HK1152840A - Mixtures comprising hydrolysis resistant organomodified disiloxane ionic surfactants - Google Patents

Description

Mixtures comprising hydrolysis-resistant organomodified disiloxane ionic surfactants

Technical Field

The present invention relates to disiloxane surfactant compositions that exhibit resistance to hydrolysis over a wide pH range. More particularly, the present invention relates to such hydrolysis resistant disiloxane surfactants having a resistance to hydrolysis between a pH of about 3 to a pH of about 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 a mixture comprising:

a) a silicone having the formula:

MM’

wherein

M is selected from R¹R²R³SiO_1/2；

M' is selected from R⁴R⁵R⁶SiO_1/2；

Wherein R is¹Selected from branched monovalent hydrocarbon groups having 3 to 6 carbon atoms and R⁷Wherein R is⁷Is selected from

R⁸R⁹R¹⁰SiR¹²And (R)⁴R⁵R⁶)SiR¹²(Si(R²R³)SiO_1/2)

Wherein R is⁸、R⁹And R¹⁰Each independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 6 carbon atoms and monovalent aryl or alkaryl hydrocarbon radicals having 6 to 13 carbon atoms, R¹²Is a divalent hydrocarbon group having 1 to 3 carbon atoms,

R²and R³Each independently selected from a monovalent hydrocarbon group having 1 to 6 carbon atoms or R¹Which isIn R⁴Is R¹³-R^A、R¹⁴-R^CAnd R¹⁵-R^z；

R¹³Is selected from R¹⁶(O)_t(R¹⁷)_u(O)_v-、And R¹⁹O(C₂H₄O)_a(C₃H₆O)_b(C₄H₈O)_c-；

Wherein R is¹⁶And R¹⁷Each independently selected from divalent hydrocarbon radicals having 1 to 4 carbon atoms, each of which may be optionally substituted with one or more OH groups;

R¹⁸is a divalent hydrocarbon group having 2 to 4 carbon atoms;

R¹⁹is a divalent hydrocarbon radical having from 1 to 6 carbon atoms, each of which may optionally be branched;

subscripts t, u, and v are 0 or 1;

subscripts a, b, and c are 0 or a positive number, satisfying the following relationship:

a + b + c is more than or equal to 1 and less than or equal to 10, wherein a is more than or equal to 1;

R^Ais a monovalent radical selected from the group consisting of-SO₃M^K、-C(＝O)CH₂CH(R²⁰)COO^-M^K、-PO₃HM^K、-COOM^K(ii) a Wherein R is²⁰Selected from H or-SO₃M^K；M^KIs a cation selected from Na⁺、K⁺、Ca²⁺、NH₄ ⁺、Li⁺And monovalent ammonium ions derived from monoalkylamines, dialkylamines and trialkylamines having 2 to 4 carbon atoms or monoalkanolamines, dialkanolamines and trialkanolamines having 2 to 4 carbon atoms;

R¹⁴is a monovalent radical selected from R²¹(O)_w(R²²)_x-and R²³O(C₂H₄O)_d(C₃H₆O)_e(C₄H₈O)_fCH₂CH(OH)CH₂-；

Wherein R is²¹And R²²Each independently selected from divalent hydrocarbon radicals having 1 to 4 carbon atoms, which may be optionally substituted with one or more OH groups;

R²³is a divalent hydrocarbon group having 2 to 4 carbon atoms; subscripts w and x are 0 or 1;

subscripts d, e, and f are 0 or a positive number, satisfying the following relationship:

d + e + f is more than or equal to 1 and less than or equal to 10, wherein d is more than or equal to 1;

R^Cis selected from N (R)²⁴)(R²⁵)，

Wherein R is²⁴And R²⁵Each independently selected from H, a branched or straight chain monovalent hydrocarbon radical having from 1 to 4 carbon atoms; r³¹N(R³⁴)(R³⁵) (ii) a and-R³²O(C₂H₄O)_g(C₃H₆O)_h(C₄H₈O)_iR³³；

Subscripts g, h, and i are 0 or a positive number, satisfying the following relationship:

g + h + i is more than or equal to 1 and less than or equal to 10, wherein g is more than or equal to 1;

R²⁶、R²⁸、R²⁹、R³⁰each independently selected from H and a branched or straight chain monovalent hydrocarbon radical having from 1 to 4 carbon atoms;

R²⁷is a monovalent radical selected from the group consisting of H, a branched or straight chain monovalent hydrocarbon radical having from 1 to 4 carbon atoms and-R³⁶O(C₂H₄O)_j(C₃H₆O)_k(C₄H₈O)₁R³⁷；

Subscripts j, k, and 1 are 0 or a positive number, satisfying the following relationship:

j + k +1 is more than or equal to 1 and less than or equal to 10, wherein j is more than or equal to 1;

R³¹is a divalent hydrocarbon radical having 1 to 6 carbon atoms or R³⁸O(C₂H₄O)_m(C₃H₆O)_n(C₄H₈O)_oR³⁹The divalent hydrocarbon group may be optionally substituted with a heterocyclic group containing nitrogen, sulfur, oxygen, or a combination thereof;

subscripts m, n, and o are 0 or a positive number, satisfying the following relationship:

m + n + o is more than or equal to 1 and less than or equal to 10, wherein m is more than or equal to 1;

R³⁴and R³⁵Independently selected from H and a branched or straight chain monovalent hydrocarbon radical having 1 to 4 carbon atoms;

R³²、R³⁶and R³⁸Independently selected from divalent hydrocarbon groups having 2 to 4 carbon atoms;

R³³is a monovalent group selected from the group consisting of H, monovalent hydrocarbon groups having 1 to 6 carbon atoms and N (R)⁴⁰)(R⁴¹)；

