NZ617125B2 - Stable high strength oil-in-water emulsions - Google Patents
Stable high strength oil-in-water emulsions Download PDFInfo
- Publication number
- NZ617125B2 NZ617125B2 NZ617125A NZ61712512A NZ617125B2 NZ 617125 B2 NZ617125 B2 NZ 617125B2 NZ 617125 A NZ617125 A NZ 617125A NZ 61712512 A NZ61712512 A NZ 61712512A NZ 617125 B2 NZ617125 B2 NZ 617125B2
- Authority
- NZ
- New Zealand
- Prior art keywords
- oil
- water
- composition
- respect
- emulsion
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000000839 emulsion Substances 0.000 title claims description 26
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 230000002363 herbicidal Effects 0.000 claims abstract description 53
- 239000004009 herbicide Substances 0.000 claims abstract description 42
- 239000007764 o/w emulsion Substances 0.000 claims abstract description 35
- 239000004094 surface-active agent Substances 0.000 claims abstract description 33
- 239000004480 active ingredient Substances 0.000 claims abstract description 30
- 239000005562 Glyphosate Substances 0.000 claims abstract description 29
- 229940097068 glyphosate Drugs 0.000 claims abstract description 29
- XDDAORKBJWWYJS-UHFFFAOYSA-O Glyphosate Chemical compound OC(=O)C[NH2+]CP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-O 0.000 claims abstract description 28
- 239000012071 phase Substances 0.000 claims abstract description 27
- 230000001804 emulsifying Effects 0.000 claims abstract description 23
- 239000008346 aqueous phase Substances 0.000 claims abstract description 22
- 239000011780 sodium chloride Substances 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- OLZQTUCTGLHFTQ-UHFFFAOYSA-N octan-2-yl 2-(4-amino-3,5-dichloro-6-fluoropyridin-2-yl)oxyacetate Chemical group CCCCCCC(C)OC(=O)COC1=NC(F)=C(Cl)C(N)=C1Cl OLZQTUCTGLHFTQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 organo ammonium salt Chemical class 0.000 claims description 22
- 229920005682 EO-PO block copolymer Polymers 0.000 claims description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-O dimethylaminium Chemical group C[NH2+]C ROSDSFDQCJNGOL-UHFFFAOYSA-O 0.000 claims description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000004581 coalescence Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000005712 crystallization Effects 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- VDCHTAFVUAPYGO-UHFFFAOYSA-N N-methylmethanamine;2-(phosphonomethylamino)acetic acid Chemical compound CNC.OC(=O)CNCP(O)(O)=O VDCHTAFVUAPYGO-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000000265 homogenisation Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000002363 auxin Substances 0.000 claims description 2
- ZXVOCOLRQJZVBW-UHFFFAOYSA-O azanium;ethanol Chemical compound [NH4+].CCO ZXVOCOLRQJZVBW-UHFFFAOYSA-O 0.000 claims description 2
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- 159000000001 potassium salts Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000002194 synthesizing Effects 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 abstract 2
- 239000003921 oil Substances 0.000 description 37
- 235000019198 oils Nutrition 0.000 description 37
- 239000004615 ingredient Substances 0.000 description 12
- 235000008504 concentrate Nutrition 0.000 description 11
- 239000012141 concentrate Substances 0.000 description 11
- 241000196324 Embryophyta Species 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- MEFQWPUMEMWTJP-UHFFFAOYSA-N Fluroxypyr Chemical compound NC1=C(Cl)C(F)=NC(OCC(O)=O)=C1Cl MEFQWPUMEMWTJP-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- WTOOLIQYCQJDBG-BJILWQEISA-N but-1-ene;(E)-but-2-ene Chemical compound CCC=C.C\C=C\C WTOOLIQYCQJDBG-BJILWQEISA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical class C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 4
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-Dichlorophenoxyacetic acid Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003849 aromatic solvent Substances 0.000 description 3
- 125000004432 carbon atoms Chemical group C* 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001983 poloxamer Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000005631 2,4-D Substances 0.000 description 2
- 239000002794 2,4-DB Substances 0.000 description 2
- YIVXMZJTEQBPQO-UHFFFAOYSA-N 2,4-DB Chemical compound OC(=O)CCCOC1=CC=C(Cl)C=C1Cl YIVXMZJTEQBPQO-UHFFFAOYSA-N 0.000 description 2
- UHZZMRAGKVHANO-UHFFFAOYSA-M 2-chloroethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 2
- 239000005468 Aminopyralid Substances 0.000 description 2
- NIXXQNOQHKNPEJ-UHFFFAOYSA-N Aminopyralid Chemical compound NC1=CC(Cl)=NC(C(O)=O)=C1Cl NIXXQNOQHKNPEJ-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000005500 Clopyralid Substances 0.000 description 2
- HUBANNPOLNYSAD-UHFFFAOYSA-N Clopyralid Chemical compound OC(=O)C1=NC(Cl)=CC=C1Cl HUBANNPOLNYSAD-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- 239000005558 Fluroxypyr Substances 0.000 description 2
- 229940060367 Inert Ingredients Drugs 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N Isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000005574 MCPA Substances 0.000 description 2
- 238000001016 Ostwald ripening Methods 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 235000019483 Peanut oil Nutrition 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 235000019485 Safflower oil Nutrition 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N Tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 229920002359 Tetronic® Polymers 0.000 description 2
- WHKUVVPPKQRRBV-UHFFFAOYSA-N Trasan Chemical compound CC1=CC(Cl)=CC=C1OCC(O)=O WHKUVVPPKQRRBV-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Trimethylglycine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000000240 adjuvant Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- KWAIHLIXESXTJL-UHFFFAOYSA-N aminocyclopyrachlor Chemical compound OC(=O)C1=C(Cl)C(N)=NC(C2CC2)=N1 KWAIHLIXESXTJL-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004006 olive oil Substances 0.000 description 2
- 235000008390 olive oil Nutrition 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000010690 paraffinic oil Substances 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001993 poloxamer 188 Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ZFCHNZDUMIOWFV-UHFFFAOYSA-N pyrimidine-2-carboxylic acid Chemical class OC(=O)C1=NC=CC=N1 ZFCHNZDUMIOWFV-UHFFFAOYSA-N 0.000 description 2
