JP2013216898A - Hydrolysis-resistant organically modified trisiloxane surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a trisiloxane surfactant composition exhibiting resistance to hydrolysis over wide pH ranges.SOLUTION: There are disclosed three types of trisiloxane surfactant having a basic formula: MDM', and uses of the surfactant, where substituents on the different M and M' groups act with a pendant polyalkylene oxide group on a D group on the surfactant to be resistant to hydrolysis under a basic or acidic condition. M=(R)(R)(R)SiO; M'=(R)(R)(R)SiO; and D=(R)(Z")SiO; Z" is an alkyleneoxide group of general formula: R(CHO)(CHO)(CHO)R.

Description

  The present invention relates to a trisiloxane surfactant composition that exhibits resistance to hydrolysis over a wide pH range. More particularly, the present invention relates to hydrolysis resistant trisiloxane surfactants that are resistant to hydrolysis between a pH of about 3 and a pH of about 12.

  The topical application of a liquid composition to the surface of both live and inanimate objects to produce the desired modification includes processes that control wetting, spreading, foaming, detergency, and the like. When used in aqueous solution, trisiloxane-type compounds are known to be useful in controlling the process and achieving the desired effect in order to improve the reach of the active ingredient to the surface being treated. It has been. However, this trisiloxane compound can only be used in a narrow pH range, ranging from a weakly acidic pH 6 to a very weak basic pH 7.5. Outside this narrow pH range, the trisiloxane compound is not stable to hydrolysis and degrades quickly.

  The present invention provides a trisiloxane compound or composition thereof useful as a surfactant selected from the group consisting of trisiloxane compounds having the formula I, II, or III.

Trisiloxane compound I has the formula:
M ¹ D ¹ M ²
Have
here,
M ¹ = (R ¹ ) (R ² ) (R ³ ) SiO _1/2
M ² = (R ⁴ ) (R ⁵ ) (R ⁶ ) SiO _1/2
D ¹ = (R ⁷ ) (Z) SiO _2/2
And
Where
R ¹ is a branched or straight chain hydrocarbon group of 2 to 4 carbon atoms, aryl, and an alkyl of 4 to 9 carbon atoms containing an aryl substituent of 6 to 20 carbon atoms Selected from hydrocarbon groups; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ include monovalent hydrocarbon radicals of 1 to 4 carbon atoms, aryl, and aryl groups Each independently selected from the group consisting of hydrocarbon groups of 4 to 9 carbon atoms;
Z is a general formula:
R ⁸ (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₄ H ₈ O) _c R ⁹
An alkylene oxide group of
Wherein R ⁸ is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, ⁸ , or 9 carbon atoms; R ⁹ is H, 1 to 6 Selected from the group consisting of a monovalent hydrocarbon radical of carbon atoms and acetyl; the subscripts, a, b, and c are zero or positive and have the following relationship:
2 ≦ a + b + c ≦ 20 and a ≧ 2
Meet.

  When the subscript a satisfies the condition of 2 ≦ a ≦ 5, it is desirable to use a cosurfactant as described below in order to obtain the effect of the composition of the present invention.

The trisiloxane compound II has the formula:
M ³ D ² M ⁴
Have
here,
M ³ = (R ¹⁰ ) (R ¹¹ ) (R ¹² ) SiO _1/2
M ⁴ = (R ¹³ ) (R ¹⁴ ) (R ¹⁵ ) SiO _1/2
D ² = (R ¹⁶ ) (Z ′) SiO _2/2
And
In which R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are monovalent hydrocarbon radicals of 1 to 4 carbon atoms, aryl, and 6 to 20 carbons. Each independently selected from the group consisting of alkyl hydrocarbon groups of 4 to 9 carbon atoms containing an aryl substituent of atoms;
R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸
An alkylene oxide group of
Wherein R ¹⁷ is a general formula:
_{-C 4 H 8 O- (C 2} H 4 O) -
Selected from branched or straight chain divalent hydrocarbon radicals,
R ¹⁸ is selected from the group consisting of H, a monovalent hydrocarbon radical of 1 to 6 carbon atoms, and acetyl; the subscripts, d, e, and f are zero or positive and have the relationship :
2 ≦ d + e + f ≦ 20 and d ≧ 2
Meet.

  When the subscript d satisfies the condition of 2 ≦ d ≦ 5, it is desirable to use a cosurfactant as described below in order to obtain the effect of the composition of the present invention.

Trisiloxane compound III has the formula:
M ⁵ D ³ M ⁶
Have
here,
M ⁵ = (R ¹⁹ ) (R ²⁰ ) (R ²¹ ) SiO _1/2
M ⁶ = (R ²² ) (R ²³ ) (R ²⁴ ) SiO _1/2
D ³ = (R ²⁵ ) (Z ″) SiO _2/2
And
In which R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ are monovalent hydrocarbon radicals of 1 to 4 carbon atoms, aryl, and aryl of 6 to 20 carbon atoms Each independently selected from the group consisting of alkyl hydrocarbon groups of 4 to 9 carbon atoms containing substituents; R ²⁵ is a linear or branched hydrocarbon radical of 2 to 4 carbon atoms Yes; Z ″ is 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
An alkylene oxide group of
Wherein R ²⁶ is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R ²⁷ is H, 1 to 6 Selected from the group consisting of monovalent hydrocarbon radicals of carbon atoms and acetyl; the subscripts, g, h, and i are zero or positive and have the following relationship:
2 ≦ g + h + i ≦ 20 and g ≧ 2
Meet.

  When the subscript g satisfies the condition of 2 ≦ g ≦ 5, it is desirable to use a cosurfactant as described below in order to obtain the effect of the composition of the present invention.

  As used herein, the integer value of the subscript for stoichiometry refers to the molecular species, and the non-integer value of the subscript for stoichiometry is the molecular weight average basis, number average basis, or mole fraction Refers to a mixture of molecular species relative to a reference. In the case of a mixture of compounds of the invention, it is easy to say that the stoichiometric subscript of the mixture has an average value of the subscript that can be an integer or non-integer, as opposed to that of a pure compound. it is obvious.

  The present invention provides a trisiloxane compound or composition thereof useful as a surfactant selected from the group consisting of trisiloxane compounds having the formula I, II, or III.