R³⁷And R³⁹Independently selected from H, a branched or straight chain monovalent hydrocarbon radical having 1 to 4 carbon atoms and R⁴²N(R⁴³)(R⁴⁴) (ii) a Wherein R is⁴²Is a divalent hydrocarbon group having 1 to 6 carbon atoms; r⁴⁰、R⁴¹、R⁴³And R⁴⁴Independently selected from H and a branched or straight chain monovalent hydrocarbon radical having 1 to 4 carbon atoms;

R¹⁵is a monovalent radical selected from R⁴⁵(O)_y(R⁴⁶)_z-and R⁴⁷O(C₂H₄O)_p(C₃H₆O)_q(C₄H₈O)_rCH₂CH(OH)CH₂-；

Wherein R is⁴⁵And R⁴⁶Each independently selected from divalent hydrocarbon radicals having 1 to 4 carbon atoms, which may be optionally substituted with one or more OH groups;

R⁴⁷is a divalent hydrocarbon group having 2 to 4 carbon atoms; subscripts y and z are 0 or 1;

subscripts p, q, and r are 0 or a positive number, satisfying the following relationship:

p + q + r is more than or equal to 1 and less than or equal to 10, wherein p is more than or equal to 1;

R^Zis-N- (R)⁴⁸)(R⁴⁹)_αR⁵⁰SO₃(M^K)_β、-N-(R⁵¹)(R⁵²)_γR⁵³COO(M^K)_δ、N⁺-(R⁵⁴)(R⁵⁵)R⁵⁶OP (═ O) (A) (B) or (-C (═ O) N (R)⁵⁷)R⁵⁸N-(R⁵⁹)(R⁶⁰))⁺-(R⁶¹OP(＝O)(A)(B))(X^-)_ε；

Wherein R is⁴⁸、R⁴⁹、R⁵¹、R⁵²、R⁵⁴、R⁵⁵、R⁵⁷、R⁵⁹And R⁶⁰Each independently selected from H, a branched or straight chain monovalent hydrocarbon group having 1 to 4 carbon atoms, and an alkanolamine group having 2 to 4 carbon atoms;

R⁵⁰is a divalent group having 3 to 4 carbon atoms;

subscripts α, β, γ, and δ are 0 or 1, satisfying the following relationships: α + β ═ 1 and γ + δ ═ 1;

R⁵³and R⁵⁶Independently a divalent group having 1 to 4 carbon atoms;

R⁵⁸and R⁶¹Each independently a divalent group having 2 to 4 carbon atoms;

b) additional components selected from the group consisting of agricultural components, coating components, personal care components, household care components, oil and gas treatment components, water treatment components, and pulp or paper treatment components,

wherein the mixture has an increased resistance to hydrolysis.

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.

The term emulsion, as used herein, is an inclusive term describing a mixture comprising two or more phases, wherein at least one phase is discontinuous, regardless of how finely divided the phase may be. The term includes, but is not limited to, simple emulsions, emulsions within emulsions, microemulsions, macroemulsions (macro-emulsions), and the like.

The present invention provides a silicone composition comprising a silicone having the formula:

MM’

wherein

M is selected from R¹R²R³SiO_1/2；

M' is selected from R⁴R⁵R⁶SiO_1/2；

Wherein R is¹Selected from branched monovalent hydrocarbon groups having 3 to 6 carbon atoms and R⁷Wherein R is⁷Is selected from

R⁸R⁹R¹⁰SiR¹²And (R)⁴R⁵R⁶)SiR¹²(Si(R²R³)SiO_1/2)

Wherein R is⁸、R⁹And R¹⁰Each independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 6 carbon atoms and monovalent hydrocarbon radicals having 6 to 13 carbon atomsA monovalent aryl or alkaryl radical of R¹²Is a divalent hydrocarbon group having 1 to 3 carbon atoms,

R²and R³Each independently selected from a monovalent hydrocarbon group having 1 to 6 carbon atoms or R¹Wherein R is⁴Is R¹³-R^A、R¹⁴-R^CAnd R¹⁵-R^z；

R¹³Is selected from R¹⁶(O)_t(R¹⁷)_u(O)_v-、And R¹⁹O(C₂H₄O)_a(C₃H₆O)_b(C₄H₈O)_c-；

Wherein R is¹⁶And R¹⁷Each independently selected from divalent hydrocarbon radicals having 1 to 4 carbon atoms, each of which may be optionally substituted with one or more OH groups;

R¹⁸is a divalent hydrocarbon group having 2 to 4 carbon atoms;

R¹⁹is a divalent hydrocarbon radical having from 1 to 6 carbon atoms, each of which may optionally be branched;

subscripts t, u, and v are 0 or 1.

Subscripts a, b, and c are 0 or a positive number, satisfying the following relationship:

a + b + c is more than or equal to 1 and less than or equal to 10, wherein a is more than or equal to 1.

R^AIs a monovalent radical selected from the group consisting of-SO₃M^K、-C(＝O)CH₂CH(R²⁰)COO^-M^K、-PO₃HM^K、-COOM^K(ii) a Wherein R is²⁰Selected from H or-SO₃M^K；M^KIs a cation selected from Na⁺、K⁺、Ca²⁺、NH₄ ⁺、Li⁺And from monoalkylamines having 2 to 4 carbon atoms,Monovalent ammonium ions of dialkylamines and trialkylamines or monoalkanolamines, dialkanolamines and trialkanolamines having 2 to 4 carbon atoms.

R¹⁴Is a monovalent radical selected from R²¹(O)_w(R²²)_x-and R²³O(C₂H₄O)_d(C₃H₆O)_e(C₄H₈O)fCH₂CH(OH)CH₂-；

Wherein R is²¹And R²²Each independently selected from divalent hydrocarbon radicals having 1 to 4 carbon atoms, which may be optionally substituted with one or more OH groups;

R²³is a divalent hydrocarbon group having 2 to 4 carbon atoms; subscripts w and x are 0 or 1.

