (1);
or by a process comprising the steps of - (a4) treating granules comprising the fertilizer mixture (3) with the (thio)phosphoric acid triamide (2); and
- (b4) treating the treated granules of step (a4) with the cation source (1);
or by a process comprising the steps of - (a5) treating granules comprising the fertilizer mixture (3) with the cation source (1); and
- (b5) treating the treated granules of step (a5) with the (thio)phosphoric acid triamide (2);
or by a process comprising the steps of - (a6) providing granules comprising the fertilizer mixture (3); and
- (b6) treating the granules of step (a6) with a—solid or liquid—mixture comprising the (thio)phosphoric acid triamide (2) and the cation source (1);
or by a process comprising the steps of - (a7) providing granules comprising the fertilizer mixture (3) and the cation source (1); and
- (b7) treating the granules of step (a7) with the (thio)phosphoric acid triamide (2).
- The use according to Embodiment 1, the method according to Embodiment 2, the mixture M according to any one of Embodiments 3 or 4, or the composition B according to any one of Embodiments 5 or 6, wherein the cation source (1) is a salt, which comprises a cation Cm+, wherein
- Cm+ is Ca2+, Mg2+, Li+, Fe2+, Fe3+, Al3+, Ag+, Cu2+, Zn2+, Hg2+, Pb2+, or Ba2+.
- The use according to any one of Embodiments 1 or 8, the method according to any one of Embodiments 2 or 8, the mixture M according to any one of Embodiments 3, 4 or 8, the granule G according to any one of Embodiments 5, 6 or 8, or the composition B according to any one of Embodiments 7 or 8, wherein the cation source (1) is a salt, which further comprises an anion An−, wherein
- An− is F−, Cl−, Br−, I−, SO4 2−, NO3 −, or CH3CO2 −.
- The use according to any one of Embodiments 1, 8 or 9, the method according to any one of Embodiments 2, 8 or 9, the mixture M according to any one of Embodiments 3, 4, 8 or 9, the granule G according to any one of Embodiments 5, 6, 8 or 9, or the composition B according to any one of Embodiments 7, 8 or 9, wherein the cation source (1) is a salt, which has a solubility of at least 33 g/L in water at a temperature of from 15° C. to 25° C.
- The use according to any one of Embodiments 1, 8, 9 or 10, the method according to any one of Embodiments 2, 8, 9 or 10, the mixture M according to any one of Embodiments 3, 4, 8, 9 or 10, the granule G according to any one of Embodiments 5, 6, 8, 9 or 10, or the composition B according to any one of Embodiments 7, 8, 9 or 10, wherein the cation source (1) is a salt, which is selected from the group consisting of Al2(SO4)3, Fe(SO4), Fe2(SO4)3, ZnSO4, CuSO4, CaSO4, AlCl3, FeCl2, FeCl3, ZnCl2, CuCl2, Mg(NO3)2, Ca(NO3)2, CaCl2, and MgSO4, and is preferably CaCl2 or MgSO4.
- The use according to any one of Embodiments 1, 8, 9, 10 or 11, the method according to any one of Embodiments 2, 8, 9, 10 or 11, the mixture M according to any one of Embodiments 3, 4, 8, 9, 10 or 11, the granule G according to any one of Embodiments 5, 6, 8, 9, 10 or 11, or the composition B according to any one of Embodiments 7, 8, 9, 10 or 11, wherein the (thio)phosphoric acid triamide (2) is N-n-butylthiophosphoric acid triamide (NBPT), N-n-propylthiophosphoric acid triamide (NPPT), or a combination thereof.
- The use according to any one of Embodiments 1, 8, 9, 10, 11 or 12, the method according to any one of Embodiments 2, 8, 9, 10, 11 or 12, the mixture M according to any one of Embodiments 4, 8, 9, 10, 11 or 12, the granule G according to any one of Embodiments 5, 6, 8, 9, 10, 11 or 12, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11 or 12, wherein the P-containing fertilizer (3b) causes a decomposition of the (thio)phosphoric acid triamide (2) of at least 10 wt.-% based on the total amount of the (thio)phosphoric acid triamide within 15 days at a temperature of from 20° C. to 25° C., if no cation source (1) is present.
- The use according to any one of Embodiments 1, 8, 9, 10, 11, 12 or 13, the method according to any one of Embodiments 2, 8, 9, 10, 11, 12 or 13, the mixture M according to any one of Embodiments 4, 8, 9, 10, 11, 12 or 13, the granule G according to any one of Embodiments 5, 6, 8, 9, 10, 11, 12 or 13, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11, 12 or 13, wherein the fertilizer (3a) is urea and/or the P-containing fertilizer (3b) is selected from the group consisting monoammonium phosphate (MAP), diammonium phosphate (DAP), calcium phosphate, super phosphate, double super phosphate, triple super phosphate (TSP), phosphate rock, ammonium polyphosphate (APP), and combinations thereof.