Trisiloxane compound I has the formula:
M ¹ D ¹ M ²
Have
here,
M ¹ = (R ¹ ) (R ² ) (R ³ ) SiO _1/2
M ² = (R ⁴ ) (R ⁵ ) (R ⁶ ) SiO _1/2
D ¹ = (R ⁷ ) (Z) SiO _2/2
And
Where
R ¹ is a branched or straight chain hydrocarbon group of 2 to 4 carbon atoms, aryl, and an alkyl of 4 to 9 carbon atoms containing an aryl substituent of 6 to 20 carbon atoms Selected from hydrocarbon groups; R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ include monovalent hydrocarbon radicals of 1 to 4 carbon atoms, aryl, and aryl groups Each independently selected from the group consisting of hydrocarbon groups of 4 to 9 carbon atoms.
Z is a general formula:
R ⁸ (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₄ H ₈ O) _c R ⁹
An alkylene oxide group of
Wherein R ⁸ is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, ⁸ , or 9 carbon atoms; R ⁹ is H, 1 to 6 Selected from the group consisting of a monovalent hydrocarbon radical of carbon atoms and acetyl; the subscripts, a, b, and c are zero or positive and have the following relationship:
2 ≦ a + b + c ≦ 20 and a ≧ 2
Meet.

  When the subscript a satisfies the condition of 2 ≦ a ≦ 5, it is desirable to use a cosurfactant as described below in order to obtain the effect of the composition of the present invention.

The trisiloxane compound II has the formula:
M ³ D ² M ⁴
Have
here,
M ³ = (R ¹⁰ ) (R ¹¹ ) (R ¹² ) SiO _1/2
M ⁴ = (R ¹³ ) (R ¹⁴ ) (R ¹⁵ ) SiO _1/2
D ² = (R ¹⁶ ) (Z ′) SiO _2/2
And
In which R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are monovalent hydrocarbon radicals of 1 to 4 carbon atoms, aryl, and 6 to 20 carbons. Each independently selected from the group consisting of alkyl hydrocarbon groups of 4 to 9 carbon atoms containing an aryl substituent of atoms;
R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸
An alkylene oxide group of
Wherein R ¹⁷ is the formula:
_{-C 4 H 8 O- (C 2} H 4 O) -
Have
R ¹⁸ is selected from the group consisting of H, a monovalent hydrocarbon radical of 1 to 6 carbon atoms, and acetyl; the subscripts, d, e, and f are zero or positive and have the relationship :
2 ≦ d + e + f ≦ 20 and d ≧ 2
Meet.
Trisiloxane compound II also has the formula:
M ³ D ² M ⁴
You may have
here,
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
And
In which R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are monovalent hydrocarbon radicals of 1 to 4 carbon atoms, aryl, and 6 to 20 carbons. Each independently selected from the group consisting of alkyl hydrocarbon groups of 4 to 9 carbon atoms containing an aryl substituent of atoms;
R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸
An alkylene oxide group of
Wherein R ¹⁷ is the formula:
_{-C 4 H 8 O- (C 2} H 4 O) -
Have
R ¹⁸ is selected from the group consisting of H, a monovalent hydrocarbon radical of 1 to 6 carbon atoms, and acetyl; the subscripts, d, e, and f are zero or positive and have the relationship :
2 ≦ d + e + f ≦ 20 and d ≧ 2, but when R ¹⁸ is methyl, d satisfies 2 to 5, or 8 to 20.

  When the subscript d satisfies the condition of 2 ≦ d ≦ 5, it is desirable to use a cosurfactant as described below in order to obtain the effect of the composition of the present invention.

Trisiloxane compound III has the formula:
M ⁵ D ³ M ⁶
Have
here,
M ⁵ = (R ¹⁹ ) (R ²⁰ ) (R ²¹ ) SiO _1/2
M ⁶ = (R ²² ) (R ²³ ) (R ²⁴ ) SiO _1/2
D ³ = (R ²⁵ ) (Z ″) SiO _2/2
And
In which R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ are monovalent hydrocarbon radicals of 1 to 4 carbon atoms, aryl, and aryl of 6 to 20 carbon atoms Each independently selected from the group consisting of alkyl hydrocarbon groups of 4 to 9 carbon atoms containing substituents; R ²⁵ is a linear or branched hydrocarbon radical of 2 to 4 carbon atoms Yes; Z ″ is 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
An alkylene oxide group of
Wherein R ²⁶ is a linear or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R ²⁷ is H, 1 to 6 Selected from the group consisting of monovalent hydrocarbon radicals of carbon atoms and acetyl; the subscripts, g, h, and i are zero or positive and have the following relationship:
2 ≦ g + h + i ≦ 20 and g ≧ 2
Meet.

  When the subscript g satisfies the condition of 2 ≦ g ≦ 5, it is desirable to use a cosurfactant as described below in order to obtain the effect of the composition of the present invention.

One method for producing the composition of the present invention is represented by the following formula:
MD ^H M
Wherein the molecule is a hydride precursor of the D ′ structural unit in the composition of the invention, where the definitions and relationships are defined later and are consistent with those previously defined, under the hydrosilylation conditions Olefins, such as allyloxypolyethylene glycols or methallyloxypolyalkylene oxides, incorporated herein by way of example but not mentioned to limit other possible olefin-modified polyalkylene oxide compositions. Reacting with a modified polyalkylene oxide. As used herein, the phrase “olefin-modified polyalkylene oxide” retains one or more alkylene oxide groups containing one or more terminal or pendant carbon-carbon double bonds. Is defined as a molecule Polyethers (precursors of substituents Z, Z ′ or Z ″) are olefin-modified polyalkylene oxides (hereinafter referred to as polyethers), which have the general formula:
_{^{CH 2 = CH (R 28)}} (R 29) j O (R 30) k (C 2 H 4 O) m (C 3 H 6 O) n (C 4 H 8 O) p R 31
Written in
Where
R ²⁸ is H or methyl; R ²⁹ is a divalent alkyl radical of 1 to 6 carbon atoms, where the subscript j may be 0 or 1, and R ³⁰ is —C ₂ H ₄ O-, the subscript k may be 0 or 1, R ³¹ is H, a monovalent hydrocarbon group of 1 to 6 carbon atoms, or acetyl, and the subscripts m, n And p are zero or positive and satisfy the relationship 2 ≦ m + n + p ≦ 20 and m ≧ 2. When the polyether consists of mixed oxyalkylene oxide groups (ie oxyethylene, oxypropylene, and oxybutylene), the units will be blocked or randomly distributed. Those skilled in the art will appreciate the advantages of a blocked or random structure. Illustrative examples of blocked structures are:-(oxyethylene) _a (oxypropylene) _b -;-(oxybutylene) _c (oxyethylene) _a- ; and-(oxypropylene) _b (oxyethylene) _a (Oxybutylene) _c- .

