MXPA97005908A - Particles of arilpirrol stable, the process for its preparation and the compositions of concentrate in suspension that compress - Google Patents
Particles of arilpirrol stable, the process for its preparation and the compositions of concentrate in suspension that compressInfo
- Publication number
- MXPA97005908A MXPA97005908A MXPA/A/1997/005908A MX9705908A MXPA97005908A MX PA97005908 A MXPA97005908 A MX PA97005908A MX 9705908 A MX9705908 A MX 9705908A MX PA97005908 A MXPA97005908 A MX PA97005908A
- Authority
- MX
- Mexico
- Prior art keywords
- weight
- particles
- alkyl
- agent
- stable
- Prior art date
Links
- 239000002245 particle Substances 0.000 title claims abstract description 141
- 239000000203 mixture Substances 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000000725 suspension Substances 0.000 title claims description 6
- 239000012141 concentrate Substances 0.000 title claims description 4
- 239000004546 suspension concentrate Substances 0.000 claims abstract description 28
- 238000003860 storage Methods 0.000 claims abstract description 17
- CWFOCCVIPCEQCK-UHFFFAOYSA-N Chlorfenapyr Chemical compound BrC1=C(C(F)(F)F)N(COCC)C(C=2C=CC(Cl)=CC=2)=C1C#N CWFOCCVIPCEQCK-UHFFFAOYSA-N 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002270 dispersing agent Substances 0.000 claims description 21
- 125000005843 halogen group Chemical group 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- -1 polycyclic aromatic compounds Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 17
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- 239000000375 suspending agent Substances 0.000 claims description 15
- 239000002562 thickening agent Substances 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 230000002335 preservative Effects 0.000 claims description 11
- 239000003755 preservative agent Substances 0.000 claims description 11
- 239000002518 antifoaming agent Substances 0.000 claims description 10
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 9
- 125000001188 haloalkyl group Chemical group 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000007859 condensation product Substances 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 229920001285 xanthan gum Polymers 0.000 claims description 6
- 229920001400 block copolymer Polymers 0.000 claims description 5
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 5
- 150000003839 salts Chemical group 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000000230 xanthan gum Substances 0.000 claims description 5
- 235000010493 xanthan gum Nutrition 0.000 claims description 5
- 229940082509 xanthan gum Drugs 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- PZZYQPZGQPZBDN-UHFFFAOYSA-N Aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims description 3
- 102100004109 HEY1 Human genes 0.000 claims description 3
- 108010081348 HRT1 protein Hairy Proteins 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- 239000007798 antifreeze agent Substances 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 2
- 244000215068 Acacia senegal Species 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 229920000084 Gum arabic Polymers 0.000 claims description 2
- 239000000205 acacia gum Substances 0.000 claims description 2
- 235000010489 acacia gum Nutrition 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 235000010987 pectin Nutrition 0.000 claims description 2
- 229920001277 pectin Polymers 0.000 claims description 2
- 239000001814 pectin Substances 0.000 claims description 2
- 238000006277 sulfonation reaction Methods 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims 2
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 2
- UQVZNLINGOJPTL-UHFFFAOYSA-N C(=O)O.C1=CC=CC2=CC=CC=C12 Chemical compound C(=O)O.C1=CC=CC2=CC=CC=C12 UQVZNLINGOJPTL-UHFFFAOYSA-N 0.000 claims 1
- 241001438449 Silo Species 0.000 claims 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N Talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 claims 1
- 125000000304 alkynyl group Chemical group 0.000 claims 1
- 230000003712 anti-aging Effects 0.000 claims 1
- 230000002354 daily Effects 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- 239000004088 foaming agent Substances 0.000 claims 1
- 125000003827 glycol group Chemical group 0.000 claims 1
- 229910052919 magnesium silicate Inorganic materials 0.000 claims 1
- 235000019792 magnesium silicate Nutrition 0.000 claims 1
- 150000003385 sodium Chemical group 0.000 claims 1
- 230000000361 pesticidal Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 11
- 238000011105 stabilization Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- DMSMPAJRVJJAGA-UHFFFAOYSA-N Benzisothiazolinone Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000087 stabilizing Effects 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- 238000001238 wet grinding Methods 0.000 description 3
- SQAINHDHICKHLX-UHFFFAOYSA-N 1-naphthaldehyde Chemical compound C1=CC=C2C(C=O)=CC=CC2=C1 SQAINHDHICKHLX-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000008504 concentrate Nutrition 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 235000012243 magnesium silicates Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N D-sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- JNYAEWCLZODPBN-CTQIIAAMSA-N Sorbitan Chemical compound OCC(O)C1OCC(O)[C@@H]1O JNYAEWCLZODPBN-CTQIIAAMSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-GDQSFJPYSA-N Sucrose Natural products O([C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O1)[C@@]1(CO)[C@H](O)[C@@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-GDQSFJPYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 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
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 230000003247 decreasing Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000640 hydroxylating Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical class C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001888 polyacrylic acid Polymers 0.000 description 1
- 235000014483 powder concentrate Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
Abstract
The present invention relates to arylpyrrole particles which are prepared by means of a process in which the particles are stabilized and milled, and to the pesticidal suspension concentrate compositions comprising them. The size of the particles of this invention remains surprisingly stable during storage.
