CN101341157B - Hydrolysis resistant organomodified disiloxane surfactants - Google Patents

Hydrolysis resistant organomodified disiloxane surfactants Download PDF

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CN101341157B
CN101341157B CN200680047036.9A CN200680047036A CN101341157B CN 101341157 B CN101341157 B CN 101341157B CN 200680047036 A CN200680047036 A CN 200680047036A CN 101341157 B CN101341157 B CN 101341157B
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composition
phase comprises
methyl
alkyl
water
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CN101341157A (en
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马克·D·莱瑟曼
乔治·A·波利塞洛
苏雷什·K·雷杰拉曼
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General Electric Co
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General Electric Co
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
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Abstract

The present invention relates to a disiloxane surfactant exhibiting resistance to hydrolysis over a wide pH range, which comprises an organic silicon composition comprising an organic silicon having the formula MM', where M is R<1>R<2>R<3>SiO1/2; M' is R<4>R<5>R<6>SiO1/2; wherein R<1> is selected from the group consisting of branched monovalent alkyl having 3 to 6 carbon atoms and R<7> having theformula R<8>R<9>R<10>SiR<12>, wherein R<8>, R<9> and R<10> are independently selected from the group consisting of branched monovalent alkyl having 1 to 6 carbon atoms and monovalent aryl or monovalent alkyl aryl having 6 to 13 carbon atoms, R<12> is a bivalent alkyl having 1 to 3 carbon atoms, R<2> and R<3> are independently selected the group consisting of monovalent alkyl having 1 to 6 carbon atoms or R<1>, wherein R4 is an alkyl polyoxyalkylene having the following formula: R<13> (C2H4O) a (C3H6O)b(C4H8O)c R<14>, wherein R<13> is a bivalent linear chain or branched alkyl having the following structure: -CH2-CH(R<15>) (R<16>)dO-, wherein R<15> is H or methyl; R<16> is a bivalent alkyl having 1 to 6 carbon atoms, wherein d is 0 or 1; R<14> is selected from the group consisting of H, monovalent alkyl having 1 to 6 carbon atoms and acetyl, wherein a, b and c are selected from the group consisting of 0 or positive numbers, and satisfy the relation: 2<a+b+c<20, and a>2, and R<5> and R<6> are independently selected from the group consisting of monovalent alkyl having 1 to 6 carbon atoms or R<4>.

Description

The organically-modified disiloxane surfactant of resistant to hydrolysis
The cross reference of related application
The application requires the rights and interests of the U.S. Provisional Application sequence number 60/726,409 of submission on October 13rd, 2005.
Technical field
The present invention relates to the disiloxane surfactant composition, it demonstrates resistance to hydrolysis in wide pH scope.More specifically, the present invention relates to this resistant to hydrolysis disiloxane surfactant of resistance to hydrolysis at about pH 3～approximately have between pH 12.
Background technology
The local paint of liquid composition is had on the surface of life and abiotic object to produce the change of expectation, comprise control wetting, sprawl, foam, the process such as cleaning.When use in the aqueous solution is arrived the transitivity on processed surface to improve active ingredient, have been found that trisiloxanes type compound can be used to make it possible to control these processes to obtain the effect of expectation.But the trisiloxanes compound only can be used for narrow pH scope, from slightly acidic pH 6 to as mild as a dove alkaline pH 7.5.Outside this narrow pH range, the trisiloxanes compound carries out fast decoupled to hydrolytically unstable.
Summary of the invention
The invention provides silicon composition, it comprises the organosilicon with following formula:
MM′
Wherein
M＝R 1R 2R 3SiO 1/2；
M′＝R 4R 5R 6SiO 1/2；
R wherein 1Be selected from monovalence alkyl and the R of the branching with 3～6 carbon atoms 7, R wherein 7Be selected from R 8R 9R 10SiR 12(R 4R 5R 6) SiR 12(Si (R 2R 3) SiO 1/2)
R wherein 8, R 9And R 10Be selected from independently of one another monovalence alkyl and monovalence aryl or alkane aryl with 6～13 carbon atoms, R with 1～6 carbon atom 12The bivalent hydrocarbon radical with 1～3 carbon atom,
R 2And R 3Be selected from independently of one another monovalence alkyl or R with 1～6 carbon atom 1, R wherein 4The alkyl polyoxygenated alkene with following general formula:
R 13(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14
R wherein 13To have the divalence straight chain of following structure or the alkyl of branching:
-CH 2-CH(R 15)(R 16) dO-
R wherein 15H or methyl; R 16Be the divalent alkyl with 1～6 carbon atom, wherein subscript d can be 0 or 1;
R 14Be selected from H, have monovalence alkyl and the ethanoyl of 1～6 carbon atom, wherein subscript a, b and c are 0 or positive number, and satisfy following relation:
2＜a+b+c＜20, and a＞2,
And R 5And R 6Be selected from independently of one another monovalence alkyl or R with 1～6 carbon atom 4
Embodiment
In the application under stoichiometry used the target round values refer to molecule thing class, under stoichiometry, the target non integer value refers to the mixture of the molecule thing class on the molar mass average basis, on number averaged basis or molar fraction basis.
