HK1141212B - Hydrolysis resistant organomodified trisiloxane surfactants - Google Patents

Description

Hydrolysis resistant organomodified trisiloxane surfactants

Technical Field

The present invention relates to trisiloxane surfactant compositions that exhibit resistance to hydrolysis over a wide pH range. More particularly, the present invention relates to such hydrolysis resistant trisiloxane surfactants having a resistance to hydrolysis between about pH 3 and about pH 12.

Background

The liquid composition is topically applied to the surface of both animate and inanimate objects to produce the desired changes, including controlling wetting, spreading, foaming, cleaning, and the like. When used in aqueous solutions to improve delivery of active ingredients to the surface being treated, it has been found that the use of trisiloxane-type compounds enables control of these processes to achieve the desired effect. However, trisiloxane compounds can only be used in a narrow pH range, from slightly acidic pH 6 to very mildly alkaline pH 7.5. Outside this narrow pH range, trisiloxane compounds are unstable to hydrolysis, undergoing rapid decomposition.

Brief description of the invention

The present invention provides an extreme environment composition for use as an agricultural composition, a personal care composition, a coating composition or a home care composition, the composition comprising a silicone composition comprising a trisiloxane compound selected from the trisiloxane compounds of formulas I, II or III or a composition thereof useful as a surfactant.

The trisiloxane compound I has the formula:

M¹D¹M²

wherein

M¹＝(R¹)(R²)(R³)SiO_1/2

M²＝(R⁴)(R⁵)(R⁶)SiO_1/2(ii) a And

D¹＝(R⁷)(Z)SiO_2/2

wherein

R¹An alkyl hydrocarbon group of 4 to 9 carbon atoms selected from a branched or straight chain hydrocarbon group of 2 to 4 carbon atoms, an aryl group, and an aryl substituent group having 6 to 20 carbon atoms; r²、R³、R⁴、R⁵、R⁶And R⁷Each independently selected from the group consisting of monovalent hydrocarbon groups of 1 to 4 carbon atoms, aryl groups, and hydrocarbon groups of 4 to 9 carbon atoms containing aryl groups; z is an oxyalkylene group having the general formula: r⁸(C₂H₄O)_a(C₃H₆O)_b(C₄H₈O)_cR⁹In the formula, R⁸Is a linear or branched divalent hydrocarbon radical having 2, 3,5, 6, 7, 8 or 9 carbon atoms; r⁹Selected from H, monovalent hydrocarbon radicals having 1 to 6 carbon atoms and acetyl, the subscripts a, b andc is zero or a positive number and satisfies the following relationship:

a + b + c is more than or equal to 2 and less than or equal to 20, wherein a is more than or equal to 2.

When the subscript a satisfies the condition 2. ltoreq. a.ltoreq.5, it is advisable to use the cosurfactants listed below in order to obtain the benefits of the composition of the invention.

The trisiloxane compound II has the formula:

M³D²M⁴

wherein

M³＝(R¹⁰)(R¹¹)(R¹²)SiO_1/2；

M⁴＝(R¹³)(R¹⁴)(R¹⁵)SiO_1/2(ii) a And

D²＝(R¹⁶)(Z′)SiO_2/2

wherein

R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Alkyl hydrocarbon groups of 4 to 9 carbon atoms each independently selected from a monovalent hydrocarbon group of 1 to 4 carbon atoms, an aryl group, and an aryl substituent group containing 6 to 20 carbon atoms; z' is an oxyalkylene group having the general formula: r¹⁷(C₂H₄O)_d(C₃H₆O)_e(C₄H₈O)_fR¹⁸In the formula, R¹⁷Selected from the general formula: -C₄H₈O-(C₂H₄A branched or straight chain divalent hydrocarbon group of O) -; r¹⁸Selected from H, monovalent hydrocarbon radicals having from 1 to 6 carbon atoms and acetyl radicals, the subscripts d, e and f being zero or positive and satisfying the following relationship:

d + e + f is more than or equal to 2 and less than or equal to 20, wherein d is more than or equal to 2.

When the subscript d satisfies the condition 2. ltoreq. d.ltoreq.5, it is advisable to use the cosurfactants listed below in order to achieve the benefits of the compositions of the invention.

The trisiloxane compound III has the formula:

M⁵D³M⁶

wherein

M⁵＝(R¹⁹)(R²⁰)(R²¹)SiO_1/2；

M⁶＝(R²²)(R²³)(R²⁴)SiO_1/2(ii) a And

D³＝(R²⁵)(Z″)SiO_2/2

wherein

R¹⁹、R²⁰、R²¹、R²²、R²³And R²⁴Each independently selected from the group consisting of a monovalent hydrocarbon group of 1 to 4 carbon atoms, an aryl group, and an alkyl hydrocarbon group of 4 to 9 carbon atoms containing an aryl substituent of 6 to 20 carbon atoms, R²⁵Is a straight chain or branched alkyl group of 2 to 4 carbon atoms; z' is an oxyalkylene group having the general formula: r²⁶(C₂H₄O)_g(C₃H₆O)_h(C₄H₈O)_iR²⁷In the formula, R²⁶Is a linear or branched divalent hydrocarbon radical having 2, 3,5, 6, 7, 8 or 9 carbon atoms; r²⁷Selected from H, monovalent hydrocarbon radicals having 1 to 6 carbon atoms and acetyl radicals, the subscripts g, H and i being zero or positive and satisfying the following relationship:

g + h + i is more than or equal to 2 and less than or equal to 20, wherein g is more than or equal to 2.

When the subscript g satisfies the condition 2. ltoreq. g.ltoreq.5, it is advisable to use the cosurfactants listed below in order to achieve the benefits of the compositions of the invention.

Detailed Description

As used herein, integer values of stoichiometric subscripts refer to molecular species, and non-integer values of stoichiometric subscripts refer to mixtures of molecular species on a molecular weight average basis, a number average basis, or a mole fraction basis. In the case of mixtures of compounds of the invention, it should be readily seen that the stoichiometric subscripts of the mixture will have the average of these tables below, compared to the pure compounds, and the average subscript value will be either an integer or a non-integer.

The present invention provides an extreme environment composition for use as an agricultural composition, a personal care composition, a coating composition or a home care composition, the composition comprising a silicone composition comprising a trisiloxane compound selected from the trisiloxane compounds of formulas I, II or III or a composition thereof useful as a surfactant.

The trisiloxane compound I has the formula:

M¹D¹M²

wherein

M¹＝(R¹)(R²)(R³)SiO_1/2

M²＝(R⁴)(R⁵)(R⁶)SiO_1/2(ii) a And

D¹＝(R⁷)(Z)SiO_2/2

wherein

R¹An alkyl hydrocarbon group of 4 to 9 carbon atoms selected from a branched or straight chain hydrocarbon group of 2 to 4 carbon atoms, an aryl group, and an aryl substituent group having 6 to 20 carbon atoms; r²、R³、R⁴、R⁵、R⁶And R⁷Each independently selected from the group consisting of monovalent hydrocarbon groups of 1 to 4 carbon atoms, aryl groups, and hydrocarbon groups of 4 to 9 carbon atoms containing aryl groups; z is an oxyalkylene group having the general formula: r⁸(C₂H₄O)_a(C₃H₆O)_b(C₄H₈O)_cR⁹In the formula, R⁸Is provided with 2,3. A linear or branched divalent hydrocarbon group of 5,6, 7, 8 or 9 carbon atoms; r⁹Selected from H, monovalent hydrocarbon radicals having from 1 to 6 carbon atoms and acetyl radicals, the subscripts a, b and c being zero or positive and satisfying the following relationship:

a + b + c is more than or equal to 2 and less than or equal to 20, wherein a is more than or equal to 2.