Illustrative examples of polyethers are given below, but are not limited to: CH ₂ ═CHCH ₂ O (CH ₂ CH ₂ O) ₈ H; CH ₂ ═CHCH ₂ O (CH ₂ CH ₂ O) _{8 CH 3; CH 2 = CHCH 2} O (CH 2 CH 2 O) 4 (CH 2 CH (CH 3) O) 5 H; CH 2 = CHO (CH 2 CH 2 O) 5 (CH 2 CH (CH 3) _{O) 5 H; CH 2 =} C (CH 3) CH 2 O (CH 2 CH 2 O) 4 (CH 2 CH (CH 3) O) 5 C (= O) CH 3; CH 2 = CHCH 2 O ( _{CH 2 CH 2 O) 5 (} CH 2 CH (CH 3) O) 2 (CH 2 CH (CH 2 CH 3) O) 2 H.

  Polyether-modified siloxanes can be obtained by conventional methods through the use of hydrosilylation reactions that bind olefin-modified (ie, vinyl, allyl, methallyl) polyalkylene oxides on the trisiloxane hydride (SiH) intermediates of the present invention. Created by.

Preferred embodiments of the trisiloxane compounds of formula I are those wherein R ¹ and R ⁴ are branched or straight chain hydrocarbon groups of 2 to 4 carbon atoms, aryl, aryl substitution of 6 to 20 carbon atoms It is selected from alkyl hydrocarbon groups of 4 to 9 carbon atoms containing the group, more preferably 3 to 4 carbon atoms or aryl. R ² , R ³ , R ⁵ , R ⁶ , and R ⁷ are carbon atoms of 4 to 9 carbon atoms containing monovalent hydrocarbon radicals of 1 to 4 carbon atoms, aryl, and aryl groups. Each is independently selected from the group consisting of a hydrogen group, more preferably a monovalent hydrocarbon radical of 1 to 2 carbon atoms, most preferably methyl.
Z is a general formula:
R ⁸ (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₄ H ₈ O) _c R ⁹
Wherein R ⁸ is 2, 3, 5, 6, 7, ⁸ , or 9 carbon atoms, more preferably 3 to 7 carbon atoms, most preferably 3 A straight or branched divalent hydrocarbon radical of from 6 to 6 carbon atoms. Subscripts a, b, and c are zero or positive and have the following relationship:
2 ≦ a + b + c ≦ 20 and a ≧ 2
Preferably a is 5 to 20, more preferably 5 to 8; preferably b is 0 to 10, more preferably 0 to 5; preferably c is 0 to 8, more preferably 0 to 4. R ⁹ is selected from the group consisting of H, a monovalent hydrocarbon radical of 1 to 6 carbon atoms, and acetyl.

Another preferred embodiment of the trisiloxane compound of formula I is a branched or straight chain wherein R ¹ , R ⁴ and R ⁷ are composed of 2 to 4 carbon atoms, more preferably 3 to 4 carbon atoms. Selected from hydrocarbon groups and aryl. R ² , R ³ , R ⁵ , and R ⁶ are from 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, a monovalent hydrocarbon radical, and aryl, most preferably methyl. Each group is independently selected. Z is as described above.

Preferred embodiments of the trisiloxane compound of formula II are R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are monovalent hydrocarbon radicals of 1 to 4 carbon atoms, And aryl are each independently selected from the group consisting of;
R ¹⁷ (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e (C ₄ H ₈ O) _f R ¹⁸
An alkylene oxide group of
Wherein R ¹⁷ is a general formula:
_{-C 4 H 8 O- (C 2} H 4 O) -
Selected from branched or straight chain divalent hydrocarbon radicals,
R ¹⁸ is selected from the group consisting of H, monovalent hydrocarbon radicals of 1 to 6 carbon atoms, and acetyl, more preferably H, and monovalent hydrocarbon radicals of 1 to 4 carbon atoms. Subscripts, d, e, and f are zero or positive and have the following relationship:
2 ≦ d + e + f ≦ 20 and d ≧ 2
Preferably d is 5 to 20, more preferably 5 to 8; preferably e is 0 to 10, more preferably 0 to 5; preferably f is 0 to 8, more preferably 0 to 4.

Preferred embodiments of the trisiloxane compound of formula III are those wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ are from a monovalent hydrocarbon radical of 1 to 4 carbon atoms, and aryl Each independently selected from the group consisting of: R ²⁵ is a straight or branched hydrocarbon radical of 2 to 4 carbon atoms, most preferably 3 to 4 carbon atoms; General formula:
R ²⁶ (C ₂ H ₄ O) _g (C ₃ H ₆ O) _h (C ₄ H ₈ O) _i R ²⁷
An alkylene oxide group of
In which R ²⁶ is 2, 3, 5, 6, 7, 8, or 9 carbon atoms, more preferably 3 to 7 carbon atoms, most preferably 3 to 6 carbon atoms. A linear or branched divalent hydrocarbon radical. R ²⁷ is selected from the group consisting of H, a monovalent hydrocarbon radical of 1 to 6 carbon atoms, and acetyl; the subscripts, g, h, and i are zero or positive and have the following relationship:
2 ≦ g + h + i ≦ 20 and g ≧ 2
Preferably g is 5 to 20, more preferably 5 to 8; preferably h is 0 to 10, more preferably 0 to 5; preferably i is 0 to 8, more preferably 0 to 4.

Suitable noble metal catalysts for making polyether substituted siloxanes are also well known in the art and contain rhodium, ruthenium, palladium, osmium, iridium, and / or platinum complexes. 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 may be selected from compounds having the formula (PtCl ₂ .olefin) and H (PtCl ₃ .olefin), as described in US Pat. No. 3,159,601, incorporated herein by reference. The further platinum-containing material is selected from the group consisting of chloroplatinic acid and alcohols, ethers, aldehydes, and mixtures thereof, as described in US Pat. No. 3,220,972, incorporated herein by reference. It may be a complex with up to 2 moles per gram platinum of the element. Yet another group of platinum-containing materials useful in the present invention is described in Karstedt US Pat. Nos. 3,715,334, 3,775,452, and 3,814,730. Additional background on this area can be found in F.C. G. A. Stone and R.C. “Advances in Organochemical Chemistry”, Volume 17, pages 407 to 447, published by Academic Press (New York, 1979). L. It can be found in "Homogeneous Catalysis of Hydrolysis by Transition Metals" by Spier. One skilled in the art can readily determine the effective amount of platinum catalyst. Generally effective amounts range from about 0.1 to 50 parts per million parts of the total amount of organically modified trisiloxane composition.