The invention provides disiloxane compound or its composition of useful as surfactants, it has following general formula:
MM′
Wherein
M＝R 1R 2R 3SiO 1/2；
M′＝R 4R 5R 6SiO 1/2；
R wherein 1Monovalence alkyl or R for branching with 3～6 carbon atoms 7, and R 7Be selected from R 8R 9R 10SiR 12(R 4R 5R 6) SiR 12(Si (R 2R 3) SiO 1/2)
R wherein 8, R 9And R 10Be selected from independently of one another monovalence alkyl and monovalence aryl or alkane aryl with 6～13 carbon atoms, R with 1～6 carbon atom 12The bivalent hydrocarbon radical with 1～3 carbon atom,
R 2And R 3Be selected from independently of one another monovalence alkyl or R with 1～6 carbon atom 1, R wherein 4For having the alkyl polyoxygenated alkene of following general formula:
R 13(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14With
R wherein 13To have the divalence straight chain of following structure or the alkyl of branching:
-CH 2-CH(R 15)(R 16) dO-
R wherein 15H or methyl; R 16Be the divalent alkyl with 1～6 carbon atom, wherein subscript d can be 0 or 1;
R 14Be selected from H, have monovalence alkyl and the ethanoyl of 1～6 carbon atom, obey following restricted condition: subscript a, b and c and be 0 or positive number, and satisfy following relation:
2＜a+b+c＜20, and a＞2,
With, R 5And R 6Be selected from independently of one another monovalence alkyl or R with 1～6 carbon atom 4When subscript a satisfied condition 2＜a＜4, hereinafter listed cosurfactant was used in suggestion, to reach the benefit of composition of the present invention.
A kind of method for preparing composition of the present invention is under the hydrosilylation condition, makes formula MM HMolecule and the reaction of olefin-modified polyoxygenated alkene (olefinically modified polyalkyleneoxide),
At formula MM HIn, M HIt is the hydride precursor of M ' structural unit in composition of the present invention, wherein its definition and relation limit hereinafter, and consistent with the above restriction of making, described olefin-modified polyoxygenated alkene is the allyloxy polyoxyethylene glycol for example, or first is for allyloxy polyoxygenated alkene, these compounds are referred in the application as an example, are not to limit other possible olefin-modified oxyalkylene component.The application's term " olefin-modified polyoxygenated alkene " used is defined as the molecule with the one or more oxyalkylene groups that contain one or more end carbon-carbon double bonds or side carbon-carbon double bond.Polyethers is olefin-modified polyoxygenated alkene (hereinafter referred to " polyethers "), and is expressed by the following formula:
CH 2＝CH(R 15)(R 16) dO(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14
Wherein
R 15H or methyl; R 16Be the divalent alkyl with 1～6 carbon atom, wherein subscript d can be 0 or 1; R 14Be H, have the simple function alkyl of 1～6 carbon atom or an ethanoyl.When polyethers is comprised of the oxyalkylene group (oxyalkyleneoxide group) (being ethylene oxide, propylene oxide and oxybutylene) that mixes, this unit can be block or random distribution.Those skilled in the art should understand that the benefit of using block or random configuration.The illustrative example of block configuration is :-(ethylene oxide) a(propylene oxide) b-(oxybutylene) c(ethylene oxide) a-; With-(propylene oxide) b(ethylene oxide) a(oxybutylene) c-.
The illustrative example of polyethers provides as follows, but is not limited to these:
CH 2＝CHCH 2O(CH 2CH 2O) 8H；CH 2＝CHCH 2O(CH 2CH 2O) 8CH 3；
CH 2＝CHCH 2O(CH 2CH 2O) 4(CH 2CH(CH 3)O) 5H；
CH 2＝CHO(CH 2CH 2O) 5(CH 2CH(CH 3)O) 5H；
CH 2＝C(CH 3)CH 2O(CH 2CH 2O) 4(CH 2CH(CH 3)O) 5C(＝O)CH 3；
CH 2＝CHCH 2O(CH 2CH 2O) 5(CH 2CH(CH 3)O) 2(CHx 2CH(CH 2CH 3)O) 2H
Prepare polyether-modified siloxanes by using hydrosilylation reactions olefin-modified (being vinyl, allyl group or methylallyl) polyoxygenated alkene to be grafted on hydride (SiH) intermediate of sily oxide of the present invention in a conventional manner.
