Hydrolysis Resistant Organomodified Trisiloxane Surfactants
Three types of trisiloxane surfactants having the basic formula: MDM′ are described wherein the substituents on the differing M and M′ groups, in conjunction with pendant polyalkylene oxide substituents on the D group render the surfactant resistant to hydrolysis under either basic or acidic conditions outside the pH range of 6.0 to 7.5. The compositions are useful in agricultural, household and cosmetic applications.
1 . An agricultural composition comprising:
a) a silicone having the formula:
M 1 D 1 M 2
wherein
M 1 =(R 1 )(R 2 )(R 3 )SiO 1/2 ;
M 2 =(R 4 )(R 5 )(R 6 )SiO 1/2 ; and
D 1 =(R 7 )(Z)SiO 2/2
where
R 1 is selected from the group of monovalent hydrocarbon radicals consisting of branched or linear hydrocarbon group consisting of 2 to 4 carbons, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing aryl substituents of 6 to 20 carbon atoms; R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and a hydrocarbon group of 4 to 9 carbons containing an aryl group; Z is an alkyleneoxide group of the general formula:
R 8 (C 2 H 4 O) a (C 3 H 6 O) b (C 4 H 8 O) c R 9 ,
where R 8 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R 9 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl, and the subscripts a, b and c are zero or positive and satisfy the following relationships: 2≦a+b+c≦20 with a≧2; and
b) an agriculturally active component
wherein said agricultural composition has an enhanced resistance to hydrolysis.
2 . The composition of claim 1 where R 1 and R 4 are selected from the group consisting of propyl, iso-propyl, butyl, sec-butyl, iso-butyl and tert-butyl.
3 . The composition of claim 1 where R 2 , R 3 , R 5 , R 6 and R 7 are methyl.
4 . The composition of claim 1 where R 8 is a divalent hydrocarbon radical having three carbon atoms.
5 . The composition of claim 1 where the subscript a ranges from 8 to 12.
6 . The composition of claim 1 where the subscript b ranges from 0 to 3.
7 . The composition of claim 1 where the subscript c is 0.
8 . The composition of claim 1 where R 9 is selected from the group consisting of hydrogen and methyl.
9 . The composition of claim 2 where R 1 and R 4 are selected from the group consisting of iso-propyl and tert-butyl.
10 . The composition of claim 5 where the subscript a is 11.
11 . The composition of claim 8 where R 9 is hydrogen.
12 . The composition of claim 9 where R 2 , R 3 , R 5 , R 6 and R 7 are methyl.
13 . The composition of claim 12 where R 8 is a divalent hydrocarbon radical having three carbon atoms.
14 . The composition of claim 13 where the subscript a is 11.
15 . The composition of claim 14 where the subscripts b and c are both zero
16 . The composition of claim 15 where R 9 is hydrogen.
17 . The agricultural composition of claim 1 wherein
the agriculturally active component is selected from the group consisting of aldimorph, tridemorph, dodemorph, dimethomorph; flusilazol, azaconazole, cyproconazole, epoxiconazole, furconazole, propiconazole, tebuconazole, imazalil, thiophanate, benomyl carbendazim, chlorothialonil, dicloran, trifloxystrobin, fluoxystrobin, dimoxystrobin, azoxystrobin, furcaranil, prochloraz, flusulfamide, famoxadone, captan, maneb, mancozeb, dodicin, dodine, bacillus thuringiensis , spinosad, abamectin, doramectin, lepimectin, pyrethrins, carbaryl, primicarb, aldicarb, methomyl, amitraz, boric acid, chlordimeform, novaluron, bistrifluoron, triflumuron, diflubenzuron, imidacloprid, diazinon, acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl, azinphos-methyl, izoxathion, chlorpyrifos, clofentezine, lambda-cyhalothrin, permethrin, bifenthrin, cypermethrin; phenoxy acetic acids, phenoxy propionic acids, phenoxy butyric acids, benzoic acids, triazines and s-triazines, substituted ureas, uracils, bentazon, desmedipham, methazole, phenmedipham, pyridate, amitrole, clomazone, fluridone, norflurazone, dinitroanilines, isopropalin, oryzalin, pendimethalin, prodiamine, trifluralin, glyphosate, glufosinate, sulfonylureas, imidazolinones, pyridinecarboxylic acids clethodim, diclofop-methyl, fenoxaprop-ethyl, fluazifop-p-butyl, haloxyfop-methyl, quizalofop, sethoxydim, dichlobenil, isoxaben, bipyridylium compounds, zinc sulfate, ferrous sulfate, ammonium sulfate, urea, urea ammonium nitrogen, ammonium thiosulfate, potassium sulfate, monoammonium phosphate, urea phosphate, calcium nitrate, boric acid, potassium salts of boric acid, sodium salts of boric acid, phosphoric acid, magnesium hydroxide, manganese carbonate, calcium polysulfide, copper sulfate, manganese sulfate, iron sulfate, calcium sulfate, sodium molybdate and calcium chloride.