- 235000005713 safflower oil Nutrition 0.000 description 2
- 239000003813 safflower oil Substances 0.000 description 2
- 239000008159 sesame oil Substances 0.000 description 2
- 235000011803 sesame oil Nutrition 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000020238 sunflower seed Nutrition 0.000 description 2
- 239000002383 tung oil Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ROBSGBGTWRRYSK-SNVBAGLBSA-N (2R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propanoic acid Chemical compound C1=CC(O[C@H](C)C(O)=O)=CC=C1OC1=CC=C(C#N)C=C1F ROBSGBGTWRRYSK-SNVBAGLBSA-N 0.000 description 1
- YUIKUTLBPMDDNQ-MRVPVSSYSA-N (2R)-2-[4-(5-chloro-3-fluoropyridin-2-yl)oxyphenoxy]propanoic acid Chemical compound C1=CC(O[C@H](C)C(O)=O)=CC=C1OC1=NC=C(Cl)C=C1F YUIKUTLBPMDDNQ-MRVPVSSYSA-N 0.000 description 1
- ADDQHLREJDZPMT-CQSZACIVSA-N (2R)-2-[4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy]-N-(2-fluorophenyl)-N-methylpropanamide Chemical compound O=C([C@H](OC=1C=CC(OC=2OC3=CC(Cl)=CC=C3N=2)=CC=1)C)N(C)C1=CC=CC=C1F ADDQHLREJDZPMT-CQSZACIVSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- YUVKUEAFAVKILW-SECBINFHSA-N (R)-fluazifop Chemical compound C1=CC(O[C@H](C)C(O)=O)=CC=C1OC1=CC=C(C(F)(F)F)C=N1 YUVKUEAFAVKILW-SECBINFHSA-N 0.000 description 1
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-Dichloroethene Chemical compound ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- XPZBNIUWMDJFPW-UHFFFAOYSA-N 2,2,3-trimethylcyclohexan-1-one Chemical compound CC1CCCC(=O)C1(C)C XPZBNIUWMDJFPW-UHFFFAOYSA-N 0.000 description 1
- MPPOHAUSNPTFAJ-UHFFFAOYSA-N 2-[4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy]propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 MPPOHAUSNPTFAJ-UHFFFAOYSA-N 0.000 description 1
- GOCUAJYOYBLQRH-UHFFFAOYSA-N 2-[4-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]oxyphenoxy]propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=NC=C(C(F)(F)F)C=C1Cl GOCUAJYOYBLQRH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005489 Bromoxynil Substances 0.000 description 1
- UPMXNNIRAGDFEH-UHFFFAOYSA-N Bromoxynil Chemical class OC1=C(Br)C=C(C#N)C=C1Br UPMXNNIRAGDFEH-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000005498 Clodinafop Substances 0.000 description 1
- 239000005501 Cycloxydim Substances 0.000 description 1
- AGPKZVBTJJNPAG-CRCLSJGQSA-N D-allo-isoleucine Chemical compound CC[C@H](C)[C@@H](N)C(O)=O AGPKZVBTJJNPAG-CRCLSJGQSA-N 0.000 description 1
- 229940079857 DISODIUM COCOAMPHODIPROPIONATE Drugs 0.000 description 1
- 239000005504 Dicamba Substances 0.000 description 1
- IWEDIXLBFLAXBO-UHFFFAOYSA-N Dicamba Chemical compound COC1=C(Cl)C=CC(Cl)=C1C(O)=O IWEDIXLBFLAXBO-UHFFFAOYSA-N 0.000 description 1
- 239000005506 Diclofop Substances 0.000 description 1
- OOLBCHYXZDXLDS-UHFFFAOYSA-N Diclofop Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=CC=C(Cl)C=C1Cl OOLBCHYXZDXLDS-UHFFFAOYSA-N 0.000 description 1
- 240000003139 Ferula foetida Species 0.000 description 1
- 239000005530 Fluazifop-P Substances 0.000 description 1
- 239000005565 Haloxyfop-P Substances 0.000 description 1
- ZCZSIDMEHXZRLG-UHFFFAOYSA-N Heptyl acetate Chemical compound CCCCCCCOC(C)=O ZCZSIDMEHXZRLG-UHFFFAOYSA-N 0.000 description 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N Hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 1
- AOGQPLXWSUTHQB-UHFFFAOYSA-N Hexyl acetate Chemical group CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 1
- 239000005595 Picloram Substances 0.000 description 1
- NQQVFXUMIDALNH-UHFFFAOYSA-N Picloram Chemical compound NC1=C(Cl)C(Cl)=NC(C(O)=O)=C1Cl NQQVFXUMIDALNH-UHFFFAOYSA-N 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Chemical class OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 229920002043 Pluronic® L 35 Polymers 0.000 description 1
- 229920002059 Pluronic® P 104 Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920001083 Polybutene Polymers 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000005600 Propaquizafop Substances 0.000 description 1
- CSPPKDPQLUUTND-NBVRZTHBSA-N Sethoxydim Chemical compound CCO\N=C(/CCC)C1=C(O)CC(CC(C)SCC)CC1=O CSPPKDPQLUUTND-NBVRZTHBSA-N 0.000 description 1
- 239000005624 Tralkoxydim Substances 0.000 description 1
- DQFPEYARZIQXRM-LTGZKZEYSA-N Tralkoxydim Chemical compound C1C(=O)C(C(/CC)=N/OCC)=C(O)CC1C1=C(C)C=C(C)C=C1C DQFPEYARZIQXRM-LTGZKZEYSA-N 0.000 description 1
- 239000005627 Triclopyr Substances 0.000 description 1
- REEQLXCGVXDJSQ-UHFFFAOYSA-N Triclopyr Chemical compound OC(=O)COC1=NC(Cl)=C(Cl)C=C1Cl REEQLXCGVXDJSQ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 Vinyl ester Polymers 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JPJLZTUSDJKKLS-UHFFFAOYSA-O azanium;2-hydroxyethyl(trimethyl)azanium Chemical compound [NH4+].C[N+](C)(C)CCO JPJLZTUSDJKKLS-UHFFFAOYSA-O 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000003115 biocidal Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- QMNOIORHZMRPLS-UHFFFAOYSA-N butan-1-ol;ethane-1,2-diol;propane-1,2-diol Chemical compound OCCO.CCCCO.CC(O)CO QMNOIORHZMRPLS-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 244000038559 crop plants Species 0.000 description 1
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical class O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 description 1
- GGWHBJGBERXSLL-UHFFFAOYSA-N cycloxydim Chemical compound C1C(=O)C(C(=NOCC)CCC)=C(O)CC1C1CSCCC1 GGWHBJGBERXSLL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 230000004059 degradation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000994 depressed Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NRXQIUSYPAHGNM-UHFFFAOYSA-N ioxynil Chemical class OC1=C(I)C=C(C#N)C=C1I NRXQIUSYPAHGNM-UHFFFAOYSA-N 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical class CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-O isopropylaminium Chemical compound CC(C)[NH3+] JJWLVOIRVHMVIS-UHFFFAOYSA-O 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M laurate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 235000014666 liquid concentrate Nutrition 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N nicotinic acid Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FROBCXTULYFHEJ-OAHLLOKOSA-N propaquizafop Chemical compound C1=CC(O[C@H](C)C(=O)OCCON=C(C)C)=CC=C1OC1=CN=C(C=C(Cl)C=C2)C2=N1 FROBCXTULYFHEJ-OAHLLOKOSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- UFGTXPLSPACVGS-UHFFFAOYSA-N pyridin-2-yl hydrogen carbonate Chemical class OC(=O)OC1=CC=CC=N1 UFGTXPLSPACVGS-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-M stearate Chemical compound CCCCCCCCCCCCCCCCCC([O-])=O QIQXTHQIDYTFRH-UHFFFAOYSA-M 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