Subscripts d, e, and f are 0 or a positive number, satisfying the following relationship:

d + e + f is more than or equal to 1 and less than or equal to 10, wherein d is more than or equal to 1;

R^Cis selected from N (R)²⁴)(R²⁵)，

Wherein R is²⁴And R²⁵Each independently selected from H, a branched or straight chain monovalent hydrocarbon radical having from 1 to 4 carbon atoms; r³¹N(R³⁴)(R³⁵) (ii) a and-R³²O(C₂H₄O)_g(C₃H₆O)_h(C₄H₈O)_iR³³。

Subscripts g, h, and i are 0 or a positive number, satisfying the following relationship:

g + h + i is more than or equal to 1 and less than or equal to 10, wherein g is more than or equal to 1.

R²⁶、R²⁸、R²⁹、R³⁰Each independently selected from H anda branched or straight chain monovalent hydrocarbon group having 1 to 4 carbon atoms.

R²⁷Is a monovalent radical selected from H, a branched or straight chain monovalent hydrocarbon radical having from 1 to 4 carbon atoms or-R³⁶O(C₂H₄O)_j(C₃H₆O)_k(C₄H₈O)₁R³⁷；

Subscripts j, k, and 1 are 0 or a positive number, satisfying the following relationship:

j + k +1 is more than or equal to 1 and less than or equal to 10, wherein j is more than or equal to 1.

R³¹Is a divalent hydrocarbon radical having 1 to 6 carbon atoms or R³⁸O(C₂H₄O)_m(C₃H₆O)_n(C₄H₈O)_oR³⁹The divalent hydrocarbon group may be optionally substituted with a heterocyclic group containing nitrogen, sulfur, oxygen, or a combination thereof;

subscripts m, n, and o are 0 or a positive number, satisfying the following relationship:

m + n + o is more than or equal to 1 and less than or equal to 10, wherein m is more than or equal to 1.

R³⁴And R³⁵Independently selected from H and branched or straight chain monovalent hydrocarbon radicals having from 1 to 4 carbon atoms.

R³²、R³⁶And R³⁸Independently selected from divalent hydrocarbon groups having 2 to 4 carbon atoms.

R³³Is a monovalent group selected from the group consisting of H, monovalent hydrocarbon groups having 1 to 6 carbon atoms and N (R)⁴⁰)(R⁴¹)。

R³⁷And R³⁹Independently selected from H, a branched or straight chain monovalent hydrocarbon radical having 1 to 4 carbon atoms and R⁴²N(R⁴³)(R⁴⁴) (ii) a Wherein R is⁴²Is a divalent hydrocarbon group having 1 to 6 carbon atoms. R⁴⁰、R⁴¹、R⁴³And R⁴⁴Independently selected from H and branched or straight chain monovalent hydrocarbon radicals having from 1 to 4 carbon atoms.

R¹⁵Is a monovalent radical selected from R⁴⁵(O)_y(R⁴⁶)_z-and R⁴⁷O(C₂H₄O)_p(C₃H₆O)_q(C₄H₈O)_rCH₂CH(OH)CH₂-；

Wherein R is⁴⁵And R⁴⁶Each independently selected from divalent hydrocarbon radicals having 1 to 4 carbon atoms, which may be optionally substituted with one or more OH groups;

R⁴⁷is a divalent hydrocarbon group having 2 to 4 carbon atoms; subscripts y and z are 0 or 1;

subscripts p, q, and r are 0 or a positive number, satisfying the following relationship:

p + q + r is more than or equal to 1 and less than or equal to 10, wherein p is more than or equal to 1.

R^Zis-N- (R)⁴⁸)(R⁴⁹)_αR⁵⁰SO₃(M^K)_β、-N-(R⁵¹)(R⁵²)_γR⁵³COO(M^K)_δ、N⁺-(R⁵⁴)(R⁵⁵)R⁵⁶OP (═ O) (A) (B) or (-C (═ O) N (R)⁵⁷)R⁵⁸N-(R⁵⁹)(R⁶⁰))⁺-(R⁶¹OP(＝O)(A)(B))(X^-)_ε；

Wherein R is⁴⁸、R⁴⁹、R⁵¹、R⁵²、R⁵⁴、R⁵⁵、R⁵⁷、R⁵⁹And R⁶⁰Each independently selected from H, a branched or straight chain monovalent hydrocarbon group having 1 to 4 carbon atoms, and an alkanolamine group having 2 to 4 carbon atoms;

R⁵⁰is a divalent bridging group having 3 to 4 carbon atoms;

subscripts α, β, γ, and δ are 0 or 1, satisfying the following relationships: α + β ═ 1 and γ + δ ═ 1.

R⁵³And R⁵⁶Independent of each otherIs a divalent bridging group having 1 to 4 carbon atoms.

R⁵⁸And R⁶¹Each independently a divalent bridging group having 2 to 4 carbon atoms.

A and B are selected from O^-And OM^K；

X is an anion selected from the group consisting of anions Cl, Br and I;

subscript ε is 0, 1, or 2.

