EP4247167A1 - Composition comprising dmpp and phosphonate - Google Patents
Composition comprising dmpp and phosphonateInfo
- Publication number
- EP4247167A1 EP4247167A1 EP21810037.8A EP21810037A EP4247167A1 EP 4247167 A1 EP4247167 A1 EP 4247167A1 EP 21810037 A EP21810037 A EP 21810037A EP 4247167 A1 EP4247167 A1 EP 4247167A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- composition according
- still
- agriculturally acceptable
- composition
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 249
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title description 2
- 150000003839 salts Chemical class 0.000 claims abstract description 152
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 75
- LXKCHCXZBPLTAE-UHFFFAOYSA-N 3,4-dimethyl-1H-pyrazole phosphate Chemical compound OP(O)(O)=O.CC1=CNN=C1C LXKCHCXZBPLTAE-UHFFFAOYSA-N 0.000 claims abstract description 64
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 46
- 150000002334 glycols Chemical class 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 32
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 75
- 239000003337 fertilizer Substances 0.000 claims description 52
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 51
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 36
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 31
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 30
- 239000011976 maleic acid Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- -1 nonadecylic ac-id Chemical compound 0.000 claims description 26
- 235000011054 acetic acid Nutrition 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 239000003112 inhibitor Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 23
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 21
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 20
- 229960004585 etidronic acid Drugs 0.000 claims description 20
- 239000000654 additive Substances 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 10
- 239000002689 soil Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 235000005985 organic acids Nutrition 0.000 claims description 6
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- 229960004889 salicylic acid Drugs 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000700 radioactive tracer Substances 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 claims description 4
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229940090496 Urease inhibitor Drugs 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002601 urease inhibitor Substances 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- MPBVHIBUJCELCL-UHFFFAOYSA-N Ibandronate Chemical compound CCCCCN(C)CCC(O)(P(O)(O)=O)P(O)(O)=O MPBVHIBUJCELCL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- TXXHDPDFNKHHGW-CCAGOZQPSA-N Muconic acid Natural products OC(=O)\C=C/C=C\C(O)=O TXXHDPDFNKHHGW-CCAGOZQPSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 239000005643 Pelargonic acid Substances 0.000 claims description 2
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 claims description 2
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 claims description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 2
- IIDJRNMFWXDHID-UHFFFAOYSA-N Risedronic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(O)CC1=CC=CN=C1 IIDJRNMFWXDHID-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- DKJJVAGXPKPDRL-UHFFFAOYSA-N Tiludronic acid Chemical compound OP(O)(=O)C(P(O)(O)=O)SC1=CC=C(Cl)C=C1 DKJJVAGXPKPDRL-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229960004365 benzoic acid Drugs 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- 229940018557 citraconic acid Drugs 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229960005236 ibandronic acid Drugs 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229960002446 octanoic acid Drugs 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- WRUUGTRCQOWXEG-UHFFFAOYSA-N pamidronate Chemical compound NCCC(O)(P(O)(O)=O)P(O)(O)=O WRUUGTRCQOWXEG-UHFFFAOYSA-N 0.000 claims description 2
- 229960003978 pamidronic acid Drugs 0.000 claims description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 229960000759 risedronic acid Drugs 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
- VUYXVWGKCKTUMF-UHFFFAOYSA-N tetratriacontaethylene glycol monomethyl ether Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO VUYXVWGKCKTUMF-UHFFFAOYSA-N 0.000 claims description 2
- 229960005324 tiludronic acid Drugs 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- 229960004276 zoledronic acid Drugs 0.000 claims description 2
- XRASPMIURGNCCH-UHFFFAOYSA-N zoledronic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(O)CN1C=CN=C1 XRASPMIURGNCCH-UHFFFAOYSA-N 0.000 claims description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 abstract description 51
- 238000002425 crystallisation Methods 0.000 abstract description 17
- 230000008025 crystallization Effects 0.000 abstract description 17
- 150000003217 pyrazoles Chemical class 0.000 abstract description 16
- VQTVFIMEENGCJA-UHFFFAOYSA-N 3,4-dimethyl-1H-pyrazole Chemical compound CC=1C=NNC=1C VQTVFIMEENGCJA-UHFFFAOYSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003905 agrochemical Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 150000003009 phosphonic acids Chemical class 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 3
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 3
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 239000007793 ph indicator Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- HEPPIYNOUFWEPP-UHFFFAOYSA-N n-diaminophosphinothioylbutan-1-amine Chemical compound CCCCNP(N)(N)=S HEPPIYNOUFWEPP-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- HFVMEOPYDLEHBR-UHFFFAOYSA-N (2-fluorophenyl)-phenylmethanol Chemical compound C=1C=CC=C(F)C=1C(O)C1=CC=CC=C1 HFVMEOPYDLEHBR-UHFFFAOYSA-N 0.000 description 1
- OBENDWOJIFFDLZ-UHFFFAOYSA-N (3,5-dimethylpyrazol-1-yl)methanol Chemical compound CC=1C=C(C)N(CO)N=1 OBENDWOJIFFDLZ-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- DXFBKDSQMUFYLD-UHFFFAOYSA-N 2-pyrazol-1-ylethanol Chemical compound OCCN1C=CC=N1 DXFBKDSQMUFYLD-UHFFFAOYSA-N 0.000 description 1
- SDTLLLOWRQPZBF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole;phosphoric acid Chemical class OP(O)(O)=O.CC=1C=C(C)NN=1 SDTLLLOWRQPZBF-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- LCDKUXJKMAFCTI-UHFFFAOYSA-N 4-chloro-5-methyl-1h-pyrazole Chemical compound CC=1NN=CC=1Cl LCDKUXJKMAFCTI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000203069 Archaea Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001282153 Scopelogadus mizolepis Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000001651 autotrophic effect Effects 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- RIKMMFOAQPJVMX-UHFFFAOYSA-N fomepizole Chemical compound CC=1C=NNC=1 RIKMMFOAQPJVMX-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 235000021073 macronutrients Nutrition 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- DCUJJWWUNKIJPH-UHFFFAOYSA-N nitrapyrin Chemical compound ClC1=CC=CC(C(Cl)(Cl)Cl)=N1 DCUJJWWUNKIJPH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 244000000000 soil microbiome Species 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
-
- 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
- C05G5/20—Liquid fertilisers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
Definitions
- composition comprising DMPP and phosphonate
- the invention relates to a composition
- a composition comprising (i) a specific pyrazole or an agriculturally acceptable salt thereof; (ii) a phosphonic acid or an agriculturally acceptable salt thereof; (iii) optionally, one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof; and (iv) optionally, one or more glycols.
- the compositions according to the invention provide improved solubility of salts of pyrazoles such as 3,4 DMPP in aqueous solution. The solutions are stabilized against crystallization by lowering the crystallization point.
- Nitrification is an aerobic process performed by small groups of autotrophic bacteria and archaea. It is an important step in the nitrogen cycle in soil, wherein ammonia is biologically oxidized to nitrite, followed by the oxidation of the nitrite to nitrate. Nitrification of nitrogen containing fertilizers reduces their efficiency, as the contained nitrogen is oxidized and no longer available for take up by crops. Therefore, nitrogen containing fertilizers commonly comprise nitrification inhibitors to reduce nitrification, when the fertilizer is applied to the soil.
- Negative side effects of nitrogen-containing fertilizers such as the production of nitrate ions to be washed out into the subterranean water and/or the production of nitrous fumes, in particular N Z O which is/are further identified to enhance the climate change, are of growing public concern. Both effects are based on metabolic activities of soil bacteria, which - in several steps - turn urea and other nitrogencontaining fertilizers into N 2 O and/or nitrate ions.
- nitrification inhibitors The key enzymes involved in nitrification can effectively be inhibited by nitrification inhibitors.
- the enzymes involved in this step can be inhibited by known nitrification inhibitors such as pyrazole derivatives. 3,4- dimethylpyrazole (3,4 DMP) and its phosphate salt 3,4-dimethylpyrazole-phosphate (3,4 DMPP) are the most widely discussed and used ones.
- pyrazole derivatives 3,4- dimethylpyrazole (3,4 DMP) and its phosphate salt 3,4-dimethylpyrazole-phosphate (3,4 DMPP) are the most widely discussed and used ones.
- Commercially available fertilizer additives have relatively low concentrations of the active substance and suffer from low stability, especially at lower temperatures. If a nitrification inhibitor
- RU 2248329 relates to a method for treatment of industrial sewage or water-return systems containing ammonium nitrogen and acid-resistant form of bacteria (microorganisms) causing acid microbiological corrosion.
- RU 2248329 relates to monomethylpyrazole having a molecular weight of 82.1 g/mol but not dimethylpyrazole, let alone dimethylpyrazole phosphates.
- US 2020 0223764 discloses a process for preparing 2-(N-3,4-dimethylpyrazole)succinic acid by chemical reaction of 3,4-dimethylpyrazole with maleic acid and/or maleic acid anhydride in the absence of organic solvents or diluents at pH values greater than 7, and subsequent crystallization from the reaction product obtained in the absence of organic solvents or diluents.
- US 2020 0288712 discloses mixtures including as active components at least one specific nitrification inhibitor (compound I) and at least one urease inhibitor (compound II). Also described are a method for improving the nitrification-inhibiting effect, or for increasing the health of a plant using mixtures of at least one compound I and at least one compound II and a method of using the mixtures comprising compounds I and compounds II for increasing the health of a plant. Also described are agrochemical compositions including these mixtures. Also described is plant propagation material including these mixtures or these agrochemical compositions.
- US 2020 0165173 relates to a process for preparing a formulation F for reducing nitrification.
- the document also relates to a formulation F obtainable by said process.
- the document relates to a process of preparing a fertilizer-nitrification inhibitor mixture, and to a fertilizer-nitrification inhibitor mixture obtainable by this process.
- the document relates to a method of fertilizing agricultural soil.
- US 2020 0102255 discloses a method for fertilizing agricultural soil by applying at least one fertilizer N to the soil, wherein the at least one fertilizer N is applied in combination with a formulation F.
- the formulation F comprises at least one nitrification inhibitor I and at least one organic solvent S, and the at least one solvent S is selected from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, diglyme, fatty acid dialkylamides, benzyl alcohol, butyrolactone, propylene carbonate, ethyl hexyl lactate, 2-butoxy ethanol, dimethylsulfoxide, or mixtures thereof.
- the formulation F is essentially free from 3,4-dimethylpyrazolphosphate.
- US 2019 0048260 relates to a nitrogen stabilizing composition.
- the composition includes 22 to 26% w/w N-(n -butyl) thiophosphoric triamide (NBPT), 4 to 8% w/w of 3,4-dimethyl pyrazole phosphate (3,4 DMPP) and/or nitrapyrin, a solvent including N-methyl -2 -pyrrolidone (NMP) and propylene glycol, 0.1 to 5% w/w vegetable oil, and 0.1 to 5% w/w lecithin.
- NMP N-methyl -2 -pyrrolidone
- US 2018 0016199 discloses pyrazole derivatives as nitrification inhibitors.
- US 2017 0362140 relates to a composition comprises a nonaqeuous, liquid carrier, an inhibitor compound, and a colorant composition comprising an azo colorant.
- a method for making the composition is also provided.
- a method for making a fertilizer composition using the disclosed composition is also provided.
- US 2016 0176769 discloses particulate compositions of reverted superphosphate substantially free of free acid containing at least one nitrification inhibitor and their methods of preparation and use .
- US 2016 0168042 relates to a method for producing a liquid compound and to the compound used to improve the results of the application of ammoniacal nitrogenated fertilizers to crops requiring same and the ammonium present in the ground, said compound being a mixture consisting mainly of 3,5 DMPP as a nitrification inhibitor, phosphorus, the main function of which is to participate in all of the processes and energetic reactions of the crop, and amino acids winch are synthesized by the plants in enzymatic reactions generated by means of the animation, where absorbed ammonium salts and organic acids are produced.
- 3,5 DMPP is otherwise known as a plasticizer for polymer compositions.
- US2012157317 discloses a composition in concentrated form (“the concentrate”) for dilution with water in the preparation of an agricultural composition for application to crops, soil or animals, comprising a carbohydrate -based pH modifying agent and a pH indicator and a process for preparing the agricultural composition by mixing the concentrate with water, and adding the agricultural chemical to the composition, if it is not already present in the concentrate.
- the agricultural composition comprises an agricultural chemical whose agricultural activity varies with the pH of the water.
- the proportions of the pH indicator and the pH modifying agent in the concentrate are selected so that when the concentrate is diluted with an appropriate amount of water, the pH indicator indicates visually by coloration of the composition, whether or not the pH of the water is suitable for acceptable agricultural activity of the chemical.
- WO 2019 012383 relates to mixtures comprising as active components a first nitrification inhibitor (compound I) and a second nitrification inhibitor (compound II); to a method for improving the nitrification-inhibiting effect, or for increasing the health of a plant using mixtures of one compound I and one compound II; to the use of mixtures comprising compounds I and compounds II for increasing the health of a plant; to agrochemical compositions comprising these mixtures; and to plant propagation material, comprising these mixtures or these agrochemical compositions.
- WO 2016 097318 discloses novel nitrification inhibitors.
- compositions of nitrification inhibitors of the prior art are not satisfactory in every respect. There is a demand for improved compositions of nitrification inhibitors with a higher concentration of the active substance and longer stability.
- compositions of nitrification inhibitors having advantages compared to the compositions of the prior art.
- the compositions should have higher weight contents of the active substance and improved stability even at low temperatures.
- aqueous solutions of salts of pyrazoles such as 3,4 DMPP comprising a phosphonic acid or salt thereof and optionally one or more carboxylic acids and/or one or more glycols can be used as nitrification inhibitors.
- a first aspect of the invention relates to a composition
- a composition comprising
- R1 means -H, or -Ci-6 -alkyl, or -C i-s-alkyl-OH; preferably -H;
- R2 means -H, -Ci-s -alkyl, -C i- ⁇ , -alkyl -OH. -NH2, -F, -Cl, or -Br; preferably -H; and
- R3 and R4 independently of one another mean -H, -Ci-6-alkyl, -C i-s-alkyl-OH, -NHz, -F, -Cl, or -Br; preferably -CH3; or an agriculturally acceptable salt thereof;
- a fertilizer is any material of natural or synthetic origin that is applied to soil or to plant tissues to supply one or more plant nutrients essential to the growth of plants .
- a fertilizer additive is a composition that can be advantageously added to (conventional) fertilizers in order to improve their properties. Typically, the fertilizer additive is no fertilizer as such.
- the composition according to the invention may contain various ingredients that are capable of forming salts with various acids or that are employed in form of acid addition salts.