Abstract
Provided is a stable high-strength herbicidal oil-in-water emulsion composition comprising: a) a discontinuous oil phase comprising, with respect to the oil-in-water emulsion, from about 25 grams active ingredient per liter (g ai/L) to about 300 g ai/L of at least one oil soluble herbicide active ingredient and from 0 grams per liter (g/L) to about 300 g/L of a water immiscible organic solvent; b) a continuous aqueous phase comprising, with respect to the oil-in-water emulsion, from about 260 g ai/L to about 570 g ai /L of a water soluble salt of glyphosate and from about 200 g/L to about 500 g/L of water; and c) at least two non-ionic ethylene oxide/propylene oxide (EO/PO) block copolymer emulsifying surfactants with at least one having a hydrophile lipophile balance (HLB) value of about 13 to about 16 and at least one having an HLB value of about 22 to about 29 and with each having a molecular weight (mw) of about 5000 or higher, with the combined emulsifying surfactants comprising, with respect to the oil-in-water emulsion, from about 1 g/L to about 200 g/L. A preferred oil soluble herbicide is fluroxypyr-meptyl. Further provided is a method of preparing the composition. ngredient and from 0 grams per liter (g/L) to about 300 g/L of a water immiscible organic solvent; b) a continuous aqueous phase comprising, with respect to the oil-in-water emulsion, from about 260 g ai/L to about 570 g ai /L of a water soluble salt of glyphosate and from about 200 g/L to about 500 g/L of water; and c) at least two non-ionic ethylene oxide/propylene oxide (EO/PO) block copolymer emulsifying surfactants with at least one having a hydrophile lipophile balance (HLB) value of about 13 to about 16 and at least one having an HLB value of about 22 to about 29 and with each having a molecular weight (mw) of about 5000 or higher, with the combined emulsifying surfactants comprising, with respect to the oil-in-water emulsion, from about 1 g/L to about 200 g/L. A preferred oil soluble herbicide is fluroxypyr-meptyl. Further provided is a method of preparing the composition.
Description
STABLE HIGH TH OIL-IN-WATER EMULSIONS
This application claims the benefit of U.S. Provisional Patent Application Serial No.
61/482,716 filed May 5, 2011.
Background
A common method of herbicidal treatment in agricultural endeavors is to treat a field
to remove or control unwanted vegetation in preparation for planting a crop plant or seed, a
method otherwise known as a wn” herbicide treatment. However, single herbicides
lly lack the weed control spectrum, e.g., the range of weed species effectively
controlled by the herbicide, to fully control the diversity of weeds in such an environment and
therefore, it is common to apply two or more ides simultaneously in order to achieve
the desired spectrum of control with the bumdown treatment. To facilitate this application of
two or more herbicides, the ides are often sold separately and mixed in a spray tank by
the end user. A more convenient way to deliver these ides is to formulate them into a
single pre-miX concentrate that can easily be measured and diluted in water by the end user
prior to application by spraying.
Glyphosate containing compositions are of particular st in bumdown herbicide
applications due to their wide um of weed control. These compositions are made more
useful by expanding their spectrum of weed control even further by the addition of an oil
soluble herbicide. An -water emulsion (EW) composition may be used to combine an
oil soluble herbicide and a water soluble herbicide, such as a glyphosate, into a x
herbicide concentrate where droplets of oil are stabilized by surfactant emulsifiers as a
te phase and are uniformly dispersed in water as a continuous phase.
Oil-in-water emulsions can have stability issues caused by one or more factors.
Interactions or reactions of an ingredient in the aqueous phase with component(s) of the
dispersed oil phase include, but are not limited to, crystal formation and growth due to
Ostwald ripening of an oil phase component or an aqueous phase component, or chemical
degradation of ients in either the oil phase or the aqueous phase. These degradations
may be caused by the ce of one or more components in the oil-in-water emulsion and
can lead to formulation instability. Migration of water into the oil phase and contact with the
active ingredient dissolved in the oil phase or migration of the active ingredient into the water
phase or to the oil-water interface can lead to one or more of active ingredient hydrolysis,
crystal formation or Ostwald ripening with possible formulation instability or ability
for agricultural spray applications.
It can be particularly challenging to develop stable oil-in-water emulsions containing
a high ionic strength aqueous solution such as, for e, a water solution containing a
soluble glyphosate salt. The high ionic strength s solution can destabilize the
emulsion leading to coalescence of the oil droplets into larger sized oil droplets which may
ultimately cause the emulsion to separate into two liquid layers. This undesired phenomenon
has been attributed to the electrolyte decreasing the electrostatic repulsive force between the
dispersed droplets, thus causing the ts to agglomerate. This stability issue becomes
more severe in a high load emulsion system, and at high ature extremes. Previous
efforts to combine oil soluble herbicides with aqueous solutions containing salts of
glyphosate in a liquid concentrate ation have been disclosed, for example, in US
6,713,433 B2, US 6,689,719 and US 6,369,001.