18 - 39 . (canceled)
40 . A non-aqueous emulsion wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of claim 17 .
41 . An agricultural composition comprising:
a) silicone having the formula:
M 3 D 2 M 4
wherein
M 3 =(R 10 )(R 11 )(R 12 )SiO 1/2 ;
M 4 =(R 13 )(R 14 )(R 15 )SiO 1/2 ; and
D 2 =(R 16 )(Z′)SiO 2/2
where
R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms; Z′ is an alkylene oxide group of the formula:
R 17 (C 2 H 4 O) d (C 3 H 6 O) e (C 4 H 8 O) f R 18 ,
where
R 17 has the formula:
—C 4 H 8 O—(C 2 H 4 O)—
with R 18 selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl, the subscripts d, e and f are zero or positive and satisfy the following relationships:
2≦ d+e+f≦ 20 with d≧ 2 and
b) an agriculturally active component wherein said agricultural composition has an enhanced resistance to hydrolysis.
42 . The composition of claim 41 where the subscript f is 0.
43 . The composition of claim 41 where the subscript e ranges from 0 to 3.
44 . The composition of claim 41 where the subscript d ranges from 8 to 11.
45 . The composition of claim 41 where R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are methyl.
46 . The composition of claim 41 where R 18 is methyl.
47 . The composition of claim 42 where the subscript e is 0.
48 . The composition of claim 47 where the subscript d is 8.
49 . The composition of claim 48 where R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are methyl.
50 . The composition of claim 49 where R 18 is methyl.
51 . The agricultural composition of claim 1 wherein
the agriculturally active component is selected from the group consisting of aldimorph, tridemorph, dodemorph, dimethomorph; flusilazol, azaconazole, cyproconazole, epoxiconazole, furconazole, propiconazole, tebuconazole, imazalil, thiophanate, benomyl carbendazim, chlorothialonil, dicloran, trifloxystrobin, fluoxystrobin, dimoxystrobin, azoxystrobin, furcaranil, prochloraz, flusulfamide, famoxadone, captan, maneb, mancozeb, dodicin, dodine, bacillus thuringiensis , spinosad, abamectin, doramectin, lepimectin, pyrethrins, carbaryl, primicarb, aldicarb, methomyl, amitraz, boric acid, chlordimeform, novaluron, bistrifluoron, triflumuron, diflubenzuron, imidacloprid, diazinon, acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl, azinphos-methyl, izoxathion, chlorpyrifos, clofentezine, lambda-cyhalothrin, permethrin, bifenthrin, cypermethrin; phenoxy acetic acids, phenoxy propionic acids, phenoxy butyric acids, benzoic acids, triazines and s-triazines, substituted ureas, uracils, bentazon, desmedipham, methazole, phenmedipham, pyridate, amitrole, clomazone, fluridone, norflurazone, dinitroanilines, isopropalin, oryzalin, pendimethalin, prodiamine, trifluralin, glyphosate, glufosinate, sulfonylureas, imidazolinones, pyridinecarboxylic acids, clethodim, diclofop-methyl, fenoxaprop-ethyl, fluazifop-p-butyl, haloxyfop-methyl, quizalofop, sethoxydim, dichlobenil, isoxaben, bipyridylium compounds, zinc sulfate, ferrous sulfate, ammonium sulfate, urea, urea ammonium nitrogen, ammonium thiosulfate, potassium sulfate, monoammonium phosphate, urea phosphate, calcium nitrate, boric acid, potassium salts of boric acid, sodium salts of boric acid, phosphoric acid, magnesium hydroxide, manganese carbonate, calcium polysulfide, copper sulfate, manganese sulfate, iron sulfate, calcium sulfate, sodium molybdate and calcium chloride.