- 3,4 DMPP may be regarded as the acid addition salt of 3,4-dimethylpyrazole (3,4 DMP) with phosphoric acid, whereas at a stochiometric ratio of 1:1 the phosphoric acid is present as dihydrogen phosphate anion and the 3,4 DMP is protonated thereby forming a pyrazolium cation.
- the composition according to the invention may further contain various acids such as one or more phosphonic acids, one or more carboxylic acids, one or more inorganic aids, and the like.
- composition according to the invention is preferably aqueous and as carboxylic acid anhydrides tend to spontaneously hydrolyze in aqueous environment.
- carboxylic acid anhydrides tend to spontaneously hydrolyze in aqueous environment.
- all percentages and weights with regard to the one or more carboxylic acids, agriculturally acceptable salts of anhydrides thereof refer to the corresponding weight of the carboxylic acid anhydride, even if it actually employed in form of the (hydrolyzed) carboxylic acid or a salt thereof.
- maleic acid (diacid) and its agriculturally acceptable salts refer to maleic acid anhydride (anhydride cyclic), whereas all percentages and weights with regard to e.g. maleic acid and its agriculturally acceptable salts with regard to e.g. acetic acid (monoacid) and its agriculturally acceptable salts refer to acetic anhydride (anhydride dimeric).
- composition according to the invention is preferably aqueous and as mixtures of salts in aqueous solution readily undergo metathesis reaction. Unless expressly stated otherwise, when the composition according to the invention is aqueous, all percentages and weights refer to the corresponding weight of the non-salt forms, i.e. the free acids and the free pyrazole, i.e. the weight contribution of the salt component is not taken into account. When the composition according to the invention is nonaqueous, however, said percentages and weights refer to the salts as such.
- the composition according to the invention is aqueous, preferably an aqueous liquid selected from solutions, emulsions and suspensions, more preferably an aqueous solution.
- the composition according to the invention is a supersaturated solution of the pyra- zole or agriculturally acceptable salt thereof.
- the composition according to the invention is sprayable; preferably over a granulated fertilizer according to a predefined mass relation, while maintaining the granulated characteristics of the granulated fertilizer.
- the weight content of water is at least 10 w.-%, relative to the total weight of composition; preferably at least 16 wt.-%, more preferably at least 22 wt.-%, still more preferably at least 28 wt.-%, yet more preferably at least 33 wt.- %, even more preferably at least 38 wt.-%, most preferably at least 43 wt.-%, and in particular at least 48 wt.-%.
- the weight content of water is at most 90 w.-%, relative to the total weight of composition; preferably at most 85 wt.-%, more preferably at most 80 wt.-%, still more preferably at most 75 wt.-%, yet more preferably at most 70 wt.- %, even more preferably at most 65 wt.-%, most preferably at most 60 wt.-%, and in particular at most 55 wt.-%.
- the weight content of water is within the range of 50 ⁇ 40 wt.-%, relative to the total weight of composition; preferably 50 ⁇ 30 wt.-%, more preferably 40 ⁇ 20 wt.-%, still more preferably 35 ⁇ 30 wt.-%, yet more preferably 35 ⁇ 26 wt.-%, even more preferably 35 ⁇ 22 wt.-%, most preferably 35 ⁇ 18 wt-%, and in particular 35 ⁇ 14 wt.- 0 //o.
- composition according to the invention contains a pyrazole of general formula (A) wherein R1 means -H, or -Ci-e-alkyl, or -Ci-s -alkyl -OH; preferably -H;
- R2 means -H, -C , -alkyl. -C
- R3 and R4 independently of one another mean -H, -Ci-6-alkyl, -Ci-6-alkyl-OH, -NH2, -F, -Cl, or -Br; preferably -CH3; or an agriculturally acceptable salt thereof.
- composition according to the invention may contain one or more pyrazoles of general formula (A) or agriculturally acceptable salts thereof
- the composition according to the invention contains a single pyrazole of general formula (A) or an agriculturally acceptable salt thereof.
- the pyrazole is selected from the group consisting of pyrazole, 3,4-dimethylpyrazole, 3,5-dimethylpyrazole, 4-chloro-3-methylpyrazole, 5-chloro-l,3-dimethylpyrazole, 5-amino-l,3-dime- thylpyrazole, 3,5-dimethylpyrazole-l-methanol, l-allyl-3,5-dimethylpyrazole, 1 -(2 -hydroxyethyl) -pyrazole, l-methyl-lH-pyrazole-4-carboxaldehyde, l//-pyrazolc-3-carbaldchydc, I //-pyrazole -5 -carb aldehyde.
- the pyrazole is 3,4-dimethylpyrazole.
- the pyrazole is present in form of an agriculturally acceptable salt.
- the pyrazole is present a agriculturally acceptable acid addition salt with phosphoric acid, whereas the protonated pyrazole forms a cation and the anion is selected from dihydrogen phosphate, hydrogen phosphate and phosphate, preferably dihydrogen phosphate.
- the pyrazole or agriculturally acceptable salt thereof is a nitrification inhibitor or a urease inhibitor; preferably a nitrification inhibitor.
- the pyra- zole is present as 3,4-dimethylpyrazole phosphate (3,4 DMPP). 3,4 DMPP is commercially available.
- the pKb value of the pyrazole is at least at least 7.9; preferably at least 8.4, more preferably at least 8.9, still more preferably at least 9.4, yet more preferably at least 9.9, even more preferably at least 10.4, most preferably at least 10.9, and in particular at least 11.4.
- the pKb value of the pyrazole is at most 13.3; preferably at most 12.8, more preferably at most 12.3, still more preferably at most 11.8, yet more preferably at most 11.3, even more preferably at most 10.8, most preferably at most 10.3, and in particular at most 9.8.
- the pKb value of the pyrazole is within the range of 10.5 ⁇ 4.5; preferably 10.5 ⁇ 4.0, more preferably 10.5 ⁇ 3.5, still more preferably 10.5 ⁇ 3.0, yet more preferably 10.5 ⁇ 2.5, even more preferably 10.5 ⁇ 2.0, most preferably 10.5 ⁇ 1.5, and in particular 10.5 ⁇ 1.0.
- the weight content of the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP is at least 4.0 wt.-%, relative to the total weight of the composition; preferably at least 8.0 wt.-%, more preferably at least 10 wt.-%, still more preferably at least 14 wt.-%, yet more preferably at least 18 wt.- %, even more preferably at least 22 wt.-%, most preferably at least 26 wt.-%, and in particular at least 30 wt.-%.
- the weight content of the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP is at most 70 wt .-%, relative to the total weight of the composition; preferably at most 65 wt.-%, more preferably at most 60 wt.-%, still more preferably at most 55 wt.-%, yet more preferably at most 50 wt- %, even more preferably at most 45 wt.-%, most preferably at most 40 wt.-%, and in particular at most 35 wt.-%.
- the weight content of the pyrazole or agriculturally acceptable salt thereof is within the range of 24 ⁇ 20 wt.-%, relative to the total weight of the composition; preferably 24 ⁇ 18 wt.- %, more preferably 24 ⁇ 16 wt.-%, still more preferably 24 ⁇ 14 wt.-%, yet more preferably 24 ⁇ 12 wt.-%, even more preferably 24 ⁇ 10 wt.-%, most preferably 24 ⁇ 8.0 wt.-%, and in particular 24 ⁇ 6.0 wt.-%.
- the pyrazole or agriculturally acceptable salt thereof is soluble in water.
- the pyrazole or agriculturally acceptable salt thereof is soluble, freely soluble or very soluble in water (pure water at 23 °C), whereas 10 to 30 mL volume of water are needed in order to dissolve a soluble pyrazole or agriculturally acceptable salt thereof, 1 to 10 mL volume of water are needed in order to dissolve a freely soluble pyrazole or agriculturally acceptable salt thereof, and less than 1 mL volume of water are needed in order to dissolve a very soluble pyrazole or agriculturally acceptable salt thereof.
- composition according to the invention contains a phosphonic acid or an agriculturally acceptable salt thereof.
- composition according to the invention may contain one or more phosphonic acids or agriculturally acceptable salts thereof.
- the composition according to the invention contains a single phosphonic acid or an agriculturally acceptable salt thereof.
- the phosphonic acid has general formula (B) wherein
- R1 means -H, -OH, -NH 2 , or -Cl; preferably -OH;
- R2 means -H, -Ci-io-alkyl, -Ci-6-alkyl-NH 2 , -Ci-6-alkyl-N(Ci-6-alkyl)-Ci-io-alkyl, or -Cl; preferably -CH 3 ;
- the phosphonic acid is a bisphosphonic acid or an agriculturally acceptable salt thereof.
- the phosphonic acid or the agriculturally acceptable salt thereof improves the solubility of the pyrazole or agriculturally acceptable salt thereof in an aqueous solution, preferably relative to the same composition not containing the phosphonic acid or the agriculturally acceptable salt thereof.
- the phosphonic acid is selected from the group consisting of etidronic acid, tiludronic acid, pamidronic acid, aledronic acid, ibandronic acid, risedronic acid, and zoledronic acid or an agriculturally acceptable salt thereof.
- the phosphonic acid or the agriculturally acceptable salt thereof is etidronic acid
- Etidronic acid is commercially available, e.g. as active solution, e.g. 40 % of a 60% active solution (such as Cublen® KT600/with 60% active).
- the weight content of the phosphonic acid, preferably etidronic acid is at least 6.0 wt.-% relative to the total weight of the composition; preferably at least 8.0 wt.-%, more preferably at least 10 wt.-%, still more preferably at least 12 wt.-%, yet more preferably at least 14 wt.-%, even more preferably at least 16 wt.-%, most preferably at least 18 wt.-%, and in particular at least 20 wt.-%.
- the weight content of the phosphonic acid or agriculturally acceptable salt thereof, preferably etidronic acid is at most 90 wt.- % relative to the total weight of the composition; preferably at most 80 wt-%, more preferably at most 70 wt.-%, still more preferably at most 60 wt.-%, yet more preferably at most 50 wt.-%, even more preferably at most 40 wt.-%, most preferably at most 30 wt.-%, and in particular at most 22 wt.-%.
- the weight content of the phosphonic acid or agriculturally acceptable salt thereof, preferably etidronic acid is within the range of 25 ⁇ 23 wt.-%, relative to the total weight of the composition; preferably 20 ⁇ 18 wt.-%, more preferably 16 ⁇ 14 wt.-%, still more preferably 16 ⁇ 12 wt.-%, yet more preferably 16 ⁇ 10 wt.-%, even more preferably 16 ⁇ 8.0 wt.-%, most preferably 16 ⁇ 6.0 wt-%, and in particular 16 ⁇ 4.0 wt.-%.
- the relative weight ratio of the phosphonic acid or agriculturally acceptable salt thereof, preferably etidronic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP is at least 1: 10; preferably at least 1:9, more preferably at least 1:8, still more preferably at least 1:7, yet more preferably at least 1:6, even more preferably at least 1:5, most preferably at least 1:4, and in particular at least 1:3.
- the relative weight ratio of the phosphonic acid or agriculturally acceptable salt thereof, preferably etidronic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP is at most 7: 1; preferably at most 6: 1, more preferably at most 5:1, still more preferably at most 4:1, yet more preferably at most 3: 1, even more preferably at most 2: 1, most preferably at most 1 : 1, and in particular at most 1:2.
- the relative weight ratio of the phosphonic acid or agriculturally acceptable salt thereof, preferably etidronic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP is within the range of 1: 10 to 7: 1; preferably 1:9 to 6: 1, more preferably 1:8 to 5:1, still more preferably 1:7 to 4: 1, yet more preferably 1:6 to 3: 1, even more preferably 1:5 to 2: 1, most preferably 1:4 to 1: 1, and in particular 1:3 to 1:2.
- the composition according to the invention contains one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof. Unless expressly stated otherwise, all percentages and weights refer to the total content of all carboxylic acids that are contained in the composition.
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof protonate the pyrazole thereby forming an agriculturally acceptable salt thereof.
- anhydrides of carboxylic acids may first interact with water, thereby hydrolyze and then protonate the pyrazole.
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof improves the solubility of the pyrazole or agriculturally acceptable salt thereof in an aqueous solution, preferably relative to the same composition not containing the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof.
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of a diacid or an agriculturally acceptable salt or anhydride thereof.
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of an unsaturated acid or an agriculturally acceptable salt or anhydride thereof.
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of an unsaturated carboxylic diacid or an agriculturally acceptable salt or anhydride thereof.
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, ara- chidic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, muconic acid, maleic acid, fumaric acid, glutaconic acid, itaconic acid, citraconic acid, salicylic acid, benzoic acid, salicylic acid, phthalic acid, mixtures thereof, agriculturally acceptable salts
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of maleic acid, maleic acid anhydride and/or acetic acid.
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof compnse or consist of maleic acid and/or maleic acid anhydride.
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of two organic acids or agriculturally acceptable salts or anhydrides thereof; preferably (i) maleic acid and/or maleic acid anhydride and (ii) acetic acid.
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof independently of one another have a pKa value of at least 0.5; preferably at least 0.7, more preferably at least 0.9, still more preferably at least 1.1, yet more preferably at least 1.3, even more preferably at least 1.5, most preferably at least 1.7, and in particular at least 1.9.
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof independently of one another have a pKa value of at most 6.2; preferably at most 6.0, more preferably at most 5.8, still more preferably at most 5.6, yet more preferably at most 5.4, even more preferably at most 5.2, most preferably at most 5.0, and in particular at most 4.8.
- the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof independently of one another have a pKa value of within the range of 3.9 ⁇ 3.5; preferably 3.9 ⁇ 3.0, more preferably 3.9 ⁇ 2.5, still more preferably 3.9 ⁇ 2.0, yet more preferably 3.4 ⁇ 3.0, even more preferably 3.4 ⁇ 2.5, most preferably 3.4 ⁇ 2.0, and in particular 3.4 ⁇ 1.5.
- a carboxylic acid carries more than a single carboxylic acid functional group, preferably at least one of the carboxylic acid functional group has a pKa value as defined above.
- the total weight content of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid is at least 1.0 wt.-%, based upon the equivalent weight of the anhydride and relative to the total weight of the composition; preferably at least 3.0 wt.- %, more preferably at least 5.0 wt.-%, still more preferably at least 7.0 wt.-%, yet more preferably at least 9.0 wt.-%, even more preferably at least 11 wt.-%, most preferably at least 13 wt.-%, and in particular at least 15 wt.-%.
- the total weight content of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid is at most 50 wt.-%, based upon the equivalent weight of the anhydride and relative to the total weight of the composition; preferably at most 45 wt.- %, more preferably at most 40 wt.-%, still more preferably at most 35 wt.-%, yet more preferably at most 30 wt.-%, even more preferably at most 25 wt.-%, most preferably at most 20 wt-%, and in particular at most 16 wt.-%.