Particularly useful embodiments of the invention are exemplified by the selection of the following classes:

R¹selected from isopropyl, isobutyl, tert-butyl or R⁷(ii) a Wherein R is⁷Having the formula R⁸R⁹R¹⁰SiR¹²Wherein R is⁸、R⁹And R¹⁰Selected from methyl, R¹²is-CH₂CH₂；R²、R³、R⁵、R⁶Is methyl; r¹⁶is-CH₂CH₂CH₂-；R¹⁷is-CH₂CH(OH)CH₂-；R¹⁸is-CH₂CH₂-；R¹⁹Is selected from-CH₂CH₂CH₂-、-CH(CH₃)CH₂CH₂-and-CH₂CH(CH₃)CH₂-; a. b and c are 0; t is 1, u is 1, v is 0; r²⁰Is H; m^kSelected from Na⁺、K⁺Or NH₄ ⁺；R²¹Is selected from-CH₂CH₂CH₂-；R²²Is CH₂CH(OH)CH₂-；R²³is-CH₂CH₂CH₂-; d. e and f are 0; w is 1 and x is 1; r²⁴And R²⁵Selected from H, methyl, ethyl, propyl, isopropyl and-R³²O(C₂H₄O)_g(C₃H₆O)_h(C₄H₈O)_iR³³；R³²is-CH₂CH₂CH₂-; g is 1-5, h and i are 0; r³³Selected from H and methyl; r²⁶And R²⁸Is H; r²⁷Selected from H, methyl and-R³⁶O(C₂H₄O)_j(C₃H₆O)_k(C₄H₈O)₁R³⁷；R³⁶Is selected from-CH₂CH₂CH₂-; j is 1-5, k and 1 are 0; r³⁷Selected from H and methyl; r²⁹And R³⁰Is selected from H; r⁴⁵is-CH₂CH₂CH₂-；R⁴⁶is-CH₂CH(CH₃)CH₂-; y and z are 1; r⁴⁷is-CH₂CH₂CH₂-; p is 1-5, q and r are 0; r⁴⁸And R⁴⁹Selected from H or methyl; r⁵⁰Is selected from-CH₂CH₂CH₂-and-CH₂CH₂CH₂CH₂-；R⁵¹And R⁵²Each independently selected from H and methyl; r⁵³Is selected from-CH₂CH₂CH₂-and-CH₂CH₂CH₂CH₂-；R⁵⁴And R⁵⁵Selected from H and methyl; r⁵⁷、R⁵⁹And R⁶⁰Selected from H and methyl. It should be noted that the silicone MM' is typically asymmetric.

One method of preparing the compositions of the present invention is to react molecules having the formula MMH with olefin-modified epoxy-containing moieties (such as allyl glycidyl ether or vinylcyclohexene oxide, which are listed here by way of example and without limitation as other possible olefin-modified epoxy components) under hydrosilylation conditions, followed by subsequent reaction with amine-containing groups,

MM^H

wherein M is^HHydride precursors which are M' building blocks in the compositions of the present invention, wherein the definitions and relationships are defined below and are consistent with those defined above.

The epoxy-modified organofunctional disiloxane is prepared directly by grafting the olefin-modified (i.e., vinyl, allyl, or methallyl) epoxy group onto the hydride (SiH) intermediate of the organomodified disiloxane of the present invention using a hydrosilylation reaction.

Noble metal catalysts suitable for use in preparing epoxy-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: spier, "Homogeneous catalysis of hydrolysis by transformation Metals", Advances in organic chemistry, Vol.17, pp.407 to 447, edited by F.G.A.Stone and R.West, published by academic Press (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 disiloxane composition.

The compositions of the present invention exhibit improved resistance to hydrolysis outside the pH range of 6 to 7.5. 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:

as used hereinafter in this application, terms such as agricultural components, coating components, personal care components, household care components, oil and gas treatment components, water treatment components, and pulp and paper treatment components are general terms that individually or cumulatively represent the individual markush groups defined and enumerated below, including the non-silicone or non-silane active components listed in each of the headings. Thus, for example, all of the non-silicone or non-silane active ingredients listed below under the heading of the paragraphs beginning with "agricultural component" include the markush group of agricultural components. Similarly, all non-silicone or non-silane active ingredients listed under the paragraph heading beginning with "personal care" include the markush group of personal care components.

The compositions of the present invention are useful in surfactant applications. The compositions of the present invention are useful as surfactants in a variety of applications. The compositions of the present invention may be used as pure components, as mixtures or as emulsions. As is generally known, emulsions comprise at least two immiscible phases, one of which is continuous and the other discontinuous. Additionally, the emulsion may be a liquid or gas, or a solid, with 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. In addition, emulsions of emulsions, which are commonly referred to as multiple emulsions, may also be prepared. These emulsions may be:

1) aqueous emulsions wherein the discontinuous phase comprises water and the continuous phase comprises the composition of the present invention;

2) aqueous emulsions wherein the discontinuous phase comprises the composition of the present invention and the continuous phase comprises water;

3) non-aqueous emulsions wherein the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the composition of the invention; and

4) non-aqueous emulsions wherein the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the composition of the present invention.

A. Agricultural ingredients-pesticides (pesticides) -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 disiloxane 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, phenoxypropionic, phenoxybutyric, benzoic, triazines and s-triazines, substituted ureas, uracils, bentazon, isobenafop, dimethenamid, benfop-butyl, dyafop-propargyl, isoxaflutole, fluridone, daminoxyfen, dinitroaniline, isoethan, oryzalin, ethazachlor, ethambucil, prodiamine, trifluralin, glyphosate, sulfonylureas, imidazolinones, clethodim, clomeprobamate, fenoxaprop-P-ethyl, fluazifop-p-butyl, sethoxydim, dichlobemil, 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.

Fertilizers and micronutrients:

fertilizers and micronutrients include, but are not limited to, zinc sulfate, ferrous sulfate, ammonium sulfate, urea ammonium nitrate, ammonium thiosulfate, potassium sulfate, monoammonium phosphate, urea phosphate, calcium nitrate, boric acid, potassium and sodium salts of boric acid, phosphoric acid, magnesium hydroxide, manganese carbonate, calcium polysulfide, copper sulfate, manganese sulfate, iron sulfate, calcium sulfate, sodium molybdate, calcium chloride.