The noble metal catalyst that is suitable for preparing the siloxanes of polyethers-replacement is also known in the art, comprises the mixture of rhodium, ruthenium, palladium, osmium, iridium and/or platinum.It is known being permitted eurypalynous platinum catalyst for this SiH alkene addition reaction, and this platinum catalyst can be used for producing composition of the present invention.Platinic compound can be selected from has formula (PtCl 2Alkene) and H (PtCl 3Alkene) those as United States Patent (USP) 3,159, described in 601, are introduced into the application by reference.Other platiniferous material can be Platinic chloride and every gram platinum 2 moles of mixtures that are selected from the member of alcohol, ether, aldehyde and composition thereof at the most, as United States Patent (USP) 3,220, described in 972, is introduced into the application by reference.Useful another kind of platiniferous substance description is in United States Patent (USP) 3,715,334 in the present invention; In 3,775,452 and 3,814,730 (Karstedt).The background about prior art in addition can find in Publication about Document: J.L.Spier, " HomogeneousCatalysis of Hydrosilation by Transition Metals ", Advances in OrganometallicChemistry, the 17th volume, the 407th～447 page, F.G.A.Stone and R.West edit, and AcademicPress (New York, 1979) publishes.Those skilled in the art can easily determine the significant quantity of platinum catalyst.Usually, significant quantity is the approximately 0.1～50ppm of all organically-modified sily oxide composition.
Composition of the present invention demonstrates the resistance to hydrolysis of raising outside 6～7.5 pH scope.The resistance to hydrolysis that improves can confirm by multiple test, but the resistance to hydrolysis of the raising of using in the application refer to the pH that is exposed to solution lower than after 6 aqueous acidic condition 24 hours or the pH that is being exposed to solution greater than 7.5 aqueous alkaline condition 24 hours after, 50mol% or above resistance to hydrolysis remaining unchanged of composition of the present invention or do not react.Under acidic conditions, composition of the present invention is 5 or following maintenance when surpassing the time of 48 hours at pH, demonstrates remaining rate (survival) and is the 50mol% of starting point concentration or larger; Particularly, composition of the present invention is 5 or following maintenance when surpassing the time in 2 weeks at pH, and demonstrating remaining rate is 50mol% or larger; More specifically, composition of the present invention is 5 or following maintenance when surpassing the time of 1 month at pH, and demonstrating remaining rate is 50mol% or larger; The most particularly, composition of the present invention is 5 or following maintenance when surpassing the time of 6 months at pH, and demonstrating remaining rate is 50mol% or larger.Under alkaline condition, composition of the present invention is 8 or above maintenance when surpassing the time in 2 weeks at pH, and demonstrating remaining rate is 50mol% or larger; Particularly, composition of the present invention is 8 or above maintenance when surpassing the time in 4 weeks at pH, and demonstrating remaining rate is 50mol% or larger; More specifically, composition of the present invention is 8 or above maintenance when surpassing the time of 6 months at pH, and demonstrating remaining rate is 50mol% or larger; The most particularly, composition of the present invention is 8 or above maintenance when surpassing the time of 1 year at pH, and demonstrating remaining rate is 50mol% or larger.
The purposes of composition of the present invention:
A. sterilant-agricultural, gardening, turf (Turf), ornamental plant (Ornamental) and forestry (Forestry):
Many sterilant application requiring are added in the spray mixing thing auxiliary agent to provide wetting and sprawl on the blade face.Auxiliary agent is usually tensio-active agent, and it can have various functions, for example increases spray droplet at the confining force that is difficult on wetting blade face, improves the fraction of coverage of sprawling to improve spraying, perhaps provides weedicide to enter the perviousness of plant epidermis.These auxiliary agents or provide with tank side additive (tank-side additive) are perhaps as the component in formulation of insecticides.
The typically used of sterilant comprises agricultural, gardening, turf, ornamental plant, family and garden, animal doctor and forestry applications.
Insecticides of the present invention also comprises at least a sterilant, wherein organically-modified disiloxane surfactant of the present invention exists with the form as the enriched material in the bucket mix formulation or dilution, and the concentration the when amount of existence is enough to final the use provides 0.005%～2%.Randomly, insecticides can comprise vehicle, cosurfactant, solvent, foam control agent, deposition aid, stop-off gent (driffretardants), biotechnological formulation, micro-nutrients, fertilizer etc.The term sterilant refers to be used to any compound that eliminates destructive insects, for example rodenticide, sterilant, miticide, mycocide and weedicide.The illustrative example of spendable sterilant comprises, but be not limited to, growth regulator, inhibitor of photosynthesis, pigment inhibitor, mitotic division disruption agent (mitotic disrupter), lipid biosynthesis inhibitor (lipid biosynthesis inhibitors), cell walls inhibitor, and membranolysis agent (cell membranedisrupter).The amount of the sterilant that uses in composition of the present invention changes along with the type of sterilant used.the pesticide compound that can use together with composition of the present invention example more specifically is, but be not limited to, weedicide and growth regulator, for example: phenoxy acetic acid, phenoxy propionic acid, phenoxy butyric acid, phenylformic acid, triazine and s-triazine, the urea that replaces, uridylic, bentazone, different phenmedipham, methazole, phenmedipham, only reach grass, amerol, clomazone, fluorine pyridine ketone (fluridone), monometflurazone, dinitraniline, isopropaline,2,6-dinitroN,N-dipropylcumidine, oryzalin, herbicide is logical, prodiamine, trifluralin, glyphosate, sulfonylurea, imidazolone, clethodim, chloroformate grass, the oxazole diclofop-methyl, efficient fluazifop, haloxyfopPmethyl, quizalofopethyl (quizalofop), sethoxydim, Niagara 5006, isoxaben, and dipyridyl (bipyridylium) compound.