- the total weight content of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid is within the range of 12 ⁇ 10 wt.-%, based upon the equivalent weight of the anhydride and relative to the total weight of the composition; preferably 12 ⁇ 9.0 wt.-%, more preferably 12 ⁇ 8.0 wt.-%, still more preferably 12 ⁇ 7.0 wt.-%, yet more preferably 12 ⁇ 6.0 wt.-%, even more preferably 12 ⁇ 5.0 wt.-%, most preferably 12 ⁇ 4.0 wt.-%, and in particular 12 ⁇ 3.5 wt.-%.
- the relative weight ratio of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at least 1:9; preferably at least 1:8, more preferably at least 1:7, still more preferably at least 1:6, yet more preferably at least 1:5, even more preferably at least 1 :4, most preferably at least 1 :3, and in particular at least 1 :2, in each case based upon the equivalent weight of the anhydride.
- the relative weight ratio of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at most 8: 1; preferably at most 7: 1, more preferably at most 6: 1, still more preferably at most 5: 1, yet more preferably at most 4: 1, even more preferably at most 3: 1, most preferably at most 2: 1, and in particular at most 1: 1, in each case based upon the equivalent weight of the anhydride.
- the relative weight ratio of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP is within the range of 1:9 to 8: 1; preferably 1:8 to 7: 1, more preferably 1 :7 to 6: 1, still more preferably 1:6 to 5: 1, yet more preferably 1:5 to 4: 1, even more preferably 1:4 to 3:1, most preferably 1:3 to 2: 1, and in particular 1:2 to 1: 1, in each case based upon the equivalent weight of the anhydride.
- the molar ratio of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof to the pyrazole or agriculturally acceptable salt thereof is stoichiometric.
- the composition comprises (i) a first carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably maleic acid and/or maleic acid anhydride, and (ii) a second carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably acetic acid, wherein the relative weight ratio of (i) : (ii) is at least 1:9; preferably at least 1:8, more preferably at least 1:7, still more preferably at least 1 :6, yet more preferably at least 1:5, even more preferably at least 1:4, most preferably at least 1:3, and in particular at least 1:2, in each case based upon the equivalent weight of the anhydrides.
- the composition comprises (i) a first carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably maleic acid and/or maleic acid anhydride, and (ii) a second carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably acetic acid, wherein the relative weight ratio of (i) : (ii) is at most 8: 1; preferably at most 7: 1, more preferably at most 6: 1, still more preferably at most 5: 1, yet more preferably at most 4: 1, even more preferably at most 3 : 1, most preferably at most 2: 1, and in particular at most 1: 1, in each case based upon the equivalent weight of the anhydrides.
- the composition comprises (i) a first carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably maleic acid and/or maleic acid anhydride, and (ii) a second carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably acetic acid, wherein the relative weight ratio of (i) : (ii) is within the range of 1:9 to 8:1; preferably 1:8 to 7:1, more preferably 1:7 to 6: 1, still more preferably 1:6 to 5: 1, yet more preferably 1:5 to 4: 1, even more preferably 1:4 to 3: 1, most preferably 1:3 to 2: 1, and in particular 1 :2 to 1 : 1, in each case based upon the equivalent weight of the anhydrides.
- the composition according to the invention contains one or more glycols. Unless expressly stated otherwise, all percentages and weights refer to the total content of all glycols that are contained in the composition.
- the one or more glycols improve the solubility of the pyrazole or agriculturally acceptable salt thereof in an aqueous solution, preferably relative to the same composition not containing the one or more glycols.
- the one or more glycols facilitate the re-dissolution of the pyrazole or agriculturally acceptable salt thereof, preferably relative to the same composition not containing the one or more glycols.
- the one or more glycols comprises or consists of a single glycol or two glycols
- the one or more glycols comprises or consists of an alkyl glycol, a polyalkyl glycol ether, or a mixture thereof.
- the one or more glycols comprise or consist of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (PEG) 200, PEG 300, PEG 400, PEG 600, PEG 1000, PEG 1500, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol (PPG) 425, PPG 725, PPG 1000, butylene glycol, and mixtures thereof; preferably PEG 200, propylene glycol or a mixture thereof.
- the one or more glycols comprise or consist of an alkyl glycol and a polyalkyl glycol ether; preferably propylene glycol and PEG 200.
- the one or more glycols comprise or consist of
- an alkyl glycol preferably propylene glycol
- a polyalkyl glycol ether preferably PEG 200.
- the total weight content of the one or more glycols, preferably alkyl glycol and/or polyalkyl glycol ether is at least 1.0 wt.-%, relative to the total weight of the composition; preferably at least 2.0 wt.-%, more preferably at least 3.0 wt.-%, still more preferably at least 4.0 wt.-%, yet more preferably at least 6.0 wt.-%, even more preferably at least 8.0 wt.-%, most preferably at least 10 wt.-%, and in particular at least 12 wt.-%.
- the total weight content of the one or more glycols is at most 50 wt.-%, relative to the total weight of the composition; preferably at most 45 wt.-%, more preferably at most 40 wt.-%, still more preferably at most 35 wt.-%, yet more preferably at most 30 wt.-%, even more preferably at most 25 wt.-%, most preferably at most 20 wt.-%, and in particular at most 16 wt.-%.
- the total weight content of the one or more glycols is within the range of 12 ⁇ 22 wt.-%, relative to the total weight of the composition; preferably 12 ⁇ 18 wt.-%, more preferably 12 ⁇ 14 wt.-%, still more preferably 12 ⁇ 10 wt-%, yet more preferably 12 ⁇ 6.0 wt.-%, even more preferably 12 ⁇ 4.0 wt.-%, most preferably 12 ⁇ 2.0 wt.-%, and in particular 12 ⁇ 1.0 wt.-%.
- the relative weight ratio of the one or more glycols, preferably alkyl glycol and/or polyalkyl glycol ether, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at least 1: 11; preferably at least 1: 10, more preferably at least 1:9, still more preferably at least 1:8, yet more preferably at least 1:7, even more preferably at least 1:6, most preferably at least 1:5, and in particular at least 2:5.
- the relative weight ratio of the one or more glycols, preferably alkyl glycol and/or polyalkyl glycol ether, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at most 7: 1; preferably at most 6: 1, more preferably at most 5: 1, still more preferably at most 4: 1, yet more preferably at most 3: 1, even more preferably at most 2: 1, most preferably at most 1: 1, and in particular at most 2:3.
- the relative weight ratio of the one or more glycols, preferably alkyl glycol and/or polyalkyl glycol ether, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP is within the range of 1 : 11 to 7: 1 ; preferably at most 1 : 10 to 6: 1, more preferably at most 1 :9 to 5 : 1, still more preferably at most 1:8 to 4: 1, yet more preferably at most 1:7 to 3: 1, even more preferably at most 1:6 to 2: 1, most preferably at most 1:5 to 1: 1, and in particular at most 2:5 to 2:3.
- a polyalkylglycol ether preferably polyethylene glycol (PEG) 200
- an alkyl glycol preferably propylene glycol
- the one or more glycols comprise or consist of (i) a polyalkylglycol ether, preferably polyethylene glycol (PEG) 200, and (ii) an alkyl glycol, preferably propylene glycol, wherein the relative weight ratio of (i) : (ii) is at most 5: 1; preferably at most 4: 1, more preferably at most 3: 1, still more preferably at most 2: 1, yet more preferably at most 1: 1, even more preferably at most 1:2, most preferably at most 1:3, and in particular at most 1 :4.
- the one or more glycols comprise or consist of (i) a polyalkylglycol ether, preferably polyethylene glycol (PEG) 200, and (ii) an alkyl glycol, preferably propylene glycol, wherein the relative weight ratio of (i) : (ii) is within the range of 1 : 12 to 5: 1; preferably 1: 11 to 4: 1, more preferably 1: 10 to 3: 1, still more preferably 1:9 to 2: 1, yet more preferably l:8 to 1: 1, even more preferably l:7 to 1:2, most preferably 1:6 to 1:3, and in particular 1:5 to 1:4.
- a polyalkylglycol ether preferably polyethylene glycol (PEG) 200
- an alkyl glycol preferably propylene glycol
- the relative weight ratio of (i) : (ii) is within the range of 1 : 12 to 5: 1; preferably 1: 11 to 4: 1, more preferably 1: 10 to 3: 1, still more preferably 1
- the pH value of the composition is at least 0.4; preferably at least 0.6, more preferably at least 0.8, still more preferably at least 1 0, yet more preferably at least 1.2, even more preferably at least 1.4, most preferably at least 1.6, and in particular at least 1.8.
- the pH value of the composition is at most 5.0; preferably at most 4.6, more preferably at most 4.2, still more preferably at most 3.8, yet more preferably at most 3.4, even more preferably at most 3.0, most preferably at most 2.6, and in particular at most 2.2.
- the pH value of the composition is within the range of 5.0 ⁇ 4.0; preferably 4.0 ⁇ 3.0, more preferably 4.0 ⁇ 2.5, still more preferably 4.0 ⁇ 2.0, yet more preferably 2.0 ⁇ 1.5, even more preferably 2.0 ⁇ 1.0, most preferably 2.0 ⁇ 0.5, and in particular 2.0 ⁇ 0.2.
- the pyrazole or agriculturally acceptable salt thereof stays in solution and does not crystallize at a temperature of at most 20 °C; preferably at most 15 °C, more preferably at most 10 °C, still more preferably at most 8.0 °C, yet more preferably at most 6.0 °C, even more preferably at most 4.0 °C, most preferably at most 2.0 °C, and in particular at most 1.0 °C.
- the pyrazole or agriculturally acceptable salt thereof stays in solution and does not crystallize at a temperature of at least - 5.0 °C; preferably at least -4.0 °C, more preferably at least -3.0 °C, still more preferably at least -2.0 °C, yet more preferably at least -1.0 °C, even more preferably at least 0 °C, most preferably at least 1.0 °C, and in particular at least 2.0 °C.
- the pyrazole or agriculturally acceptable salt thereof stays in solution and does not crystallize at a temperature within the range of 1.5 ⁇ 7.0 °C; preferably 1 5 ⁇ 6.0 °C, more preferably 1.5 ⁇ 5 0 °C, still more preferably 1.5 ⁇ 4.0 °C, yet more preferably 1.5 ⁇ 3.0 °C, even more preferably 1.5 ⁇ 2.0 °C, most preferably 1.5 ⁇ 1.0 °C, and in particular 1.5 ⁇ 0.5 °C.
- the pyrazole or agriculturally acceptable salt thereof stays in solution and does not crystallize for at least 1 day; preferably at least 2 days, more preferably at least 3 days, still more preferably at least 4 days, yet more preferably at least 5 days, even more preferably at least 6 days, most preferably at least 7 days, and in particular at least 8 days.
- the composition according to the invention additionally comprises a tracer, preferably a dye.
- Another aspect of the invention relates to a process for preparing of a composition according to the invention as described above, the process comprising the steps of:
- Another aspect of the invention relates to a process for preparing of a fertilizer additive comprising a composition according to the invention as described above, the process comprising the process for preparing of a composition according to the invention as described above.
- Another aspect of the invention relates to a process for preparing of a fertilizer comprising a fertilizer additive, the process comprising the steps of
- step (c) applying the composition provided in step (a) to the fertilizer provided in step (b).
- Another aspect of the invention relates to a fertilizer additive comprising or consisting of the composition according to the invention as described above; preferably wherein the fertilizer additive is obtainable by the process for preparing of a fertilizer additive according to the invention as described above.
- Another aspect of the invention relates to a fertilizer comprising a fertilizer additive, wherein the fertilizer additive comprises or consists of the composition according to the invention as described above; preferably wherein the fertilizer is obtainable by the process for preparing of a fertilizer according to the invention as described above.
- Another aspect of the invention relates to the use of a composition according to the invention as described above as fertilizer additive.
- Another aspect of the invention relates to a method for reducing nitrification comprising the step of applying a fertilizer comprising a composition according to the invention as described above to soil or a plant.
- maleic acid anhydride as acidic component provided a significant decrease of the crystallization temperature and for some time a stable supersaturated solution was formed.
- maleic acid anhydride should readily hydrolyze to maleic acid.
- maleic acid was chosen as the best available organic acid for the protonation of the pyrazole.
- Example 5 [0137] Aqueous mixtures of 3,4 DMPP, maleic acid (added in form of maleic acid anhydride) and etidronic acid showed a further decrease of the crystallization temperature towards low refrigerator temperature like 1-2°C. It was observed that this effect is proportional to the amount of added etidronic acid until a threshold is reached.
- the possible amount of etidronic acid is restricted to 40 wt.-% of a 60 wt.-% active solution (such as Cublen® KT600/with 60% active).
- a 60 wt.-% active solution such as Cublen® KT600/with 60% active.
- a solution of 3,4 DMPP having a somewhat lower concentration of about 18 wt.-% active was less difficult to obtain/stabilize.
- Such solutions can be prepared by half-stoichiometric replacement of the maleic acid by acetic acid and a reduction of the etidronic acid addition down to 12 wt.-%:
- compositions of 100 mL aliquots fix in 30 wt.-% 3,4 DMPP, 10 wt.-% propylene glycol, and 2 wt.-% PEG 200 were prepared with various amounts of maleic acid anhydride (MSA), etidronic acid, 2-phosphono-l,2,4-butanetricarboxylic acid (PBTC) and/or acetic acid, respectively.
- MSA maleic acid anhydride
- PBTC 2-phosphono-l,2,4-butanetricarboxylic acid
- acetic acid acetic acid
- a phosphonic acid etidronic acid or PBTC
- PBTC phosphonic acid
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Abstract
The invention relates to a composition comprising (i) a specific pyrazole or an agriculturally acceptable salt thereof; (ii) a phosphonic acid or an agriculturally acceptable salt thereof; (iii) optionally, one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof; and (iv) optionally, one or more glycols. Compared to conventional compositions, the compositions according to the invention provide improved solubility of salts of pyrazoles such as 3,4 DMPP in aqueous solution. The solutions are stabilized against crystallization by lowering the crystallization point.
Description
Composition comprising DMPP and phosphonate
FIELD OF THE INVENTION
[0001] Priority is claimed of European patent application no. 20209124.5, filed on November 23, 2020
[0002] The invention relates to a composition comprising (i) a specific pyrazole or an agriculturally acceptable salt thereof; (ii) a phosphonic acid or an agriculturally acceptable salt thereof; (iii) optionally, one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof; and (iv) optionally, one or more glycols. Compared to conventional compositions, the compositions according to the invention provide improved solubility of salts of pyrazoles such as 3,4 DMPP in aqueous solution. The solutions are stabilized against crystallization by lowering the crystallization point.