High-strength formulations are desirable for a variety of economic and nmental
reasons. For example, it is desirable to provide a high-strength concentrate in order to reduce
ng and handling costs and to reduce the amount of packaging material that must be
disposed after use of the product. The high-strength concentrates should be stable and retain
potency during storage and ng. Furthermore, the high-strength concentrate should be a
homogeneous liquid emulsion that is stable at temperatures at least as high as about 50 °C
and should not exhibit any precipitation of solids at temperatures as low as about 0 °C.
A stable high-strength herbicidal -water emulsion is disclosed that includes:
a) a tinuous oil phase comprising, with respect to the oil-in-water
emulsion, from about 25 grams active ingredient per liter (g ai/L) to about 300 g ai/L of at
least one oil soluble herbicide active ingredient and from 0 grams per liter (g/L) to about 300
g/L of a water immiscible organic solvent;
b) a continuous aqueous phase comprising, with respect to the oil-in-water
emulsion, from about 260 g ai/L to about 570 g ai/L of a water e salt of glyphosate and
from about 200 g/L to about 500 g/L of water; and
c) at least two non-ionic EO/PO block copolymer emulsifying surfactants with at
least one having a hydrophile lipophile balance (HLB) value of about 13 to about 16 and at
least one having an HLB value of about 22 to about 29 and each having a molecular weight
(mw) of about 5000 or higher, with the combined emulsifying tants comprising, with
respect to the oil-in-water emulsion, from about 1 g/L to about 200 g/L.
Additionally, a method of ing a stable high-strength herbicidal oil-in-water
emulsion ition is disclosed that es:
a) ing a discontinuous oil phase comprising, with respect to the oil-in-
water emulsion, from about 25 grams active ingredient per liter (g ai/L) to about 300 g ai/L of
at least one oil soluble herbicide active ingredient and from 0 grams per liter (g/L) to about
300 g/L of a water immiscible organic solvent;
b) preparing a continuous aqueous phase comprising, with respect to the oil-in-
water emulsion, from about 260 g ai/L to about 570 g ai /L of a water soluble salt of
glyphosate and from about 200 g/L to about 500 g/L of water, and at least two non-ionic
EO/PO block copolymer emulsifying surfactants with at least one having a hydrophile
lipophile balance (HLB) value of about 13 to about 16 and at least one having an HLB value
of about 22 to about 29 and with each having a molecular weight (mw) of about 5000 or
higher, with the combined emulsifying surfactants comprising, with respect to the oil-in-
water emulsion, from about 1 g/L to about 200 g/L; and
c) adding the oil phase into the aqueous phase under high shear homogenization
until an emulsion is achieved.
Detailed ption
A high-strength, herbicidal oil-in-water emulsion pre-mix composition comprising a
dispersed oil phase containing at least one oil soluble herbicide and a water immiscible
organic solvent, a continuous aqueous phase containing a water soluble salt of glyphosate,
and at least two non-ionic EO/PO block copolymer emulsifying surfactant, one having an
hydrophile lipophile balance (HLB) value of about 13 to about 16 and the other having an
HLB value of about 22 to about 29, both having a molecular weight (mw) of about 5000 or
higher is disclosed. The ition may optionally include onal active ingredients
and inert formulation ingredients.
The oil soluble herbicide active ingredient contained in the discontinuous oil phase of
the compositions disclosed herein may generally be ed from the class of synthetic auxin
and lipid synthesis inhibitor (ACCase inhibitors) herbicides. Preferred herbicide active
ingredients include, but are not limited to, oil soluble derivatives of carboxylic acid
herbicides, such as esters of the following: benzoic acid herbicides, such as dicamba;
phenoxyalkanoic acid herbicides, such as 2,4-D, MCPA and 2,4-DB; pyridinecarboxylic acid
herbicides, such as aminopyralid, picloram and clopyralid; pyridinyloxyalkanoic acid
ides such as fluroxypyr and pyr; pyrimidinecarboxylic acids, such as
aminocyclopyrachlor; and, esters of the aryloxyphenoxypropionic acids, such as cyhalofop,
clodinafop, diclofop, fenoxaprop, fluazifop-P, haloxyfop, haloxyfop-R, metamifop,
propaquizafop and ofop-P. Preferred oil-soluble herbicide active ingredients also
include cyclohexanediones, such as cycloxydim, sethoxydim, tralkoxydim and the like. The
oil soluble herbicide active ingredient of the itions disclosed herein lly has a
water solubility of less than about 3000 parts per million (ppm) and ably less than about
1000 ppm. The oil soluble herbicide active ingredient comprises, with respect to the oil-in-
water on, from about 25 g ai/L to about 300 g ai/L.
The water immiscible organic solvent of the compositions disclosed herein lly
has a water solubility of less than about 1000 ppm and may e, but is not limited to, one
or more of petroleum fractions or hydrocarbons such as mineral oil, kerosene, paraffinic oils,
mixed naphthalene and alkyl naphthalene fractions, aromatic solvents, particularly alkyl
substituted benzenes such as xylene or propylbenzene fractions, and the like; heavy aromatic
solvent naphtha such as Aromatic 150 fluid (Exxon Mobil al; Houston, TX), dialkyl
amides of carboxylic acids, particularly the dimethyl amides of fatty acids such as the
dimethyl amide of ic acid and the like; vegetable, animal, algae or seed oils such as
soybean oil, rape seed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cotton
seed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters
of the above vegetable, animal, algae or seed oils; chlorinated aliphatic and aromatic
hydrocarbons such as l,l,l-trichloroethane and chlorobenzene; ketones such as isophorone
and trimethylcyclohexanone roisophorone); and acetate esters of C4-C10 alcohols such
as hexyl, or heptyl acetate, and the like. In some instances, where the herbicide active
ingredient is a liquid under normal operating conditions, the oil phase may contain very little
or none of the water immiscible organic solvent.