Description
, AND THE CONCENTRATE COMPOSITIONS IN SUSPENSION THAT COMPRISE THEM "
BACKGROUND OF THE INVENTION Pests such as insects and acarids cause tremendous global economic losses by reducing crop products and decreasing the quality of crops. The aryipyrrole compounds are useful for the control of insect pests and acarids. However, it has been discovered that the aryipyrrole particles present in a suspension concentrate may not maintain a stable particle size. In particular, it has been found that certain arylpyrrole particles grow to an unacceptable size during storage. Certain compounds of apipirrol pesticides and methods for their preparation and use are described in U.S. Patent Nos. 5,010,098 and 5,233,051; and Canadian Patent Application No. 2,076,937. Chlorfenapyr (4-bromo-2- (p-chlorophenyl) -1- (ethoxymethyl) «5- (trifluoromethyl) pyrrol-3-carbonrtrion) was the first pesticide of arylpyrrole to be marketed. Chlorfenaptr and methods for its preparation and use are described in U.S. Patent No. 5,010,098. Suspension concentrate compositions comprising arylpyrrole particles are described in U.S. Patent No. 5,496,845. However, it has been found that the particle size stability of the arylpyrrole compounds in the reference compositions is variable. Commonly, the arylpyrrhal particles known in the art increase in size during storage, for example, an initial amount of relatively small particles becomes the smallest amount of larger particles. It is convenient to have particles whose sizes are stable over time, in order to avoid unwanted variations in the characteristics of the formulations that contain this particle.
REF: 25383 SUMMARY OF THE INVENTION The present invention provides stable arylpyrrole particles in which more than about 20% of the arylpyrrole has a stable crystalline form. The present invention also provides a process for the preparation of "stable arylpyrrole particles whose process comprises: a) providing a first mixture comprising particles of arylpyrrole, a dispersing agent and water; b) maintaining the first mixture in a temperature range of about 25 ° C to 80 ° C to obtain a stabilized mixture; and c) grinding the stabilized mixture to obtain the stabilized arylpyrrole particles. The present invention also provides stable arylpyrrole particles prepared by means of! process of this invention, and suspension concentrate compositions comprising the arylpyrroid particles of this invention. It is, therefore, an object of the present invention to provide a process for stabilizing the arylpyrrole particles. It is another object of this invention to provide stable arylpyrrole particles.
It is another object of this invention to provide suspension concentrate compositions comprising stable arylpyrrole particles. These and other objects and advantages of the present invention will be obvious from the detailed description below, and from the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a characteristic infrared absorption spectrum of the polymorphism of chlorfenapyr designated as "Polymorph t" Figure 2 is the infrared absorption spectrum characteristic of the polymorphism of chlorfenapyr designated as "Polymorph 11 ° DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In an important aspect, the present invention provides stable arylpyrrole 4 particles that grow insignificantly during storage in suspension concentrate compositions.We have discovered that arylpyrroles can exist in at least two forms of crystals. of chlorfenapyr, for example, are designated here as Polymorph I and Polymorph I. Polymorph I has a melting point of 95 β C and the characteristic infrared absorption spectrum illustrated in Figure 1. Polymorph II has a melting point of 101 βC. and the infrared absorption spectrum We have also discovered that certain forms of arylpyrrole crystal are more stable than other forms of aryipyrrole crystal. Surprisingly, compositions containing chlorfenapyr particles having a ratio between Polymorph I and Polymorph II greater than about 1: 4, are significantly more stable in storage than compositions having a relationship between Polymorph I and Polymorph II from 1 4 to 0: 1. Advantageously, the present invention relates to aryl pyrroi particles comprising a stabilizing amount of a stable crystal form of arylpyrrole.
The stabilizing amount of the stable crystal form is that amount which prevents unacceptable particle growth during storage in the compositions comprising the aplpyrrole and water particles. The unacceptable particle growth reduces the pesticidal efficacy of the arylpyrroles and / or adversely affects the physical properties of the compositions.
Until now, the stability of arylpyrrole particles was unpredictable because commercial production methods provide particles that have widely varying amounts of stable crystal form. The existence and importance of the different forms of crystal were not known and understood, and there was no method to achieve stable predictable particles. Now it has been discovered that different forms of crystal, or polymorphs, can be identified. It has also been found that suspension concentrate compositions of arylpyrrole comprising a high percentage of a polymorph are more stable than suspension concentrate compositions comprising a low percentage of that polymorph. In particular, chlorfenapyr suspension concentrate compositions comprising chlorfenapyr particles containing a high percentage of Polymorph I are more stable than suspension concentrate compositions containing a low percentage of Polymorph I. Because the amount of each crystal form, the stable arylpyrrole suspension concentrates can now be achieved consistently and predictably by forming the suspension of arilpyrroi particles having a sufficient stable crystal content. The arylpyrrole particles having the desired amount of the stable crystal form can be selected from a variety of particles formed by means of commercial production processes Batches of arylpyrrole having different ratios between the stable crystal form and the unstable crystal form can be mixed, using the mixing methods known in the art for achieve rel desired action. The ratio of the polymorphs present in a particular batch of chlorfenapyr particles can be determined by means of infrared analysis.