In the present invention, spendable fungicide composition can include, but not limited to aldimorph, tridemorph, dodemorfe, dimethomorph; Fluzilazol, penta ring azoles, cyproconazole, oxole bacterium, furconazole, Wocosin 50TK, tebuconazole etc.; IMAZALIL, thiophanate, F-1991, derosal, m-tetrachlorophthalodinitrile (chlorothialonil), dicloran, oxime bacterium ester (trifloxystrobin), fluoxastrobin (fluoxystrobin), dimoxystrobin (dimoxystrobin), nitrile Azoxystrobin (azoxystrobin), sterilization amine (furcaranil), Prochloraz, flusulfamide, Famoxate (famoxadone), Vancide 89, maneb, zinc manganese ethylenebisdithiocarbamate, oppose bacterium, dodine more, and metaxanin.
the sterilant that can use together with composition of the present invention, larvacide, miticide and ovicide (ovacide) compound comprises, but be not limited to, Bacillus thuringiensis, spinosad (spinosad), avermectin, doramectin (doramectin), lepimectin, pyrethrin, SevinCarbaryl, Aphox (pirimicarb), aldicarb, methomyl, U-36059, boric acid, chlordimeform, Rimon (novaluron), bistrifluron (bistrifluron), desinsection is grand, TH-6040, imidacloprid, diazinon, acephate, 5a,6,9,9a-hexahydro-6,9-methano-2,4, Ke Laifan, Rogor, triazotion, R-1582, izoxathion, Chlorpyrifos 94, clofentezine, cyhalothrin, permethrin, bifenthrin, Cypermethrin etc.
Fertilizer and micro-nutrients:
Fertilizer and micro-nutrients comprise, but be not limited to the sylvite of zinc sulfate, ferrous sulfate, ammonium sulfate, urea, urea ammonium nitrogen (urea ammonium nitrogen), ammonium thiosulfate, vitriolate of tartar, monoammonium phosphate, Ureaphil, nitrocalcite, boric acid, boric acid and sodium salt, phosphoric acid, magnesium hydroxide, manganous carbonate, calcium polysulfide, copper sulfate, manganous sulfate, ferric sulfate (iron sulfate), calcium sulfate, Sodium orthomolybdate, calcium chloride.
Sterilant or fertilizer can be liquid or solid.If solid, preferably it is solvable in solvent or organically-modified sily oxide of the present invention before using, and organosilicon can be used as solvent, perhaps is used for this deliquescent tensio-active agent, and perhaps other tensio-active agent can be completed this function.
The agricultural vehicle:
Damping fluid known in the art, sanitas and other standard excipients also can be included in said composition.
Solvent also can be included in composition of the present invention.These solvents are liquid in room temperature.Example comprises lower alkyl esters, lipid acid, ketone, glycol, polyoxyethylene glycol, glycol, paraffin of water, alcohol, aromatic solvent, oils (being mineral oil, vegetables oil, silicone oil etc.), vegetables oil etc.Concrete solvent can be as United States Patent (USP) 5,674, described in 832 2,2,4-trimethylammonium-1,3-pentane diol and oxyalkylated (especially ethoxylation) variant thereof, or N-methyl-pyrrolidone (n-methyl-pyrrilidone), described United States Patent (USP) is incorporated this paper into by reference.
Cosurfactant:
The useful cosurfactant of the application comprises the tensio-active agent of nonionogenic tenside, cats product, anion surfactant, amphoterics, zwitterionics, polymerization, or its any mixture.Tensio-active agent normally based on hydrocarbon, based on organosilyl or based on fluorocarbon.
In addition, also other cosurfactant usefully, it has and does not hinder the super short chain hydrophobic grouping of sprawling (superspreading), and as United States Patent (USP) 5,558, described in 806, described United States Patent (USP) is incorporated the application into by reference.