Preferred water immiscible organic solvents include one or more of petroleum
fractions or hydrocarbons such as mineral oil, paraffinic oils and aromatic solvents like
xylene, benzene fractions, alkyl naphthalene ons, and the like; dialkyl amides of
carboxylic acids, particularly the dimethyl amides of fatty acids such as the dimethyl amide
of caprylic acid and the like; vegetable or seed oils such as soybean oil, rape seed oil, olive
oil, castor oil, sunflower seed oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil,
peanut oil, safflower oil, sesame oil, tung oil and the like; and C1-C5 esters of vegetable or
seed oils and the like. The water immiscible organic solvent may comprise, with respect to
the oil-in-water emulsion, from about 0 g/L to about 300 g/L, preferably from about 10 g/L to
about 300 g/L.
Optional ingredients that may be added to the discontinuous oil phase described
herein include emulsion stabilizers such as, but not limited to, one or more low molecular
weight homopolymers (<5000 mw) of the following: polyolefins, such as polybutadiene,
polyisoprene, poly(substituted butadienes), such as poly(2-t—butyl-l,3-butadiene),
hylene, chlorinated polyethylene, polypropylene, polybutene, polyisobutene,
clopentylethylene and polycyclolhexylethylene; polyacrylates, including
polyalkylacrylates and polyarylacrylates; polymethacrylates, including
polyalkylmethacrylates and polyarylmethacrylates; polydisubstituted esters, such as in-butylitaconate
) and poly(amylfumarate); polyvinylethers, such as utoxyethylene) and
poly(benzyloxyethylene); poly(methyl penyl ketone); polyvinyl chloride; polyvinyl
carboxylate esters such as polyvinyl acetate, polyvinyl propionate, polyvinyl butyrate,
polyvinyl caprylate, polyvinyl laurate, nyl stearate and polyvinyl te;
polystyrenes, like polystyrene, —butyl styrene, poly (substituted styrene) and
poly(biphenyl ethylene); polycyclodienes, like poly(l,3-cyclohexadiene) and
polycyclopentadiene and the like; and low molecular weight (<5000 mw) co-polymers of
styrene, alkyl styrenes, isoprene, butenes, isobutenes, of which Indopol® H-15 is a preferred
example (Indopol is trademark of INEOS Oligomers), butadiene, acrylonitrile, alkyl
acrylates, alkyl methacrylates, vinyl chloride, vinylidene chloride, vinyl esters of lower
ylic acids and alpha, beta-ethylenically unsaturated carboxylic acids and esters thereof,
including ymers containing three or more different monomer species, and the like.
Additional on stabilizers include paraffinic hydrocarbons such as tetradecane,
hexadecane and the like.
The continuous aqueous phase of the compositions disclosed comprises water
as the solvent medium and a water soluble salt of glyphosate. Typically, water in the aqueous
phase of the emulsion formulation is used to dissolve the salt of glyphosate and any other
water soluble ingredients and to e the final composition. The continuous aqueous phase
of the compositions disclosed herein may comprise, with respect to the oil-in-water emulsion,
from about 200 g/L to about 500 g/L, preferably from about 200 g/L to about 400 g/L of
water.
The water soluble salt of glyphosate contained in the continuous aqueous phase of the
itions disclosed hereinmay comprise one or more of an organo ammonium salt and
the potassium salt of glyphosate. Suitable water soluble organo ammonium salts of
glyphosate include, but are not limited to, dimethyl ammonium, isopropyl ammonium,
monoethanol ammonium and the N,N,N,N—trimethylethanol ammonium (choline) salt of
glyphosate. The water soluble salt of glyphosate may comprise, with respect to the oil-in-
water emulsion, from about 260 g ai/L to about 570 g ai/L, ably from about 260 g ai/L
to about 450 g ai/L.
The compositions described herein also include at least two non-ionic EO/PO block
copolymer emulsifying surfactants with a hile lipophile balance (HLB) value of 13 or
higher and a molecular weight (mw) of about 5000 or higher. The utility of non-ionic
tants in emulsifying an oil-water e may in part be predicted by the Hydrophile-
Lipophile e (HLB) values of the tants. The HLB value of a surfactant estimates
the balance n the oil soluble and water soluble moieties in a surface active molecule
(i.e., a surfactant). A more oil-soluble emulsifier will have a lower HLB value (less than
about 7) and a more water-soluble emulsifier will have a larger HLB value (greater than
about 7). The HLB approach is a useful method to select an emulsifier for a particular
application and is more fully described in “The HLB System” an online ation available
from the crodalubricants.com website at the following link:
www.crodalubricants.com/download.aspx?s= l 33&m=doc&id=267 .
The non-ionic EO/PO block copolymer emulsifying tants of the compositions
disclosed herein include at least one surfactant with an HLB value of about 13 to about 16
and at least one surfactant with an HLB value of about 22 to about 29, with the surfactants
having a molecular weight of a least about 5000. The EO/PO block copolymer emulsifying
surfactants described herein include both di- and tri-block co-polymers of ethylene oxide
(EO) and propylene oxide (PO). Preferred non-ionic EO/PO block copolymer surfactants of
the compositions disclosed herein e, but are not limited to, Pluronic® L35, L44, L64,
P65, P75, P84, P85, P104, P105, F77, F87, F88, F68, F68 LF, F98, F108, F127, 17R8 and
25R8; Tetronic® 704, 707, 904, 1104, 1107, 1307, 1504, 1508, 50R8 and 90R8; Macol® 15-
; Toximul® 8323 and 8323/33; Step-Flow® 26, 26F and 1500; Synperonic® PE 30/40, PE
/80 and PE 39/70; Pegol® 10R8, 17R8, 25R8, F-68LF, F-108, F-127, L-10, L-35, L-44, P-
65, P-75 and P-85; Antarox® 724/13, T-Det® BP-l, EPO-64 and EPO-104; Agrilan® AEC167;
Monolan® 4500, 6400, 8000 E/80 and 12,000 E/80; Genapol® PF80 Powder; Hartopol® P85;
ic® POA-L44 and L64; Soprophor® 796P, BSU, CY8, $25 and 825/80; and Atlas® G-
5000. (Pluronic, Tetronic and Macol are arks of BASF Aktiengesellschaft; Toximul
and Step-Flow are trademarks of Stepan; onic and Pegol are trademarks of Croda;
Antarox and Soprophor are trademarks of Rhodia Inc., T-Det is a trademark of Harcos;
Agrilan and Monolan are trademarks of Akzo Nobel; Genapol is a trademark of Clariant;
Hartopol and Surfonic are trademarks of Huntsman; Atlas is a trademark of Uniqema). The
non-ionic EO/PO block copolymer emulsifying surfactants of the compositions sed
herein may comprise, with respect to the oil-in-water emulsion, from about 1 g/L to about
200 g/L, ably from about 1 g/L to about 100 g/L.