When the subscript a satisfies the condition 2. ltoreq. a.ltoreq.5, it is advisable to use the cosurfactants listed below in order to achieve the benefits of the composition of the invention.

The trisiloxane compound II has the formula:

M³D²M⁴

wherein

M³＝(R¹⁰)(R¹¹)(R¹²)SiO_1/2；

M⁴＝(R¹³)(R¹⁴)(R¹⁵)SiO_1/2(ii) a And

D²＝(R¹⁶)(Z′)SiO_2/2

wherein

R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Alkyl hydrocarbon groups of 4 to 9 carbon atoms each independently selected from a monovalent hydrocarbon group of 1 to 4 carbon atoms, an aryl group, and an aryl substituent group containing 6 to 20 carbon atoms; z' is an oxyalkylene group having the general formula: r¹⁷(C₂H₄O)_d(C₃H₆O)_e(C₄H₈O)_fR¹⁸In the formula, R¹⁷Having the formula: -C₄H₈O-(C₂H₄O)-；R¹⁸Selected from H, monovalent hydrocarbon radicals having from 1 to 6 carbon atoms and acetyl radicals, the subscripts d, e and f being zero or positive and satisfying the following relationship:

d + e + f is more than or equal to 2 and less than or equal to 20, wherein d is more than or equal to 2.

The trisiloxane compound II may also have the formula:

M³D²M⁴

wherein

M³＝(R¹⁰)(R¹¹)(R¹²)SiO_1/2；

M⁴＝(R¹³)(R¹⁴)(R¹⁵)SiO_1/2(ii) a And

D²＝(R¹⁶)(Z′)SiO_2/2

wherein

R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Alkyl hydrocarbon groups of 4 to 9 carbon atoms each independently selected from a monovalent hydrocarbon group of 1 to 4 carbon atoms, an aryl group, and an aryl substituent group containing 6 to 20 carbon atoms; z' is an oxyalkylene group having the formula: r¹⁷(C₂H₄O)_d(C₃H₆O)_e(C₄H₈O)_fR¹⁸In the formula, R¹⁷Having the formula: -C₄H₈O-(C₂H₄O)-；R¹⁸Selected from H, monovalent hydrocarbon radicals having from 1 to 6 carbon atoms and acetyl radicals, the subscripts d, e and f being zero or positive and satisfying the following relationship:

d + e + f is not less than 2 and not more than 20, wherein d is not less than 2, with the proviso that when R is¹⁸When it is methyl, d is 2 to 5 or 8 to 20.

When the subscript d satisfies the condition 2. ltoreq. d.ltoreq.5, it is advisable to use the cosurfactants listed below in order to achieve the benefits of the compositions of the invention.

The trisiloxane compound III has the formula:

M⁵D³M⁶

wherein

M⁵＝(R¹⁹)(R²⁰)(R²¹)SiO_1/2；

M⁶＝(R²²)(R²³)(R²⁴)SiO_1/2(ii) a And

D³＝(R²⁵)(Z″)SiO_2/2

wherein

R¹⁹、R²⁰、R²¹、R²²、R²³And R²⁴Each independently selected from the group consisting of a monovalent hydrocarbon group of 1 to 4 carbon atoms, an aryl group, and an alkyl hydrocarbon group of 4 to 9 carbon atoms containing an aryl substituent of 6 to 20 carbon atoms, R²⁵Is a branched or straight chain alkyl group of 2 to 4 carbon atoms; z' is an oxyalkylene group having the general formula: r²⁶(C₂H₄O)_g(C₃H₆O)_h(C₄H₈O)_iR²⁷In the formula, R²⁶Is a linear or branched divalent hydrocarbon radical having 2, 3,5, 6, 7, 8 or 9 carbon atoms; r²⁷Selected from H, monovalent hydrocarbon radicals having 1 to 6 carbon atoms and acetyl radicals, the subscripts g, H and i being zero or positive and satisfying the following relationship:

g + h + i is more than or equal to 2 and less than or equal to 20, wherein g is more than or equal to 2.

When the subscript g satisfies the condition 2. ltoreq. g.ltoreq.5, it is advisable to use the cosurfactants listed below in order to achieve the benefits of the compositions of the invention.

One method of preparing the compositions of the present invention is to react a molecule of the formula with an olefin-modified polyalkylene oxide under hydrosilylation conditions:

MD^HM

in the formula, D^HIs a hydride precursor of the D' structural unit in the composition of the invention, wherein the definitions and relationships thereof are defined below and made in connection with the aboveConsistent with the definition of (a) above, the olefin-modified polyalkylene oxides, such as allyloxypolyethylene glycol, or methallyloxypolyalkylene oxide, are incorporated herein by way of example, and are not intended to limit other possible olefin-modified alkylene oxide components. The phrase "olefin-modified polyalkylene oxide" as used herein is defined as a molecule having one or more oxyalkylene groups containing one or more terminal or pendant carbon-carbon double bonds. The polyether (precursor of the substituted moiety Z, Z' or Z ") is an olefin-modified polyalkylene oxide (hereinafter referred to as" polyether ") represented by the general formula:

CH₂＝CH(R²⁸)(R²⁹)_jO(R³⁰)_k(C₂H₄O)_m(C₃H₆O)_n(C₄H₈O)_pR³¹

in the formula

R²⁸Is H or methyl; r²⁹Is a divalent alkyl radical having 1 to 6 carbon atoms, where the subscript j may be 0 or 1; r³⁰is-C₂H₄O-, where subscript k is 0 or 1; r³¹Is H, a monofunctional hydrocarbyl group having 1 to 6 carbon atoms, or an acetyl group, and subscripts m, n, and p are zero or positive and satisfy the relationship: m + n + p is more than or equal to 2 and less than or equal to 20, wherein m is more than or equal to 2. When the polyether is composed of mixed oxyalkylene groups (i.e., oxyethylene, oxypropylene and oxybutylene), the units may be blocky or randomly distributed. One skilled in the art will appreciate the benefits of using a block or random configuration. Illustrative examples of block configurations are: - (ethylene oxide)_a(propylene oxide)_b(ii) a - (butylene oxide)_c(ethylene oxide)_a-; and- (propylene oxide)_b(ethylene oxide)_a(butylene oxide)_c-。

Illustrative examples of polyethers are provided below, but are not limited to these:

CH₂＝CHCH₂O(CH₂CH₂O)₈H；CH₂＝CHCH₂O(CH₂CH₂O)₈CH₃；

CH₂＝CHCH₂O(CH₂CH₂O)₄(CH₂CH(CH₃)O)₅H；

CH₂＝CHO(CH₂CH₂O)₅(CH₂CH(CH₃)O)₅H；

CH₂＝C(CH₃)CH₂O(CH₂CH₂O)₄(CH₂CH(CH₃)O)₅C(＝O)CH₃；

CH₂＝CHCH₂O(CH₂CH₂O)₅(CH₂CH(CH₃)O)₂(CH₂CH(CH₂CH₃)O)₂H

polyether modified siloxanes are prepared in a conventional manner by grafting olefin modified (i.e., vinyl, allyl, or methallyl) polyalkylene oxide onto the hydride (SiH) intermediate of the trisiloxanes of the present invention using a hydrosilylation reaction.