The chlorfenapyr particles of the present invention preferably comprise at a ratio between Polymorph I and Polymorph II of about 1: # to 1: 0 and more preferably of about 1: 1 to 1: 0. The average volume diameter of the arylpyrrole particles of this invention. preferably it is less than about 100 μm, more preferably less than about 15 μm, and more preferably between about 0.5 μ to 10 μm. The arylpyrrole particles of this invention can be formulated as suspension concentrates, dispersible granules, wettable powders, powders, powder concentrates, microemulstones and the like, by methods well known in the art. These compositions include the arylpyrrole particles of this invention and one or more agronomically acceptable solid or liquid carriers. In particular, the present invention provides stable suspension concentrate compositions comprising between about 10% to 50% by weight of the arylpyrrole particles of this invention, about 0.1% to 2% by weight of an agent dispersant, about 0.5% to 5% of a steric stabilizer, about 0.1% to 1% by weight of a suspending agent, about 0.01% to 0.5% by weight of a thickener, up to about 5% by weight of an anti-freezing agent, up to about 1% by weight of an antifoam agent, up to about 0.5% by weight of a preservative and water. The stable suspension concentrate compositions of this invention preferably comprise between 10% and 40% by weight of the arylpyrrole particles, between 0.5% to 1%., 5% by weight of a dispersing agent, between 1.5% to 3.5% by weight of a spherical stabilizer, between 0.1% to 1% by weight of a suspending agent, among 0 , 01% up to 0.5% by weight of a spinal agent, between 5% to 10% by weight of an anti-freezing agent, between 0.1% to 1% by weight of an antifoam agent, between 0.01% to 0.5% by weight of a preservative, and water. In the suspension concentrate compositions of the present invention, the ratio between the total amount of the dispersing agent and the spherical stabilizer with the arylpyrrole particles is preferably from about 1: 5 to 1:15 and more preferably from 1.8 to 1.10. . The average volume diameter of the aryipyrrole particles present in the suspension concentrate compositions of this invention is preferably less than 15 μm, more preferably between about 0.5 μm and 10 μm, and more preferably between about 0, 5 μm to 4 μm. The arylpyrrole compounds of this invention include those having the structural formula I
(i)
where X is H, F, Cl, Br, I, haloalkyl of C1-C4 or S (O) m (haloalkyl of C1-C4), and is F, Cl, Br, I, haloalkyl of dC * or CN; W is CN or NO2. A is a C 1 -C 4 alkyl optionally substituted with between one and three halogen atoms, a cyano, a hydroxy, a C 1 -C 4 alkoxy, a C 4 -C 4 alkyl, a phenyl optionally substituted with C 1 -C 4 alkyl -C3, C?-C3 alkoxy, or one to three halogen atoms, a phenoxy optionally substituted with one to three halogen atoms, or a benzyloxy optionally substituted with a halogen atom, C 1 -C 4 carbalkoxymethyl, C 3 alkenyl -C4 optionally substituted with between one and three halogen atoms, cyano, C3-C4 aikinyl optionally substituted with a halogen atom, di (C1-C4 alkyl) aminocarbonyl !, or benzoyl optionally substituted with between one and three halogen atoms or between one and three C1-C4 alkyl groups; L is H, F, Cl or Br; M and R are each independently H, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkyl, C 1 -C 3 alkylsulphthin, C 1 -C 3 alkylsulfonyl, cyano, F, Cl, Br, I, nitro, C1-C3 haloalkyl, RiCFsZ, R2CO or NR3, or when M and R are in adjacent positions and taken together with the carbon atoms to which they are attached they can form a ring in which MR represents the structure: -OCH2O -, OCF2O-, -OCRßR / CRgRβO-, -OCHjCHs-, OCH2CH2CHs- or -CH = CH-CH = CH; Z is S (O) "or O; R, is H, F, CHF2, CHFCI or CF3; R2 is C1-C3 alkyl, C1-C3 alkoxy or NR3R4; R3 is H or C1-C3 alkyl; R 4 is H, alkyl of d-Ca or R 5 CO; R5 TS H O C1-C3 alkyl; Re. R7, e and R are each independently hydrogen, halogen or alkyl
and m and n are each independently an integer of 0, 1 or 2. Preferred arylpyrrole compounds suitable for use in the present invention are those having the structural formula II
(II)
where X; Y, W, A, L, M and R are as we have described above. The most preferred arylpyrrole compounds that are particularly suitable for use in this invention are those having the structural formula II where X and Y are each independently Cl, Br or CF3; W is CN; A is C1-C4 alkoxymethyl; L is H or F; M is H, F, Cl or Br; and R is F, Cl, Br, CF3 or OCF3. Another important aspect of this invention is a process for preparing stable arylpyrrole particles, which process comprises: a) providing a first mixture comprising particles of arylpyrrole, a dispersing agent and water; b) maintaining the first mixture in a temperature range of around 25 ° C to 80 ° C to obtain a stabilized mixture; and c) grinding the stabilized mixture to obtain the stabilized arylprrrol particles. The process of the present invention hereinafter sometimes referred to as "stabilization process". In this context, stabilization refers to maintaining a relatively constant particle size. The stable particles do not grow significantly during storage at room temperature for up to three months or more in a suspension concentrate composition. It has now been found that when the content of the stable polymorph of arylpyrroi is less than about 80%, especially less than about 50%, and more especially less than about 25% by weight, (stability of the aplpyrrole particles can The amount of time necessary to obtain a sufficiently stabilized mixture will vary, and will depend to some extent on the initial content of the crystal form, the particle size and the temperature. It is especially useful for stabilizing chlorfenapyr particles
To solve the problems associated with the use of the arylpyrrole particles containing the less stable polymorph, it is convenient to subject all the arylpyrrole particles to the stabilization process of this invention. The stabilization process of this invention is especially useful for improving the particle size stability of chlorfenapyr containing less than 80% of Polymorph I. The average volume diameter of the arylpyrrole particles used in the process of this invention is preferably less than about 100 μm and more preferably between about 0, 5 μm to 30 μm. The average volume diameter of the stabilized arylpyrrole particles prepared by the stabilization process is preferably between about 0.5 μm to 10 μm and more preferably about 0.5 μm to 4 μm. Dispersing agents suitable for use in this invention include, but are not limited to, the salts of the condensation products of formaldehyde with the sulfonation products of the polycyclic aromatic compounds.; the salts of the polyacrylic acids, the products of the condensation of fatty acids or amines or air-amides containing at least about 12 carbon atoms in the molecule with ethylene oxide and / or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaertritol and their condensation products with ethylene oxide and / propylene oxide; the condensation products of fatty alcohols or alkyl phenols with ethylene oxide and / or propylene oxide and their sulfates or sulphonates; and alkali metal or alkaline earth metal salts of sulfuric or sulfonic acid esters containing at least ten carbon atoms in the molecule, for example, sodium lauryl sulfate and dodecyl (benzene sulfonate.