  The compositions of the present invention exhibit enhanced resistance to hydrolysis outside the pH range of 6 to 7.5. Although enhanced resistance to hydrolysis is evidenced by various tests, enhanced resistance to hydrolysis as used herein is 24 hours to aqueous acidic conditions where the solution has a pH of less than 6. After exposure, or after 24 hours exposure to aqueous basic conditions where the solution has a pH greater than 7.5, 50 mole percent or more of the hydrolysis resistant composition of the present invention remains unchanged or unreacted Means that Under acidic conditions, the composition of the present invention exhibits a residual rate of 50 mole percent or more of the initial concentration for a period of more than 48 hours at pH 5 or lower; specifically, the composition of the present invention comprises: show a residual rate of 50 mole percent or more at a pH of 5 or less for more than 2 weeks; more specifically, the composition of the present invention is 50 mole percent for a period of more than 1 month at pH 5 or less Or, more specifically, a residual rate; and most particularly, the compositions of the present invention exhibit a residual rate of 50 mole percent or higher for a period of more than 6 months at pH 5 or lower. Under basic conditions, the composition of the present invention exhibits a residual rate of 50 mole percent or more at a pH of 8 or higher for a period of more than 2 weeks; specifically, the composition of the present invention has a pH of 8 or higher More than 4 weeks, showing a 50 mole percent or more survival rate; more specifically, the composition of the present invention has a pH of 8 or more and more than 6 months, 50 mole percent or more And, most particularly, the compositions of the present invention exhibit a residual rate of 50 mole percent or higher for a period of more than 1 year at pH 8 or higher.

Applications of the composition of the present invention Pesticides-agriculture, horticulture, lawn, ornamental plants, and forestry Many pesticide applications require the addition of an adjunct to the spray mixture to provide wetting and spreading on the leaf surface. This adjuvant is often a surfactant, which increases the retention of spray droplets on leaf surfaces that are difficult to wet, improves spreading and improves the sprayed area. Or it can provide various functions such as the ability to impart herbicide penetration into the plant coat. This adjuvant is provided as a tank-side additive or used as a component of an agrochemical formulation.

  Typical uses for pesticides include agriculture, horticulture, lawn, ornamental plants, home and garden, veterinary, and forestry applications.

  The agrochemical composition of the present invention also includes at least one agrochemical, wherein the organically modified trisiloxane surfactant of the present invention is diluted as a concentrate or in a tank mixture to a final use concentration of 0. It is present in an amount sufficient to reach between 005% and 2%. The pesticide composition may optionally include excipients, co-surfactants, solvents, foam control agents, deposition aids, drift scatter inhibitors, biologics, micronutrients, fertilizers, and the like. The term pesticide means any compound used to control pests, such as rodenticides, insecticides, acaricides, fungicides, and herbicides. Illustrative examples of pesticides that can be employed include, but are not limited to, growth regulators, photosynthesis inhibitors, dye inhibitors, mitotic disruptors, lipid biosynthesis inhibitors, cell wall inhibitors, and cell membrane disruptors. Not. The amount of pesticide employed in the composition of the present invention varies depending on the type of pesticide employed. More specific examples of pesticidal ingredients that may be used with the compositions of the present invention include phenoxyacetic acid, phenoxypropionic acid, phenoxybutyric acid, benzoic acid, triazine and s-triazine, substituted urea, urea, bentazone, desmedifam, metazole, Fenmedifam, pyridate, amitrole, chromazone, fluridone, norflurazon, dinitroaniline, isopropaline, oryzalin, pendimethalin, prodiamine, trifluralin, glyphosate, sulfonylurea, imidazolinone, cretodim, diclohop-methyl, phenoxaprop-ethyl, fluazihop With herbicides and growth regulators, such as compounds of p-butyl, haloxyhop-methyl, quizalofop, cetoxydim, diclobenil, isoxaben, and bipyridylium That, but is not limited to these.

  Antifungal compositions that can be used with the present invention include: aridimorph, tridemorph, dodemorph, dimethomorph; flusilazole, azaconazole, cyproconazole, epoxiconazole, fluconazole, propiconazole, tebuconazole, etc .; imazalyl, thiophanate, benomyl, carbendazim , Chlorothiononyl, dichlorane, trifloxystrobin, furoxystrobin, dimoxystrobin, azoxystrobin, flucaranyl, prochloraz, flusulfamide, famoxadone, captan, manneb, mancozeb, dodicine, dodine, and metalaxyl It is not limited to.

  Insecticides, larvicides, acaricides, and ovicidal compounds that may be used with the compositions of the present invention include Bacillus thuringiensis, spinosad, abamectin, doramectin, repimectin, pyrethrin, carbaryl, primicarb, aldicarb, methomyl , Amitraz, boric acid, chlordimeform, nobarulone, bistrifluron, triflumuron, diflubenzuron, imidacloprid, diazinon, acephate, endosulfan, kerebane, dimethoate, azinephosethyl, azinephosmethyl, izoxathione, chlorpyrifos, chlorfenteline, fenmethaline , But not limited to, cypermethrin.

  The pesticide may be liquid or solid. If solid, it is preferable to dissolve in a solvent or an organo-modified trisiloxane of the present invention before use, and the silicon acts as a solvent or surfactant for such dissolution, or otherwise Of surfactants may serve this role.

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

  A solvent may also be included in the composition of the present invention. These solvents are in a liquid state at room temperature. Examples include water, alcohols, aromatic solvents, oils (ie, mineral oils, vegetable oils, silicone oils, etc.), lower alkyl esters of vegetable oils, fatty acids, ketones, glycols, polyethylene glycols, diols, paraffins, and the like. Certain solvents are 2,2,4-trimethyl-1,3-pentanediol and their alkoxylated derivatives (as exemplified in US Pat. No. 5,674,832, incorporated herein by reference). In particular ethoxylated derivatives) or N-methylpyrrolidone.

Co-surfactants In addition, other co-surfactants are described in US Pat. No. 5,558,806, US Pat. No. 5,104,647, and US Pat. No. 6,221,811, incorporated herein by reference. And having a short-chain hydrophobic substance that does not interfere with super spread.

  Co-surfactants useful herein include nonionic, cationic, anionic, amphoteric, zwitterionic, polymeric surfactants, or any mixture thereof . Surfactants are typically hydrocarbon-based, silicone-based, or fluorocarbon-based.