Useful tensio-active agent comprises the alcoxylates that contains segmented copolymer, ethoxylate especially, and described segmented copolymer comprises the multipolymer of oxyethane, propylene oxide, butylene oxide ring and composition thereof; Alkylaryl alcoxylates, especially ethoxylate or propoxylated glycerine, and their derivative comprise alkyl phenol ethoxylate; Aryl alkoxy aryl compound, especially ethoxylate or propoxylated glycerine, and their derivative; Amine alcoxylates, especially amine ethoxylate; Fatty acid alkoxylates; Fatty alcohol alkoxy compound; Alkylsulfonate; Alkylbenzene and sulfonated alkyl naphathalene; Sulphated fatty alcohol, amine or acid amides; The acid esters of hydroxyethyl sulfonate (acid estersof sodium isethionate); The ester of sodium sulfo-succinate; Sulfation or sulfonated fatty acid ester; Sulfonated petro-leum; The N-acyl sarcosinate; APG (alkyl polyglycoside); The amine of alkyl ethoxylated; Deng.
concrete example comprises alkyl acetylenic glycol (SURFONYL-Air Products), based on the tensio-active agent of pyrrolidone (pyrrilodone) (for example, SURFADONE-LP 100-ISP), 2-ethylhexyl vitriol, the isodecyl alcohol ethoxylate (for example, RHODASURF DA 530-Rhodia), quadrol alcoxylates (TETRONICS-BASF), ethylene oxide/propylene oxide multipolymer (PLURONICS-BASF), Gemini type tensio-active agent (Rhodia) and phenyl ether Gemini type tensio-active agent (for example DOWFAX-Dow Chemical).
Preferred tensio-active agent comprises ethylene oxide/propylene oxide multipolymer (EO/PO); The amine ethoxylate; APG; Oxo-tridecyl alcohol ethoxylate, etc.
In preferred embodiment, agricultural chemical composition of the present invention also comprises one or more agrochemicals compositions.Suitable agrochemicals composition comprises, but be not limited to, weedicide, sterilant, growth regulator, mycocide, Acaricide (miticide), miticide (acaricide), fertilizer, biotechnological formulation, plant nutrient, micro-nutrients, biocide, paraffin mineral oil, the seed oil that methylates (being methyl soybean fat acid metal salt (methylsoyate) or methyl Canola oil metal-salt (methylcanolate)), vegetables oil (for example soybean oil and Canola oil), water conditioner be Choice for example The clay of (Loveland Industries, Greeley, CO) and Quest (Helena Chemical, Collierville, TN), modification is Surround for example
Figure S2006800470369D00082
(Englehard Corp.), foam control agent, tensio-active agent, wetting agent, dispersion agent, emulsifying agent, deposition aid, antidrip component (antidriftcomponent), and water.
Suitable agricultural chemical composition gets by combination system with manner known in the art, for example, and by one or more said components are mixed with organically-modified sily oxide of the present invention, as the bucket mix formulation, perhaps as " canned " preparation.Term " bucket mix formulation " refers to when being about to use, at least a agrochemicals are added to the spraying medium, for example in water or oil.Term " canned " refers to contain preparation or the enriched material of at least a agrochemicals component.Then, " canned " preparation can be diluted to working concentration when being about to use, normally be diluted in barrel mix formulation, perhaps can not dilute and directly use it.
B. coating:
For the increase-volume of emulsification, component, homogenize (leveling), flow and reduce the purpose of surface imperfection, coating formulation needs wetting agent or tensio-active agent usually.In addition, these additives bring improvement, wear resistance, adhesion inhibiting properties, wetting ability and the hydrophobicity for example improved can for the film that solidifies or do.Coating formulation can be used as solvent-laden coating, moisture coating and powder coating exists.
Coating composition can be used as: building coating; OEM product coating is car paint and coil coating for example; Tailor-(made) coating is industry maintenance coating (industrial maintenance coating) and marine finish for example;
Typical resinous type comprises: polyester, Synolac, acrylic acid or the like (acrylics), epoxy compounds.
C. personal care articles
In preferred embodiment, personal care articles composition based on every 100 weight parts (" pbw "), organically-modified disiloxane surfactant of the present invention comprises 0.1～99pbw, more preferably 0.5pbw～30pbw, the more preferably organically-modified disiloxane surfactant of 1～15pbw also, and 1pbw～99.9pbw, more preferably 70pbw～99.5pbw, the also more preferably personal care articles composition of 85pbw～99pbw.
Organically-modified disiloxane surfactant composition of the present invention can with the personal care articles emulsion, for example reveal and white form use.As known, emulsion comprises at least two immiscible phases, one of them is continuous, another is discontinuous.Other emulsion can be the liquid or solid of the vicissitudinous viscosity of tool.In addition, it is microemulsion that the granularity of emulsion can make emulsion, and when enough hour, microemulsion can be transparent.Also may prepare the emulsion of emulsion, they are commonly called multiple emulsion.These emulsions can be:
Water miscible liquid, wherein discontinuous phase comprises water, external phase comprises organically-modified disiloxane surfactant of the present invention;
Water miscible liquid, wherein discontinuous phase comprises organically-modified disiloxane surfactant of the present invention, external phase comprises water;
Nonaqueous emulsion, wherein discontinuous phase comprises non-water hydroxylic solvent, external phase comprises organically-modified disiloxane surfactant of the present invention; With
Nonaqueous emulsion, wherein external phase comprises non-water hydroxyl organic solvent, discontinuous phase comprises organically-modified disiloxane surfactant of the present invention.