BACKGROUND ART
[0003] Nitrification is an aerobic process performed by small groups of autotrophic bacteria and archaea. It is an important step in the nitrogen cycle in soil, wherein ammonia is biologically oxidized to nitrite, followed by the oxidation of the nitrite to nitrate. Nitrification of nitrogen containing fertilizers reduces their efficiency, as the contained nitrogen is oxidized and no longer available for take up by crops. Therefore, nitrogen containing fertilizers commonly comprise nitrification inhibitors to reduce nitrification, when the fertilizer is applied to the soil.
[0004] Negative side effects of nitrogen-containing fertilizers, such as the production of nitrate ions to be washed out into the subterranean water and/or the production of nitrous fumes, in particular NZO which is/are further identified to enhance the climate change, are of growing public concern. Both effects are based on metabolic activities of soil bacteria, which - in several steps - turn urea and other nitrogencontaining fertilizers into N2O and/or nitrate ions.
[0005] The key enzymes involved in nitrification can effectively be inhibited by nitrification inhibitors. The use of nitrification inhibitors to reduce negative side effects of nitrogen containing fertilizers, such as the production of nitrate ions and nitrous gases, has significantly grown in recent years. The enzymes involved in this step can be inhibited by known nitrification inhibitors such as pyrazole derivatives. 3,4- dimethylpyrazole (3,4 DMP) and its phosphate salt 3,4-dimethylpyrazole-phosphate (3,4 DMPP) are the most widely discussed and used ones.
[0006] Commercially available fertilizer additives have relatively low concentrations of the active substance and suffer from low stability, especially at lower temperatures. If a nitrification inhibitor comprises 3,4 DMPP, crystallization of the active substance hurdles the usability and shortens the storage life. Users often lack appropriate equipment for stirring or heating to re-dissolve the crystals.
[0007] RU 2248329 relates to a method for treatment of industrial sewage or water-return systems containing ammonium nitrogen and acid-resistant form of bacteria (microorganisms) causing acid microbiological corrosion. RU 2248329 relates to monomethylpyrazole having a molecular weight of 82.1 g/mol but not dimethylpyrazole, let alone dimethylpyrazole phosphates.
[0008] US 2020 0223764 discloses a process for preparing 2-(N-3,4-dimethylpyrazole)succinic acid by chemical reaction of 3,4-dimethylpyrazole with maleic acid and/or maleic acid anhydride in the absence of organic solvents or diluents at pH values greater than 7, and subsequent crystallization from the reaction product obtained in the absence of organic solvents or diluents.
[0009] US 2020 0288712 discloses mixtures including as active components at least one specific nitrification inhibitor (compound I) and at least one urease inhibitor (compound II). Also described are a method for improving the nitrification-inhibiting effect, or for increasing the health of a plant using mixtures of at least one compound I and at least one compound II and a method of using the mixtures comprising compounds I and compounds II for increasing the health of a plant. Also described are agrochemical compositions including these mixtures. Also described is plant propagation material including these mixtures or these agrochemical compositions.
[0010] US 2020 0165173 relates to a process for preparing a formulation F for reducing nitrification. The document also relates to a formulation F obtainable by said process. Furthermore, the document relates to a process of preparing a fertilizer-nitrification inhibitor mixture, and to a fertilizer-nitrification inhibitor mixture obtainable by this process. Moreover, the document relates to a method of fertilizing agricultural soil.
[0011] US 2020 0102255 discloses a method for fertilizing agricultural soil by applying at least one fertilizer N to the soil, wherein the at least one fertilizer N is applied in combination with a formulation F. The formulation F comprises at least one nitrification inhibitor I and at least one organic solvent S, and the at least one solvent S is selected from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, diglyme, fatty acid dialkylamides, benzyl alcohol, butyrolactone, propylene carbonate, ethyl hexyl lactate, 2-butoxy ethanol, dimethylsulfoxide, or mixtures thereof. The formulation F is essentially free from 3,4-dimethylpyrazolphosphate.
[0012] US 2019 0048260 relates to a nitrogen stabilizing composition. The composition includes 22 to 26% w/w N-(n -butyl) thiophosphoric triamide (NBPT), 4 to 8% w/w of 3,4-dimethyl pyrazole phosphate (3,4 DMPP) and/or nitrapyrin, a solvent including N-methyl -2 -pyrrolidone (NMP) and propylene glycol, 0.1 to 5% w/w vegetable oil, and 0.1 to 5% w/w lecithin.
[0013] US 2018 0016199 discloses pyrazole derivatives as nitrification inhibitors.
[0014] US 2017 0362140 relates to a composition comprises a nonaqeuous, liquid carrier, an inhibitor compound, and a colorant composition comprising an azo colorant. A method for making the composition is also provided. A method for making a fertilizer composition using the disclosed composition is also provided.
[0015] US 2016 0176769 discloses particulate compositions of reverted superphosphate substantially free of free acid containing at least one nitrification inhibitor and their methods of preparation and use .
[0016] US 2016 0168042 relates to a method for producing a liquid compound and to the compound used to improve the results of the application of ammoniacal nitrogenated fertilizers to crops requiring same and the ammonium present in the ground, said compound being a mixture consisting mainly of 3,5 DMPP as a nitrification inhibitor, phosphorus, the main function of which is to participate in all of the processes and energetic reactions of the crop, and amino acids winch are synthesized by the plants in enzymatic reactions generated by means of the animation, where absorbed ammonium salts and organic acids are produced. 3,5 DMPP is otherwise known as a plasticizer for polymer compositions.
[0017] US2012157317 discloses a composition in concentrated form (“the concentrate”) for dilution with water in the preparation of an agricultural composition for application to crops, soil or animals, comprising a carbohydrate -based pH modifying agent and a pH indicator and a process for preparing the agricultural composition by mixing the concentrate with water, and adding the agricultural chemical to the composition, if it is not already present in the concentrate. The agricultural composition comprises an agricultural chemical whose agricultural activity varies with the pH of the water. The proportions of the pH indicator and the pH modifying agent in the concentrate are selected so that when the concentrate is diluted with an appropriate amount of water, the pH indicator indicates visually by coloration of the composition, whether or not the pH of the water is suitable for acceptable agricultural activity of the chemical.
[0018] WO 2019 012383 relates to mixtures comprising as active components a first nitrification inhibitor (compound I) and a second nitrification inhibitor (compound II); to a method for improving the nitrification-inhibiting effect, or for increasing the health of a plant using mixtures of one compound I
and one compound II; to the use of mixtures comprising compounds I and compounds II for increasing the health of a plant; to agrochemical compositions comprising these mixtures; and to plant propagation material, comprising these mixtures or these agrochemical compositions.
[0019] WO 2016 097318 discloses novel nitrification inhibitors.
[0020] However, the compositions of nitrification inhibitors of the prior art are not satisfactory in every respect. There is a demand for improved compositions of nitrification inhibitors with a higher concentration of the active substance and longer stability.
[0021] It is an object of the invention to provide compositions of nitrification inhibitors having advantages compared to the compositions of the prior art. The compositions should have higher weight contents of the active substance and improved stability even at low temperatures. In particular, it would be desirable to provide a solution of agriculturally acceptable salts of pyrazoles such as 3,4 DMPP in water which contain approximately 30 wt.-% and which are stable for a reasonable time period under cold („wmterly“) conditions, such as 2 degrees centigrade.
[0022] This object has been achieved by the subject-matter of the patent claims.
[0023] It has been surprisingly found that the solubility of salts of pyrazoles such as 3,4 DMPP in aqueous solutions can be improved by the addition of acids and the resulting reduction of the pH value.
[0024] Further, it has been surprisingly found that the addition of organic acids, such as maleic acid, improves the solubility of salts of pyrazoles such as 3,4 DMPP in aqueous solutions and stabilizes the solution by lowering the crystallization point to about 10 °C.
[0025] Still further, it has been surprisingly found that the addition of phosphonic acids or salts thereof, especially bisphosphonic acids or salts thereof, further stabilizes aqueous solutions of salts of pyrazoles such as 3,4 DMPP by reducing the crystallization point to about 2 °C.
[0026] Yet further, it has been surprisingly found that the addition of one or more glycols to an aqueous solution of salts of pyrazoles such as 3,4 DMPP facilitates the re-dissolution, thereby making solutions easier to handle even at low temperatures.
[0027] Furthermore, it has been surprisingly found that the addition of a phosphonic acid or salt thereof and optionally of one or more carboxylic acids and/or one or more glycols improves the solubility of salts of pyrazoles such as 3,4 DMPP in an aqueous solution compared to conventional compositions.
This enables providing compositions with a higher concentration of the active compound and an improved stability, even at low temperatures. The compositions provided are easier to handle and have a relatively long storage life.
[0028] Moreover, it has been surprisingly found that aqueous solutions of salts of pyrazoles such as 3,4 DMPP comprising a phosphonic acid or salt thereof and optionally one or more carboxylic acids and/or one or more glycols can be used as nitrification inhibitors.
SUMMARY OF THE INVENTION
[0029] A first aspect of the invention relates to a composition comprising
(i) a pyrazole of general formula (A)
wherein
R1 means -H, or -Ci-6 -alkyl, or -C i-s-alkyl-OH; preferably -H;
R2 means -H, -Ci-s -alkyl, -C i-<, -alkyl -OH. -NH2, -F, -Cl, or -Br; preferably -H; and
R3 and R4 independently of one another mean -H, -Ci-6-alkyl, -C i-s-alkyl-OH, -NHz, -F, -Cl, or -Br; preferably -CH3; or an agriculturally acceptable salt thereof;
(ii) a phosphonic acid or an agriculturally acceptable salt thereof;
(iii) optionally, one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof; and
(iv) optionally, one or more glycols.
[0030] For the purpose of the specification, a fertilizer is any material of natural or synthetic origin that is applied to soil or to plant tissues to supply one or more plant nutrients essential to the growth of plants . Many sources of fertilizer exist, both natural and industrially produced. They typically provide the three main macronutrients nitrogen, phosphorus, and potassium in varying proportions. The mainly used nitrogen containing fertilizers compose ammonium compounds or derivatives thereof.
[0031] For the purpose of the specification, a fertilizer additive is a composition that can be advantageously added to (conventional) fertilizers in order to improve their properties. Typically, the fertilizer additive is no fertilizer as such.
[0032] The composition according to the invention may contain various ingredients that are capable of forming salts with various acids or that are employed in form of acid addition salts. For example, 3,4 DMPP may be regarded as the acid addition salt of 3,4-dimethylpyrazole (3,4 DMP) with phosphoric acid, whereas at a stochiometric ratio of 1:1 the phosphoric acid is present as dihydrogen phosphate anion and the 3,4 DMP is protonated thereby forming a pyrazolium cation. The composition according to the invention may further contain various acids such as one or more phosphonic acids, one or more carboxylic acids, one or more inorganic aids, and the like. A skilled person recognized that in solution is certain solvents such as water, the various anions (conjugate bases of the acids) which exchange with one another by metathesis reactions such that in the solution it can be difficult to clearly specify the various ion pairs that may be involved and that are attracted to one another by electrostatic forces.
[0033] Certain ingredients can be added or may be present in the composition according to the invention in form of carboxylic acid anhydrides. The composition according to the invention is preferably aqueous and as carboxylic acid anhydrides tend to spontaneously hydrolyze in aqueous environment. Unless expressly stated otherwise, irrespective of whether the composition according to the invention is aqueous or non-aqueous, all percentages and weights with regard to the one or more carboxylic acids, agriculturally acceptable salts of anhydrides thereof refer to the corresponding weight of the carboxylic acid anhydride, even if it actually employed in form of the (hydrolyzed) carboxylic acid or a salt thereof. Thus, all percentages and weights with regard to e g. maleic acid (diacid) and its agriculturally acceptable salts refer to maleic acid anhydride (anhydride cyclic), whereas all percentages and weights with regard to e.g. maleic acid and its agriculturally acceptable salts with regard to e.g. acetic acid (monoacid) and its agriculturally acceptable salts refer to acetic anhydride (anhydride dimeric).
[0034] Likewise, certain ingredients can be added or may be present in the composition according to the invention in form of agriculturally acceptable salts of carboxylic acids, phosphonic acids, pyrazoles, and the like. The composition according to the invention is preferably aqueous and as mixtures of salts in aqueous solution readily undergo metathesis reaction. Unless expressly stated otherwise, when the composition according to the invention is aqueous, all percentages and weights refer to the corresponding weight of the non-salt forms, i.e. the free acids and the free pyrazole, i.e. the weight contribution of the salt component is not taken into account. When the composition according to the invention is nonaqueous, however, said percentages and weights refer to the salts as such.
[0035] Preferably, the composition according to the invention is aqueous, preferably an aqueous liquid selected from solutions, emulsions and suspensions, more preferably an aqueous solution.
[0036] Preferably, the composition according to the invention is a supersaturated solution of the pyra- zole or agriculturally acceptable salt thereof.
[0037] Preferably, the composition according to the invention is sprayable; preferably over a granulated fertilizer according to a predefined mass relation, while maintaining the granulated characteristics of the granulated fertilizer.
[0038] In preferred embodiments of the composition according to the invention, the weight content of water is at least 10 w.-%, relative to the total weight of composition; preferably at least 16 wt.-%, more preferably at least 22 wt.-%, still more preferably at least 28 wt.-%, yet more preferably at least 33 wt.- %, even more preferably at least 38 wt.-%, most preferably at least 43 wt.-%, and in particular at least 48 wt.-%.
[0039] In preferred embodiments of the composition according to the invention, the weight content of water is at most 90 w.-%, relative to the total weight of composition; preferably at most 85 wt.-%, more preferably at most 80 wt.-%, still more preferably at most 75 wt.-%, yet more preferably at most 70 wt.- %, even more preferably at most 65 wt.-%, most preferably at most 60 wt.-%, and in particular at most 55 wt.-%.
[0040] In preferred embodiments of the composition according to the invention, the weight content of water is within the range of 50±40 wt.-%, relative to the total weight of composition; preferably 50±30 wt.-%, more preferably 40±20 wt.-%, still more preferably 35±30 wt.-%, yet more preferably 35±26 wt.-%, even more preferably 35±22 wt.-%, most preferably 35±18 wt-%, and in particular 35±14 wt.- 0 //o.
[0041] The composition according to the invention contains a pyrazole of general formula (A)
wherein
R1 means -H, or -Ci-e-alkyl, or -Ci-s -alkyl -OH; preferably -H;
R2 means -H, -C , -alkyl. -C|_(, -alkyl -OH. -NH2, -F, -Cl, or -Br; preferably -H; and
R3 and R4 independently of one another mean -H, -Ci-6-alkyl, -Ci-6-alkyl-OH, -NH2, -F, -Cl, or -Br; preferably -CH3; or an agriculturally acceptable salt thereof.