  Useful surfactants include alkoxylates, particularly ethoxylates having block copolymers including copolymers of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof; alkylaryl alkoxylates, particularly ethoxylates or propoxylates And arylphenol alkoxylates, especially ethoxylates or propoxylates, and derivatives thereof; amine alkoxylates, especially amine ethoxylates; fatty acid alkoxylates; fatty alcohol alkoxylates; alkyl sulfonates Alkylbenzene sulfonates and alkyl naphthalene sulfonates; sulfated fatty alcohols, sulfated fatty acid amines, or sulfated fats Amide; and the like; esters of sodium isethionate, esters of sodium sulfosuccinate; fatty acid esters or sulfonated fatty acid ester sulfuric, petroleum sulfonates; N- acyl sarcosinates, alkyl polyglycosides, alkyl ethoxylated amines.

  Specific examples include alkyl acetylenic diols (SURFONYL, Air Products), pyrrolidone surfactants (eg, SURFADONE-LP100, ISP), 2-ethylhexyl sulfate, isodecyl alcohol ethoxylate (eg, RHODASURF DA530, Rhodia). , Ethylenediamine alkoxylate (TETRONICS, BASF), and ethylene oxide / propylene oxide copolymer (PLURONICS, BASF), and gemini surfactants (Rhodia).

  Preferred surfactants include ethylene oxide / propylene oxide copolymers (EO / PO); amine ethoxylates; alkyl polyglycosides; oxo-tridecyl alcohol ethoxylates;

  In a preferred embodiment, the pesticidal composition of the present invention further comprises one or more pesticidal ingredients. Suitable pesticide ingredients are herbicides, insecticides, growth regulators, fungicides, acaricides, acaricides, fertilizers, biologics, phytonutrients, micronutrients, biocides, paraffinic mineral oils, methylated Seed oil (ie, soybean oil fatty acid methyl, methylated canola oil), vegetable oil (such as soybean oil and canola oil), Choice® (Loveland Industries, Greley, CO) and QUEST (Helena Chemical, Colliveville, TN) ), A modified clay such as Surround (registered trademark; Englehard Corp.), a foam control agent, a surfactant, a wetting agent, a dispersing agent, an emulsifier, a deposition aid, a drifting scattering inhibiting component, and Including but not limited to water.

  Suitable agrochemical compositions are prepared by mixing one or more of the above-described components with the organo-modified trisiloxane of the present invention as a tank-mix or as an “In-can” formulation. Made by integration in a manner known in the art. The term “tank mixing” means that at the time of use, at least one pesticide is added to a spray medium such as water or oil. The term “canned” refers to a formulation or concentrate having at least one agrochemical component. The “canned” formulation may then be diluted to the concentration of use, typically in tank mixing, at the point of use, or may be used undiluted.

B. Coating Typically, a coating formulation will require a wetting agent or surfactant for the purposes of emulsification, component compatibilization, smoothness, flow, and reduction of surface defects. Moreover, these additives will provide improvements in cured or dry films such as improved abrasion resistance, antiblocking properties, hydrophilicity, and hydrophobicity. The coating formulation may exist as a solvent based coating, an aqueous coating, and a powder coating.

  The coating components may be used as special purpose coatings such as coatings for OEM products such as architectural coatings, automotive coatings, and coil coatings, factory maintenance coatings, and marine coatings.

Typical synthetic resin types include polyester, alkyd, acrylic, and epoxy.

C. Personal Care In a more preferred embodiment, the organically modified trisiloxane surfactant of the present invention is from 0.1 to 99 pbw of the organically modified trisiloxane surfactant per 100 parts by weight (“pbw”) personal care composition. More preferably from 0.5 pbw to 30 pbw, and even more preferably from 1 to 15 pbw, and from 1 pbw to 99.9 pbw of personal care compositions, more preferably from 70 pbw to 99.5 pbw, and even more preferably It consists of 85 pbw to 99 pbw.

The organically modified trisiloxane composition of the present invention may be utilized in personal care emulsions such as lotions and creams. As is generally known, an emulsion contains at least two immiscible phases, one of which is continuous and the other is discontinuous. Furthermore, the emulsion may be a liquid or a solid having various viscosities. In addition, the particle size of the emulsions may make them microemulsions, and when the particle size is sufficiently small, the microemulsions may be transparent. Furthermore, it is possible to prepare emulsions of emulsions and these are generally known as multiple emulsions. This emulsion is:
1) an aqueous emulsion in which the discontinuous phase contains water and the continuous phase contains the organo-modified trisiloxane of the present invention;
2) An aqueous emulsion in which the discontinuous phase contains the organo-modified trisiloxane of the present invention and the continuous phase contains water;
3) a non-aqueous emulsion in which the discontinuous phase contains a non-aqueous hydroxy solvent and the continuous phase contains an organo-modified trisiloxane of the present invention;
4) a non-aqueous emulsion in which the continuous phase contains a non-aqueous hydroxy organic solvent and the discontinuous phase contains an organo-modified trisiloxane of the present invention,
Would be.

  Non-aqueous emulsions containing a silicone phase are described in US Pat. Nos. 6,060,546 and 6,271,295, the disclosures of which are hereby incorporated in detail by reference.

  As used herein, the term “non-aquatic hydroxy organic compound” refers to alcohols, glycols, polyhydric alcohols that are liquid at room temperature, eg, at about 25 ° C. and at about 1 atmosphere. And hydroxy-containing organic compounds exemplified by polymeric glycols and mixtures thereof. The non-aqueous organic hydroxy solvent is a group consisting of hydroxy-containing organic compounds containing alcohols, glycols, polyhydric alcohols, and polymeric glycols, and mixtures thereof that are liquid at room temperature, eg, about 25 ° C. and about 1 atmosphere. More selected. Preferably, the non-aqueous hydroxy organic solvent is ethylene glycol, ethanol, propyl alcohol, isopropyl alcohol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, isobutylene glycol, methylpropanediol, glycerin, sorbitol, polyethylene glycol, polypropylene It is selected from the group consisting of glycol monoalkyl ethers, polyoxyalkylene copolymers, and mixtures thereof.

  Desirable forms are either a silicone-only phase, an anhydrous mixture containing a silicone phase, a water-containing mixture containing a silicone phase, a water-in-oil emulsion, an oil-in-water emulsion, or two non-aqueous emulsions or variations thereof. Once achieved, the resulting material is usually a cream or lotion with improved adhesion and good tactile properties. It can be formulated into formulations for hair care, skin care, antiperspirants, sunscreens, cosmetics, color cosmetics, insect repellents, vitamin carriers, hormone carriers, fragrance carriers and the like.