The nonaqueous emulsion that comprises the organosilicon phase is described in United States Patent (USP) 6,060,546 and United States Patent (USP) 6,271,295 in, their content is by with reference to introducing particularly the application.
The application's term " non-water hydroxyl organic compound " used refers to for example approximately 25 ℃ and be approximately the organic compound of the hydroxyl of liquid during 1 normal atmosphere of room temperatures, and exemplary have alcohol, dibasic alcohol, polyvalent alcohol and poly-dihydric alcohol and composition thereof.The organic hydroxylic solvent of non-water is selected from for example approximately 25 ℃ and be approximately the organic compound of the hydroxyl of liquid during 1 normal atmosphere of room temperatures, and it comprises alcohol, dibasic alcohol, polyvalent alcohol and poly-dihydric alcohol and composition thereof.Preferably, non-water hydroxyl organic solvent is selected from ethylene glycol, ethanol, propyl alcohol, Virahol, propylene glycol, dipropylene glycol, tripropylene glycol, butyleneglycol, different-butyleneglycol, methylpropane glycol, glycerine, Sorbitol Powder, polyoxyethylene glycol, polypropylene glycol monoalky lether, polyoxyalkylene multipolymer and composition thereof.
In case obtain the form of expectation, no matter as organosilyl single-phase, the anhydrous mixture that comprises the organosilicon phase, the aqueous mixture that comprises the organosilicon phase, water-in-oil emulsion, O/w emulsion, perhaps any or its variant of two kinds of nonaqueous emulsions, the material that obtains are usually all have the frost of the deposit properties of improvement and good touch characteristic or reveal.It can be blended in the preparation of hair product, skin care product, antiperspirant, opalizer, makeup, colour cosmetic (color cosmetic), wormer, Metabolism Vitamins and Hormones carrier, fragrance carrier etc.
can use organically-modified disiloxane surfactant of the present invention and be used by the personal care articles of its derivative silicon composition of the present invention and comprise, but be not limited to, reodorant, antiperspirant, antiperspirant/deodorant, product shaves, skin liquid, wetting Agent for Printing Inks, toning agent, bathhouse article, cleaning product, hair products are such as shampoo, amendment, mousse, hair styling gel having, close and send out spray, hair dye, hair dyeing product, the bleached hair agent, the hair-waving product, straighter, have a manicure product such as nail varnish, enamel remover, nail frost and dew, the stratum corneum tenderizer, protective cream is such as opalizer, wormer and aging products, the additive color makeup are such as lipstick, foundation cream, face powder, eyeliner, eye shadow, kermes, cosmetics, mascara and common other personal care formulations of organosilicon component that added, and the drug delivery system of topical application that is used for to be applied to the medicinal compositions of skin.
In preferred embodiment, personal care articles composition of the present invention also comprises one or more personal care articles compositions.suitable personal care articles composition comprises, for example, tenderizer, wetting Agent for Printing Inks, wetting agent, pigment, comprise for example mica of pearl white and titanium dioxide-coated of pearly pigment, tinting material, spices, biocide, sanitas, antioxidant, biocide, anti-mycotic agent, antiperspirant, keratoderma stripper (exfoliant), hormone, enzyme, medicinal compound, VITAMIN, salt, ionogen, alcohol, polyvalent alcohol, UV light absorber, plant milk extract, tensio-active agent, silicone oil, organic oil (organic oil), wax, membrane-forming agent, viscosifying agent is pyrogenic silica or hydrated SiO 2 for example, particulate filler is talcum for example, kaolin, starch, modified starch, mica, nylon, clay is wilkinite and organically-modified clay for example.
Suitable personal care articles composition for example, makes by one or more said components are mixed with described organically-modified disiloxane surfactant by getting with the manner known in the art combination system.Suitable personal care articles composition can be single-phase form or the form of emulsion, described emulsion form comprises that organosilicon wherein can be oil-in-water, water-in-oil and the anhydrous emulsion of discontinuous phase or external phase mutually, and multiple emulsion, for example, water-in-oil bag fat liquor and water-in-oil-in-water compositions.
In a kind of useful embodiment, Antipers pirant compositions comprises organically-modified disiloxane surfactant of the present invention and one or more active antiperspirant.suitable antiperspirant comprises, for example, U.S.Food and Drug Administration ' s October 10, the active antiperspirant composition of the I class of listing in 1993 Monograph onantiperspirant drug products for over-the-counter human use, aluminum halide for example, hydroxyhalides (aluminum hydroxyhalide) is as Wickenol CPS 325 (aluminum chlorohydrate), and with mixture or the mixture of halogenation oxygen zirconium (zirconyl oxyhalide) and alkali formula halogenation oxygen zirconium (zirconyl hydroxyhalide), for example, Wickenol CPS 325-zirconium (aluminum-zirconium chlorohydrate), aluminium zirconium glycine mixture (aluminum zirconiumglycine complexe) is as aluminum zirconium tetrachlorohydrate glycine mixture (aluminum zirconiumtetrachlorohydrex gly).