The insecticide or fertilizer may be liquid or solid. If solid, it is preferably soluble in a solvent or in the organomodified disiloxane 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 ingredients-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:

co-surfactants 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.

Also useful are other cosurfactants that have short chain hydrophobic groups that do not interfere with superspreading, as described in U.S. patent 5,558,806, which is incorporated herein by reference. In addition, the above compositions are also useful as alkyl chloride, alkyl iodide, and alkyl bromide analogs, as well as acid pairs (acid pairs) with HCl, acetic acid, propionic acid, glycolic acid, gibberellic acid, and the like. Those skilled in the art understand the benefits of quaternization, which increases solubility and the potential for interaction with nonionic and anionic cosurfactants.

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), Gemini-type surfactants (Rhodia), and diphenyl ether Gemini-type surfactants (e.g., DOWFAX-Dow Chemical).

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 components), 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 disiloxanes of the present invention, as a tank mix, or as a "pot-in" 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. The coating comprises the following components:

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, epoxy compounds.

C. Personal care product component

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

The organomodified disiloxane surfactant compositions of the present invention can 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 disiloxane surfactant of the present invention;

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

4) non-aqueous emulsions wherein the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises an organomodified disiloxane 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 disiloxane 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 disiloxane 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 disiloxane surfactant 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 chlorohydrate (aluminum chlorohydrate) glycine tetrachloride.

In another useful embodiment, the skin care composition includes an organomodified disiloxane 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 disiloxane 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 care component

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.

E. Oil and/or gas treatment component

The organomodified silylated surfactant compositions of the present invention are useful in oil and gas applications, including demulsification.

F. Water treatment component

Compositions comprising the organomodified silylated surfactants of the present invention are useful in applications involving: commercial and industrial open recirculating cooling water towers, closed cooling water systems, cooling water conduits, heat exchangers, condensers, once-through cooling systems, pasteurizers, air purifiers, heat exchange systems, air conditioning/humidifier/dehumidifier, hydrostatic cookers (hydro static cookers), safety and/or fire-proof water-protected storage systems, water scrubbers, recharge wells, influent systems, including filtration and purifiers, wastewater treatment tanks, conduits, filter beds, digesters (digesterers), purifiers, holding tanks, settling lagoons (lagoons), canals, odor control, ion exchange resin beds, membrane filtration, reverse osmosis, microfiltration and ultrafiltration, to facilitate biofilm removal in cooling tower applications, heat exchangers, and industrial water systems, and the like.

G. Pulp and/or paper processing components

The organomodified silylated surfactant compositions of the present invention are useful in pulp and paper applications, such as paperboard defoamers and wetting agents used in pulping processes.

Experiment of

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

Preparation of example 1

1, 1, 3, 3-tetramethyl-3- (3-oxiranylmethoxy-propyl) -1- (2-trimethylsilyl-ethyl) -disiloxane (1, 1, 3, 3-tetramethy-3- (3-oxiranylmethoxy-propyl) -1- (2-trimethyl-ethyl) -disiloxane) (FIG. 1).

1- (2-Trimethylsilylethyl) -1, 1, 3, 3-tetramethyldisiloxane (18.8g) and chloroplatinic acid catalyst (ethanol solution, 30ppm Pt) were charged in a magnetic stirrer, reflux condenser and N₂Imported 100ml Round Bottom (RB) flask. The mixture was stirred and heated to 90 ℃. 2-allyloxymethyl-ethylene oxide (10g) was placed in an addition funnel and added dropwise to the flask. The mixture was stirred and held at 90 ℃ for an additional 4 hours. The progress of the reaction was monitored by NMR spectroscopic analysis. At the end of the reaction, the excess 2-allyloxymethyl-oxirane was removed by vacuum distillation.

FIG. 1-reaction scheme for preparing organomodified disiloxane intermediate 1

Preparation of example 2

1- (4- (2-hydroxy-ethyl) -piperazin-1-yl) -3- (3- (1, 1, 3, 3-tetramethyl-3- (2-trimethylsilyl-ethyl) -disiloxanyl) -propoxy) -propan-2-ol (figure 2).

2-piperazin-1-ylethanol (0.74g) and 20ml of ethanol were charged to a 100ml RB flask equipped with a magnetic stirrer. The mixture was stirred and heated to 70 ℃.1, 1, 3, 3-tetramethyl-3- (3-oxiranylmethoxy-propyl) -1- (2-trimethylsilyl-ethyl) -disiloxane (2.0g) was placed in an addition funnel and added dropwise to the flask. The mixture was stirred and held at 70 ℃ for an additional 4 hours. The progress of the reaction was monitored by NMR spectroscopic analysis. At the end of the reaction, the ethanol was removed under vacuum and the mixture was subjected to vacuum distillation to remove impurities.

FIG. 2-reaction scheme for preparation of organomodified disiloxane surfactant 2

Preparation of example 3

1- (2- (2-hydroxy-ethoxy) -ethylamino) -3- (3- (1, 1, 3, 3-tetramethyl-3- (2-trimethylsilyl-ethyl) -disiloxanyl) -propoxy) -propan-2-ol (FIG. 3).

2- (2-Aminoethoxy) -ethanol (3.02g) and ethanol (40ml) were charged to a 100ml RB flask equipped with a magnetic stirrer. The mixture was stirred and heated to 70 ℃.1, 1, 3, 3-tetramethyl-3- (3-oxiranylmethoxy-propyl) -1- (2-trimethylsilyl-ethyl) -disiloxane (2.0g) mixed with ethanol (10mL) was placed in an addition funnel and added dropwise to the flask. The mixture was stirred and held at 70 ℃ for an additional 4 hours. The progress of the reaction was monitored by NMR spectroscopic analysis. At the end of the reaction, the ethanol is removed under vacuum and the mixture is subjected to vacuum distillation to remove impurities and excess starting material.