  Personal care applications in which the organically modified trisiloxane surfactants of the present invention and the silicone compositions derived therefrom of the present invention can be used include deodorants, antiperspirants, antiperspirants / deodorants, shaving products, skins Hair care products such as lotions, moisturizers, cosmetic liquids, bath products, cleansing products such as shampoos, conditioners, mousses, hair gels, hair sprays, hair dyes, hair color products, hair bleaching agents, wave products, hair straighteners, Nail polish products such as nail polish, nail polish remover, nail cream, nail lotion, linse softener, protective creams such as sunscreens, insect repellents, and anti-aging products such as lipsticks, foundations, funniers, Eyeliner, eyeshadow, blusher, makeup, mascara, etc. Over cosmetics and other personal care formulations silicone components are generically additives, as well, as well as drug delivery systems for the topical pharmaceutical composition is applied to the skin coating, without limitation.

  In a more 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, humectants, wetting agents, pigments including pearlescent pigments such as bismuth oxychloride and titanium dioxide-coated mica, colorants, fragrances, biocides, preservatives, Antioxidants, antibacterial agents, antifungal agents, antiperspirants, cosmetics for scraping skin waste cells, hormones, enzymes, pharmaceutical compounds, vitamins, salts, electrolytes, alcohols, polyols, UV absorbers, plant extracts, surface activity Agents, silicone oils, organic oils, waxes, film forming elements such as fumed silica or hydrous silicic acid thickeners such as talc, kaolin, starch, modified starch, mica, nylon and other fine particle fillers such as bentonite And clays such as organically modified clays.

  Suitable personal care compositions are made by integrating, for example, one or more of the above-described components in a manner known in the art such as by mixing with an organically modified trisiloxane surfactant. Suitable personal care compositions are in the form of a single phase, or the silicone phase is a discontinuous or continuous phase, oil-in-water emulsions, water-in-oil emulsions, and anhydrous emulsions, and, for example, in water It may be in the form of emulsions including multiple emulsions such as oil-in-oil emulsions and oil-in-water emulsions.

  In one useful embodiment, the antiperspirant composition contains an organically modified trisiloxane surfactant of the present invention and one or more active antiperspirants. Suitable antiperspirants are, for example, aluminum halides, hydroxyaluminum halides, such as aluminum chlorohydrate, and, for example, aluminum-zirconium chlorohydrate, and aluminum zirconium tetrachloro, for example. Commercially available, for example, by the US Food and Drug Administration dated 10/10/1993, such as complexes or mixtures thereof with zirconyl oxyhalogenates and zirconyl hydroxyhalides, such as aluminum zirconium glycine complexes such as hydrex glycine. Contains Category I active antiperspirant ingredients listed in General Drug Standards for Human Antiperspirant Products.

  In other useful embodiments, the skin care composition contains an organic job-trisiloxane surfactant and a vehicle such as silicone oil or organic oil. Skin care compositions optionally include emollients such as, for example, triglyceride esters, wax esters, fatty acid alkyl esters, fatty acid alkenyl esters, or polyhydric alcohol esters, and pigments such as vitamin A, vitamin C, and vitamins. Sunscreens such as vitamins such as E, such as titanium dioxide, zinc oxide, oxybenzone, octylmethoxycinnamate, butylmethoxydibenzoylmuethane, paraaminobenzoic acid, and octyldimethylparaaminobenzoic acid. One or more known ingredients commonly used in skin care compositions, such as

  In other useful embodiments, color cosmetic compositions such as lipstick, makeup, or mascara compositions contain organically modified trisiloxane surfactants and colorants such as pigments, water-soluble or fat-soluble dyes. contains.

  In other useful embodiments, the compositions of the present invention are utilized in conjunction with fragrant materials. These fragrance materials may be fragrance compounds, encapsulated fragrance compounds, or undiluted or encapsulated fragrance release compounds. In particular, the compositions of the present invention are compatible with US Pat. Nos. 6,046,156; 6,054,547; 6,075,111; 6,077,923; 6,083,901; and 6,153,578; aromatic-diffusing silicon-containing compounds, all of which are hereby incorporated by reference.

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

D. Home care Home care applications include laundry detergents and fabric softeners, dish detergents, wood and furniture brighteners, floor polishes, bath and tile cleaners, toilet cleaners, hard surface cleaners, window cleaners Agents, anti-fogging agents, water pipe cleaners, automatic dishwasher detergents and sheeting agents, carpet cleaners, prewash stain removers, rust cleaners, and scale removers.

  Hydride intermediates and comparative compositions for the organic modified trisiloxane surfactant compositions of the present invention were made as described in the following examples.

Production Example 1
1,5-di (t-butyl) -1,1,3,5,5 pentamethyltrisiloxane (FIG. 1, structure 1)

100 g tBuMe ₂ SiCl and 46 g MeHSiCl ₂ were dissolved in 150 ml isopropyl ether (IPE) and poured into the addition funnel. 150 g of water and 250 ml of IPE were charged into a 1 L round bottom flask equipped with a mechanical stirrer, reflux condenser, and N ₂ inlet. Chlorosilane was added dropwise via an addition funnel over 1 hour at room temperature (23 ° C.). After the addition was complete, the temperature was adjusted to 70 ° C. and the reaction was carried out at reflux temperature for 20 hours and the outcome was followed by GC (yield 88% over 20 hours). After the reaction was complete, water was drained through the separatory funnel. The liquid was washed 3 times with 100 g of water each. 25 g NaHCO ₃ was mixed with 100 g water, added slowly to the mixture and stirred for 30 minutes. The water was drained again and dried over sodium sulfate. After filtration, IPE was blown off by a rotary evaporator, and the crude product was fractionated under reduced pressure to obtain 63 g of tBuMe ₂ SiOMe (H) SiOSiMe ₂ tBu (purity by GC is 97%).

Production Example 1
1,5-di (isopropyl) -1,1,3,5,5, pentamethyltrisiloxane (FIG. 2, structure 2)

25 g iPrMe ₂ SiCl (0.183 mol) and 13.1 g MeHSiCl ₂ (0.114 mol) were dissolved in 80 ml isopropyl ether (IPE) and injected into the addition funnel. 50 g of water and 100 ml of IPE were charged into a 500 mL round bottom flask equipped with a mechanical stirrer, reflux condenser, and N ₂ inlet. Chlorosilane was added dropwise via an addition funnel over 40 minutes at room temperature (23 ° C.). After the addition was complete, the temperature was adjusted to 80 ° C. and the reaction was carried out at reflux temperature for 4 hours and the outcome was followed by GC (yield 75% over 4 hours). After the reaction was complete, water was drained through the separatory funnel. The liquid was washed 3 times with 80 g of water each. 25 g NaHCO ₃ was mixed with 100 g water, added slowly to the mixture and stirred for 30 minutes. The water was drained again and dried over sodium sulfate. After filtration, IPE was blown off using a rotary evaporator, and the crude product was fractionated under reduced pressure to obtain 10 g of iPrMe ₂ SiOMe (H) SiOSiMe ₂ iPr (93% purity by GC).