In another useful embodiment, skin care compositions comprises organically-modified disiloxane surfactant and carrier for example silicone oil or organic oil.skin care compositions optionally also comprises tenderizer, triglyceride level for example, wax ester (wax ester), the alkyl or alkenyl ester of lipid acid, or polyol ester, be generally used for known component in skin care compositions with one or more, pigment for example, VITAMIN such as vitamin A, vitamins C and vitamin-E, opalizer or sun screening compound (sunblockcompound) be titanium dioxide for example, zinc oxide, BP-3, octyl methoxycinnamate, butyl methoxydibenzoylmethise, para-amino benzoic acid and octyldimethyl para-amino benzoic acid (octyl dimethyl-p-aminobenzoic acid).
In another useful embodiment, additive color make-up composition for example lipstick, cosmetics or mascara composition comprises organically-modified disiloxane surfactant, and tinting material, for example pigment, water-soluble dye or oil-soluble colourant.
In another useful embodiment, composition of the present invention is combined with fragrance material.These fragrance materials can be the flavor compounds of flavor compounds, encapsulate or discharge the compound of fragrance, and they can be pure compound or for encapsulate.Compatible especially with composition of the present invention is the organosilyl compound that contains that discharges fragrance, as United States Patent (USP) 6,046, and 156,6,054,547,6,075,111,6,077,923,6,083,901 and 6,153, disclosed in 578; All these patents are incorporated this paper into particularly by reference.
The purposes of composition of the present invention is not limited to the personal care articles composition, also can expect with the other products of compositions-treated of the present invention for example wax, lustering agent and textiles.
D. home care product
The home care product are used and are comprised laundry detergent and fabric softener, tableware detergent, timber and furniture polish, floor wax, bathtub and tile cleaner, detergent for water closet, hard surface cleaner, window sanitising agent, antifogging agent, drain cleaner agent, automatic dishwashing detergent and coverlet washing composition, carpet cleaner, pre-washing agent indicator (prewash spotter), rust remover and scale remover.
Experiment
Be used for organically-modified disiloxane surfactant composition of the present invention, and the hydride intermediate of comparative composition prepares according to described in following examples.
Preparation Example 1
1-(2-trimethyl silyl ethyl)-1,1,3,3-tetramethyl disiloxane (structural formula 1).Tetramethyl disiloxane (51.6g) and Wilkinson ' s catalyzer ((PPh pack in the 250mL round-bottomed flask 3) 3RhCl, 10 () ppm), stir under nitrogen, and be warming up to 60 ℃.With trimethyl-ethylene base silane (25.6g) feed hopper of packing into, dropwise add, the speed that adds make cooling lower maintenance temperature of reaction＜70 ℃ (～1g/min).To react 65 ℃ of maintenances 1 hour, then sampling is used for GC; Find remaining tetramethyl disiloxane and the M ' M of 94: 6 R: M RM RMaterial the lower fractionation of vacuum (approximately 30mm Hg) obtains obtains 51.6g M ' M RProduct, 99.1%GC purity.Find that by gasometric titration (gasiometric titration) the Si-H content of this product is 96cc H 2/ g.
Structural formula 1
Figure S2006800470369D00121
Preparation Example 2
1-(3,3-dimethylbutyl)-1,1,3,3-tetramethyl disiloxane (structural formula 2).The tetramethyl disiloxane (46.1g) of packing in the 250mL round-bottomed flask stirs under nitrogen.With the Karstedt ' s catalyzer (Pt in divinyl tetramethyl disiloxane (0), 10ppm) 3, solution in 3-dimethyl-1-butylene (19.3g) is packed in feed hopper, dropwise add, the speed that adds make cooling lower maintenance temperature of reaction＜40 ℃ (～0.5g/min).To react 50 ℃ of maintenances 1 hour, then sampling is used for GC; Find remaining tetramethyl disiloxane, M ' M RProduct and M RM RBy product (32: 53: 9).Use 25-cm dimension lattice Lou fractional columns (Vigreux column) at the material that the lower fractionation of vacuum (approximately 30mm Hg) obtains, obtain 25.0g M ' M RProduct,＞98.1%GC purity.Find that by gasometric titration the Si-H content of this product is 100cc H 2/ g.
Structural formula 2
Figure S2006800470369D00122
Preparation Example 3
1-(2-methyl-propyl)-1,1,3,3-tetramethyl disiloxane (structural formula 3).Tetramethyl disiloxane (10.0g), toluene (10.0g) and Wilkinson ' s catalyzer ((PPh pack in the 80mL Fischer-Porter bomb 3) 3RhCl, 40ppm), stir, and be warming up to 60 ℃.Should be connected with manifold by bottle, and with iso-butylene supercharging (25psig), and 60-70 ℃ of maintenance 8 hours.Emptying pressure, and the reaction sampling is used for the GC analysis; Find remaining tetramethyl disiloxane, M ' M RProduct and M RM RBy product (2: 95: 3).Under 40 ℃, vacuum (approximately 150mm Hg), the material that obtains is carried out stripping, to remove alkene and M ' M ', then use diatomite filtration, obtain 21.3g M ' M RProduct/toluene solution, 94%GC purity.Find that by gasometric titration the Si-H content of this product is 11cc H 2/ g.