[0042] The composition according to the invention may contain one or more pyrazoles of general formula (A) or agriculturally acceptable salts thereof Preferably, the composition according to the invention contains a single pyrazole of general formula (A) or an agriculturally acceptable salt thereof.
[0043] Preferably, the pyrazole is selected from the group consisting of pyrazole, 3,4-dimethylpyrazole, 3,5-dimethylpyrazole, 4-chloro-3-methylpyrazole, 5-chloro-l,3-dimethylpyrazole, 5-amino-l,3-dime- thylpyrazole, 3,5-dimethylpyrazole-l-methanol, l-allyl-3,5-dimethylpyrazole, 1 -(2 -hydroxyethyl) -pyrazole, l-methyl-lH-pyrazole-4-carboxaldehyde, l//-pyrazolc-3-carbaldchydc, I //-pyrazole -5 -carb aldehyde. l/F-pyrazole-3-carboxylic acid, 2//-pyrazolc-3-carboxylic acid, l .5-dimethyl-l//-pyrazolc-4- carboxylic acid, 4-bromo-l,3-dimethyl-177-pyrazole-5-carboxylic acid, 17/-pyrazole-4, 5 -diamine.
[0044] Preferably, the pyrazole is 3,4-dimethylpyrazole.
[0045] In preferred embodiment of the composition according to the invention, the pyrazole is present in form of an agriculturally acceptable salt.
[0046] Preferably, the pyrazole is present in form of an agriculturally acceptable acid addition salt with an acid selected from the group consisting of hydrochloric acid, hydrobromic acid, hydrofluoric acid, water (anion = hydroxide), sulfuric acid (anion = hydrogen sulfate or sulfate), amidosulfonic acid, phosphoric acid (anion = dihydrogen phosphate, hydrogen phosphate, or phosphate), nitric acid, carbonic acid (anion = bicarbonate or carbonate), perchloric acid (anion = perchlorate), hexafluorosilicic acid (H2SIF6), and hexafluorophosphoric acid (HPF5).
[0047] Preferably, the pyrazole is present a agriculturally acceptable acid addition salt with phosphoric acid, whereas the protonated pyrazole forms a cation and the anion is selected from dihydrogen phosphate, hydrogen phosphate and phosphate, preferably dihydrogen phosphate.
[0048] Preferably, the pyrazole or agriculturally acceptable salt thereof is a nitrification inhibitor or a urease inhibitor; preferably a nitrification inhibitor.
[0049] In a particularly preferred embodiment of the composition according to the invention, the pyra- zole is present as 3,4-dimethylpyrazole phosphate (3,4 DMPP). 3,4 DMPP is commercially available.
[0050] In preferred embodiments of the composition according to the invention, the pKb value of the pyrazole is at least at least 7.9; preferably at least 8.4, more preferably at least 8.9, still more preferably at least 9.4, yet more preferably at least 9.9, even more preferably at least 10.4, most preferably at least 10.9, and in particular at least 11.4.
[0051] In preferred embodiments of the composition according to the invention, the pKb value of the pyrazole is at most 13.3; preferably at most 12.8, more preferably at most 12.3, still more preferably at most 11.8, yet more preferably at most 11.3, even more preferably at most 10.8, most preferably at most 10.3, and in particular at most 9.8.
[0052] In preferred embodiments of the composition according to the invention, the pKb value of the pyrazole is within the range of 10.5±4.5; preferably 10.5±4.0, more preferably 10.5±3.5, still more preferably 10.5±3.0, yet more preferably 10.5±2.5, even more preferably 10.5±2.0, most preferably 10.5±1.5, and in particular 10.5±1.0.
[0053] In preferred embodiments of the composition according to the invention, the weight content of the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at least 4.0 wt.-%, relative to the total weight of the composition; preferably at least 8.0 wt.-%, more preferably at least 10 wt.-%, still more preferably at least 14 wt.-%, yet more preferably at least 18 wt.- %, even more preferably at least 22 wt.-%, most preferably at least 26 wt.-%, and in particular at least 30 wt.-%.
[0054] In preferred embodiments of the composition according to the invention, the weight content of the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at most 70 wt .-%, relative to the total weight of the composition; preferably at most 65 wt.-%, more preferably at most 60 wt.-%, still more preferably at most 55 wt.-%, yet more preferably at most 50 wt- %, even more preferably at most 45 wt.-%, most preferably at most 40 wt.-%, and in particular at most 35 wt.-%.
[0055] In preferred embodiments of the composition according to the invention, the weight content of the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is within the range of 24±20 wt.-%, relative to the total weight of the composition; preferably 24±18 wt.- %, more preferably 24±16 wt.-%, still more preferably 24±14 wt.-%, yet more preferably 24±12 wt.-%, even more preferably 24±10 wt.-%, most preferably 24±8.0 wt.-%, and in particular 24±6.0 wt.-%.
[0056] Preferably, the pyrazole or agriculturally acceptable salt thereof is soluble in water.
[0057] Preferably, the pyrazole or agriculturally acceptable salt thereof is soluble, freely soluble or very soluble in water (pure water at 23 °C), whereas 10 to 30 mL volume of water are needed in order to dissolve a soluble pyrazole or agriculturally acceptable salt thereof, 1 to 10 mL volume of water are needed in order to dissolve a freely soluble pyrazole or agriculturally acceptable salt thereof, and less than 1 mL volume of water are needed in order to dissolve a very soluble pyrazole or agriculturally acceptable salt thereof.
[0058] The composition according to the invention contains a phosphonic acid or an agriculturally acceptable salt thereof.
[0059] The composition according to the invention may contain one or more phosphonic acids or agriculturally acceptable salts thereof. Preferably, the composition according to the invention contains a single phosphonic acid or an agriculturally acceptable salt thereof.
[0060] Preferably, the phosphonic acid has general formula (B)
wherein
R1 means -H, -OH, -NH2, or -Cl; preferably -OH;
R2 means -H, -Ci-io-alkyl, -Ci-6-alkyl-NH2, -Ci-6-alkyl-N(Ci-6-alkyl)-Ci-io-alkyl, or -Cl; preferably -CH3; and
R3 means -H, -Ci-io-alkyl, -Ci-e-alkyl-NH2, -Ci-6-alkyl-N(Ci-6-alkyl)-Ci-io-alkyl, -Cl, or -P(=O)(OH)2; preferably -P(=O)(OH)2.
[0061] Preferably, the phosphonic acid is a bisphosphonic acid or an agriculturally acceptable salt thereof.
[0062] Preferably, the phosphonic acid or the agriculturally acceptable salt thereof improves the solubility of the pyrazole or agriculturally acceptable salt thereof in an aqueous solution, preferably relative to the same composition not containing the phosphonic acid or the agriculturally acceptable salt thereof.
[0063] Preferably, the phosphonic acid is selected from the group consisting of etidronic acid, tiludronic acid, pamidronic acid, aledronic acid, ibandronic acid, risedronic acid, and zoledronic acid or an agriculturally acceptable salt thereof.
[0064] In a particularly preferred embodiment of the invention, the phosphonic acid or the agriculturally acceptable salt thereof is etidronic acid
H3C OH TO V OH HO-ip-^^^p' -OH II II
O 0 or an agriculturally acceptable salt thereof. Etidronic acid is commercially available, e.g. as active solution, e.g. 40 % of a 60% active solution (such as Cublen® KT600/with 60% active).
[0065] In preferred embodiments of the composition according to the invention, the weight content of the phosphonic acid, preferably etidronic acid, is at least 6.0 wt.-% relative to the total weight of the composition; preferably at least 8.0 wt.-%, more preferably at least 10 wt.-%, still more preferably at least 12 wt.-%, yet more preferably at least 14 wt.-%, even more preferably at least 16 wt.-%, most preferably at least 18 wt.-%, and in particular at least 20 wt.-%.
[0066] In preferred embodiments of the composition according to the invention, the weight content of the phosphonic acid or agriculturally acceptable salt thereof, preferably etidronic acid, is at most 90 wt.- % relative to the total weight of the composition; preferably at most 80 wt-%, more preferably at most 70 wt.-%, still more preferably at most 60 wt.-%, yet more preferably at most 50 wt.-%, even more preferably at most 40 wt.-%, most preferably at most 30 wt.-%, and in particular at most 22 wt.-%.
[0067] In preferred embodiments of the composition according to the invention, the weight content of the phosphonic acid or agriculturally acceptable salt thereof, preferably etidronic acid, is within the range of 25±23 wt.-%, relative to the total weight of the composition; preferably 20±18 wt.-%, more preferably 16±14 wt.-%, still more preferably 16±12 wt.-%, yet more preferably 16±10 wt.-%, even more preferably 16±8.0 wt.-%, most preferably 16±6.0 wt-%, and in particular 16±4.0 wt.-%.
[0068] In preferred embodiments of the composition according to the invention, the relative weight ratio of the phosphonic acid or agriculturally acceptable salt thereof, preferably etidronic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at least 1: 10; preferably at least 1:9, more preferably at least 1:8, still more preferably at least 1:7, yet more preferably at least 1:6, even more preferably at least 1:5, most preferably at least 1:4, and in particular at least 1:3.
[0069] In preferred embodiments of the composition according to the invention, the relative weight ratio of the phosphonic acid or agriculturally acceptable salt thereof, preferably etidronic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at most 7: 1; preferably at most 6: 1, more preferably at most 5:1, still more preferably at most 4:1, yet more preferably at most 3: 1, even more preferably at most 2: 1, most preferably at most 1 : 1, and in particular at most 1:2.
[0070] In preferred embodiments of the composition according to the invention, the relative weight ratio of the phosphonic acid or agriculturally acceptable salt thereof, preferably etidronic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is within the range of 1: 10 to 7: 1; preferably 1:9 to 6: 1, more preferably 1:8 to 5:1, still more preferably 1:7 to 4: 1, yet more preferably 1:6 to 3: 1, even more preferably 1:5 to 2: 1, most preferably 1:4 to 1: 1, and in particular 1:3 to 1:2.
[0071] Optionally, the composition according to the invention contains one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof. Unless expressly stated otherwise, all percentages and weights refer to the total content of all carboxylic acids that are contained in the composition.
[0072] Preferably, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof protonate the pyrazole thereby forming an agriculturally acceptable salt thereof. A skilled person recognizes that anhydrides of carboxylic acids may first interact with water, thereby hydrolyze and then protonate the pyrazole.
[0073] Preferably, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof improves the solubility of the pyrazole or agriculturally acceptable salt thereof in an aqueous solution, preferably relative to the same composition not containing the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof.
[0074] Preferably, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of a diacid or an agriculturally acceptable salt or anhydride thereof.
[0075] Preferably, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of an unsaturated acid or an agriculturally acceptable salt or anhydride thereof.
[0076] Preferably, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of an unsaturated carboxylic diacid or an agriculturally acceptable salt or anhydride thereof.
[0077] Preferably, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, ara- chidic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, muconic acid, maleic acid, fumaric acid, glutaconic acid, itaconic acid, citraconic acid, salicylic acid, benzoic acid, salicylic acid, phthalic acid, mixtures thereof, agriculturally acceptable salts or anhydrides thereof.
[0078] Preferably the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of maleic acid, maleic acid anhydride and/or acetic acid.
[0079] Preferably, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof compnse or consist of maleic acid and/or maleic acid anhydride.
[0080] Preferably, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of two organic acids or agriculturally acceptable salts or anhydrides thereof; preferably (i) maleic acid and/or maleic acid anhydride and (ii) acetic acid.
[0081] In preferred embodiments of the composition according to the invention, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of
(a) maleic acid alone;
(b) maleic acid anhydride alone;
(c) acetic acid alone;
(d) maleic acid in combination with acetic acid; or
(e) maleic acid anhydride in combination with acetic acid.
[0082] In preferred embodiments of the composition according to the invention, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof (anhydrides in their corresponding hydrolyzed form) independently of one another have a pKa value of at least 0.5; preferably at least 0.7, more preferably at least 0.9, still more preferably at least 1.1, yet more preferably at least 1.3, even more preferably at least 1.5, most preferably at least 1.7, and in particular at least 1.9.
[0083] In preferred embodiments of the composition according to the invention, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof (anhydrides in their corresponding hydrolyzed form) independently of one another have a pKa value of at most 6.2; preferably at most 6.0, more preferably at most 5.8, still more preferably at most 5.6, yet more preferably at most 5.4, even more preferably at most 5.2, most preferably at most 5.0, and in particular at most 4.8.
[0084] In preferred embodiments of the composition according to the invention, the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof (anhydrides in their corresponding hydrolyzed form) independently of one another have a pKa value of within the range of 3.9±3.5; preferably 3.9±3.0, more preferably 3.9±2.5, still more preferably 3.9±2.0, yet more preferably 3.4±3.0, even more preferably 3.4±2.5, most preferably 3.4±2.0, and in particular 3.4±1.5.
[0085] When a carboxylic acid carries more than a single carboxylic acid functional group, preferably at least one of the carboxylic acid functional group has a pKa value as defined above.
[0086] In preferred embodiments of the composition according to the invention, the total weight content of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid, is at least 1.0 wt.-%, based upon the equivalent weight of the anhydride and relative to the total weight of the composition; preferably at least 3.0 wt.- %, more preferably at least 5.0 wt.-%, still more preferably at least 7.0 wt.-%, yet more preferably at least 9.0 wt.-%, even more preferably at least 11 wt.-%, most preferably at least 13 wt.-%, and in particular at least 15 wt.-%.
[0087] In preferred embodiments of the composition according to the invention, the total weight content of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid, is at most 50 wt.-%, based upon the equivalent weight of the anhydride and relative to the total weight of the composition; preferably at most 45 wt.- %, more preferably at most 40 wt.-%, still more preferably at most 35 wt.-%, yet more preferably at most 30 wt.-%, even more preferably at most 25 wt.-%, most preferably at most 20 wt-%, and in particular at most 16 wt.-%.
[0088] In preferred embodiments of the composition according to the invention, the total weight content of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid, is within the range of 12±10 wt.-%, based upon the equivalent weight of the anhydride and relative to the total weight of the composition; preferably 12±9.0 wt.-%, more preferably 12±8.0 wt.-%, still more preferably 12±7.0 wt.-%, yet more preferably
12±6.0 wt.-%, even more preferably 12±5.0 wt.-%, most preferably 12±4.0 wt.-%, and in particular 12±3.5 wt.-%.
[0089] In preferred embodiments of the composition according to the invention, the relative weight ratio of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at least 1:9; preferably at least 1:8, more preferably at least 1:7, still more preferably at least 1:6, yet more preferably at least 1:5, even more preferably at least 1 :4, most preferably at least 1 :3, and in particular at least 1 :2, in each case based upon the equivalent weight of the anhydride.