Production Example 3
The hydride intermediates of Examples 1-2 were further modified with various allyl polyalkylene oxides to obtain organically modified trisiloxane surfactant compositions (Table 1) of the present invention. The comparative trisiloxane surfactant (from Table 2) was also made the same.

  The organo-modified trisiloxane surfactant composition of the present invention is made by the usual method of platinum-mediated hydrosilylation, as described in Bailey, US Pat. No. 3,299,112, incorporated herein by reference. It was done.

Table 1 provides details of the compositions of the present invention. Some of those compositions have the structure:
M ^* D'M ^*
Described by
here,
M ^* = R ¹ Si (CH ₃ ) ₂ O _0.5 ;
D ′ = OSi (CH ₃ ) CH ₂ CH (R ³² ) CH ₂ O— (CH ₂ CH ₂ O) _r — (CH ₂ CH ₂ O) sR ³³ , wherein R ¹ , R ³² , R ³³ , Subscripts r, and s are listed in Table 1.

Table 2 shows the general structure:
MD _X D '' _Y M
Provides details of the comparative trisiloxane and organosilicone polyether surfactants of
here,
M = (CH ₃ ) ₃ SiO _0.5 ; D = OSi (CH ₃ ) ₂ ; and D ″ = OSi (CH ₃ ) CH ₂ CH ₂ CH ₂ O— (CH ₂ CH ₂ O) _d R ⁹ is there.

  In addition, Comparative Example OPE (octylphenol ethoxylate containing 10 polyoxyethylene units) is a non-silicone organic surfactant. This product is available as Triton® X-100 from Dow Chemical Company, Midland, MI.

Example 4
This example demonstrates the performance of the organically modified trisiloxane composition of the present invention that reduces the surface tension of water and thereby exhibits utility as a surfactant. The surface tension was measured using a Kruss surface tension meter equipped with a sandblasted platinum blade as a sensor. Solutions of various components were made at 0.1 wt% in 0.005M NaCl water (deionized) as an equilibrium aid.

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

  The composition of the present invention also provides the same spreading ability as the comparative trisiloxane surfactants (A, B). Furthermore, the organically modified trisiloxane surfactants of the present invention provide improved spreading compared to conventional silane polyether (C) and conventional organic surfactant product OPE.

  Spreading is performed by applying 10 μl droplets of surfactant solution to a polycarbonate film (USI, “Crystal Clear Write on Film”) and between 50% and 70% (at 22 ° C. to 25 ° C.). It was measured by measuring the spread diameter (mm) after 30 seconds at the relative humidity. The solution was applied by an automatic pipette to provide a reproducible volume of droplets. Deionized water, further purified by a Millipore filtration system, was used to make the surfactant solution.

Example 5
Hydrolytic stability was measured in a representative composition of the present invention using HPLC. Solutions of various components were made at 0.5 wt% over a pH range of pH 4 to pH 11, and degradation was observed as a function of time by HPLC.

Analytical Methods Samples were analyzed by reverse phase chromatography using the experimental conditions listed in Table 4.

  Tables 5-8 demonstrate that the compositions of the present invention provide improved resistance to hydrolysis compared to the standard comparative siloxane surfactant siloxane A at similar pH conditions. .

  While the comparative siloxane A exhibits rapid hydrolysis at pH values lower than 5 and at pH values higher than 7, the organo-modified trisiloxane surfactant of the present invention is resistant to hydrolysis under the same conditions. Demonstrate higher tolerance.

Example 6
Unlike conventional siloxane surfactants that are prone to rapid hydrolysis under acidic and basic conditions (pH values of 5 or lower and pH values of 9 or higher), the organic modified trisiloxane surfactant of the present invention is Provides improved resistance to hydrolysis compared to conventional trisiloxane alkoxylates (Comparative Example A). The side effect of hydrolysis is observed as a decrease in spreading ability over time. Therefore, the organic modified trisiloxane surfactant solution of the present invention, as well as the comparative surfactant, were made at the desired use concentration and pH. Spread was measured to reveal resistance to hydrolysis as a function of time.

  Table 9 is an illustrative example of an organically modified trisiloxane surfactant, where product number 3 is particularly well spread and compared to a conventional trisiloxane ethoxylate surfactant (product A), Has improved resistance to hydrolysis over pH values ranging from pH 3 to pH 10.

  The influence of other components on spreading was measured by mixing the organically modified disiloxane surface activity of the present invention with a conventional organic co-surfactant. Co-surfactants are listed in Table 10.

  The mixture is made as a physical mixture, where the weight fraction of silicone is expressed as α (alpha), indicating that the co-surfactant forms a balance of the mixing ratio. For example, when α = 0, this is a composition containing 0% silicone component and 100% co-surfactant, while α = 1.0 is co-surfactant with 100% silicone composition. It indicates that no agent is contained (0%). The mixture of the two components is represented by the weight fraction α, where α is in the following range: 0 ≦ α ≦ 1.0 For example, when α = 0.25, this is 25 for the surfactant mixture. % Of silicone and 75% co-surfactant. These mixtures are then diluted in water to the desired concentration for spreading evaluation.

  Spread was measured with 0.2 wt% total surfactant as described in Example 4.

  Table 11 provides an unexpected synergistic improvement where representative examples of the co-surfactants of the present invention provide favorable spreading results, and in some cases, the spreading diameter of the mixture is superior to that of the individual components. Prove that it provides.

The above-described embodiments are merely illustrative of the present invention and merely illustrate some of the features of the present invention. The appended claims are intended to claim the invention as broadly as the invention was conceived, and the examples presented here were chosen from a variety of all possible embodiments It is an illustration of an embodiment. Accordingly, it is Applicants' intention that the appended claims should not be limited by the choice of examples used to illustrate features of the present invention. As used in the claims, the term “comprises” and its grammatical variations include, for example, “consisting essentially of,” or “consisting of”. of) ”, including but not limited to logically encompassing and including ranges of phrases that vary or differ. Where necessary, ranges are listed, but this range includes all sub-ranges therein. Such a range may be thought of as a Markush group consisting of a limited number of pairs of numbers, this group being numerically and, where appropriate, an integer, increasing regularly from the lower limit to the upper limit, Fully defined by lower and upper limits. Changes in this range should, of course, be expected to suggest those skilled in the art per se, and unless otherwise known, this change will be covered where possible by the appended claims. Should be interpreted as. Advances in science and technology are also expected to allow equivalents and alternatives that are currently unpredictable due to language inaccuracies, but this change is also possible where covered by the appended claims. Should be interpreted. All U.S. patents (and patent applications) cited herein are hereby incorporated herein by reference in their entirety as if fully set forth.