In a preferred embodiment of the trisiloxane compounds of the formula I, R¹And R⁴An alkyl hydrocarbon group of 4 to 9 carbon atoms selected from a branched or straight chain hydrocarbon group of 2 to 4 carbon atoms, an aryl group, and an aryl substituent group having 6 to 20 carbon atoms; more preferably a branched or straight chain hydrocarbon group of 3 to 4 carbon atoms or an aryl group. R²、R³、R⁵、R⁶And R⁷Each independently selected from the group consisting of monovalent hydrocarbon groups of 1 to 4 carbon atoms, aryl groups, and hydrocarbon groups of 4 to 9 carbon atoms containing aryl groups; more preferably monovalent hydrocarbon groups of 1 to 2 carbon atoms and aryl groups; most preferred is methyl. Z is an oxyalkylene group having the general formula: r⁸(C₂H₄O)_a(C₃H₆O)_b(C₄H₈O)_cR⁹In the formula, R⁸Is provided with2. A linear or branched divalent hydrocarbon group of 3,5, 6, 7, 8 or 9 carbon atoms, more preferably 3 to 7 carbon atoms, and most preferably 3 to 6 carbons. Subscripts a, b, and c are zero or positive and satisfy the following relationship: a + b + c is more than or equal to 2 and less than or equal to 20, wherein a is more than or equal to 2; preferably, a is 5-20, and more preferably 5-8; preferably, b is 0 to 10, and more preferably 0 to 5; preferably, c is 0 to 8, and more preferably 0 to 4. R⁹Selected from H, monovalent hydrocarbon groups having 1 to 6 carbon atoms and acetyl groups.

In another preferred embodiment of the trisiloxane compounds of formula I, R¹、R⁴And R⁷Selected from branched or straight chain alkyl and aryl of 2-4 carbon atoms; more preferably a branched or straight chain hydrocarbon group of 3 to 4 carbon atoms. R²、R³、R⁵And R⁶Each independently selected from the group consisting of monovalent hydrocarbon radicals of 1 to 4 carbon atoms, and aryl radicals; more preferably a monovalent hydrocarbon group of 1 to 2 carbon atoms; most preferred is methyl. Z is as defined above.

In a preferred embodiment of the trisiloxane compounds of formula II, R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Each independently selected from the group consisting of monovalent hydrocarbon groups of 1 to 4 carbon atoms, and aryl groups; z' is an oxyalkylene group of the formula: r¹⁷(C₂H₄O)_d(C₃H₆O)_e(C₄H₈O)_fR¹⁸In the formula, R¹⁷Selected from the general formula-C₄H₈O-(C₂H₄A branched or straight chain divalent hydrocarbon group of O) -; r¹⁸Selected from the group consisting of H, monovalent hydrocarbon groups having 1 to 6 carbon atoms and acetyl groups, more preferably H and monovalent hydrocarbon groups having 1 to 4 carbon atoms, and subscripts d, e and f are zero or positive and satisfy the following relationship:

d + e + f is more than or equal to 2 and less than or equal to 20, wherein d is more than or equal to 2; d is preferably 5 to 20, and more preferably 5 to 8; preferably, e is 0-10; more preferably 0 to 5; preferably, f is 0 to 8, and more preferably 0 to 4.

In a preferred embodiment of the trisiloxane compounds of formula III, R¹⁹、R²⁰、R²¹、R²²、R²³And R²⁴Each independently selected from the group consisting of monovalent hydrocarbon groups of 1 to 4 carbon atoms and aryl groups; r²⁵Is a linear or branched hydrocarbyl group of 2 to 4 carbon atoms, most preferably 3 to 4 carbon atoms; z' is an oxyalkylene group having the general formula: r²⁶(C₂H₄O)_g(C₃H₆O)_h(C₄H₈O)_iR²⁷In the formula, R²⁶Is a linear or branched divalent hydrocarbon radical having 2, 3,5, 6, 7, 8 or 9 carbon atoms, more preferably 3 to 7 carbon atoms, most preferably 3 to 6 carbon atoms;

R²⁷selected from the group consisting of H, monovalent hydrocarbon groups having 1 to 6 carbon atoms and acetyl groups, more preferably H and monovalent hydrocarbon groups having 1 to 4 carbon atoms; subscripts g, h, and i are zero or positive and satisfy the following relationship:

g + h + i is more than or equal to 2 and less than or equal to 20, wherein g is more than or equal to 2; preferably, g is 5-20, and more preferably 5-8; preferably, h is 0 to 10, and more preferably 0 to 5; preferably, i is 0 to 8, and more preferably 0 to 4.

Noble metal catalysts suitable for use in preparing polyether-substituted siloxanes are also well known in the art and include complexes of rhodium, ruthenium, palladium, osmium, iridium, and/or platinum. Many types of platinum catalysts for this SiH olefin addition reaction are known, and such platinum catalysts may be used to produce the compositions of the present invention. The platinum compound can be selected from compounds having the formula (PtCl)₂Olefins) and H (PtCl)₃Olefins) as described in U.S. Pat. No. 3,159,601, which is incorporated herein by reference. An additional platinum-containing material may be a complex of chloroplatinic acid with up to 2 moles per gram of platinum of a material selected from the group consisting of alcohols, ethers, aldehydes and mixtures thereof, as described in U.S. Pat. No. 3,220,972 hereby incorporated by reference. Another class of platinum-containing materials useful in the present invention is described in U.S. Pat. nos. 3,715,334; 3,775,452 and 3,814,730 (Karstedt). Additional background on the prior art can be found in the following documents: L.Spier, "Homogeneous catalysis of hydrolysis by transformation Metals", Advances in organic chemistry, Vol.17, pp.407 to 447, FEdited by g.a.stone and r.west, published by academycpress (New York, 1979). The effective amount of platinum catalyst can be readily determined by one skilled in the art. Generally, an effective amount is about 0.1 to 50ppm of the total organomodified trisiloxane composition.