FIG. 3-reaction scheme for preparing organomodified disiloxane surfactant 3

Preparation of example 4

1- (2- (2- (2-hydroxy-ethoxy) -ethylamino) -3- (3- (1, 1, 3, 3-tetramethyl-3- (2-trimethylsilyl-ethyl) -disiloxanyl) -propoxy) -propan-2-ol (FIG. 4).

2- (2- (2-aminoethoxy) -ethoxy) -ethanol (4.25g) and ethanol (40ml) were charged to a 100ml RB flask equipped with a magnetic stirrer. The mixture was stirred and heated to 70 ℃.1, 1, 3, 3-tetramethyl-3- (3-oxiranylmethoxy-propyl) -1- (2-trimethylsilyl-ethyl) -disiloxane (2.0g), mixed with ethanol (10g), was placed in an addition funnel and added dropwise to the flask. The mixture was stirred and held at 70 ℃ for an additional 4 hours. The progress of the reaction was monitored by NMR spectroscopic analysis. At the end of the reaction, the ethanol was removed under vacuum and the mixture was subjected to vacuum distillation to remove impurities and excess starting material.

FIG. 4-reaction scheme for preparing organomodified disiloxane surfactant 4

In addition, comparative trisiloxane alkoxylates were prepared by a conventional platinum-mediated hydrosilylation process, as described in U.S. Pat. No. 3,299,112 to Bailey, which is incorporated herein by reference.

Comparative sample a is a trisiloxane ethoxylated surfactant containing 8.5 polyoxyethylene repeat units. The product is prepared fromL-77 is available from Momentive Performance Materials, Wilton, CT.

In addition, the comparison sample OPE (octylphenol ethoxylate, containing 10 polyoxyethylene units) is a non-silicone organic surfactant. The product is prepared fromX-100 was purchased from Dow chemical company, Midland, MI.

Example 1

This example demonstrates the ability of the organomodified disiloxane surfactant compositions of the present invention to reduce the surface tension of water, thereby demonstrating utility as a surfactant. Surface tension was measured using hanging drop analysis. To be in water (deionized water) or 2M NH₄Solutions of the various components were prepared at a concentration of 0.1 wt% in Cl solution.

Table 1 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 surfactant a. Furthermore, the organomodified disiloxane surfactants of the present invention provide improved spreading relative to the conventional organic surfactant product OPE.

The spreading was determined as follows: a10. mu.L drop of the surfactant solution was applied to a polystyrene Petri dish (Fisher Scientific) 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 to provide droplets of reproducible volume. Deionized water further purified with a microfiltration system was used to prepare the surfactant solution.

TABLE 1 surface tension and spreading Properties

Example 2

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

Table 2 is an illustrative example of a conventional organomodified trisiloxane ethoxylate surfactant that exhibits reduced spreading over time properties associated with hydrolytic breakdown in the pH range of pH3 to pH 10. Here, 0.4 wt% solutions of sample A were prepared at pH3, 4,5 and 10. The spreading was determined as follows: a10 μ L droplet of a surfactant solution was applied to a polyvinyl acetate Film (USI, "CrystalClear Write on Film") at a relative humidity of 50-70% (at 22-25 deg.C), and the spread diameter (mm) after 30 seconds was measured. The solution was applied using an automatic pipette to provide droplets of reproducible volume. Deionized water further purified with a microfiltration system was used to prepare the surfactant solution.

TABLE 2 influence of pH on spreading Properties as a function of time

Example 3

Table 3 is an illustrative example of an organomodified disiloxane surfactant of the present invention in which sample No. 4 superspreader has improved resistance to hydrolysis over the conventional trisiloxane ethoxylate surfactant (product a) in the pH range of pH 4 to pH 11. As described above, the hydrolysis resistance was observed by monitoring the spreading properties over time. Here, 0.1 wt% surfactant solutions were prepared in distilled water containing 10 wt% NaCl at pH 4,5, 9 and 11. The spreading was determined as follows: a10. mu.L drop of the surfactant solution was applied to a polystyrene Petri dish (Fisher Scientific) 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 to provide droplets of reproducible volume.

TABLE 3 influence of pH on spreading behavior versus time

Example 4

Table 4 is an illustrative example of an organomodified disiloxane surfactant of the present invention in which sample No. 5 superspreaders have improved resistance to hydrolysis over the conventional trisiloxane ethoxylate surfactant (product a) in the pH range of pH 4 to pH 11. As described above, the hydrolysis resistance was observed by monitoring the spreading properties over time. Here, 0.1 wt% surfactant solutions were prepared in distilled water containing 10 wt% NaCl at pH 4,5, 9 and 11. The spreading was determined as follows: a10. mu.L drop of the surfactant solution was applied to a polystyrene Petri dish (Fisher Scientific) 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 to provide droplets of reproducible volume.