The compositions described herein may optionally contain additional water soluble
herbicide active ingredients if they cause no incompatibility or active ingredient stability
issues to other ients of the composition. These water soluble herbicide active
ients may be selected from, but are not limited to, alkali metal salts or amine salts of
benzoic acids, phenoxyalkanoic acids, pyridinecarboxylic acids, pyrimidinecarboxylic acids
and pyridinyloxycarboxylic acids such as, a, 2,4-D, MCPA, 2,4-DB, aminopyralid,
aminocyclopyrachlor, am, clopyralid, fluroxypyr and triclopyr, and alkali metal salts of
bromoxynil and ioxynil. The amines are comprised of primary, secondary or ry
alkylamines, alkanolamines, alkylalkanolamines or alkoxyalkanolamines wherein the alkyl
and alkanol groups are saturated and contain C1-C4 alkyl groups individually. The alkali
metals are comprised of sodium and ium.
The compositions described herein may ally contain inert formulation
ingredients such as, but not limited to, adjuvants, antifoam agents, dispersants, tants,
spray drift reduction agents, stabilizers and wetting agents. These optional inert ingredients
may include surfactants conventionally used in the art of formulation that are described, inter
alia, in “McCutcheon’s Detergents and Emulsifiers Annual,” MC hing Corp.,
Ridgewood, New Jersey, 1998 and in the “Encyclopedia of Surfactants,” Vol. I-III, Chemical
Publishing Co., New York, 1980-81. Adjuvants that are particularly well-suited for use in the
compositions disclosed herein may include one or more of: alkylamine surfactants having 8
to 22 carbon atoms such as Armeen® DMTD and Duomeen® TTM; alkoxylated alkylamine
surfactants having 8 to 22 carbon atoms and a total of 1 — 20 ne oxide groups such as
Ethomeen® C/12, Ethomeen® T/12, Ethoduomeen® T/13 and Propomeen® T/12; etheramine
surfactants such as Tomah® , Tomah® E5 and Tomah® PA-17; amine oxide
tants such as Aromox® C/12, ® DMC, x® LO, Ammonyx® CD0 and
Tomah® 2; amidoamine surfactants such as Adsee® C80W; quaternary ammonium
surfactants such as Arquad® T/50, Arquad® APA-E, Duoquad® T/50, Ethoquad® C/12,
Ethoquad® 18/12 and Tomah® Q2; amphoteric surfactants such as Dehyton® AB-30,
Geronol® CF/AS 30, Tego® Betaine F 50t and Miranol® C2M-SF (Disodium Cocoampho
Dipropionate); alcohol ethoxylates such as Tergitol® 15S20; alcohol late phosphate
esters such as Geranol® CF/AR; alkyl polyglycosides such as Akzo Nobel’s AG 6202 and
AG 6210, and Cognis’ Agnique PG 8107-U (CS-16 alkyl ucoside in which the alkyl
group contains 8 to 10 carbon atoms and having an average degree of polymerization of 1.7);
and ester derivatives of alkyl polyglycosides such as the Eucarol® AGE surfactants. (Armeen,
Duomeen, Ethomeen, Ethoduomeen, Propomeen, Aromox, Arquad, Duoquad, Ethoquad and
Adsee are trademarks of Akzo Nobel; Tomah is a trademark of Air Products; x is a
trademark of Stepan; Dehyton and Agnique are a trademarks of Cognis; Geronol and Miranol
are arks of Rhodia Inc.; Tego is a trademark of Goldschmidt; Tergitol is a trademark
of The Dow Chemical Company; Eucarol is a trademark of Lamberti)
The compositions disclosed herein e a high-strength herbicidal oil-in-water
emulsion composition that is storage stable at high temperatures. That is, the composition
forms a stable, homogeneous emulsion that does not exhibit coalescence under the storage
conditions. More preferably, the composition described herein is stable at temperatures of
greater than or equal to about 40 °C for a period of at least 4 weeks, more preferably, at
temperatures greater than or equal to about 54 °C for a period of at least about 4 weeks.
Furthermore, the high-strength oil-in-water on composition described herein
also does not exhibit separation or precipitation (or crystallization) of any of the components
at low temperatures. For e, the composition remains a neous emulsion at
temperatures below about 20 °C, more preferably at temperatures below about 10 °C and
most preferably at a temperature equal to or less than about 5 °C for a period of at least about
4 weeks.
In a typical procedure for preparing the high-strength oil-in-water emulsion
compositions described , the aqueous phase is prepared by mixing the water with water
soluble or water dispersible ingredients including, but not limited to, water e or water
dispersible dispersing or emulsifying surfactants, water soluble active ingredients and
optionally, other inert ingredients such as thickeners, pH buffers, wetting agents, antifreeze
agents, antifoam agents, biocides, etc. The oil phase is ed by mixing the oil-soluble
emulsifying surfactants with oil miscible or soluble ingredients, including but not limited to,
water immiscible organic ts and oil soluble active ingredients. The final emulsion
formulation is prepared by slowly adding the oil phase into the aqueous phase under high
shear homogenization until a desired emulsion droplet size is achieved. Emulsion droplet
sizes can be, for example, between 0.1 um and 5 um, between 01 um and 4 um, 01 um and
3 um, 01 um and 2 um, or 01 um and l um.