The compositions of the present invention exhibit improved resistance to hydrolysis outside the pH range of 6 to 7.5, i.e., under the extreme environmental conditions defined herein. The improved hydrolysis resistance may be confirmed by various tests, but as used herein, improved hydrolysis resistance means that 50 mol% or more of the hydrolysis resistant composition of the present invention remains unchanged or unreacted after exposure to aqueous acidic conditions at a solution pH of less than 6 for 24 hours or after exposure to aqueous basic conditions at a solution pH of greater than 7.5 for 24 hours. Under acidic conditions, the composition of the present invention exhibits a residual ratio (survival) of 50 mol% or more of the initial concentration when maintained at a pH of 5 or less for a period of more than 48 hours; specifically, the composition of the present invention shows a residual rate of 50 mol% or more at a pH of 5 or less for a period of more than 2 weeks; more specifically, the composition of the present invention shows a residual rate of 50 mol% or more at a pH of 5 or less for a period of more than 1 month; most particularly, the compositions of the present invention exhibit a residual rate of 50 mol% or greater at a pH of 5 or less for a period of more than 6 months. Under alkaline conditions, the composition of the present invention exhibits a residual rate of 50 mol% or more when maintained at a pH of 8 or more for a period of more than 2 weeks; specifically, the composition of the present invention shows a residual rate of 50 mol% or more at a pH of 8 or more for a period of more than 4 weeks; more specifically, the composition of the present invention shows a residual rate of 50 mol% or more at a pH of 8 or more for a period of more than 6 months; most specifically, the composition of the present invention exhibits a residual rate of 50 mol% or more at a pH of 8 or more for a period of more than 1 year.

Use of the composition of the invention:

A. pesticide (pesticide) -agriculture, horticulture, Turf (Turf), Ornamental (Ornamental) and Forestry (forest):

many pesticide applications require the addition of adjuvants to the spray mixture to provide wetting and spreading on the foliage. Adjuvants are often surfactants which can serve various functions, such as increasing the retention of spray droplets on difficult to wet foliage, increasing spreading to improve spray coverage, or providing penetration of the herbicide into the plant cuticle. These adjuvants are either provided as tank-side additives or are used as components in pesticide formulations.

Typical applications for pesticides include agricultural, horticultural, turf, ornamental, home and garden, veterinary and forestry applications.

The pesticidal compositions of the present invention also include at least one pesticide, wherein the organomodified trisiloxane surfactant of the present invention is present in an amount sufficient to provide an end-use concentration of 0.005% to 2% as a concentrate or dilution in a tank mix. Optionally, the pesticide composition may include excipients, co-surfactants, solvents, foam control agents, deposition aids, flow blockers (drift retadants), biologics, micronutrients, fertilizers, and the like. The term pesticide refers to any compound used to destroy pests, such as rodenticides, insecticides (insecticides), acaricides, fungicides and herbicides. Illustrative examples of pesticides that can be used include, but are not limited to, growth regulators, photosynthesis inhibitors, pigment inhibitors, mitotic disruptors (mitotic disrupters), lipid biosynthesis inhibitors (lipid biosynthesis inhibitors), cell wall inhibitors, and cell membrane disrupters (cell membrane disrupters). The amount of pesticide used in the composition of the present invention varies with the type of pesticide used. More specific examples of pesticidal compounds that may be used with the compositions of the present invention are, but are not limited to, herbicides and growth regulators, such as: phenoxyacetic acid, phenoxypropionic acid, phenoxybutyric acid, benzoic acid, triazines and s-triazines, substituted ureas, uracil, bentazone, isobenafop-propargyl, dimethenamid, benfop-butyl, dyafop-propargyl, isoxaflutole, fluridone, norfluridone, dinitroaniline, isoethamate, oryzalin, ethambucil, prodiamine, trifluralin, glyphosate, glufosinate, sulfonylurea, imidazolinones, picolinic acids, clethodim, chlorothalofop, fenoxaprop-p-ethyl, fluazifop-p-methyl, diclofop-p-ethyl, dichlobenil, isoxaflutole, and bipyridinium (bipyridylium) compounds.

Fungicidal compositions that may be used in the present invention may include, but are not limited to, aldimorph, tridemorph, dodemorph, dimethomorph; flusilazole, azaconazole, cyproconazole, epoxiconazole, furconazole, propiconazole, tebuconazole and the like; imazalil, thiophanate, benomyl, carbendazim, chlorothalonil (chlorothialoninil), niclosamide, trifloxystrobin (trifloxystrobin), fluoxastrobin (fluoxystrobin), dimoxystrobin (dimoxystrobin), azoxystrobin (azoxystrobin), sterilisexamine (furcaranil), prochloraz, flusulfamide, famoxadone (famoxadone), captan, maneb, mancozeb, dichlofluthrin, dodine, and metalaxyl.

Insecticide, larvicide, acaricide and ovicide (ovacide) compounds that can be used with the compositions of the present invention include, but are not limited to, bacillus thuringiensis, spinosad 105, abamectin (abamectin), doramectin (doramectin), lepimectin, pyrethrin, carbaryl, pirimicarb (pirimicarb), aldicarb, methomyl, chlorfenamidine, boric acid, chlordimeform, novaluron (novaluron), bistrifluron (bistrifluron), chlorflubenzuron, fluflubenzuron, imidacloprid, diazinon, acephate, endosulfan, captan, colam, dimethoate, ethoprophos, glutethion, isoxathion (izoxathion), chlorpyrifos, clofentezine, cyhalothrin, permethrin, cyfluthrin, cypermethrin, etc.

The pesticide may be a liquid or a solid. If solid, it is preferably soluble in the solvent or organomodified trisiloxane of the present invention prior to application, the silicone may serve as a solvent, or a surfactant for such solubility, or another surfactant may perform this function.

Agricultural excipients:

buffers, preservatives and other standard excipients known in the art may also be included in the composition.

Solvents may also be included in the compositions of the present invention. These solvents are liquid at room temperature. Examples include water, alcohols, aromatic solvents, oils (i.e., mineral oil, vegetable oil, silicone oil, etc.), lower alkyl esters of vegetable oils, fatty acids, ketones, glycols, polyethylene glycols, paraffins, and the like. Specific solvents may be 2, 2, 4-trimethyl-1, 3-pentane diol and alkoxylated, especially ethoxylated, variants thereof, or N-methyl-pyrrolidone as described in U.S. patent No. 5,674,832, which is incorporated herein by reference.

Cosurfactant:

also useful are other cosurfactants that have short chain hydrophobic groups that do not interfere with superspreading, as described in U.S. Pat. Nos. 5,558,806, 5,104,647, and 6,221,811, which are incorporated herein by reference.

Cosurfactants useful herein include nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, zwitterionic surfactants, polymeric surfactants, or any mixture thereof. The surfactant is typically hydrocarbon-based, silicone-based, or fluorocarbon-based.

Useful surfactants include alkoxylates, especially ethoxylates, containing block copolymers including copolymers of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof; alkylaryl alkoxylates, especially ethoxylates or propoxylates, and their derivatives, including alkylphenol ethoxylates; aryl alkoxylates, especially ethoxylates or propoxylates, and their derivatives; amine alkoxylates, especially amine ethoxylates; fatty acid alkoxylates; a fatty alcohol alkoxylate; an alkyl sulfonate; alkyl benzene and alkyl naphthalene sulfonates; sulfated fatty alcohols, amines or amides; acid esters of sodium isethionate (acid esters of sodium isethionate); esters of sodium sulfosuccinate; sulfated or sulfonated fatty acid esters; petroleum sulfonate; n-acyl sarcosinate; alkyl polyglycosides (alkyl polyglycosides); alkyl ethoxylated amines; and the like.