TABLE 4 influence of pH on spreading Properties as a function of time

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 (25)

1. A mixture, comprising:

a) a silicone having the formula:

MM’

wherein

M is selected from R¹R²R³SiO_1/2；

M' is selected from R⁴R⁵R⁶SiO_1/2；

Wherein R is¹Selected from branched monovalent hydrocarbon groups having 3 to 6 carbon atoms and R⁷Wherein R is⁷Is selected from R⁸R⁹R¹⁰SiR¹²And (R)⁴R⁵R⁶)SiR¹²(Si(R²R³)SiO_1/2)

Wherein R is⁸、R⁹And R¹⁰Each independently selected from the group consisting of monovalent hydrocarbon radicals having 1 to 6 carbon atoms and monovalent aryl or alkaryl hydrocarbon radicals having 6 to 13 carbon atoms, R¹²Is a divalent hydrocarbon group having 1 to 3 carbon atoms,

R²and R³Each independently selected from a monovalent hydrocarbon group having 1 to 6 carbon atoms or R¹Wherein R is⁴Is R¹³-R^A、R¹⁴-R^CAnd R¹⁵-R^z；

R¹³Is selected from R¹⁶(O)_t(R¹⁷)_u(O)_v-、And R¹⁹O(C₂H₄O)_a(C₃H₆O)_b(C₄H₈O)_c-；

Wherein R is¹⁶And R¹⁷Each independently selected from divalent hydrocarbon radicals having 1 to 4 carbon atoms, each of which may be optionally substituted with one or more OH groups;

R¹⁸is a divalent hydrocarbon group having 2 to 4 carbon atoms;

R¹⁹is a divalent hydrocarbon radical having from 1 to 6 carbon atoms, each of which may optionally be branched;

subscripts t, u, and v are 0 or 1;

subscripts a, b, and c are 0 or a positive number, satisfying the following relationship:

a + b + c is more than or equal to 1 and less than or equal to 10, wherein a is more than or equal to 1;

R^Ais a monovalent radical selected from the group consisting of-SO₃M^K、-C(＝O)CH₂CH(R²⁰)COO^-M^K、-PO₃HM^K、-COOM^K(ii) a Wherein R is²⁰Selected from H or-SO₃M^K；M^KIs a cation selected from Na⁺、K⁺、Ca²⁺、NH₄ ⁺、Li⁺And monovalent ammonium ions derived from monoalkylamines, dialkylamines and trialkylamines having 2 to 4 carbon atoms or monoalkanolamines, dialkanolamines and trialkanolamines having 2 to 4 carbon atoms;

R¹⁴is a monovalent radical selected from R²¹(O)_w(R²²)_x-and R²³O(C₂H₄O)_d(C₃H₆O)_e(C₄H₈O)_fCH₂CH(OH)CH₂-；

Wherein R is²¹And R²²Each independently selected from divalent hydrocarbon radicals having 1 to 4 carbon atoms, which may be optionally substituted with one or more OH groups;

R²³is a divalent hydrocarbon group having 2 to 4 carbon atoms; subscripts w and x are 0 or 1;

subscripts d, e, and f are 0 or a positive number, satisfying the following relationship:

d + e + f is more than or equal to 1 and less than or equal to 10, wherein d is more than or equal to 1;

R^Cis selected from N (R)²⁴)(R²⁵)，

Wherein R is²⁴And R²⁵Each independently selected from H, a branched or straight chain monovalent hydrocarbon radical having from 1 to 4 carbon atoms; r³¹N(R³⁴)(R³⁵) (ii) a and-R³²O(C₂H₄O)_g(C₃H₆O)_h(C₄H₈O)_iR³³；

Subscripts g, h, and i are 0 or a positive number, satisfying the following relationship:

g + h + i is more than or equal to 1 and less than or equal to 10, wherein g is more than or equal to 1;

R²⁶、R²⁸、R²⁹、R³⁰each independently selected from H and a branched or straight chain monovalent hydrocarbon radical having from 1 to 4 carbon atoms;

R²⁷is a monovalent radical selected from H, having 1 to 4 carbon atomsA branched or straight chain monovalent hydrocarbon group and-R³⁶O(C₂H₄O)_j(C₃H₆O)_k(C₄H₈O)₁R³⁷；

Subscripts j, k, and 1 are 0 or a positive number, satisfying the following relationship:

j + k +1 is more than or equal to 1 and less than or equal to 10, wherein j is more than or equal to 1;

R³¹is a divalent hydrocarbon radical having 1 to 6 carbon atoms or R³⁸O(C₂H₄O)_m(C₃H₆O)_n(C₄H₈O)_oR³⁹The divalent hydrocarbon group may be optionally substituted with a heterocyclic group containing nitrogen, sulfur, oxygen, or a combination thereof;

subscripts m, n, and o are 0 or a positive number, satisfying the following relationship:

m + n + o is more than or equal to 1 and less than or equal to 10, wherein m is more than or equal to 1;

R³⁴and R³⁵Independently selected from H and a branched or straight chain monovalent hydrocarbon radical having 1 to 4 carbon atoms;

R³²、R³⁶and R³⁸Independently selected from divalent hydrocarbon groups having 2 to 4 carbon atoms;

R³³is a monovalent group selected from the group consisting of H, monovalent hydrocarbon groups having 1 to 6 carbon atoms and N (R)⁴⁰)(R⁴¹)；

R³⁷And R³⁹Independently selected from H, a branched or straight chain monovalent hydrocarbon radical having 1 to 4 carbon atoms and R⁴²N(R⁴³)(R⁴⁴) (ii) a Wherein R is⁴²Is a divalent hydrocarbon group having 1 to 6 carbon atoms; r⁴⁰、R⁴¹、R⁴³And R⁴⁴Independently selected from H and a branched or straight chain monovalent hydrocarbon radical having 1 to 4 carbon atoms;

R¹⁵is a monovalent radical selected from R⁴⁵(O)_y(R⁴⁶)_z-and R⁴⁷O(C₂H₄O)_p(C₃H₆O)_q(C₄H₈O)_rCH₂CH(OH)CH₂-；

Wherein R is⁴⁵And R⁴⁶Each independently selected from the group consisting of 1-4 carbon atomsA divalent hydrocarbon group of a subgroup which may be optionally substituted with one or more OH groups;

R⁴⁷is a divalent hydrocarbon group having 2 to 4 carbon atoms; subscripts y and z are 0 or 1;

subscripts p, q, and r are 0 or a positive number, satisfying the following relationship:

p + q + r is more than or equal to 1 and less than or equal to 10, wherein p is more than or equal to 1;