An e of a , high-strength oil-in-water emulsion ition bed
herein in which coalescence of the dispersed oil phase and crystallization and Oswald
ripening of an oil soluble active ingredient is retarded comprises:
a) a discontinuous oil phase comprising, with respect to the oil-in-water emulsion,
from about 25 g ai/L to about 300 g ai/L of fluroxypyr-meptyl and from about 1 g/L to about
300 g/L of naphthalene depleted Aromatic 150 fluid;
b) a continuous aqueous phase comprising, with respect to the oil-in-water emulsion,
from about 310 g ai/L to about 570 g ai/L of glyphosate dimethyl ammonium and from about
200 g/L to about 500 g/L of water;
c) two non-ionic EO/PO block copolymer emulsifying tants with at least one
having a hydrophile lipophile e (HLB) value of about 13 to about 16 and at least one
having an HLB value of about 22 to about 29 and with each surfactant having a molecular
weight (mw) of about 5000 or higher together comprising, with respect to the oil-in-water
emulsion, from about 1 g/L to about 200 g/L each of Pluronic® F68 LF and Soprophor®
796/P; and
WO 51455
d) optionally, other inert ation ingredients.
In addition to the compositions and uses set forth above, also described herein are
itions and use of oil-in-water emulsions in combination with one or more additional
compatible ingredients. Other additional ingredients may include, for example, one or more
other pesticides, dyes, and any other additional ingredients providing functional utility, such
as, for example, stabilizers, compatibility agents, fragrants, ity-modifying additives,
suspension aids, dispersants, and freeze-point depressants.
The aqueous herbicidal compositions described herein may optionally be diluted in an
aqueous spray mixture for agricultural ation such as for bumdown weed control in crop
fields prior to planting. Such compositions are typically d with an inert carrier, such as
water, before ation. The diluted compositions, which are usually applied to weeds, the
locus of weeds or the locus of where weeds may eventually emerge, generally contain about
0.0001 to about 1 weight percent active ingredient and preferably contain about 0.001 to
about 0.05 weight percent active ingredient. The compositions disclosed herein can be
applied to weeds or their locus by the use of conventional ground or aerial sprayers, by
addition to irrigation water and by other conventional means known to those skilled in the art.
The herbicidal compositions described herein may be applied in conjunction with one
or more other ides to control a wider variety of undesirable vegetation. When used in
conjunction with other herbicides, the presently claimed compositions can be formulated with
the other herbicide or herbicides as premix concentrates, tank mixed with the other herbicide
or herbicides for spray application or applied sequentially with the other herbicide or
herbicides in separate spray ations.
The ing Examples are presented to illustrate various s of the
compositions and methods described herein and should not be construed as limitations to the
claims.
Example 1. Preparation of a Stable Oil-in-Water Emulsion ning Glyphosate
Dimethyl um {DMA} and Fluroxypyr Meptyl (MHE)
A glyphosate DMA salt concentrate was prepared by mixing 247.4 g glyphosate acid
technical y 97%) with 1.1 molar equivalents of dimethylamine aqueous solution (40%
in water) to form a homogeneous clear solution at ambient temperature. To the glyphosate
DMA solution were then added 31.2 g of Agnique® PG 8107-U (Agnique is a ered
trademark of Cognis) and 154.9 g of water to achieve a concentration of 608 g ai/L [480
grams acid equivalent per liter (g ae/L)] of glyphosate DMA. An oil phase was prepared by
dissolving 35.6 g of fluroxypyr MHE (purity 97.1%) in 53.4 g of Aromatic 150 ND fluid
(ExxonMobil Chemical Company; Houston, TX) containing 13.7 g of Pluronic® F68 LF
(Pluronic is a registered trademark of BASF Aktiengesellschaft), 5.1 g of Soprophor® 796/P
(Soprophor is a registered trademark of Rhodia Inc) and 3.4 g of Indopol® H15 (Indopol is a
registered trademark of INEOS Oligomers) to e a solution while maintaining the
temperature at 50 0C. Finally, to prepare a 300 mL sample (Sample A in Table 1) of an oil-
in-water emulsion containing 115 g ai/L [80 g ae/L] of fluroxypyr MHE and 380 g ai/L [ 300
g ae/L] of glyphosate DMA, respectively, the above oil phase containing fluroxypyr MHE
was slowly added into 229 g of the glyphosate DMA salt concentrate at 7,000-11,000 rpm
(depending on the desired on size) by using a son high-shear homogenizer. 1.8 g
water was eventually added to achieve the desired concentration. A stable, homogenous oil-
in-water emulsion concentrate containing pyr MHE and glyphosate DMA was
generated in this manner.
Table 1. Oil-in-Water on Concentrates (ingredients in weight percent)
Component
ypyr—meptyl
Haloxyfop-R-methyl
Glyphosate DMA
Agnique® PG 8107-U 5.5
ic® F-68 LF
Pluronic® P-104
Soprophor® 796P
1001305135
Aromatic 150 ND
lndopol® H—1 5
water
lSamples A and B n 115 grams active ingredient per liter (g ai/L) of fluroxypyr meptyl
and 380 g ai/L of glyphosate dimethyl ammonium (DMA). 2Samples C and D contain 86 g
ai/L of fluroxypyr meptyl and 355 g ai/L of glyphosate DMA. 3 Sample E contains 29 g ai/L
of haloxyfop—R—methyl and 380 g ai/L of glyphosate DMA.
The homogenous oil-in—water emulsion concentrates es A, B, C, D and E) thus
prepared were stable to coalescence and crystallization while stored at 54 0C for 4 weeks or
while stored at 5 0C for 4 weeks.
The present invention is not limited in scope by the embodiments disclosed herein
which are ed as illustrations of a few aspects of the invention and any embodiments
which are functionally equivalent are within the scope of this invention. Various
modifications ofthe compositions and methods in addition to those shown and described
herein will become apparent to those skilled in the art and are intended to fall within the
scope of the ed claims. Further, while only certain representative combinations of the
composition components and method steps disclosed herein are specifically discussed in the
embodiments above, other combinations of the composition components and method steps
will become nt to those skilled in the art and also are intended to fall within the scope
of the appended claims. Thus a combination of components or method steps may be
explicitly mentioned herein; however, other combinations of ents and method steps
are included, even though not explicitly stated. The term “comprising” and variations f
as used herein is used synonymously with the term “including” and variations thereof and are
open, non-limiting terms.
Reference to any prior art in the ication is not, and should not be taken as, an
acknowledgment or any form of suggestion that this prior art forms part of the common
general dge in New Zealand or any other jurisdiction.