Specific examples include alkylacetylenic diols (SURFONYL-Air Products), pyrrolidone-based surfactants (e.g., SURFODONE-LP 100-ISP), 2-ethylhexyl sulfate, isodecyl alcohol ethoxylates (e.g., RHODASURURF DA 530-Rhodia), ethylene diamine alkoxylates (TETRONICS-BASF), ethylene oxide/propylene oxide copolymers (PLURONICS-BASF), and Gemini-type surfactants (Rhodia).

Preferred surfactants include ethylene oxide/propylene oxide copolymers (EO/PO); an amine ethoxylate; an alkyl polyglycoside; oxo-tridecyl alcohol ethoxylates, and the like.

In a preferred embodiment, the agrochemical composition of the present invention further comprises one or more agrochemical ingredients. Suitable agrochemical ingredients include, but are not limited to, herbicides, insecticides, growth regulators, fungicides, miticides (miticides), acaricides (acarcides), fertilizers, biologicals, plant nutrients, micronutrients, biocides, paraffinic mineral oil, methylated seed oil (i.e., metal methyl soyate or methyl rape oil), vegetable oils (e.g., soybean oil and rape oil), water quality regulators such as(Loveland Industries, greeney, CO) and Quest (Helena Chemical, Collierville, TN), modified clays such as(Englehard corp.,), foam control agents, surfactants, wetting agents, dispersants, emulsifiers, deposition aids, anti-drip components (antidrift component), and water.

Suitable agrochemical compositions are prepared by combining in a manner known in the art, for example, by mixing one or more of the above components with the organomodified trisiloxanes of the present invention, as a tank mix formulation, or as a "canned" formulation. The term "tank mix formulation" means that at least one agrochemical is added to the spraying medium, e.g. water or oil, at the point of use. The term "in-can" refers to a formulation or concentrate containing at least one agrochemical component. The "in-can" formulation can then be diluted to use concentration at the point of use, typically in a tank mix, or it can be used directly without dilution.

B. Coating:

coating formulations typically require wetting agents or surfactants for the purposes of emulsification, compatibilization of components, leveling, flow, and reduction of surface defects. In addition, these additives may impart improvements to the cured or dried film, such as improved abrasion resistance, antiblocking properties, hydrophilicity, and hydrophobicity. The coating formulations can be present as solvent-containing coatings, aqueous coatings and powder coatings.

The coating composition can be used as: building coatings; OEM product coatings such as automotive coatings and coil coatings; specialty coatings such as industrial maintenance coatings (industrial maintenace coatings) and marine coatings;

typical resin types include: polyesters, alkyds, acrylics, polyurethanes, and epoxies.

C. Personal care product

In a preferred embodiment, the organomodified trisiloxane surfactant of the present invention comprises from 0.1 to 99pbw, more preferably from 0.5pbw to 30pbw, still more preferably from 1 to 15pbw of the organomodified trisiloxane surfactant and from 1pbw to 99.9pbw, more preferably from 70pbw to 99.5pbw, still more preferably from 85pbw to 99pbw of the personal care composition per 100 parts by weight ("pbw") of the personal care composition.

The organomodified trisiloxane surfactant compositions of the present invention may be used in the form of personal care emulsions, such as lotions and creams. As is generally known, emulsions comprise at least two immiscible phases, one of which is continuous and the other discontinuous. The additional emulsion may be a liquid or solid of varying viscosity. In addition, the particle size of the emulsion may be such that the emulsion is a microemulsion, which when sufficiently small may be transparent. It is also possible to prepare emulsions of emulsions, which are generally referred to as multiple emulsions. These emulsions may be:

1) an aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises an organomodified trisiloxane surfactant of the present invention;

2) an aqueous emulsion wherein the continuous phase comprises the organomodified trisiloxane surfactant of the present invention and the discontinuous phase comprises water;

3) a non-aqueous emulsion wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises an organomodified trisiloxane surfactant of the present invention; and

4) a non-aqueous emulsion wherein the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises an organomodified trisiloxane surfactant of the present invention.

Non-aqueous emulsions comprising a silicone phase are described in U.S. Pat. No. 6,060,546 and U.S. Pat. No. 6,271,295, the contents of which are specifically incorporated by reference herein.

As used herein, the term "non-aqueous hydroxyl organic compound" refers to hydroxyl containing organic compounds that are liquid at room temperature, e.g., about 25℃ and about 1 atmosphere, illustrative of alcohols, glycols, polyols, and polyglycols, and mixtures thereof. The non-aqueous organic hydroxylic solvent is selected from hydroxyl-containing organic compounds that are liquid at room temperature, e.g., about 25 ℃ and about 1 atmosphere, including alcohols, glycols, polyols, and polyglycols, and mixtures thereof. Preferably, the non-aqueous hydroxylic organic solvent is selected from the group consisting of ethylene glycol, ethanol, propanol, isopropanol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, iso-butylene glycol, methyl propane diol, glycerol, sorbitol, polyethylene glycol, polypropylene glycol monoalkyl ether, polyoxyalkylene copolymer and mixtures thereof.

Once the desired form is obtained, whether as a single silicone phase, an anhydrous mixture comprising a silicone phase, an aqueous mixture comprising a silicone phase, a water-in-oil emulsion, an oil-in-water emulsion, or either of two non-aqueous emulsions or variations thereof, the resulting material is often a cream or lotion with improved deposition properties and good handling characteristics. It can be blended into the formulation of hair care products, skin care products, antiperspirants, sunscreens, cosmetics, color cosmetics, insect repellents, vitamin and hormone carriers, perfume carriers, etc.

Personal care applications in which the organomodified trisiloxane surfactants of the present invention and the silicone compositions of the present invention derived therefrom may be used include, but are not limited to deodorants, antiperspirants, antiperspirant/deodorants, shaving products, skin lotions, moisturizers, toners, bath products, cleansing products, hair care products such as shampoos, conditioners, mousses, styling gels, hair sprays, hair dyes, hair coloring products, hair bleaches, hair perming products, hair straighteners, manicure products such as nail polishes, nail polish removers, nail creams and lotions, cuticle softeners, protective creams such as sunscreens, insect repellants, and anti-aging products, color cosmetics such as lipsticks, foundations, face powders, eyeliners, eye shadows, blushers, cosmetics, mascaras, and other personal care formulations to which silicone components have generally been added, and drug delivery systems for topical application of medical compositions to be applied to the skin.

In a preferred embodiment, the personal care composition of the present invention further comprises one or more personal care ingredients. Suitable personal care ingredients include, for example, emollients, moisturizers, humectants, pigments, including pearlescent pigments such as bismuth oxychloride and titanium dioxide coated mica, colorants, fragrances, biocides, preservatives, antioxidants, antimicrobials, antifungal agents, antiperspirants, exfoliants, hormones, enzymes, pharmaceutical compounds, vitamins, salts, electrolytes, alcohols, polyols, ultraviolet light absorbers, botanical extracts, surfactants, silicone oils, organic oils (organic oils), waxes, film formers, thickeners such as fumed or hydrated silica, particulate fillers such as talc, kaolin, starch, modified starch, mica, nylons, clays such as bentonite and organically modified clays.