Claims (37)

A silicone composition having the formula:
M ⁵ D ³ M ⁶
Containing silicone having
here,
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.
And
Wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ are a monovalent hydrocarbon radical of 1 to 4 carbon atoms, aryl, and aryl of 6 to 20 carbon atoms Each independently selected from the group consisting of alkyl hydrocarbon groups of 4 to 9 carbon atoms containing substituents; R ²⁵ is a linear or branched hydrocarbon radical of 2 to 4 carbon atoms Yes; Z ″ is 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
An alkylene oxide group of
In which R ²⁶ is a straight or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R ²⁷ is H, 1 to 6 Selected from the group consisting of monovalent hydrocarbon radicals of carbon atoms and acetyl; the subscripts, g, h, and i are zero or positive, and the following relationship:
2 ≦ g + h + i ≦ 20 and g ≧ 2
Satisfying the silicone composition. R ²⁷ is selected from the group consisting of hydrogen and methyl, A composition according to claim 1.   The composition of claim 1, wherein the subscript i is 0.   The composition of claim 1, wherein the subscript h is in the range of 0 to 3.   The composition according to claim 1, wherein the subscript g is in the range of 8 to 11. The composition of claim 1, wherein R ²⁵ is selected from the group consisting of monovalent hydrocarbon radicals of 3 and 4 carbon atoms. The composition of claim 1, wherein R ²⁶ is a monovalent hydrocarbon radical of 3 carbon atoms. The composition of claim 1, wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ are methyl. R ²⁵ is a four monovalent hydrocarbon radical of carbon atoms The composition of claim 8. R ²⁵ is a four monovalent hydrocarbon radical of carbon atoms The composition according to claim 9. ^{R 19, R 20, R 21} , R 22, R 23, and ^{R 24} is methyl A composition according to claim 10.   The composition according to claim 11, wherein the subscript g is 8.   The composition according to claim 12, wherein the subscript h is 0.   14. The composition of claim 13, wherein the subscript i is 0. A silicone composition having the formula:
M ⁵ D ³ M ⁶
Containing silicone having
here,
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.
And
Wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ are a monovalent hydrocarbon radical of 1 to 4 carbon atoms, aryl, and aryl of 6 to 20 carbon atoms Each independently selected from the group consisting of alkyl hydrocarbon groups of 4 to 9 carbon atoms containing substituents; R ²⁵ is a linear or branched hydrocarbon radical of 2 to 4 carbon atoms Yes; Z '' is 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
An alkylene oxide group of
In which R ²⁶ is a straight or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R ²⁷ is H, 1 to 6 Selected from the group consisting of monovalent hydrocarbon radicals of carbon atoms and acetyl; the subscripts, g, h, and i are zero or positive, and the following relationship:
2 ≦ g + h + i ≦ 20 and g ≧ 2
Wherein the silicone composition has improved resistance to hydrolysis. R ²⁷ is selected from the group consisting of hydrogen and methyl, A composition according to claim 15.   The composition according to claim 15, wherein the subscript i is 0.   16. A composition according to claim 15, wherein the subscript h is in the range of 0 to 3.   16. A composition according to claim 15, wherein the subscript g is in the range of 8-11. R ²⁵ is selected from the group consisting of 3 and 4 monovalent hydrocarbon radicals of carbon atoms The composition of claim 15. R ²⁶ is a three monovalent hydrocarbon radicals of carbon atoms The composition of claim 15. ^{R 19, R 20, R 21} , R 22, R 23, and ^{R 24} is methyl A composition according to claim 15. R ²⁵ is a four monovalent hydrocarbon radical of carbon atoms The composition of claim 22. R ²⁵ is a four monovalent hydrocarbon radical of carbon atoms The composition of claim 23. ^{R 19, R 20, R 21} , R 22, R 23, and ^{R 24} is methyl A composition according to claim 24.   26. The composition of claim 25, wherein the subscript g is 8.   27. The composition of claim 26, wherein the subscript h is 0.   28. The composition of claim 27, wherein the subscript i is 0.   An aqueous emulsion, wherein the discontinuous phase contains water and the continuous phase contains the composition of claim 1.   16. An aqueous emulsion, wherein the discontinuous phase contains water and the continuous phase contains the composition of claim 15.   An aqueous emulsion, wherein the continuous phase contains water and the discontinuous phase contains the composition of claim 1.   16. An aqueous emulsion, wherein the continuous phase contains water and the discontinuous phase contains the composition of claim 15.   A non-aqueous emulsion wherein the discontinuous phase contains a non-aqueous hydroxy solvent and the continuous phase contains the composition of claim 1.   16. A non-aqueous emulsion wherein the discontinuous phase contains a non-aqueous hydroxy solvent and the continuous phase contains the composition of claim 15.   A non-aqueous emulsion wherein the continuous phase contains a non-aqueous hydroxy solvent and the discontinuous phase contains the composition of claim 1.   16. A non-aqueous emulsion wherein the continuous phase contains a non-aqueous hydroxy solvent and the discontinuous phase contains the composition of claim 15. A method of preparing a silicone composition comprising:
formula:
M ⁵ D ³ M ⁶
Using a silicone having
here,
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.
And
Wherein R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , and R ²⁴ are a monovalent hydrocarbon radical of 1 to 4 carbon atoms, aryl, and aryl of 6 to 20 carbon atoms Each independently selected from the group consisting of alkyl hydrocarbon groups of 4 to 9 carbon atoms containing substituents; R ²⁵ is a linear or branched hydrocarbon radical of 2 to 4 carbon atoms Yes; Z ″ is 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
An alkylene oxide group of
In which R ²⁶ is a straight or branched divalent hydrocarbon radical of 2, 3, 5, 6, 7, 8, or 9 carbon atoms; R ²⁷ is H, 1 to 6 Selected from the group consisting of monovalent hydrocarbon radicals of carbon atoms and acetyl; the subscripts, g, h, and i are zero or positive, and the following relationship:
2 ≦ g + h + i ≦ 20 and g ≧ 2
Meet the way.