[0090] In preferred embodiments of the composition according to the invention, the relative weight ratio of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at most 8: 1; preferably at most 7: 1, more preferably at most 6: 1, still more preferably at most 5: 1, yet more preferably at most 4: 1, even more preferably at most 3: 1, most preferably at most 2: 1, and in particular at most 1: 1, in each case based upon the equivalent weight of the anhydride.
[0091] In preferred embodiments of the composition according to the invention, the relative weight ratio of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof, preferably maleic acid, maleic acid anhydride and/or acetic acid, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is within the range of 1:9 to 8: 1; preferably 1:8 to 7: 1, more preferably 1 :7 to 6: 1, still more preferably 1:6 to 5: 1, yet more preferably 1:5 to 4: 1, even more preferably 1:4 to 3:1, most preferably 1:3 to 2: 1, and in particular 1:2 to 1: 1, in each case based upon the equivalent weight of the anhydride.
[0092] Preferably, the molar ratio of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof to the pyrazole or agriculturally acceptable salt thereof is stoichiometric.
[0093] In preferred embodiments of the composition according to the invention, the composition comprises (i) a first carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably maleic acid and/or maleic acid anhydride, and (ii) a second carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably acetic acid, wherein the relative weight ratio of (i) : (ii) is at least 1:9; preferably at least 1:8, more preferably at least 1:7, still more preferably at least 1 :6, yet more preferably at least 1:5, even more preferably at least 1:4, most preferably at least 1:3, and in particular at least 1:2, in each case based upon the equivalent weight of the anhydrides.
[0094] In preferred embodiments of the composition according to the invention, the composition comprises (i) a first carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably maleic acid and/or maleic acid anhydride, and (ii) a second carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably acetic acid, wherein the relative weight ratio of (i) : (ii) is at most 8: 1; preferably at most 7: 1, more preferably at most 6: 1, still more preferably at most 5: 1, yet more preferably at most 4: 1, even more preferably at most 3 : 1, most preferably at most 2: 1, and in particular at most 1: 1, in each case based upon the equivalent weight of the anhydrides.
[0095] In preferred embodiments of the composition according to the invention, the composition comprises (i) a first carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably maleic acid and/or maleic acid anhydride, and (ii) a second carboxylic acid, an agriculturally acceptable salt or anhydride thereof, preferably acetic acid, wherein the relative weight ratio of (i) : (ii) is within the range of 1:9 to 8:1; preferably 1:8 to 7:1, more preferably 1:7 to 6: 1, still more preferably 1:6 to 5: 1, yet more preferably 1:5 to 4: 1, even more preferably 1:4 to 3: 1, most preferably 1:3 to 2: 1, and in particular 1 :2 to 1 : 1, in each case based upon the equivalent weight of the anhydrides.
[0096] Optionally, the composition according to the invention contains one or more glycols. Unless expressly stated otherwise, all percentages and weights refer to the total content of all glycols that are contained in the composition.
[0097] Preferably, the one or more glycols improve the solubility of the pyrazole or agriculturally acceptable salt thereof in an aqueous solution, preferably relative to the same composition not containing the one or more glycols.
[0098] Preferably, the one or more glycols facilitate the re-dissolution of the pyrazole or agriculturally acceptable salt thereof, preferably relative to the same composition not containing the one or more glycols.
[0099] Preferably, the one or more glycols comprises or consists of a single glycol or two glycols
[0100] Preferably, the one or more glycols comprises or consists of an alkyl glycol, a polyalkyl glycol ether, or a mixture thereof.
[0101] Preferably, the one or more glycols comprise or consist of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (PEG) 200, PEG 300, PEG 400, PEG 600, PEG 1000, PEG 1500, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol (PPG) 425, PPG 725,
PPG 1000, butylene glycol, and mixtures thereof; preferably PEG 200, propylene glycol or a mixture thereof.
[0102] Preferably, the one or more glycols comprise or consist of an alkyl glycol and a polyalkyl glycol ether; preferably propylene glycol and PEG 200.
[0103] In preferred embodiments of the composition according to the invention, the one or more glycols comprise or consist of
(a) an alkyl glycol alone, preferably propylene glycol alone;
(b) a polyalkyl glycol ether alone, preferably PEG 200 alone; or
(c) an alkyl glycol, preferably propylene glycol, in combination with a polyalkyl glycol ether, preferably PEG 200.
[0104] In preferred embodiments of the composition according to the invention, the total weight content of the one or more glycols, preferably alkyl glycol and/or polyalkyl glycol ether, is at least 1.0 wt.-%, relative to the total weight of the composition; preferably at least 2.0 wt.-%, more preferably at least 3.0 wt.-%, still more preferably at least 4.0 wt.-%, yet more preferably at least 6.0 wt.-%, even more preferably at least 8.0 wt.-%, most preferably at least 10 wt.-%, and in particular at least 12 wt.-%.
[0105] In preferred embodiments of the composition according to the invention, the total weight content of the one or more glycols, preferably alkyl glycol and/or polyalkyl glycol ether, is at most 50 wt.-%, relative to the total weight of the composition; preferably at most 45 wt.-%, more preferably at most 40 wt.-%, still more preferably at most 35 wt.-%, yet more preferably at most 30 wt.-%, even more preferably at most 25 wt.-%, most preferably at most 20 wt.-%, and in particular at most 16 wt.-%.
[0106] In preferred embodiments of the composition according to the invention, the total weight content of the one or more glycols, preferably alkyl glycol and/or polyalkyl glycol ether, is within the range of 12±22 wt.-%, relative to the total weight of the composition; preferably 12±18 wt.-%, more preferably 12±14 wt.-%, still more preferably 12±10 wt-%, yet more preferably 12±6.0 wt.-%, even more preferably 12±4.0 wt.-%, most preferably 12±2.0 wt.-%, and in particular 12±1.0 wt.-%.
[0107] In preferred embodiments of the composition according to the invention, the relative weight ratio of the one or more glycols, preferably alkyl glycol and/or polyalkyl glycol ether, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at least 1: 11; preferably at least 1: 10, more preferably at least 1:9, still more preferably at least 1:8, yet more preferably at least 1:7, even more preferably at least 1:6, most preferably at least 1:5, and in particular at least 2:5.
[0108] In preferred embodiments of the composition according to the invention, the relative weight ratio of the one or more glycols, preferably alkyl glycol and/or polyalkyl glycol ether, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is at most 7: 1; preferably at most 6: 1, more preferably at most 5: 1, still more preferably at most 4: 1, yet more preferably at most 3: 1, even more preferably at most 2: 1, most preferably at most 1: 1, and in particular at most 2:3.
[0109] In preferred embodiments of the composition according to the invention, the relative weight ratio of the one or more glycols, preferably alkyl glycol and/or polyalkyl glycol ether, to the pyrazole or agriculturally acceptable salt thereof, preferably 3,4-dimethyl pyrazole or 3,4 DMPP, is within the range of 1 : 11 to 7: 1 ; preferably at most 1 : 10 to 6: 1, more preferably at most 1 :9 to 5 : 1, still more preferably at most 1:8 to 4: 1, yet more preferably at most 1:7 to 3: 1, even more preferably at most 1:6 to 2: 1, most preferably at most 1:5 to 1: 1, and in particular at most 2:5 to 2:3.
[0110] In preferred embodiments of the composition according to the invention, the one or more glycols compnse or consist of (i) a polyalkylglycol ether, preferably polyethylene glycol (PEG) 200, and (ii) an alkyl glycol, preferably propylene glycol, wherein the relative weight ratio of (i) : (ii) is at least 1: 12; preferably at least 1: 11, more preferably at least 1:10, still more preferably at least 1:9, yet more preferably at least 1:8, even more preferably at least 1 : 7, most preferably at least 1:6, and in particular at least 1:5.
[0111] In preferred embodiments of the composition according to the invention, the one or more glycols comprise or consist of (i) a polyalkylglycol ether, preferably polyethylene glycol (PEG) 200, and (ii) an alkyl glycol, preferably propylene glycol, wherein the relative weight ratio of (i) : (ii) is at most 5: 1; preferably at most 4: 1, more preferably at most 3: 1, still more preferably at most 2: 1, yet more preferably at most 1: 1, even more preferably at most 1:2, most preferably at most 1:3, and in particular at most 1 :4.
[0112] In preferred embodiments of the composition according to the invention, the one or more glycols comprise or consist of (i) a polyalkylglycol ether, preferably polyethylene glycol (PEG) 200, and (ii) an alkyl glycol, preferably propylene glycol, wherein the relative weight ratio of (i) : (ii) is within the range of 1 : 12 to 5: 1; preferably 1: 11 to 4: 1, more preferably 1: 10 to 3: 1, still more preferably 1:9 to 2: 1, yet more preferably l:8 to 1: 1, even more preferably l:7 to 1:2, most preferably 1:6 to 1:3, and in particular 1:5 to 1:4.
[0113] In preferred embodiments of the composition according to the invention, the pH value of the composition is at least 0.4; preferably at least 0.6, more preferably at least 0.8, still more preferably at
least 1 0, yet more preferably at least 1.2, even more preferably at least 1.4, most preferably at least 1.6, and in particular at least 1.8.
[0114] In preferred embodiments of the composition according to the invention, the pH value of the composition is at most 5.0; preferably at most 4.6, more preferably at most 4.2, still more preferably at most 3.8, yet more preferably at most 3.4, even more preferably at most 3.0, most preferably at most 2.6, and in particular at most 2.2.
[0115] In preferred embodiments of the composition according to the invention, the pH value of the composition is within the range of 5.0±4.0; preferably 4.0±3.0, more preferably 4.0±2.5, still more preferably 4.0±2.0, yet more preferably 2.0±1.5, even more preferably 2.0±1.0, most preferably 2.0±0.5, and in particular 2.0±0.2.
[0116] In preferred embodiments of the composition according to the invention, the pyrazole or agriculturally acceptable salt thereof stays in solution and does not crystallize at a temperature of at most 20 °C; preferably at most 15 °C, more preferably at most 10 °C, still more preferably at most 8.0 °C, yet more preferably at most 6.0 °C, even more preferably at most 4.0 °C, most preferably at most 2.0 °C, and in particular at most 1.0 °C.
[0117] In preferred embodiments of the composition according to the invention, the pyrazole or agriculturally acceptable salt thereof stays in solution and does not crystallize at a temperature of at least - 5.0 °C; preferably at least -4.0 °C, more preferably at least -3.0 °C, still more preferably at least -2.0 °C, yet more preferably at least -1.0 °C, even more preferably at least 0 °C, most preferably at least 1.0 °C, and in particular at least 2.0 °C.
[0118] In preferred embodiments of the composition according to the invention, the pyrazole or agriculturally acceptable salt thereof stays in solution and does not crystallize at a temperature within the range of 1.5±7.0 °C; preferably 1 5±6.0 °C, more preferably 1.5±5 0 °C, still more preferably 1.5±4.0 °C, yet more preferably 1.5±3.0 °C, even more preferably 1.5±2.0 °C, most preferably 1.5±1.0 °C, and in particular 1.5±0.5 °C.
[0119] In preferred embodiments of the composition according to the invention, the pyrazole or agriculturally acceptable salt thereof, preferably under the temperature conditions defined above, stays in solution and does not crystallize for at least 1 day; preferably at least 2 days, more preferably at least 3 days, still more preferably at least 4 days, yet more preferably at least 5 days, even more preferably at least 6 days, most preferably at least 7 days, and in particular at least 8 days.
[0120] Preferably, the composition according to the invention additionally comprises a tracer, preferably a dye.
[0121] Preferred contents of preferred ingredients of particularly preferred aqueous compositions ac- cording to the invention are compiled as embodiments A1 to A3 in the following tables:
[0122] Preferred contents of preferred ingredients of particularly preferred aqueous compositions ac- cording to the invention are compiled as embodiments B1 to B3 in the following tables:
[0123] Another aspect of the invention relates to a process for preparing of a composition according to the invention as described above, the process comprising the steps of:
(a) providing a pyrazole of general formula (A) or an agriculturally acceptable salt thereof according to the invention as described above;
(b) providing a phosphonic acid or an agriculturally acceptable salt thereof according to the invention as described above;
(c) optionally, providing one or more organic acids, agriculturally acceptable salts or anhydrides thereof according to the invention as described above;
(d) optionally, providing one or more glycols according to the invention as described above;
(e) optionally, providing a tracer, preferably a dye;
(f) optionally, providing water or an aqueous liquid; and
(g) mixing the components provided in steps (a) to (f) with one another to produce a composition.
[0124] Another aspect of the invention relates to a process for preparing of a fertilizer additive comprising a composition according to the invention as described above, the process comprising the process for preparing of a composition according to the invention as described above.
[0125] Another aspect of the invention relates to a process for preparing of a fertilizer comprising a fertilizer additive, the process comprising the steps of
(a) providing a composition according to the invention as described above;
(b) providing a fertilizer, preferably a granulated fertilizer; and
(c) applying the composition provided in step (a) to the fertilizer provided in step (b).
[0126] Another aspect of the invention relates to a fertilizer additive comprising or consisting of the composition according to the invention as described above; preferably wherein the fertilizer additive is obtainable by the process for preparing of a fertilizer additive according to the invention as described above.
[0127] Another aspect of the invention relates to a fertilizer comprising a fertilizer additive, wherein the fertilizer additive comprises or consists of the composition according to the invention as described above; preferably wherein the fertilizer is obtainable by the process for preparing of a fertilizer according to the invention as described above.
[0128] Another aspect of the invention relates to the use of a composition according to the invention as described above as fertilizer additive.
[0129] Another aspect of the invention relates to a method for reducing nitrification comprising the step of applying a fertilizer comprising a composition according to the invention as described above to soil or a plant.
[0130] The following examples further illustrate the invention but are not to be construed as limiting its scope.
Example 1:
[0131] The solubility of 3,4-dimethylpyrazole dihydrogen phosphate salt (3,4 DMPP)
in pure water (pH 7.0) at room temperature was investigated. Solubility was rather poor and formation of an oily phase on top of the aqueous layer indicated phase separation already at comparatively low concentrations of 3,4 DMPP.
Example 2:
[0132] Various combinations of 3,4 DMPP with organic or inorganic acids were prepared including fumaric acid, malonic acid, salicylic acid, acetic acid, amidosulfonic acid, and hydrochloric acid. The solubility of these combinations in pure water (pH 7.0) at room temperature was also investigated. It was observed that in comparison to the absence of the above acids, solubility of the pyrazole was significantly enhanced.
[0133] However, it was observed that at considerable concentrations of the pyrazole, such systems tend to crystallization of pyrazole salts around 10-12°C yielding a solid block of hard crystals. Such behavior would compromise the usability in winterly conditions.
Example 3:
[0134] Surprisingly, the use of maleic acid anhydride as acidic component provided a significant decrease of the crystallization temperature and for some time a stable supersaturated solution was formed. In aqueous solution maleic acid anhydride should readily hydrolyze to maleic acid. In view of these preliminary experimental results, maleic acid was chosen as the best available organic acid for the protonation of the pyrazole.