Suitable personal care compositions are prepared by combining in a manner known in the art, for example, by mixing one or more of the above components with the organomodified trisiloxane surfactant. Suitable personal care compositions may be in the form of a single phase or in the form of an emulsion, including oil-in-water, water-in-oil, and anhydrous emulsions where the silicone phase may be a discontinuous phase or a continuous phase, as well as multiple emulsions, such as oil-in-water-in-oil emulsions and water-in-oil-in-water emulsions.

In one useful embodiment, an antiperspirant composition comprises the organomodified trisiloxane surfactants of the present invention and one or more active antiperspirant agents. Suitable antiperspirant agents include, for example, the class I active antiperspirant ingredients listed in U.S. food and Drug Administration's October 10, 1993 Monograph on polar devices Drug products for over-the-counter human use, such as aluminum halides, aluminum hydroxyhalides (aluminum chlorohydrate) such as aluminum chlorohydrate (aluminum chlorohydrate), and complexes or mixtures thereof with zirconyl halides (zirconium chlorohydrate) and zirconyl hydroxyhalides (zirconium chlorohydrate), for example, aluminum-zirconium chlorohydrate (aluminum-zirconium chlorohydrate), aluminum zirconium glycine complexes (aluminum zirconyl glycine complexes) such as aluminum zirconium chlorohydrate glycine (aluminum zirconyl chlorohydrate).

In another useful embodiment, the skin care composition includes an organomodified trisiloxane surfactant and a carrier such as a silicone oil or an organic oil. The skin care composition may optionally further comprise emollients such as triglycerides, wax esters (wax esters), alkyl or alkenyl esters of fatty acids, or polyol esters, and one or more known components commonly used in skin care compositions, for example pigments, vitamins such as vitamin a, vitamin C and vitamin E, sunscreens or sunscreen compounds (sunscreens) such as titanium dioxide, zinc oxide, 2-hydroxy-4-methoxy-benzophenone, octyl methoxycinnamate, butyl methoxydibenzoylmethane, p-aminobenzoic acid and octyl dimethyl-p-aminobenzoic acid (octyl dimethyl-p-aminobenzoic acid).

In another useful embodiment, an additive color cosmetic composition, such as a lipstick, make-up or mascara composition, includes an organomodified trisiloxane surfactant, and a colorant, such as a pigment, a water-soluble dye or an oil-soluble dye.

In another useful embodiment, the compositions of the present invention are used in combination with a fragrance material. These perfume materials may be perfume compounds, encapsulated perfume compounds or aroma-releasing compounds, which may be pure compounds or encapsulated. Particularly compatible with the compositions of the present invention are fragrance-releasing silicone-containing compounds, as disclosed in U.S. Pat. nos. 6,046,156, 6,054,547, 6,075,111, 6,077,923, 6,083,901 and 6,153,578; all of these patents are specifically incorporated herein by reference.

The use of the compositions of the present invention is not limited to personal care compositions, but other products treated with the compositions of the present invention such as waxes, polishes and textiles are also contemplated.

D. Household nursing product

Household care applications include laundry detergents and fabric softeners, dishwashing liquids, wood and furniture polishes, floor polishes, tub and tile cleaners, toilet bowl cleaners, hard surface cleaners, window cleaners, antifogging agents, drain cleaners, automatic dishwashing and sheeting detergents, carpet cleaners, pre-wash spotter, rust removers, and descalers.

Experiment of

The hydride intermediates for the organomodified trisiloxane surfactant compositions of the present invention, as well as the comparative compositions, were prepared as described in the examples below.

Preparation of example 1

1, 5-di-tert-butyl-1, 1, 3,5, 5, pentamethyltrisiloxane (FIG. 1, Structure 1).

100g of tBuMe₂SiCl and 46g MeHSiCl₂Dissolved in 150ml isopropyl ether (IPE) and placed in an addition funnel. 150g of water and 250ml of IPE were charged with a mechanical stirrer, reflux condenser and N₂Imported 1 liter round bottom flask. The chlorosilane was added dropwise over 1h at room temperature (23 ℃) via an addition funnel. After the addition was complete, the temperature was adjusted to 70 ℃ and the reaction was carried out at reflux temperature for 20h, the progress being monitored by GC (88% yield at 20 h). At the end of the reaction, water was drained through a separatory funnel. The liquid was washed three times with 100g of water each time. 25g of NaHCO₃Mixed with 100g of water and slowly added to the mixture and stirred for 30 minutes. The water was drained again and dried over sodium sulfate. After filtration, the IPE was stripped in a rotary evaporator and the crude product was further fractionated under reduced pressure to give 63gtBuMe₂SiOMe(H)SiOSi Me₂tBu (97% GC purity).

FIG. 1-reaction scheme for preparing hydride intermediates

tBuMe₂SiCl+MeHSiCl H₂O/IPE tBuMe₂SiOMe(H)SiOSi Me₂tBu

Structure 1 →

Preparation of example 2

1, 5-bis (isopropyl) -1, 1, 3,5, 5, pentamethyltrisiloxane (figure 2, structure 2).

Mixing 25g of iPrMe₂SiCl (0.183 mol) and 13.1g MeHSiCl₂(0.114 mol) was dissolved in 80ml isopropyl ether (IPE) and placed in an addition funnel. 50g of water and 100ml of IPE were charged with a mechanical stirrer, reflux condenser and N₂Imported 500ml round bottom flask. The chlorosilane was added dropwise over 40 minutes at room temperature (23 ℃) via an addition funnel. After the addition was complete, the temperature was adjusted to 80 ℃ and the reaction was carried out at reflux temperature for 4h, the course of which was monitored by GC (75% yield at 4 h). At the end of the reaction, water was drained through a separatory funnel. The liquid was washed three times with 80g of water each time. 25g of NaHCO₃Mixed with 100g of water and slowly added to the mixture and stirred for 30 minutes. The water was drained again and dried over sodium sulfate. After filtration, the IPE was stripped in a rotary evaporator and the crude product was further fractionated under reduced pressure to give 10g of iPrMe₂SiOMe(H)SiOSi Me₂iPr (GC purity 93%).

FIG. 2-reaction scheme for preparing hydride intermediates

iPrMe₂SiCl+MeHSiCl H₂O/IPE iPrMe₂SiOMe(H)SiOSi Me₂iPr

Structure 2 →

Preparation of example 3

The hydride intermediates of examples 1-2 were further modified with various allyl polyalkylene oxides to provide organomodified trisiloxane surfactant compositions of the present invention (Table 1), as well as comparative trisiloxane surfactants (from Table 2).

The organomodified trisiloxane surfactant compositions of the present invention are prepared by conventional methods of platinum-mediated hydrosilation, as described in U.S. Pat. No. 3,299,112 to Bailey, which is incorporated herein by reference.

Table 1 provides a description of the compositions of the present invention. Some of these compositions are described by the following structures:

M^*D′M^*

wherein M is^*＝R¹Si(CH₃)₂O_0.5；

D′＝OSi(CH₃)CH₂CH(R³²)CH₂O-(CH₂CH₂O)_r-(CH₂CH₂O)_sR³³

Wherein R is¹、R³²、R³³Subscripts r and s are as set forth in Table 1.