- The use according to any one of Embodiments 1, 8, 9, 10, 11, 12, 13 or 14, the method according to any one of Embodiments 2, 8, 9, 10, 11, 12, 13 or 14, the mixture M according to any one of Embodiments 3, 4, 8, 9, 10, 11, 12, 13 or 14, the granule G according to any one of Embodiments 6, 8, 9, 10, 11, 12, 13 or 14, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11, 12, 13 or 14, wherein the (thio)phosphoric acid triamide (2) is provided in combination with at least one amine (4).
- The use according to any one of Embodiments 1, 8, 9, 10, 11, 12, 13, 14 or 15, the method according to any one of Embodiments 2, 8, 9, 10, 11, 12, 13, 14 or 15, the mixture M according to any one of Embodiments 3, 4, 8, 9, 10, 11, 12, 13, 14 or 15, the granule G according to any one of Embodiments 6, 8, 9, 10, 11, 12, 13, 14 or 15, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11, 12, 13, 14 or 15, wherein the thio)phosphoric acid triamide (2) is provided in combination with at least one amine (4) selected from the group consisting of
- (4a) a polymeric polyamine; and
- (4b) an amine containing not more than one amino group and at least three alkoxy or hydroxy-substituted C2 to C12 alkyl groups R21, wherein at least one of the groups R21 is different to the other groups R21; and
- (4c) an amine containing not more than one amino group and at least two alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R22, wherein at least one of the groups R22 bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom and wherein at least one of the groups R22 is different to the other group(s) R22; and
- (4d) an amine containing at least one saturated or unsaturated C8 to C40 alkyl group R23; and
- (4e) a saturated or unsaturated heterocyclic amine which contains at least one oxygen atom as ring atom and which does not contain a further alkoxy group; and
- (4f) an amine having a boiling point of more than 100° C., preferably more than 150° C., more preferably more than 200° C. at ambient pressure (1 bar), and
- (4g) a primary amine, and
- (4h) a secondary amine, and
- (4i) a tertiary amine,
- (4j) an amine containing not more than one amino group and at least two alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R22,
- (4k) an amine containing not more than one amino group and at least three alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R22,
- (4l) an amine containing not more than one amino group and at least three alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R41, wherein all groups R41 within said amine are identical, and
- (4m) an amine containing not more than one amino group and at least two alkoxy- or hydroxy-substituted C2 to C12 alkyl groups R42, wherein at least one of the groups R42 bears the alkoxy or hydroxy substituent at a secondary or tertiary carbon atom and wherein all groups R42 with said amine are identical, and
- (4n) an amine selected from the group consisting of methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, N,N′,N″-tris(dimethylaminopropyl)hexahydrotriazine, and 2,2′-dimorpholinyldiethyl ether, and
- (4o) an amine selected from the group consisting of (L10), (L11), (L12), (L13), (L14), (L15), (L16), (L17), (L18), (L19), (L20), (L21), (L22), (L23), (L24) and (L29) as disclosed in the PCT application PCT/IB2015/059864.
- The use according to any one of Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the method according to any one of Embodiments 2, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the mixture M according to any one of Embodiments 3, 4, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the granule G according to any one of Embodiments 5, 6, 8, 9, 10, 11, 12, 13, 14, 15 or 16, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, wherein the cation source (1) is used in an amount of at least 0.25 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 0.5 wt.-% based on the total weight of the P-containing fertilizer (3b).
- The use according to any one of Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the method according to any one of Embodiments 2, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the mixture M according to any one of Embodiments 3, 4, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the granule G according to any one of Embodiments 5, 6, 8, 9, 10, 11, 12, 13, 14, 15 or 16, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, wherein the cation source (1) is used in an amount of at most 5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at most 10 wt.-% based on the total weight of the P-containing fertilizer (3b).
- The use according to any one of Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the method according to any one of Embodiments 2, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the mixture M according to any one of Embodiments 3, 4, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the granule G according to any one of Embodiments 5, 6, 8, 9, 10, 11, 12, 13, 14, 15 or 16, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, wherein the cation source (1) is used in an amount of at least 0.5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at least 1 wt.-% based on the total weight of the P-containing fertilizer (3b).
- The use according to any one of Embodiments 1, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the method according to any one of Embodiments 2, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the mixture M according to any one of Embodiments 3, 4, 8, 9, 10, 11, 12, 13, 14, 15 or 16, the granule G according to any one of Embodiments 5, 6, 8, 9, 10, 11, 12, 13, 14, 15 or 16, or the composition B according to any one of Embodiments 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, wherein the cation source (1) is used in an amount of at most 2.5 wt.-% based on the total weight of the fertilizer mixture (3), or in an amount of at most 5 wt.-% based on the total weight of the P-containing fertilizer (3b).
Claims (21)
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PCT/IB2017/051675 WO2017168288A1 (en) | 2016-04-01 | 2017-03-23 | Use of a cation source to prevent decomposition of (thio)phosphoric acid triamide urease inhibitors when a phosphorus-containing fertilizer is present |
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