Preferred dispersing agents include the salts of the condensation products of formaldehyde with the surfonation products of aromatic polycyclic compounds such as, for example, the salts of the condensation products of formaldehyde with naphthalene sulfonates, petroleum suifonates and suifonates. of lignin. Preferred month dispersion agents include the sodium sulfonate of the naphthalene formaidehyde condensates such as, for example, MORWET® D425 (Witco, Houston, Texas), LOMAR® PW (Henkel, Cincinpati, Ohio) and DARVAN® 1 (RT Vanderbilt Co., Norwalk, Connecticut). In a preferred process of the present invention, the first mixture is maintained in a temperature range of around 40 ° C to 60 ° C. In another preferred process of this invention, the first mixture is preferably kept within a temperature range between about 1 hour to 72 hours, more preferably for about 2 hours to 48 hours and more for about 2 hours to 24 hours . The first mixture of the present invention preferably comprises about 10% haßat 85% by weight of the aplpyrrole particles, about 0.1% to 3.5% by weight of a dispersing agent, about 0.5. % up to 8.5% by weight of a stabilizer are co, about 0.1% up to 2% by weight of a suspending agent, up to about 25% by weight of an anti-freeze agent, up to about 2% by weight of an antifoaming agent.
up to about 1% by weight of a preservative, up to about 1% by weight of a thickening agent, and water. More preferably, the first mixture comprises between 20% to 70% by weight of arylpyrrole particles having an average volume diameter of less than * about 100 μm, between 0.5% to 2.5% by weight of a dispersing agent, between 1.5% and 6% by weight of a spherical stabilizer, between 0.1% to 2% by weight of a suspending agent, between 5% and 20% by weight weight of an apti-freezing agent, between 0.1% to 2% by weight of an antifoaming agent. between 0.01% to 1% by weight of a preservative and water. The present invention further provides suspension concentrate compositions comprising between about 10% to 50% by weight of stabilized arylpyrrole particles prepared by means of the process of this invention, between about 0.1% to 2% by weight of a dispersing agent, between about 0.5% to 5% by weight of a spherical stabilizer, between about 0.1% to 1% by weight of a suspending agent, between about 0.01% up to 0.5% by weight of a thickener, between about 5% to 15% by weight of an anti-freezing agent, up to about 1% by weight of an antifoaming agent, up to about 0.5% in weight of a preservative, and water. The suspension concentrate compositions of this invention preferably comprise between 10% to 40% by weight of the stabilized arylpyrrole particles having an average volume diameter of 0.5 μm up to
μ, between 0.5% to 1.5% by weight of a dispersing agent, between
1.5% up to 3.5% by weight of a spherical stabilizer, between 0.1% to 1% by weight of a suspending agent, between 0.01% to 0.5% by weight of a thickening agent, between 5% to 10% by weight of an anti-freezing agent, between 0.1% to 1% by weight of an antifoam people, between 0.01% to 0.5% by weight of a preservative and water IN the suspension concentrate compositions and the first mixtures. Preferred of the present invention, the ratio of the total amount of the dispersing agent and the spherical stabilizer to the suitable arylpyrrole particles is preferably between about 1: 5 to 1:15 and more preferably between about 1 8 to 1:10. . Spherical stabilizers suitable for use in the present invention include, but are not limited to, ethylene oxide polymers and copolymers of ethylene oxide and propylene oxide such as, for example, ethylene oxide propylene oxide block copolymers. Preferred spherical stabilizers are butyl-ometa-hydroxyl poly (oxypropylene) block polymers with poly (oxyethylene) having an average molecular weight in a range of about 2,400 to 3,500 with alpha-butyl-omega-block copolymers ethylene-propylene oxide hydroxy-oxide such as TOX1MUL® 8320 (Stepan Chemical Co., Winder, Georgia), W1TCONOL® NS 500 LQ (Witco) and TERGITOL® XD (Union Carbide, Danbury, Connecticut) as the most preferred . Suspending agents for use in this invention include, but are not limited to, natural and synthetic clays and silicates, for example, natural silicas such as, for example, diatomaceous earths; magnesium silicates such as talcs, magnesium aluminum silicates such as, for example, attapulgites and vermiculites; and aluminum silicates such as kaolinites, montmorillonites and micas. The preferred suspending agents are magnesium silicates, magnesium aluminum silicates and aluminum silicates with magnesium aluminum silicates such as, for example, VANGEL® ES (.T: Vanderbilt). , VEEGUM® (RT Vanderbilt), VEEGUM® T (RT Vanderbilt) and GELWHITE® (Southern Ctay Products, Gopzales, Texas) as the most preferred. Thickening agents useful in this invention include, but are not limited to, natural thickening agents such as, for example, xanthan gum, carrageenin, pectin, gum arabic, guar gum and the like; semi-synthetic thickening agents such as, for example, methylaproducts, carboxylation products and hydroxylation products of cellulose derivatives or starch; and synthetic thickeners such as polyacrylates, polymaleate and polyvinylpyrrolidopa with xanthan gums such as KELZSN® (Kelco, San Diego, California) and RHODOPOL® 23 (Rhone-Poulenc, Cranbury, New Jersey) are preferred. Suitable apti-copgelamiepto agents for use in the present invention include glycols such as, for example, propylene glycol, ethylene glycol, and the like, with propylene glycol being preferred. Suitable antifoam agents include emulsions of silicone oils, emulsions of fatty alcohols and the like. Preservatives suitable for use in this invention include 1, 2-benzisothiazolin-3-one, epichiorhydrin, phenyl glycidyl ether, allyl glycidyl ether, formaldehyde compositions and the like, with 1,2-benzisothiazolipa-3-one being preferred. The suspension concentrate compositions of the present invention can be conveniently prepared by mixing arylpyrrole particles, a dispersing agent, a spherical stabilizer, a suspending agent and an antifreeze agent with water to obtain a first mixture, keeping the first mixture in accordance with the process of this invention to obtain a stabilized mixture, by grinding the stabilized mixture to obtain a mixture comprising particles of stabilized arylpyrrole, and mixing the mixture comprising the particles of stabilized arylpyrrole with a thickener and additional water to obtain the concentrate composition in desired suspension. The suspension concentrate compositions of this invention preferably have a pH between about