TABLE 1 description of organomodified trisiloxane surfactant compositions

Table 2 provides a description of comparative trisiloxanes and silicone polyether (organosilicon polyether) based surfactants having the general structure:

MDxD″_YM

wherein M ═ CH₃)₃SiO_0.5；D＝OSi(CH₃)₂(ii) a And

D″＝OSi(CH₃)CH₂CH₂CHO-(CH₂CH₂O)_dR⁹

TABLE 2 comparative Silicone polyether surfactant compositions

In addition, the comparative sample OPE (octylphenol ethoxylate, containing 10 polyoxyethylene units) is a non-silicone organic surfactant. The product can be prepared byX-100 was obtained from Dow chemical Company, Midland, MI.

Example 4

This example demonstrates the ability of the organomodified trisiloxane compositions of the present invention to reduce the surface tension of water, thereby demonstrating utility as a surfactant. The surface tension was measured using a Kruss surface tensiometer using a sandblasted platinum sheet (platingblade) as a sensor. Solutions of the various components were prepared in 0.005M NaCl in deionized water at a concentration of 0.1 wt% as equilibrium adjuvant.

Table 3 shows that solutions of these unique compositions result in a significant reduction in surface tension relative to conventional surfactants.

The compositions of the present invention also provide spreading properties (spreading properties) similar to the comparative trisiloxane surfactants (A, B). Furthermore, the organomodified trisiloxane surfactants of the present invention provide improved spreading relative to conventional silicone polyether (C) and conventional organic surfactant product OPE.

The spreading was determined as follows: a10 μ L droplet of the surfactant solution was applied to a polyvinyl acetate Film (USI, "Crystal ClearWrite on Film") at a relative humidity of 50-70% (at 22-25 ℃), and the spreading diameter (mm) after 30 seconds was measured. The solution was applied using an automatic pipette so that the volume of the drop was reproducible. Deionized water further purified with a microfiltration system was used to prepare the surfactant solution.

TABLE 3 surface tension and spreading Properties

Example 5

Hydrolytic stability was determined using HPLC on representative compositions of the invention. Solutions of the various compositions were prepared at a concentration of 0.5% by weight in the pH range from pH 4 to pH 11 and monitored for degradation over time by HPLC.

The analysis method comprises the following steps:

samples were analyzed by reverse phase chromatography techniques using the experimental conditions listed in table 4.

TABLE 4 solvent gradient for HPLC method

A detector: ELSD/LTA (Evaporative light Scattering with Low Temperature Adapter)

Conditions are as follows: 30 ℃ 1.95 SLPM N₂

Column: phenomenex LUNA C18 end cap, 5 micron, 75x4.6mm

Flow rate: 1.0mL/min

Volume injection volume (inj): 10 microliter

Sample preparation: 0.050g/mL in methanol

Tables 5-8 demonstrate that the compositions of the present invention provide improved hydrolysis resistance relative to the standard comparative silicone-based surfactant, silicone a, under similar pH conditions.

The comparative siloxane A showed rapid hydrolysis at pH < 5 and pH > 7, whereas the organomodified trisiloxane surfactants of the present invention showed higher resistance to hydrolysis under the same conditions.

TABLE 5 hydrolytic stability of siloxane-based surfactants as determined by HPLC

TABLE 6 hydrolytic stability of siloxane-based surfactants as determined by HPLC

TABLE 7 hydrolytic stability of siloxane-based surfactants by HPLC

TABLE 8 hydrolytic stability of comparative siloxane-based surfactants as determined by HPLC

Example 6

Unlike conventional silicone-based surfactants that undergo rapid hydrolysis under acidic and basic conditions (pH < 5 and pH > 9), the organomodified trisiloxane surfactants of the present invention provide increased resistance to hydrolysis relative to conventional trisiloxane alkoxylates (comparative a). As the spreadability decreased over time, hydrolysates were observed. Thus, solutions of the organomodified trisiloxane surfactants of the present invention, as well as comparative surfactants, were prepared at the desired use concentrations and pH. Spreading was measured as a function of time to illustrate hydrolysis resistance.

Table 9 is an illustrative example of an organomodified trisiloxane surfactant, wherein product No. 3 overspread surfactant has improved resistance to hydrolysis over the conventional trisiloxane ethoxylate surfactant (product a) in the pH 3 to pH 10 range. As described above, the hydrolysis resistance was observed by monitoring the spreading properties over time. Here, 0.4 wt% solutions were prepared at pH 3, 4,5 and 10. The spreading was determined according to the procedure of example 4.

TABLE 9 influence of pH on spreading behavior versus time

Example 7

The effect of the other ingredients on spreading was determined by mixing the silicone disiloxane surfactants of the present invention with a conventional organic based co-surfactant. The co-surfactants are described in table 10.

The blend is prepared as a physical mixture in which the weight fraction of silicone is represented by α, indicating that the co-surfactant makes up the balance of the blend proportions. For example, when α ═ 0, this indicates that the composition contains 0% silicone component, and 100% co-surfactant, whereas α ═ 1.0 indicates that the composition contains 100% silicone, and no (0%) co-surfactant. The mixture of these two components is represented by the weight fraction α, where α varies within the following ranges: alpha is more than or equal to 0 and less than or equal to 1.0. For example, when α is 0.25, this indicates that the surfactant mixture consists of 25% silicone and 75% co-surfactant. These blends were then diluted in water to the desired concentration for spread evaluation.

At 0.2 wt% total surfactant, spreading was determined as described in example 4.

Table 11 demonstrates that representative examples of co-surfactants of the present invention provide favorable spreading results, and in some cases unexpected synergistic increases, where the spreading diameter of the mixture exceeds that of the individual components.

TABLE 10 description of conventional co-surfactants

TABLE 11 Effect of cosurfactants on spreading Properties of the blends

The foregoing examples are merely illustrative of the present invention, serving to illustrate only some of the features of the invention. The appended claims are intended to claim the invention as broadly as possible, the examples of which illustrate selected embodiments from a wide variety of all possible embodiments. Accordingly, it is applicants' intention that the appended claims are not to be limited by the embodiments selected to illustrate features of the present invention. The term "comprising" and its grammatical variants as used in the claims also logically means and includes the various degrees of terminology such as, but not limited to, "consisting essentially of and" consisting of. Where necessary, ranges have been provided; those ranges are inclusive of all subranges therebetween. Such a range may be viewed as a markush group or groups consisting of different pairs of numerical limits, said markush group or groups being defined entirely by its lower and upper limits and increasing numerically from the lower to the upper limit in the normal way. It is expected that variations in these ranges will occur to those skilled in the art and are to be considered as being covered by the appended claims if not already dedicated to the public. It is also expected that advances in technology will make equivalents possible that are not presently contemplated due to imprecision of language and these variations should also be construed where possible to be covered by the appended claims. All U.S. patents (and patent applications) referred to herein are incorporated by reference in their entirety as if fully set forth herein.