52 - 68 . (canceled)
69 . An agricultural composition comprising:
a) a silicone having the formula:
M 5 D 3 M 6
wherein
M 5 =(R 19 )(R 20 )(R 21 )SiO 1/2 ;
M 6 =(R 22 )(R 23 )(R 24 )SiO 1/2 ; and
D 3 =(R 25 )(Z″)SiO 2/2
where
R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently selected from the group consisting of 1 to 4 carbon monovalent hydrocarbon radicals, aryl, and an alkyl hydrocarbon group of 4 to 9 carbons containing an aryl substituents of 6 to 20 carbon atoms, R 25 is a linear or branched hydrocarbon radical of 2 to 4 carbons; Z″ is an alkylene oxide group of the general formula:
R 26 (C 2 H 4 O) g (C 3 H 6 O) h (C 4 H 8 O) i R 27 ,
where
R 26 is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R 27 is selected from the group consisting of H, monovalent hydrocarbon radicals of from 1 to 6 carbon atoms and acetyl and the subscripts g, h and i are zero or positive and satisfy the following relationships:
2≦ g+h+i≦ 20 with g≧ 2 and
b) an agriculturally active component wherein said agricultural composition has an enhanced resistance to hydrolysis.
70 . The composition of claim 69 where R 27 is selected from the group consisting of hydrogen and methyl.
71 . The composition of claim 69 where the subscript i is 0.
72 . The composition of claim 69 where the subscript h ranges from 0 to 3.
73 . The composition of claim 69 where the subscript g ranges from 8 to 11.
74 . The composition of claim 69 where R 25 is selected from the group of 3 and 4 carbon monovalent hydrocarbon radicals.
75 . The composition of claim 69 where R 26 is a 3 carbon monovalent hydrocarbon radical.
76 . The composition of claim 69 where R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are methyl.
77 . The composition of claim 76 where R 25 is a 4 carbon monovalent hydrocarbon radical.
78 . The composition of claim 77 where R 25 is a 4 carbon monovalent hydrocarbon radical.
79 . The composition of claim 78 where R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are methyl.
80 . The composition of claim 79 where the subscript g is 8.
81 . The composition of claim 80 where the subscript h is 0.
82 . The composition of claim 81 where the subscript i is 0.
83 . The agricultural composition of claim 69 wherein
the agriculturally active component is selected from the group consisting of aldimorph, tridemorph, dodemorph, dimethomorph; flusilazol, azaconazole, cyproconazole, epoxiconazole, furconazole, propiconazole, tebuconazole, imazalil, thiophanate, benomyl carbendazim, chlorothialonil, dicloran, trifloxystrobin, fluoxystrobin, dimoxystrobin, azoxystrobin, furcaranil, prochloraz, flusulfamide, famoxadone, captan, maneb, mancozeb, dodicin, dodine, bacillus thuringiensis , spinosad, abamectin, doramectin, lepimectin, pyrethrins, carbaryl, primicarb, aldicarb, methomyl, amitraz, boric acid, chlordimeform, novaluron, bistrifluoron, triflumuron, diflubenzuron, imidacloprid, diazinon, acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl, azinphos-methyl, izoxathion, chlorpyrifos, clofentezine, lambda-cyhalothrin, permethrin, bifenthrin, cypermethrin; phenoxy acetic acids, phenoxy propionic acids, phenoxy butyric acids, benzoic acids, triazines and s-triazines, substituted ureas, uracils, bentazon, desmedipham, methazole, phenmedipham, pyridate, amitrole, clomazone, fluridone, norflurazone, dinitroanilines, isopropalin, oryzalin, pendimethalin, prodiamine, trifluralin, glyphosate, glufosinate, sulfonylureas, imidazolinones, pyridinecarboxylic acids, clethodim, diclofop-methyl, fenoxaprop-ethyl, fluazifop-p-butyl, haloxyfop-methyl, quizalofop, sethoxydim, dichlobenil, isoxaben, bipyridylium compounds, zinc sulfate, ferrous sulfate, ammonium sulfate, urea, urea ammonium nitrogen, ammonium thiosulfate, potassium sulfate, monoammonium phosphate, urea phosphate, calcium nitrate, boric acid, potassium salts of boric acid, sodium salts of boric acid, phosphoric acid, magnesium hydroxide, manganese carbonate, calcium polysulfide, copper sulfate, manganese sulfate, iron sulfate, calcium sulfate, sodium molybdate and calcium chloride.
84 - 113 . (canceled)