pH 5 to pH 9 and more preferably between about pH 6 to a pH of 8. To adjust the pH in the desired range, acids such as example, acetic acid, propionic acid, sulfuric acid, phosphoric acid, hydrocropic acid and the like. In order to facilitate an understanding of the invention, the following examples are presented to illustrate more specific details. The scope of the invention is not limited to the illustrated embodiments, but includes the entire subject matter of the appended claims. EXAMPLE 1 Preparation of stabilized chlorfenapyr particles Sequentially added propylene glycol (331 g), a 1, 2-benzisothiazolin-3-opa solution 17% (PROXEL® GXL, Zeneca) (6.35 g), a silicone emulsion 30% (AF 30 IND® Harcros Chemical Co.) (29.9 g), a block copolymer of alpha-butyl-omega-hydroxy-ethylene oxide / propylene oxide (TOXIMUL® 8320, Stepap Chemical Co.) (132 , 5 g), a sodium suffonate of a condensate of naphthalene formaldehyde (MORWET® D425, Witco) (44 g), magnesium aluminum silicate (VANGEL® ES, R, T, Vanderbilt) (22.2 g), and chlorfepaptr (1.542 g, 90% real, 0% Polymorph I), stirring the water (976 g) The resulting mixture is stirred until homogeneous and passed through a wet grinding device to obtain a mixture identified with or the composition number 1 below, formed by chlorfenapyr particles having a mean volume diameter of about 158 μm. Composition Number 1 Ingredient% weight / weight Chlorfenapyr 50.00 MORWET® D425 1, 43 TOXIMUL® 8320 4.30 VANGEL®ES 0.72 Propylene glycol 10.73 AF 30 IND® 0.97 PROXEL® GXL 0.21 Water 31, 65 The individual samples of composition number 1 are stirred at 40 ° C, 55 ° C and 70 ° C, for 17 hours and passed through a wet milling device to obtain compositions 2, 3 and 4 comprising particles Stabilized ctorfenapyr The compositions numbers 1-4 are then stored at room temperature for two months and the average volume diameter of the chlorfenapyr particles in each composition is measured.The results are summarized in Table I. As can be seen from the As shown in Table I, the average volume diameter of the stabilized chlorfenapyr particles present in the compositions 2, 3 and 4 increases significantly less than the average volume diameter of the ctorfenapyr particles present in the omposition number 1.
TABLE I Stability of CJorfenapir Particles Composition Temperature (° C) to Mean Diameter of Mean Diameter of number that was shaken Initial Volume Volume for 17 hours Cporfenapir Particle Particles (μm) Chlorfenapyr (μm) After Storage at room temperature for 2 months 1 N / A 1, 58 4.47 2 40 1, 42 1, 41 3 55 1, 49 1, 41 4 70 1, 50 2.72 EE PLO 2 Effect of the initial particle size of the chlorfenapyr particles Using the same procedure described in Example 1, but varying the particle size of the chlorfenapyr particles present in the compositions before maintaining the temperature at 55 ° C, the compositions numbers 5-7 are obtained comprising the stabilized ciorfenapyr particles, these compositions and composition number 8, which is identical to composition number 1 of Example 1 except that the ciorfenapyr particles have an average diameter of lumens of 1, 44 μ, are stored at room temperature for three weeks. The average volume diameter of the chlorfenapyr particles in each fire composition is measured and the results are summarized in Table II. As can be seen from the data in Table ll. the average volume diameter of the stabilized ciorfenapyr particles present in compositions numbers 5-7 increases significantly less than the average volume diameter of the chlorfenapyr particles present in composition number 8.
ro or ui
TABLE II Effect of Initial Particle Size of Clorfenapyr Particles
Number Average Diameter of Agitation Hours Average Diameter of Weeks of Average Diameter of Volume of the 55 'C volume of the Storage to final volume composi Particle Particle Temperature Partitions chlorofarpir (μm) Clorfenapir Clorfenapir Environment Before Stabilized process (μm) (μm) Stabilization 5 > 30 17 1.48 3 2.36 6 4.5 17 1.45 3 1, 40 < £ > s? 7 1, 6 17 1.53 3 1.33 8 * 1.44 - - 3 3.88 * unstabilized
EXAMPLE 3 Effect of various maintenance periods Using the same procedure described in Example 1, but grinding the chlorfenapyr particles present in the compositions to about 4 μm t before maintaining the temperature at 55 βC for several periods of time, the compositions numbers 9-15 comprising the stabilized chlorfenapyr particles. Compositions numbers 9-15 and composition number 16 with unstabilized chlorfenapyr, which is identical to composition 1 in Example 1 except that the chlorfenapyr particles have a volume average diameter of 1.41 μm, are stored at temperature environment for three months. The average volume diameter of the ciorfenapyr particles in each composition is then measured and the results summarized in Table III. As can be seen from the data in Table III, the average volume diameter of the stabilized chlorfenapyr particles present in compositions numbers 9-15 increases significantly less than the average volume diameter of the chlorfenapyr particles present in the composition number 16
Not O (Jl TABLE III
Effect of Various Maintenance Periods
Number Mean Diameter of Agitation Hours Average Diameter of Average Volume Diameter of the a dd 'C volume of final volume ias Composition Particle Particles of the Chlorphenapyr Partition (μm) Chlorphenapyr Clorfenapyr
Before the Stabilized Process (μ) (μm) After the
Stabilization Storage at room temperature for 3 months 9 4.1 2 1, 46 1.92 10 4.1 5 1, 41 1.89 11 4.1 9 1.42 1.70 12 4.1 17 1.25 1.38 13 4.0 17 1.41 1.69 14 4.0 24 1.36 1.51 15 4.0 41 1.40 1.47 16 * 1, 40 - - 3.94 * unstabilized
EXAMPLE 4 Effect of various chlorfenapyr polymorph ratios on storage stability of chlorfenapyr Using the same procedure described in Example 1, but using. Different batches of the chlorfenapyr particles and maintaining at 55 [deg.] C. for 17 hours, various compositions are obtained which comprise the stabilized chlorfenapyr particles and are identified in Table IV. The compositions comprising the stabilized chlorfenapyr particles and the suitable unstabilized composition are stored at room temperature for various periods of time. Then the average volume diameter of the chlorphepapir particles in each composition is measured and the results are summarized in Table IV. As can be seen in the data in Table IV, the chlorfenapyr particles present in the stabilized compositions prepared using chlorphepapir particles. which have less than about 80% of Polymorph I are, in general, significantly more stable than the chlorfenapyr particles present in the corresponding non-stabilized compositions.
or L?