Claims (43)

1. A silicone composition having the formula:

M¹D¹M²

wherein

M¹＝(R¹)(R²)(R³)SiO_1/2

M²＝(R⁴)(R⁵)(R⁶)SiO_1/2(ii) a And

D¹＝(R⁷)(Z)SiO_2/2

wherein

R¹A monovalent hydrocarbon group selected from the group consisting of branched or straight-chain hydrocarbon groups of 2 to 4 carbon atoms, aryl groups, and alkyl hydrocarbon groups of 4 to 9 carbon atoms containing aryl substituents of 6 to 20 carbon atoms; r²、R³、R⁴、R⁵、R⁶And R⁷Each independently selected from the group consisting of monovalent hydrocarbon groups of 1 to 4 carbon atoms, aryl groups, and hydrocarbon groups of 4 to 9 carbon atoms containing aryl groups; z is an oxyalkylene group having the general formula: r⁸(C₂H₄O)_a(C₃H₆O)_b(C₄H₈O)_cR⁹In the formula, R⁸Is a linear or branched divalent hydrocarbon radical having 2, 3,5, 6, 7, 8 or 9 carbon atoms; r⁹Selected from H, monovalent hydrocarbon radicals having from 1 to 6 carbon atoms and acetyl radicals, the subscript a is greater than or equal to 2, b and c are zero or positive and satisfy the following relationship:

a + b + c is more than or equal to 2 and less than or equal to 20, wherein a is more than or equal to 2;

wherein the silicone composition has improved hydrolysis resistance.

2. The composition of claim 1, wherein R¹And R⁴Selected from the group consisting of propyl, isopropyl, butyl, sec-butyl, isobutyl, and tert-butyl.

3. The composition of claim 1, wherein R²、R³、R⁵、R⁶And R⁷Is methyl.

4. The composition of claim 1, wherein R⁸Is a divalent hydrocarbon group having three carbon atoms.

5. The composition of claim 1 wherein the subscript a ranges from 8 to 12.

6. The composition of claim 1 wherein 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, wherein R⁹Selected from hydrogen and methyl.

9. The composition of claim 2, wherein R¹And R⁴Selected from isopropyl and tert-butyl.

10. The composition of claim 5 where the subscript a is 11.

11. The composition of claim 8, wherein R⁹Is hydrogen.

12. The composition of claim 9, wherein R²、R³、R⁵、R⁶And R⁷Is methyl.

13. The composition of claim 12, wherein R⁸Is a divalent hydrocarbon group having three carbon atoms.

14. The composition of claim 13 where the subscript a is 11.

15. The composition of claim 14 where subscripts b and c are both zero.

16. The composition of claim 15, wherein R⁹Is hydrogen.

17. An agricultural composition comprising:

a) the silicone composition of claim 1; and

b) an agriculturally active component, wherein the agriculturally active component is selected from the group consisting of: aldimorph, tridemorph, moroxydine, dimethomorph; flusilazole, azaconazole, cyproconazole, epoxiconazole, furconazole, propiconazole, tebuconazole, imazalil, thiophanate, benomyl, carbendazim, chlorothalonil, niclosamide, trifloxystrobin, fluoxastrobin, dimoxystrobin, azoxystrobin, sterilisexamine, prochloraz, sulfsulfamide, famoxadone, captan, manganese dioxide, mancozeb, dichlofluthrin, bacillus thuringiensis, spinosad 105, abamectin, doramectin, lepictmen, pyrethrin, sevin, pirimicarb, aldicarb, dichlorcarb, methomyl, chlorfenapyr, trifloxystrobin, prochloraz, diazinon, acephate, endosulfan, captan, colaton, dimethoate, oryfos, valthiofos, isofos, chlorpyrifos, clofenthiflufenthiuron, cyhalothrin, permethrin, cyhalothrin, cy, Benzoic acid, triazines and s-triazines, substituted ureas, uracil, bentazone, isophenylene, imazalil, phenmedipham, dyafop, desmodium, isoxaflutole, norflurazon, dinitroaniline, isofluralin, oryzalin, butachlor, prodiamine, trifluralin, glyphosate, glufosinate, sulfonylureas, imidazolinones, pyridine carboxylic acids, clethodim, clomeprop, fenoxaprop, fluazifop-p, haloxyfop, diclofop, dichlobemide, bipyridinium compounds, zinc sulfate, ferrous sulfate, ammonium sulfate, urea ammonium nitrate, ammonium thiosulfate, potassium sulfate, monoammonium phosphate, urea phosphate, calcium nitrate, boric acid, potassium salt of boric acid, sodium salt of boric acid, phosphoric acid, magnesium hydroxide, manganese carbonate, calcium polysulfide, copper sulfate, iron sulfate, calcium sulfate, sodium molybdate, and calcium chloride,

wherein the agricultural composition has improved resistance to hydrolysis.

18. The composition of claim 17, wherein R¹And R⁴Selected from the group consisting of propyl, isopropyl, butyl, sec-butyl, isobutyl, and tert-butyl.

19. The composition of claim 17, wherein R²、R³、R⁵、R⁶And R⁷Is methyl.

20. The composition of claim 17, wherein R⁸Is a divalent hydrocarbon group having three carbon atoms.

21. The composition of claim 17 wherein the subscript a ranges from 8 to 12.

22. The composition of claim 17 wherein subscript b ranges from 0 to 3.

23. The composition of claim 17 where the subscript c is 0.

24. The composition of claim 17, wherein R⁹Selected from hydrogen and methyl.

25. The composition of claim 18, wherein R¹And R⁴Selected from isopropyl and tert-butyl.

26. The composition of claim 21 where the subscript a is 11.

27. The composition of claim 24, wherein R⁹Is hydrogen.

28. The composition of claim 25, wherein R²、R³、R⁵、R⁶And R⁷Is methyl.

29. The composition of claim 28, wherein R⁸Is a divalent hydrocarbon group having three carbon atoms.

30. The composition of claim 29 where the subscript a is 11.

31. The composition of claim 30 where subscripts b and c are both zero.

32. The composition of claim 31, wherein R⁹Is hydrogen.

33. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the composition of claim 1.

34. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the composition of claim 17.

35. An aqueous emulsion wherein the continuous phase comprises water and the discontinuous phase comprises the composition of claim 1.

36. An aqueous emulsion wherein the continuous phase comprises water and the discontinuous phase comprises the composition of claim 17.

37. A non-aqueous emulsion wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of claim 1.

38. A non-aqueous emulsion wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of claim 17.

39. A non-aqueous emulsion wherein the continuous phase comprises a non-aqueous hydroxylic solvent and the discontinuous phase comprises the composition of claim 1.

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. A personal care composition comprising:

a) the composition of claim 1; and

b) a personal care composition comprising a combination of ingredients selected from the group consisting of,

wherein the personal care composition has improved hydrolysis resistance.

42. A home care composition comprising:

a) the composition of claim 1; and

b) a surfactant selected from the group consisting of hydrocarbon-based surfactants and fluorocarbon-based surfactants,

wherein the home care composition has improved hydrolysis resistance.

43. A coating composition comprising:

a) the composition of claim 1; and

b) a resin selected from the group consisting of polyesters, alkyds, acrylics, polyurethanes, and epoxies, wherein the coating composition has improved hydrolysis resistance.