[0135] However, stoichiometric addition of maleic acid (added in form of maleic caid anhydride) after some time still ended up in crystallization of pyrazole salt at around 5°C. The desired concentration of pyrazole in solution of about 30 wt.-% corresponds to an approximately concentration of 1.55 mol/L. An equivalent proportional addition of 1.55 mol/L maleic acid anhydride corresponds to an addition level of 15.2 wt.-%.
Example 4:
[0136] It was investigated whether crystallization of pyrazole salts from aqueous solutions can be inhibited by adding guanidinium chloride, benzyl alcohol, quaternary surfactants or imidazole, e.g. due to complex formation. However, these additives did not show any effect on crystallization behavior.
Example 5:
[0137] Aqueous mixtures of 3,4 DMPP, maleic acid (added in form of maleic acid anhydride) and etidronic acid showed a further decrease of the crystallization temperature towards low refrigerator temperature like 1-2°C. It was observed that this effect is proportional to the amount of added etidronic acid until a threshold is reached.
[0138] For solubility reasons, the possible amount of etidronic acid is restricted to 40 wt.-% of a 60 wt.-% active solution (such as Cublen® KT600/with 60% active). Thus, 3,4 DMPP solutions at intermediate concentration, i.e. distant from the inflection point between solution and crystallization, can be stabilized with lower amounts/lower stoichiometric addition levels of etidronic acid.
Example 6:
[0139] It was found that if during exposure to harsh conditions (winter at the farmland or during transport through extreme climate zones) crystallization occurs, the addition of polyethylene glycol (PEG) 200 and propylene glycol significantly facilitates the re-dissolution of the 3,4 DMPP. Therefore, appropriate amounts were added to make the solution easier to handle for final users.
[0140] A solution of 3,4 DMPP having a somewhat lower concentration of about 18 wt.-% active was less difficult to obtain/stabilize. Such solutions can be prepared by half-stoichiometric replacement of the maleic acid by acetic acid and a reduction of the etidronic acid addition down to 12 wt.-%:
Example 7:
[0141] A multitude of identical samples was prepared each containing identical amounts of 3,4 DMPP, propylene glycol and polyethylene glycol (PEG 200) in water. To each sample, a different amount of (ii) a phosphonic acid or an agriculturally acceptable salt thereof and (iii) a carboxylic acids, agriculturally acceptable salts or anhydrides thereof was added in order to investigate the enhancing effect on solubility. All substances used were industrial grade or directly taken out of production stocks. PBTC was bought from Carl Roth.
[0142] For sample preparation, compositions of 100 mL aliquots fix in 30 wt.-% 3,4 DMPP, 10 wt.-% propylene glycol, and 2 wt.-% PEG 200 were prepared with various amounts of maleic acid anhydride (MSA), etidronic acid, 2-phosphono-l,2,4-butanetricarboxylic acid (PBTC) and/or acetic acid, respectively. The total amount of each sample was adjusted to 100 wt.-% by addition of demineralized water.
[0143] Those samples that did not provide clear solutions at room temperature, i.e. that remained suspensions, were visually inspected and ranked with regard to the quantity of undissolved material (3,4 DMPP). With respect to solubility, samples with a high amount of undissolved material were ranked as "very poor", whereas samples with a lower amount of undissolved material were ranked as "poor".
[0144] Those samples that provided clear solutions at room temperature were subjected to additional testing in order to reveal temperature dependence of solubility. Samples were placed a climate chamber and slowly cooled down at a rate of one degree centigrade per day (temperature was allowed to equilibrate at least for 24 hours, or over the weekend, respectively). The solubility status was monitored visually every morning. In case of precipitation, the temperature at the first day of precipitation was noted. The temperature noted is the exact temperature measured every morning (taking daily climate changes into account).
[0145] The solubility assessment for samples comprising maleic acid anhydride (MSA) and/or etidronic acid are compiled in the table here below:
[0146] The solubility assessment for samples comprising maleic acid anhydride (MSA) and/or 2-phos- phono-l,2,4-butanetricarboxylic acid (PBTC) are compiled in the table here below:
[0147] The solubility assessment for samples comprising maleic acid anhydride (MSA) and/or acetic acid are compiled in the table here below:
[0148] At most of the concentrations monitored, the solubility is very poor and 3,4 DMPP stayed undissolved in suspension. Only at an almost stoichiometrically addition level of maleic acid anhydride (MSA), a solubility at minimum room temperature was observed. However, such co-solution still crys- talized at approximately 12 °C. The same was observed with an addition of acetic acid (industrial grade).
[0149] In contrast, addition of a phosphonic acid (etidronic acid or PBTC) further decreased the crystallization point, i.e. further enhanced solubility. In this regard, etidronic acid was more effective than PBTC.
Example 8:
[0150] During the development of a 3,4 DMPP-MSA/etidromc acid co-solution, an optimal point of freeze stability was identified to be at the 1: 1 stoichiometric addition of maleic acid anhydride (MSA), followed by a subsequent addition of 20 wt.-% etidromc acid.
[0151] 300 kg of such solution were produced, filled into a small IBC (International Bulk Container) of appr. 375 L volume and subjected to a freeze stability experiment under almost real-life conditions in a big scale climate chamber. The solution stayed stable without visible crystal formation for at least six weeks at 0-2 °C.
[0152] Results are shown in Figure 1.
Claims
26
Patent claims:
1. A composition comprising
(i) 3,4-dimethylpyrazole phosphate (3,4 DMPP);
(ii) a phosphonic acid or an agriculturally acceptable salt thereof;
(iii) optionally, one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof; and
(iv) optionally, one or more glycols; wherein the weight content of the 3,4 DMPP is at least 10 wt.-%, relative to the total weight of the composition.
2. The composition according to claim 1, which is aqueous, preferably an aqueous solution.
3. The composition according to claim 1 or 2, wherein the weight content of water is
- at least 10 w.-%, relative to the total weight of the composition; preferably at least 16 wt.-%, more preferably at least 22 wt.-%, still more preferably at least 28 wt.-%, yet more preferably at least 33 wt.-%, even more preferably at least 38 wt.-%, most preferably at least 43 wt.-%, and in particular at least 48 wt.-%; and/or
- at most 90 w.-%, relative to the total weight of the composition; preferably at most 85 wt.-%, more preferably at most 80 wt.-%, still more preferably at most 75 wt-%, yet more preferably at most 70 wt.-%, even more preferably at most 65 wt.-%, most preferably at most 60 wt.-%, and in particular at most 55 wt.-%; and/or
- within the range of 50±40 wt.-%, relative to the total weight of the composition; preferably 50±30 wt.-%, more preferably 40±20 wt.-%, still more preferably 35±30 wt.-%, yet more preferably 35±26 wt.-%, even more preferably 35±22 wt.-%, most preferably 35±18 wt.-%, and in particular 35±14 wt.-%.
4. The composition according to any of the preceding claims, wherein the composition is a supersaturated solution of the 3,4 DMPP.
5. The composition according to any of the proceeding claims, wherein the composition is sprayable ; preferably over a granulated fertilizer according to a predefined mass relation, while maintaining the granulated characteristics of the granulated fertilizer.
The composition according to any of the preceding claims, wherein the pKb value of the 3,4 DMPP is
- at least at least 7.9; preferably at least 8.4, more preferably at least 8.9, still more preferably at least 9.4, yet more preferably at least 9.9, even more preferably at least 10.4, most preferably at least 10.9, and in particular at least 11.4; and/or
- at most 13.3; preferably at most 12.8, more preferably at most 12.3, still more preferably at most 11.8, yet more preferably at most 11.3, even more preferably at most 10.8, most preferably at most 10.3, and in particular at most 9.8; and/or
- within the range of 10.5±4.5; preferably 10.5±4.0, more preferably 10.5±3.5, still more preferably 10.5±3.0, yet more preferably 10.5±2.5, even more preferably 10.5±2.0, most preferably 10.5±1.5, and in particular 10.5±1.0. The composition according to any of the preceding claims, wherein the weight content of the 3,4 DMPP is
- at least 14 wt.-%, relative to the total weight of the composition; preferably at least 18 wt.-%, more preferably at least 22 wt.-%, still more preferably at least 26 wt.-%, and yet more preferably at least 30 wt.-%; and/or
- at most 70 wt.-%, relative to the total weight of the composition; preferably at most 65 wt.-%, more preferably at most 60 wt.-%, still more preferably at most 55 wt.-%, yet more preferably at most 50 wt.-%, even more preferably at most 45 wt.-%, most preferably at most 40 wt.-%, and in particular at most 35 wt.-%; and/or
- within the range of 24±14 wt.-%, relative to the total weight of the composition; preferably 24±12 wt.-%, more preferably 24±10 wt.-%, still more preferably 24±8.0 wt.-%, and yet more preferably 24±6.0 wt.-%. The composition according to any ofthe preceding claims, wherein the 3,4 DMPP is a nitrification inhibitor or a urease inhibitor; preferably a nitrification inhibitor. The composition according to any of the preceding claims, wherein the 3,4 DMPP is soluble in water. The composition according to any of the preceding claims, wherein the phosphonic acid has general formula (B)
wherein
R1 means -H, -OH, -NH2, or -Cl; preferably -OH;
R2 means -H, -Ci-io-alkyl, -Ci-6-alkyl-NH2, -Ci-6-alkyl-N(Ci-6-alkyl)-Ci-io-alkyl, or -Cl; preferably -CH3; and
R3 means -H, -Ci-io-alkyl, -Ci-6-alkyl-NH2, -Ci-6-alkyl-N(Ci-6-alkyl)-Ci-io-alkyl, -Cl, or - P(=O)(OH)2; preferably -P(=O)(OH)2. The composition according to any of the preceding claims, wherein the phosphonic acid is a bisphosphonic acid or an agriculturally acceptable salt thereof. The composition according to any of the preceding claims, wherein the phosphonic acid is selected from the group consisting of etidronic acid, tiludronic acid, pamidronic acid, aledronic acid, ibandronic acid, risedronic acid, and zoledronic acid or an agriculturally acceptable salt thereof; preferably etidronic acid or an agriculturally acceptable salt thereof. The composition according to any of the preceding claims, wherein the weight content of the phosphonic acid or agriculturally acceptable salt thereof is
- at least 6.0 wt.-% relative to the total weight of the composition, preferably at least 8.0 wt.-%, more preferably at least 10 wt.-%, still more preferably at least 12 wt.-%, yet more preferably at least 14 wt.-%, even more preferably at least 16 wt.-%, most prefer-ably at least 18 wt.-%, and in particular at least 20 wt.-%; and/or
- at most 90 wt.-% relative to the total weight of the composition; preferably at most 80 wt.-%, more preferably at most 70 wt.-%, still more preferably at most 60 wt.-%, yet more preferably at most 50 wt.-%, even more preferably at most 40 wt.-%, most preferably at most 30 wt.-%, and in particular at most 22 wt.-%; and/or
- within the range of 25±23 wt.-%, relative to the total weight of the composition; preferably 20±18 wt.-%, more preferably 16±14 wt.-%, still more preferably 16±12 wt.-%, yet more preferably 16±10 wt.-%, even more preferably 16±8.0 wt.-%, most preferably 16±6.0 wt.-%, and in particular 16±4.0 wt .-%.
29 The composition according to any of the preceding claims, wherein the relative weight ratio of the phosphonic acid or agriculturally acceptable salt thereof to the 3,4 DMPP is
- at least 1: 10; preferably at least 1:9, more preferably at least 1:8, still more preferably at least 1:7, yet more preferably at least 1:6, even more preferably at least 1:5, most preferably at least 1:4, and in particular at least 1:3; and/or
- at most 7:1; preferably at most 6:1, more preferably at most 5: 1, still more preferably at most 4: 1, yet more preferably at most 3: 1, even more preferably at most 2: 1, most preferably at most 1: 1, and in particular at most 1:2; and/or
- within the range of 1: 10 to 7: 1; preferably 1:9 to 6:1, more preferably 1:8 to 5: 1, still more preferably 1:7 to 4: 1, yet more preferably 1:6 to 3: 1, even more preferably 1:5 to 2: 1, most preferably 1:4 to 1: 1, and in particular 1:3 to 1:2. The composition according to any of the preceding claims, wherein the phosphonic acid or the agriculturally acceptable salt thereof improves the solubility of the 3,4 DMPP in an aqueous solution. The composition according to any of the preceding claims, wherein the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of a diacid or an agriculturally acceptable salt or anhydride thereof. The composition according to any of the preceding claims, wherein the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of an unsaturated acid or an agriculturally acceptable salt or anhydride thereof. The composition according to any of the preceding claims, wherein the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of an unsaturated carboxylic diacid or an agriculturally acceptable salt or anhydride thereof. The composition according to any of the preceding claims, wherein the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentade- cylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic ac-id, arachidic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, muconic acid, maleic acid, fumaric acid, glutaconic acid, itaconic acid, citraconic acid, salicylic acid, benzoic acid, salicylic acid, phthalic acid, mixtures thereof, agriculturally
30 acceptable salts or anhydrides thereof; preferably maleic acid, maleic acid anhydride and/or acetic acid. The composition according to any of the preceding claims, wherein the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of maleic acid and/or maleic acid anhydride. The composition according to any of the preceding claims, wherein the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof comprise or consist of two organic acids or agriculturally acceptable salts or anhydrides thereof; preferably (i) maleic acid and/or maleic acid anhydride and (ii) acetic acid. The composition according to any of the preceding claims, wherein the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof have a pKa value of
- at least 0.5; preferably at least 0.7, more preferably at least 0.9, still more preferably at least 1.1, yet more preferably at least 1.3, even more preferably at least 1.5, most preferably at least 1.7, and in particular at least 1.9; and/or
- at most 6.2; preferably at most 6.0, more preferably at most 5.8, still more preferably at most 5.6, yet more preferably at most 5.4, even more preferably at most 5.2, most preferably at most 5.0, and in particular at most 4.8; and/or
- within the range of 3.9±3.5; preferably 3.9±3.0, more preferably 3.9±2.5, still more preferably 3.9±2.0, yet more preferably 3.4±3.0, even more preferably 3.4±2.5, most preferably 3.4±2.0, and in particular 3 ,4± 1. . The composition according to any of the preceding claims, wherein the total weight content of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof is
- at least 1.0 wt.-%, relative to the total weight of the composition; preferably at least 3.0 wt- %, more preferably at least 5.0 wt-%, still more preferably at least 7.0 wt.-%, yet more preferably at least 9.0 wt-%, even more preferably at least 11 wt.-%, most preferably at least 13 wt.-%, and in particular at least 15 wt.-%; and/or
- at most 50 wt.-%, relative to the total weight of the composition; preferably at most 45 wt.-%, more preferably at most 40 wt.-%, still more preferably at most 35 wt.-%, yet more preferably at most 30 wt.-%, even more preferably at most 25 wt.-%, most preferably at most 20 wt.-%, and in particular at most 16 wt.-%; and/or
- within the range of 12±10 wt.-%, relative to the total weight of the composition; prefer-ably 12±9.0 wt-%, more preferably 12±8.0 wt.-%, still more preferably 12±7.0 wt.-%, yet more
31 preferably 12±6.0 wt.-%, even more preferably 12±5.0 wt.-%, most preferably 12±4.0 wt.-%, and in particular 12±3.5 wt.-%. The composition according to any of the preceding claims, wherein the relative weight ratio of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof to the 3,4 DMPP is
- at least 1:9; preferably at least 1:8, more preferably at least 1:7, still more preferably at least 1:6, yet more preferably at least 1:5, even more preferably at least 1:4, most preferably at least 1:3, and in particular at least 1:2; and/or
- at most 8:1; preferably at most 7:1, more preferably at most 6: 1, still more preferably at most 5 : 1 , yet more preferably at most 4: 1, even more preferably at most 3: 1, most preferably at most 2: 1, and in particular at most 1: 1; and/or
- within the range of 1:9 to 8: 1; preferably 1:8 to 7: 1, more preferably 1:7 to 6:1, still more preferably 1:6 to 5: 1, yet more preferably 1:5 to 4: 1, even more preferably 1:4 to 3: 1, most preferably 1:3 to 2: 1, and in particular 1:2 to 1: 1. The composition according to any of the preceding claims, wherein the molar ratio of the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof to the 3,4 DMPP is stoichiometric. The composition according to any of the preceding claims, wherein the composition comprises (i) a first carboxylic acid, an agriculturally acceptable salt or anhydride thereof and (ii) a second carboxylic acid, an agriculturally acceptable salt or anhydride thereof, where-in the relative weight ratio of (i) : (ii) is
- at least 1:9; preferably at least 1:8, more preferably at least 1:7, still more preferably at least 1:6, yet more preferably at least 1:5, even more preferably at least 1:4, most preferably at least 1:3, and in particular at least 1:2; and/or
- at most 8:1; preferably at most 7:1, more preferably at most 6:1, still more preferably at most 5 : 1 , yet more preferably at most 4: 1, even more preferably at most 3: 1, most preferably at most 2: 1, and in particular at most 1: 1; and/or
- within the range of 1:9 to 8: 1; preferably 1:8 to 7: 1, more preferably 1:7 to 6:1, still more preferably 1:6 to 5: 1, yet more preferably 1:5 to 4: 1, even more preferably 1:4 to 3: 1, most preferably 1:3 to 2: 1, and in particular 1:2 to 1: 1. The composition according to claim 30, wherein (i) is maleic acid and/or maleic acid an-hydride.