TABLE IV
Effect of Various Polymorph Relations
Number% of Polymorph I Mean Diameter of Average Diameters of Average Diameters of Volume of Volume of Storage to Final Volume Composition of Particle Temperature Particles Partition Chlorfenapyr (μ) Clorfßnapir Clorfenapir Environment Before Stabilized Process ( μ) (μ) of Stabilization 17 0 3.7 1.45 1 1.38 0 1.55 unstabilized 15.04 t
18 0 3.3 1.51 3 1, 51 0 1.45 unstabilized 3 1, 56 19 14 4.4 1.39 8 days 1.88 14 1.36 unstabilized 1 2.41 20 14 1.9 1.53 12 1.48 14 1.45 unstabilized 12 2.10 21 20 2.8 1.76 6 1.97 20 1.32 unstabilized 6 5.05
TABLE IV (continued)
Effect of Various Polymorph Relations
Number% of Polymorph I Average Diameter of Average Diameters of Average Diameters of Volume of the Volume of Storage to Final Volume Composition Particles Particle Temperature Particles Chlorphenapir (μi Clorfenapir Clorfenapyror Environment Before Stabilized Proce (μm ) { μm) Stabilization 22 20 3.1 1, 76 6 1.64 20 1, 63 not stabilized 6 2.55 23 20 4.0 1.37 2 1.28 20 1.18 unstabilized 2. 1.25 24 23 3.5 1.37 9 days 2.75 23 1, 55 not stabilized 11 days 5.82 25 55 3.4 1 56 12 1, 75 55 1.47 unstabilized 12 1.84 26 56 4.5 1.48 12 1, 48 56 1.55 unstabilized 12 1.59
ro in or in
TABLE IV (continued)
Effect of Various Polymorph Relations
Number% of Polymorph I Average Diameter of Average Diameters of Weeks of Diameter of volume of the volume of the Storage to final volume Composition of Particle Temperature Particles of Chlorfenapyr (μm) Chlorfenapir Cporfenapir Environment Before Stabilized Process ( μm) (μm) of Stabilization ro cp
27 65 3.2 1.45 16 1.55 65 1.42 unstabilized 16 1.54 28 76 2.9 1.38 3 1.45 76 1.01 unstabilized 3 1.36 29 80 3.4 1.66 6 1, 62 80 1.45 not stabilized 6 1, 39
87 2.9 1.56 12 1.63 87 1.71 unstabilized 12 1.71
EXAMPLE 5 Effect of various polymorph ratios on the storage stability of the suspension concentrate compositions Sequentially add glycol (730 g), a solution of 1,2-benzisothiazolin-3-one 17% (PROXEL® GXL, Zenßca) (14.0 g), a 30% silicone emulsion (AF 30 IND®, Harcros Chemical Co) (66.0 g), block copolymer alpha-butyl-omega-hydroxyl-ethylene oxide-propylene oxide ( TOXIMUL® 8320. Stepan Chemical Co.) (292 g), sodium sulfonate of the naphthalene formaldehyde condensate (MORWET® D425, Witco) (97.0 g), magnesium aluminum silicate (VANGEL® ES, RT Vanderbilt) ( 49.0 g) and chlorfenapyr (3400 g, 90% real, 6.7: 1 ratio between Polymorph I and Polymorph II), stirring the water (2.152 g). The resulting mixture was stirred until homogeneous and passed through a wet grinding device to obtain a grinding base where the chlorphepapir particles have a volume average diameter of about 1.5 μm. The grinding base was loaded into a vessel, stirred and adjusted to a pH of 6.5 to 7.2 with acetic acid (19.0 g) 1% xaptapo ai gum gel (1, 459 g) previously prepared xanthan gum (15.0 g), a solution of 1, 2- benzisothiazolin-3-one 17% (PROXEL® GXL, Zeneca) (1.0 g) and water (1443 g)) and water (1453 g) were added to the grinding base with adjusted pH and mixing continued to obtain the suspension concentrate composition identified below as composition number 3. Composition Number 31 Ingredient% weight weight Chlorfenapyr '' 34.94 MORWET® D425 1, 00 TOXIMUL® 8320 3.00 VANGEL® ES 0.50 Propylene glycol 7.50 AF 30 IND® 0.68 PROXEL® GXL 0.15 Xanthan gum 0.15 Acetic acid 0.20 Water 51, 88 0 1The ratio between Polymorph I and Polymorph II is 6.7: 1. Using the same procedure, but varying the ratio between Polymorph I and Polymorph II, the suspension concentrate compositions identified as the compositions numbers 32-38 are obtained in Table V. Samples of suspension concentrate compositions are stored at room temperature for several periods of time. The mean volume diameter of the chlorphepapir particles in each sample is then measured and the results are summarized in Table V. As can be seen from the data in Table V, chlorfenapyr particles comprising a ratio between Polymorph I and Polymorph II of more than about 1: 4 (compositions numbers 31-35) are significantly more stable than chlorfenapyr particles which comprise a ratio between Polymorph I and Polymorph II from 1: 4 to 0: 1 (compositions numbers 36-38).