R^Zis-N- (R)⁴⁸)(R⁴⁹)_αR⁵⁰SO₃(M^K)_β、-N-(R⁵¹)(R⁵²)_γR⁵³COO(M^K)_δ、N⁺-(R⁵⁴)(R⁵⁵)R⁵⁶OP (═ O) (A) (B) or (-C (═ O) N (R)⁵⁷)R⁵⁸N-(R⁵⁹)(R⁶⁰))⁺-(R⁶¹OP(＝O)(A)(B))(X^-)_ε；

Wherein R is⁴⁸、R⁴⁹、R⁵¹、R⁵²、R⁵⁴、R⁵⁵、R⁵⁷、R⁵⁹And R⁶⁰Each independently selected from H, a branched or straight chain monovalent hydrocarbon group having 1 to 4 carbon atoms, and an alkanolamine group having 2 to 4 carbon atoms;

R⁵⁰is a divalent group having 3 to 4 carbon atoms;

subscripts α, β, γ, and δ are 0 or 1, satisfying the following relationships: α + β ═ 1 and γ + δ ═ 1;

R⁵³and R⁵⁶Independently a divalent group having 1 to 4 carbon atoms;

R⁵⁸and R⁶¹Each independently a divalent group having 2 to 4 carbon atoms;

b) additional components selected from the group consisting of agricultural components, coating components, personal care components, household care components, oil and gas treatment components, water treatment components, and pulp or paper treatment components,

wherein the mixture has an increased resistance to hydrolysis.

2. The mixture of claim 1, wherein

R¹Selected from isopropyl, isobutylAlkyl, tert-butyl and R⁷；

Wherein R is⁷Having the formula R⁸R⁹R¹⁰SiR¹²Wherein R is⁸、R⁹And R¹⁰Each independently selected from methyl, R¹²is-CH₂CH₂；R²、R³、R⁵、R⁶Is methyl; r¹⁶is-CH₂CH₂CH₂-；

R¹⁷is-CH₂CH(OH)CH₂-；R¹⁸is-CH₂CH₂-；

R¹⁹Is selected from-CH₂CH₂CH₂-、-CH(CH₃)CH₂CH₂-and-CH₂CH(CH₃)CH₂-；

R²⁰Is H; m^kSelected from Na⁺、K⁺Or NH₄ ⁺；

R²¹Is selected from-CH₂CH₂CH₂-；

R²²Is CH₂CH(OH)CH₂-；

R²³is-CH₂CH₂CH₂-；

R²⁴And R²⁵Selected from H, methyl, ethyl, propyl, isopropyl and-R³²O(C₂H₄O)_g(C₃H₆O)_h(C₄H₈O)_iR³³；

R³²is-CH₂CH₂CH₂-；R³³Selected from H and methyl;

R²⁶and R²⁸Is H;

R²⁷selected from H, methyl and-R³⁶O(C₂H₄O)_j(C₃H₆O)_k(C₄H₈O)₁R³⁷；

R³⁶Is selected from-CH₂CH₂CH₂-；

R³⁷Selected from H and methyl; r²⁹And R³⁰Is selected from H;

R⁴⁵is-CH₂CH₂CH₂-；R⁴⁶is-CH₂CH(CH₃)CH₂-; y and z are 1;

R⁴⁷is-CH₂CH₂CH₂-；

R⁴⁸And R⁴⁹Selected from H and methyl;

R⁵⁰is selected from-CH₂CH₂CH₂-and-CH₂CH₂CH₂CH₂-；

R⁵¹And R⁵²Each independently selected from H and methyl;

R⁵³is selected from-CH₂CH₂CH₂-and-CH₂CH₂CH₂CH₂-；

R⁵⁴And R⁵⁵Selected from H and methyl;

R⁵⁷、R⁵⁹and R⁶⁰Selected from H and methyl.

3. The mixture of claim 2 wherein Z is R⁸-R^A。

4. The mixture of claim 2 wherein Z is R⁹-R^c。

5. The mixture of claim 2 wherein Z is R¹⁰-R^z。

6. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the mixture of claim 1.

7. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the mixture of claim 2.

8. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the mixture of claim 3.

9. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the mixture of claim 4.

10. An aqueous emulsion wherein the discontinuous phase comprises water and the continuous phase comprises the mixture of claim 5.

11. An aqueous emulsion wherein the discontinuous phase comprises the mixture of claim 1 and the continuous phase comprises water.

12. An aqueous emulsion wherein the discontinuous phase comprises the mixture of claim 2 and the continuous phase comprises water.

13. An aqueous emulsion wherein the discontinuous phase comprises the mixture of claim 3 and the continuous phase comprises water.

14. An aqueous emulsion where the discontinuous phase comprises the mixture of claim 4 and the continuous phase comprises water.

15. An aqueous emulsion wherein the discontinuous phase comprises the mixture of claim 5 and the continuous phase comprises water.

16. A non-aqueous emulsion where the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the mixture of claim 1.

17. A non-aqueous emulsion where the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the mixture of claim 2.

18. A non-aqueous emulsion where the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the mixture of claim 3.

19. A non-aqueous emulsion where the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the mixture of claim 4.

20. A non-aqueous emulsion where the discontinuous phase comprises a non-aqueous hydroxylic solvent and the continuous phase comprises the mixture of claim 5.

21. A non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the mixture of claim 1.

22. A non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the mixture of claim 2.

23. A non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the mixture of claim 3.

24. A non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the mixture of claim 4.

25. A non-aqueous emulsion where the continuous phase comprises a non-aqueous hydroxylic organic solvent and the discontinuous phase comprises the mixture of claim 5.