32 The composition according to any of claims 30 or 31, wherein (ii) is acetic acid. The composition according to any of the preceding claims, wherein the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof protonate the 3,4 DMPP thereby forming an agriculturally acceptable salt thereof. The composition according to any of the preceding claims, wherein the one or more carboxylic acids, agriculturally acceptable salts or anhydrides thereof improves the solubility of the 3,4 DMPP in an aqueous solution. The composition according to any of the preceding claims, wherein the one or more glycols comprises or consists of a single glycol or two glycols. The composition according to any of the preceding claims, wherein the one or more glycols comprises or consists of an alkyl glycol, a polyalkyl glycol ether, or a mixture thereof. The composition according to any of the preceding claims, wherein the one or more gly-cols comprise or consist of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (PEG) 200, PEG 300, PEG 400, PEG 600, PEG 1000, PEG 1500, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol (PPG) 425, PPG 725, PPG 1000, butylene glycol, and mixtures thereof; preferably PEG 200, propylene glycol or a mixture thereof. The composition according to any of the preceding claims, wherein the one or more glycols comprise or consist of an alkyl glycol and a polyalkyl glycol ether; preferably propylene glycol and PEG 200. The composition according to any of the preceding claims, wherein the total weight content of the one or more glycols is
- at least 1.0 wt.-%, relative to the total weight of the composition; preferably at least 2.0 wt.- %, more preferably at least 3.0 wt.-%, still more preferably at least 4.0 wt.-%, yet more preferably at least 6.0 wt.-%, even more preferably at least 8.0 wt.-%, most preferably at least 10 wt.-%, and in particular at least 12 wt.-%; and/or
- at most 50 wt.-%, relative to the total weight of the composition; preferably at most 45 wt.-%, more preferably at most 40 wt.-%, still more preferably at most 35 wt.-%, yet more preferably at most 30 wt.-%, even more preferably at most 25 wt.-%, most preferably at most 20 wt.-%, and in particular at most 16 wt.-%; and/or
33
- within the range of 12±22 wt.-%, relative to the total weight of the composition; prefer-ably 12±18 wt.-%, more preferably 12±14 wt.-%, still more preferably 12±10 wt.-%, yet more preferably 12±6.0 wt.-%, even more preferably 12±4.0 wt.-%, most preferably 12±2.0 wt.-%, and in particular 12±1.0 wt.-%. The composition according to any of the preceding claims, wherein the relative weight ratio of the one or more glycols to the 3,4 DMPP is
- at least 1: 11; preferably at least 1: 10, more preferably at least 1 : 9, still more preferably at least 1:8, yet more preferably at least 1:7, even more preferably at least 1:6, most preferably at least 1:5, and in particular at least 2:5; and/or
- at most 7:1; preferably at most 6:1, more preferably at most 5: 1, still more preferably at most 4: 1, yet more preferably at most 3: 1, even more preferably at most 2: 1, most preferably at most 1: 1, and in particular at most 2:3; and/or
- within the range of 1 : 11 to 7: 1 ; preferably at most 1 : 10 to 6 : 1 , more preferably at most 1 : 9 to 5: 1, still more preferably at most 1 : 8 to 4 : 1 , yet more preferably at most 1 : 7 to 3 : 1 , even more preferably at most 1:6 to 2: 1, most preferably at most 1:5 to 1: 1, and in particular at most 2:5 to 2:3. The composition according to any of the preceding claims, wherein the one or more glycols comprise or consist of (i) a polyalkylglycol ether and (ii) an alkyl glycol, wherein the relative weight ratio of (i) : (ii) is
- at least 1: 12; preferably at least 1:11, more preferably at least 1: 10, still more preferably at least 1:9, yet more preferably at least 1:8, even more preferably at least 1:7, most preferably at least 1:6, and in particular at least 1:5; and/or
- at most 5:1; preferably at most 4:1, more preferably at most 3: 1, still more preferably at most 2: 1, yet more preferably at most 1: 1, even more preferably at most 1:2, most preferably at most 1:3, and in particular at most 1:4; and/or
- within the range of 1: 12 to 5: 1; preferably 1: 11 to 4: 1, more preferably 1: 10 to 3:1, still more preferably 1:9 to 2: 1, yet more preferably 1:8 to 1: 1, even more preferably 1:7 to 1:2, most preferably 1:6 to 1:3, and in particular 1:5 to 1:4. The composition according to claim 41, wherein (i) is polyethylene glycol (PEG) 200. The composition according to any of claims 41 or 42, wherein (ii) is propylene glycol.
34 The composition according to any of the preceding claims, wherein the one or more glycols improve the solubility of the 3,4 DMPP in an aqueous solution. The composition according to any of the preceding claims, wherein the one or more glycols facilitate the re-dissolution of the 3,4 DMPP. The composition according to any of the preceding claims, wherein the pH value of the composition is
- at least 0.4; preferably at least 0.6, more preferably at least 0.8, still more preferably at least 1.0, yet more preferably at least 1.2, even more preferably at least 1.4, most preferably at least
1.6, and in particular at least 1.8; and/or
- at most 5.0; preferably at most 4.6, more preferably at most 4.2, still more preferably at most 3.8, yet more preferably atmost 3.4, even more preferably atmost 3.0, most preferably at most
2.6, and in particular at most 2.2; and/or
- within the range of 5.0±4.0; preferably 4.0±3.0, more preferably 4.0±2.5, still more preferably 4.0±2.0, yet more preferably 2.0±1.5, even more preferably 2.0±1.0, most preferably 2.0±0.5, and in particular 2.0±0.2. The composition according to any of the preceding claims, wherein the 3,4 DMPP stays in solution and does not crystallize at a temperature of
- at most 20 °C; preferably at most 15 °C, more preferably at most 10 °C, still more preferably at most 8.0 °C, yet more preferably at most 6.0 °C, even more preferably at most 4.0 °C, most preferably at most 2.0 °C, and in particular at most 1.0 °C; and/or
- at least -5.0 °C; preferably at least -4.0 °C, more preferably at least -3.0 °C, still more preferably at least -2.0 °C, yet more preferably at least -1.0 °C, even more preferably at least 0 °C, most preferably at least 1.0 °C, and in particular at least 2.0 °C; and/or
- within the range of 1.5±7.0 °C; preferably 1.5±6.0 °C, more preferably 1.5±5.0 °C, still more preferably 1.5±4.0 °C, yetmore preferably 1.5±3.0 °C, even more preferably 1.5±2.0 °C, most preferably 1.5±1.0 °C, and in particular 1.5±0.5 °C. The composition according to any of the preceding claims, wherein the 3,4 DMPP stays in solution and does not crystallize for at least 1 day; preferably at least 2 days, more preferably at least 3 days, still more preferably at least 4 days, yet more preferably at least 5 days, even more preferably at least 6 days, most preferably at least 7 days, and in particular at least 8 days.
35 The composition according to any of the preceding claims, wherein the composition comprises a tracer, preferably a dye. A process for preparing of a composition according to any of claims 1 to 49, the process comprising the steps of:
(a) providing 3,4 DMPP;
(b) providing a phosphonic acid or an agriculturally acceptable salt thereof;
(c) optionally, providing one or more organic acids, agriculturally acceptable salts or anhydrides thereof;
(d) optionally, providing one or more glycols;
(e) optionally, providing a tracer;
(f) optionally, providing water or an aqueous liquid; and
(g) mixing the components provided in steps (a) to (f) with one another to produce a composition. A process for preparing of a fertilizer additive comprising a composition as defined in the preceding claims 1 to 45, the process comprising the process of claim 46. A process for preparing of a fertilizer comprising a fertilizer additive, the process comprising the steps of:
(a) providing a composition as defined in any of claims 1 to 45;
(b) providing a fertilizer, preferably a granulated fertilizer; and
(c) applying the composition provided in step (a) to the fertilizer provided in step (b). A fertilizer additive comprising or consisting of the composition according to any of claims 1 to 45; preferably wherein the fertilizer additive is obtainable by the process according to claim 47. A fertilizer comprising a fertilizer additive, wherein the fertilizer additive comprises or consists of the composition according to any of claims 1 to 45; preferably wherein the fertilizer is obtainable by the process according to claim 48. Use of a composition according to any of claims 1 to 45 as fertilizer additive.
36
52. A method for reducing nitrification comprising the step of applying a fertilizer comprising a composition according to any of claims 1 to 45 to soil or a plant.
Applications Claiming Priority (2)
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EP20209124 | 2020-11-23 | ||
PCT/EP2021/082260 WO2022106596A1 (en) | 2020-11-23 | 2021-11-19 | Composition comprising dmpp and phosphonate |
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EP21810037.8A Pending EP4247167A1 (en) | 2020-11-23 | 2021-11-19 | Composition comprising dmpp and phosphonate |
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EP (1) | EP4247167A1 (en) |
CA (1) | CA3202392A1 (en) |
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WO (1) | WO2022106596A1 (en) |
Family Cites Families (13)
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UA66669C2 (en) | 2003-09-08 | 2006-05-15 | A composition for the prevention of acid microbiological corrosion of water , a method for water treatment and a method for utilization of industrial waters containing ammonium nitrogen | |
US20110079062A1 (en) | 2008-03-28 | 2011-04-07 | Terrence Smith | Particulate nitrification inhibitor systems |
CA2726064C (en) | 2010-12-21 | 2014-03-11 | Nutriag Ltd. | Agricultural composition comprising ph sensitive agricultural chemicals and organic ph buffer |
CL2013002188A1 (en) | 2013-07-30 | 2014-02-28 | Tivar Helicopteros Asesorias E Inversiones Ltda | Method for the preparation of a composition comprising the dimethylpyrazole phosphate compound, to improve the efficiency of the application of ammoniacal nitrogen fertilizers or soil ammonium, which comprises mixing phosphoric acid with 3,5-dimethyl-pyrazole, stirring the mixture, adding water, and amino acids; and said composition. |
SI3623362T1 (en) | 2013-12-13 | 2023-03-31 | Eurochem Agro Gmbh | Nitrification inhibitor containing fertiliser mixture |
US20190048260A1 (en) | 2014-12-04 | 2019-02-14 | Active Agriscience Inc. | Compositions and methods for reducing nitrogen volatilization of urea fertilizers |
AU2015366289B2 (en) | 2014-12-18 | 2020-04-02 | Basf Se | Alkynylpyrazoles as nitrification inhibitors |
US10556844B2 (en) | 2015-02-06 | 2020-02-11 | Basf Se | Pyrazole compounds as nitrification inhibitors |
CN109415278B (en) | 2016-06-18 | 2022-02-22 | 美利肯公司 | Compositions suitable for use in the preparation of fertilizers, methods of preparing these compositions, and methods of preparing fertilizers using the compositions |
WO2018228866A1 (en) | 2017-06-14 | 2018-12-20 | Basf Se | New method for fertilizing agricultural soil |
BR112019027547A2 (en) | 2017-07-10 | 2020-07-07 | Basf Se | mixture, agrochemical composition, use of the mixture, methods to reduce nitrous oxide emission and to increase the health of a plant and plant propagating material |
CA3066991A1 (en) | 2017-07-10 | 2019-01-17 | Basf Se | Mixtures comprising an urease inhibitor (ui) and a nitrification inhibitor such as 2-(3,4-dimethyl-1h-pyrazol-1-yl)succinic acid (dmpsa) or 3,4-dimethyl pyrazolium glycolate (dmpg) |
WO2019035069A1 (en) | 2017-08-18 | 2019-02-21 | Basf Se | Process for preparing improved 3,4-dimethyl-1h-pyrazole phosphate formulations |
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- 2021-11-19 MX MX2023006008A patent/MX2023006008A/en unknown
- 2021-11-19 CA CA3202392A patent/CA3202392A1/en active Pending
- 2021-11-19 WO PCT/EP2021/082260 patent/WO2022106596A1/en active Application Filing
- 2021-11-19 EP EP21810037.8A patent/EP4247167A1/en active Pending
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