L? or tn o
TABLE V
Effect of Various Polymorph Relations
Number Relation between the Average Diameter of Weeks stored Average diameter of% increase / of Polymorph I and the Initial volume of at the final volume temperature of (decrease in the composition Polymorph II of the Particulate matter particles of the diameter m 5 of chlorination of Clorfenapir (μm) ciorfenapir (μm) volume chlorfenapir particles fNJ CD
31 6.7.1 1.55 4 1.38 (12) 8 1.40 (11) 32 2 1 1.59 8 1.40 (14) 33 1: 1 1.96 3 2.26 15 8 2.03 4 34 1: 1.3 1.55 8 1.59 3 35 1: 3 2.3 3 2.77 20 8 241 5 36 1: 4 1.32 6 5.05 283
ro t o o
TABLE V (continued)
Effect of Various Polymorph Relations
Number Reladóp between the Average Diameter of Weeks stored Average diameter of% increase / of Polymorph i and the Initial volume of at final volume temperature of (decrease in the composition Polymorph II the Particulate particles the particles of average diameter of chlorofarpir (μm) ciorfenapir (μm) volume of ciorfenapyr INJ particles
37 1: 6.1 1.58 4 4 2 2..4499 5 588 8 2.57 63 12 2.60 65 38 0: 1 1.56 1 7.93 408 4 7.06 353 8 7.17 360
Claims (25)
- CLAIMS 1. A process for the preparation of stable arilpirtoi particles cued by Doraue includes the following: a) providing a first mixture comprising the particles of arypiperan a dispersing agent and water; b) maintain the first mixture in a temperature range between about 25 ° C and 80 ° C to obtain a stabilized mixture; and c) grinding the stabilized mixture to obtain the stable arylpyrrole particles.
- 2. The process according to claim 1, characterized in that the particles of arypropyrole in step (a) have an average volume diameter of about 100 UGÑ.
- 3. The process according to claim 2, characterized in that Dailies of ArylDirrol Ti'pnpn a riiflmp m mprlin HP vnli mpn rip aln = rlprlnr n, R? P? rw to 30 / jn.
- 4. The process according to claim 1, characterized in that the first one is maintained in a temperature range between about 1 hour to 72 hours.
- 5. The process according to claim 4, characterized in that the first m is maintained in a temperature range between about 2 hours to 48 hours 6. The process according to claim 4, characterized in that the first m is maintains within a temperature range between about 2 hours to 24 hours. 7. The process according to any of claims 1-6, characterized in that the temperature range is between 40 ^ and 60 * 0. 8. The process according to claim 1, characterized in that the dispersing agent is present in the condensation products of the topnayBilao with the sulfopation products of the polycyclic aromatic compounds. 9. The process according to any of claims 1-8, characterized in that the dispersion agent is sodium sulfonate of the naphthalene formate condensate. The process according to any of claims 1-9, characterized in that the arylpyrrole has the structural formula: wherein X is H, F, Cl, Br, l, C 1 -C 4 haloalkyl or S (O) "(C 1 -C 4 haloalkyl); Y is F, Cl, Br, I, haloalkyl of C, -C4 or CN; W is CN or NO2; A is a C1-C4 alkyl optionally substituted with between one and three halogen atoms, a cyano, a hydroxy, a d-C4 alkoxy, a C1-C4 alkyl, a phenyl optionally substituted with C1-C3 alkyl, C?-C3 alkoxy, or one to three halogen atoms, a phenoxy optionally substituted with one to three halogen atoms, or a benzyloxy optionally substituted with a halogen atom, C 1 -C 4 carbalkoxymethyl, C 3 -C 4 alkenyl optionally substituted with one to three halogen atoms, year, C3-C4 aikinyl optionally substituted with a halogen atom, di (aikil C? -C4) aminocarbonyl, or benzoyl optionally substituted with between one and three halogen atoms or between one and three C1-C4 alkyl groups, L is H, F, Cl or Bp M and R are each independently H, C, -C3 alkyl, C? -C3 akoxy, C1-C3 alkyl, alkylsulfinyl C, -C3, C?-C3 alkylsulfonyl, cyano, F, Cl, Br, I, nitro, C halo-C3 haloaicyl, R1CF2Z, R2CO or RsR *. or when M and R are in adjacent positions and taken together with the carbon atoms to which they are attached they can form a ring in which MR represents the structure -OCH, O-, OCF2O-, -OCRßRrCRßRβO-, -OCHsCHj-, OCHaCH2CHa- or -CH = CH-CH = CH: R, TS H, F, CHF2, CHFCI or CF3; R2 is Ci-Co alkyl, C?-C3 alkoxy or NRaR ^; Rj ßs H or CT-C alkyl; R 4 is H, C, -C, or RsCO alkyl; R5 TS H or C?-C3 alkyl, R «, R7 (Rt and Re are each independently hydrogen, halogen or alkyl -Ca, and m and n are each independently an integer of 0, 1 or 2. 1 1. according to claim 10, characterized in that arylpyrrole has the structural formula 12. The process according to claim 11, characterized in that X and Y are each independently Cl, Br or CF3; W is CN; A is alkoxymethi! of C -C4; M is H, F. Ct or Br; and R is F; Cl, Br, CF3 or OCF3. 13. The process according to claim 11, characterized in that arilpirr chlorfepapir. 14. The process according to claim 13, characterized in that the chlorfenapyr particles in the first mixture comprise less than 80 percent of the polymorph, l. The process according to claim 1, characterized in that the first m comprises between about 10% up to 85% by weight of arylpyrrole particles, about 0.1% up to 3.5% by weight of an agent dispersant, about 0.5% to 8.5% by weight of a sealed stabilizer, about 0.1% to 2% by weight of a suspending agent, up to about 25% by weight of an anti-aging agent freezing, up to about 2% by weight of an apt foaming agent, up to about 1% by weight of a preservative, up to about 1% by weight of a thickening agent and water. 16. The process according to claim 15, characterized in that the first m comprises between 20% and 70% by weight of arylpyrrole particles having an average volume diameter of less than about 100 μm. 0.5% up to 2.5% by weight of a dispersing agent, 1.5% up to 6% by weight of a spherical stabilizer, 0.1% up to 2% by weight of a suspending agent, 5% up to 20% by weight % by weight of an anti-freeze-labile agent, 0.1% to 2% by weight of an antifoaming agent, 0.01% to 1% by weight of a preservative and water. 