1001359428
Claims (20)
1. A stable high—strength herbicidal -water emulsion composition comprising: a) a discontinuous oil phase comprising, with respect to the oil—in-water emulsion, from about 25 grams active ingredient per liter (g ai/L) to about 300 g ai/L of at least one oil soluble herbicide active ingredient and from 0 grams per liter (g/L) to about 300 g/L of a water immiscible organic solvent; b) a uous aqueous phase comprising, with respect to the oil—in—water emulsion, from about 260 g ai/L to about 570 g ai /L of a water soluble salt of glyphosate and from about 200 g/L to about 500 g/L of water; and 10 c) at least two nic EO/PO block eopolymer emulsifying surfactants with at least one having a hydrophile lipophile balance (HLB) value of about 13 to about 16 and at least one having an HLB value of about 22 to about 29 and with each having a molecular weight (mw) of about 5000 or higher, with the ed emulsifying surfactants sing, with respect to the —water emulsion, from about 1 g/L to about 200 g/L. 15
2. The composition of claim 1, wherein the at least one oil soluble herbicide active ingredients is a synthetic auxin or a lipid synthesis inhibitor herbicide.
3. The composition ofclaim l or 2, wherein the at least one oil soluble herbicide active ingredient has a water solubility of less than about 3000 parts per million (ppm).
4. The composition of any one of claims 1 to 3, wherein the water immiscible organic 20 solvent has a water solubility of less than about 1000 ppm.
5. The ition of any one of claims 1 to 4, wherein the tinuous oil phase further includes an emulsion stabilizer.
6. The composition of any one of claims 1 to 5, wherein the continuous aqueous phase includes from about 200 g/L to about 400 g/L of water. 25
7. The composition of any one of claims 1 to 6, wherein the water soluble salt of glyphosate is an organo ammonium salt or a potassium salt. 1001359428
8. The composition of claim 7, n the organo ammonium salt is a dimethyl ammonium, a pyl ammonium, a monoethanol ammonium, or a N,N,N,N— trimethylethanol ammonium (choline) salt.
9. The ition of any one of claims 7 to 8, wherein the continuous aqueous phase includes about 260 g ai/L to about 450 g ai/L of the water soluble salt of glyphosate.
10. The composition of any one of claims 1 to 9, wherein the at least two non—ionic EO/PO block copolymer emulsifying tants include both di— and tri-block co—polymers of ethylene oxide (E0) and propylene oxide (PO).
1 l. The composition of any one of claims 1 to 10, wherein the combined emulsifying 10 tants comprise, with respect to the —water emulsion, about 1 g/L to about 100 g/L.
12. The composition of any one of claims 1 to l 1, further including additional water soluble herbicide active ients.
13. The composition of any one of claims 1 to 12, wherein the composition forms a stable, homogeneous emulsion that does not exhibit coalescence under the storage conditions. 15
14. The composition of any one of claims 1 to 13, wherein the composition is stable at temperatures of greater than or equal to about 40 °C for a period of at least 4 weeks.
15. The composition of any one of claims 1 to 14, n the composition does not exhibit separation or precipitation (or crystallization) of any 01" the components at temperatures below about 20 0C. 20
16. The composition of any one of claims 1 to 15, wherein the discontinuous oil phase comprises fluroxypyr-meptyl and naphthalene depleted Aromatic 150 fluid, and the continuous aqueous phase comprises glyphosate dimethyl ammonium and water.
17. A method of preparing a stable trength herbicidal oil—in-water emulsion composition comprising: 25 a) ing a discontinuous oil phase comprising, with respect to the oil—in— water emulsion, from about 25 grams active ingredient per liter (g ai/L) to about 300 g ai/L of at least one oil soluble herbicide active ingredient and from 0 grams per liter (g/L) to about 300 g/L of a water immiscible organic solvent; 1001359428 b) preparing a continuous aqueous phase comprising, with respect to the oil-in- water emulsion, from about 260 g ai/L to about 570 g ai /L of a water soluble salt of glyphosate and from about 200 g/L to about 500 g/L of water, and at least two non-ionic EO/PO block copolymer emulsifying surfactants with at least one having a hydrophile lipophile balance (HLB) value of about 13 to about 16 and at least one having an HLB value of about 22 to about 29 and with each having a molecular weight (mw) of about 5000 or , with the combined emulsifying surfactants comprising, with respect to the oil—in- water emulsion, from about 1 g/L to about 200 g/L; and 0) adding the oil phase into the aqueous phase under high shear homogenization 10 until an emulsion is ed.
18. The method of preparing the stable high—strength herbicidal oil—in~water emulsion composition ol’claim 17, wherein the on t size is between 0.1 um and 5 um.
19. The composition ofclaim l, substantially as herein described.
20. The method of claim 17, substantially as herein described.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201161482716P | 2011-05-05 | 2011-05-05 | |
US61/482,716 | 2011-05-05 | ||
PCT/US2012/036422 WO2012151455A1 (en) | 2011-05-05 | 2012-05-04 | Stable high strength oil-in-water emulsions |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ617125A NZ617125A (en) | 2016-02-26 |
NZ617125B2 true NZ617125B2 (en) | 2016-05-27 |
Family
ID=
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11058108B2 (en) | Stable high strength oil-in-water emulsions | |
EP3054774B1 (en) | Aqueous herbicidal concentrates | |
US20090227460A1 (en) | Stabilized oil-in-water emulsions including meptyl dinocap | |
EP2858506B1 (en) | High strength herbicidal suspension concentrates | |
MX2011004587A (en) | Stable emulsifiable concentrates containing a first herbicidal carboxylic acid salt and a second herbicidal carboxylic acid ester. | |
AU2014346624C1 (en) | Pesticide emulsion concentrates containing natural or petroleum derived oils and methods of use | |
EP2823296B1 (en) | Organic colloid-stabilized emulsion for controlling pesticide spray drift | |
AU2014331782B2 (en) | Aqueous herbicidal concentrates | |
EP3131392A1 (en) | Aqueous pesticide concentrates containing paraffinic oils and methods of use | |
NZ617125B2 (en) | Stable high strength oil-in-water emulsions | |
WO2022118818A1 (en) | Agrochemical composition |