17. The process according to claim 15, characterized in that the dispersing agent is a salt of the condensation products of formaldehyde with the ß-sulfonation products of the polycyclic aromatic compounds; the spherical stabilizer is a block copolymer of ethylene oxide / propylene oxide; the suspending agent is selected from the group consisting of a magnesium aluminum silicate, a magnesium silicate and an aluminum silicate; the antifreeze agent is a glycol; and the thickening agent is selected from the group consisting of xanthan gum, carrageepip, pectin, gum arabic and guar gum 18. The process according to claim 17, characterized in that the dispersing agent is the sodium sulfopate of the formaldehyde condensates. of naphthalene, the ßstéric stabilizer is a block copolymer of arfa-butyl-omßga-hydroxy-ethylene oxide-propylene oxide, the suspending agent is a magnesium aluminum silicate, the anti-freezing agent is propylene glycol, and the Thickening agent is xanthan gum. 19. The stable aplpyrole particles prepared by the process of any of Claims 1-18. 20. A suspension concentrate composition, characterized in that it comprises from about 10% up to 50% by weight of stable aplpyrole particles prepared by the process of claim 1, between about 0.1% to 2% by weight of a dispersing agent, about 0.5% up to 5% by weight of a sealed stabilizer, about 0.1% up to 1% by weight of a suspending agent, about 0.01% up to 0.5% by weight weight of a thickening agent, about 5% up to 15% by weight of an anti-freezing agent, up to about 1% by weight of an antifoaming agent, up to about 0.5% by weight of a preservative and water. 21. The composition according to claim 20, characterized in that the stable arylpyri particles have a volume average diameter of about 0.5 μ to 10 μm. 22. A stable arylpyrrole particle, characterized in that it comprises an arylpyrrole that exists as at least two different polymorphs, at least one of silos has a stable particle size during storage as a suspension at room temperature, where the ratio between the stable polymorph and The non-stable polymorph in said particle is greater than about 1: 4, said arylpyrrole being represented by the formula where X is H. F. Cl, Br, l. haloalkyl of C 1 -C 4 or S (O) m (haloalkyl of C, -C); And it is F, Cl, Br, i, haioalkyl of Ct-C «or CN; W is CN or NO2; A is a C, -C4 alkyl optionally substituted with between one and three halogen atoms, a cyano, a hydroxy, a C 1 -C 4 alkoxy, a C 1 -C 4 alkyl. a phenyl optionally substituted with C?-C3 alkyl, d-Cj akoxy, or one to three halogen atoms, a phenoxy optionally substituted with one to three halogen atoms, or a benzyloxy optionally substituted with a halogen atom, carbalkoxymethyl of C1-C4, C3-C4-ainnyl optionally substituted with one to three halogen atoms, cyano, C3-C4 atquinyl optionally substituted with a halogen atom, di (a-C1-Cyl) aminocarbonyl, or benzoyl optionally substituted with between one and three halogen atoms or between one and three C1-C4 alkyl groups; L is H, F, Cl or Br; M and R are each independently H, C 1 -C 3 alkyl, C alkoxy, C 3 -C 1 C 3 alkyl, C 1 -C 3 alkylsulfinyl, C 3 -C 3 alkynyl, cyano, F, Cl, Br, I, nitro , haloalkyl or C1-C3. R1CF2Z, R2CO or NR3 », or when M and R are in adjacent positions and taken together with the carbon atoms to which they are attached can form a ring in which MR represents the structure: -OCH2O-, OCFaO-, -OCR .R7CR.R9O-, -OCHjCH, -, OCH2CH, CHt- or -CH = CH-CH = CH; Z is S (O) "or O; R1 is H, F, CHF2, CHFCI or CF3; R2 is C1-C3 alkyl. C1-C3 alkoxy or R3R4; R3 is H or C1-C3 alkyl; R 4 is H, C 1 -C 3 alkyl or RsCO; Rs is H or C1-C3 alkyl; Re, Rr, R. and R "are each independently hydrogen, halogen or C1-C3 alkyl; R and m and n are each independently an integer of 0, 1 or 2 A particle according to claim 22, characterized in that diene aryipyrrole is represented by the formula: 24. A particle according to claim 22, characterized in that dieno aplpirroi is ciorfenapir and said stable polymorph is Polymorph 1. A particle according to claim 22, characterized in that said ratio is between about 1: 1 to 10. 26? A composition comprising an arylpyrrole particle as claimed in any of the. claims 22-25. 27 A composition, characterized in that it comprises between about 10% to 5% by weight of arylpyrrole particles according to Claim 27; between about 0.1% to 2% by weight of a dispersing agent, between about 0.5% to 5% by weight of a steric stabilizer. between about 0.1% to 1% by weight of a suspending agent, between about 0.1% to 0.5 % by weight of a thickening agent, between about 5% to 15% by weight of an anti-copgelamieptide agent, up to about 1% by weight of an anti-foam agent, up to about 0.5% by weight of a preservative and water. STABLE ARILPIRROL PARTICLES, THE PROCESS FOR ITS PREPARATION AND THE CONCENTRATE COMPOSITIONS IN SUSPENSION THAT YOU UNDERSTAND THEM SUMMARY OF THE INVENTION The present invention relates to particles of arilpjrrole which are prepared by means of a process in which the particles are stabilized and milled, and to the pesticide suspension concentrate compositions comprising them. The size of the particles of this invention remains surprisingly stable during storage.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US69147896A | 1996-08-02 | 1996-08-02 | |
US08/691,478 | 1996-08-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
MX9705908A MX9705908A (en) | 1998-08-30 |
MXPA97005908A true MXPA97005908A (en) | 1998-11-12 |
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