Structural formula 3
Figure S2006800470369D00131
Preparation Example 4
1-propyl group-1,1,3,3-tetramethyl disiloxane (structural formula 4).Tetramethyl disiloxane (10.0g), toluene (10.0g) and Wilkinson ' s catalyzer ((PPh pack in the 80mL Fischer-Porter bomb 3) 3RhCl, 40ppm), stir and be warming up to 50 ℃.Should be connected with manifold by bottle, and with propylene supercharging (40psig), and 50 ℃ of maintenances 2 hours.Emptying pressure, and the reaction sampling is used for the GC analysis; Find M ' M RProduct and M RM RBy product (40: 60).The mixture that obtains directly uses, and does not carry out other purifying, output 14.1g.
Structural formula 4
Figure S2006800470369D00132
Preparation Example 5
The 1-tertiary butyl-1,1,3,3-tetramethyl disiloxane (structural formula 5).Water (95g) and the diisopropyl ether (50g) of packing in the 1L round-bottomed flask also stirs.The solution of tert-butyldimethylsilyl chloride compound (39.5g) in isopropyl ether (50g) is packed in feed hopper, dropwise join in water/IPE mixture, the speed that adds makes and keeps temperature of reaction between 30-35 ℃.Add complete after, temperature of reaction is risen to 40 ℃ and kept 1 hour.Then the solution of dimethylchlorosilane (24.8g) in isopropyl ether (50g) is packed in feed hopper, dropwise add this solution at 40-45 ℃.Add complete after, with reaction mixture reflux 1 hour, make it cooling.At water processing (aqueous workup) (water and moisture NaHCO 3Washing, and at MgSO 4Upper dry organic fraction) afterwards, come separated product by fractionation under vacuum, obtain 39.2g M (R) M ' product/isopropyl ether solution (it is 70%/20% that GC analyzes).Find that by gasometric titration the Si-H content of this product is 79cc H 2/ g.
Structural formula 5
Preparation Example 6
1-(dicyclopentadienyl)-1,1,3,3-tetramethyl disiloxane (1-(dicyclopentadienyl)-1,1,3,3-tetramethyldisiloxane) (structural formula 6).The tetramethyl disiloxane (45.3g) of packing in the 250mL RBF stirs and is warming up to 40 ℃ under nitrogen.With the Karstedt ' s catalyzer (Pt in divinyl tetramethyl disiloxane (0), 40ppm) the feed hopper of packing into of the solution in Dicyclopentadiene (DCPD) (29.8g), dropwise add, the speed that adds make cooling lower maintenance temperature of reaction＜60 ℃ (～0.5g/min).Add complete after, will react at 60 ℃ and keep 1 hour.In 100 ℃ of vacuum (～30mm Hg), reaction mixture is carried out stripping, obtain 41.1g M ' M RProduct,＞96%GC purity.Find that by gasometric titration the Si-H content of this product is 81cc H 2/ g.
Structural formula 6
Preparation Example 7
Hydride intermediate with the further modification embodiment of various allyl group polyoxygenated alkene 1-6, obtain organically-modified sily oxide composition of the present invention (from embodiment 1,2,3 and 5), and the disiloxane surfactant (from embodiment 4 and 6) of contrast.
The trisiloxanes alcoxylates of contrast in addition prepares by the ordinary method of the hydrosilation reaction that platinum mediates, and as the United States Patent (USP) 3,299 of Bailey, described in 112, this patent is incorporated the application into by reference.
Table 1 provides the description of composition of the present invention.These compositions are expressed by the following formula:
M *M″
M wherein *=R 1Si (CH 3) 2O 0.5M "=O 0.5Si (CH 3) 2Q
R wherein 1Be described in table 2;
Q＝-CH 2CH 2CH 2O(CH 2CH 2O) a(CH 2CH(CH 3)O) bR 2
The description of the disiloxane surfactant composition that table 1-is organically-modified
I.D. R 1 a b R 2
1 (CH 3) 2CHCH 2- 7.5 0 CH 3
2 CH 3CH 2CH 2- 7.5 0 CH 3
3 (CH 3) 2CHCH 2- 7.5 0 H
4 (CH 3) 2CHCH 2- 11 0 H
5 (CH 3) 3C- 7.5 0 CH 3
6 (CH 3) 2CHCH 2- 7.5 0 H
7 (CH 3) 2CHCH 2- 11 0 H
8 (CH 3) 2CHCH 2- 7.5 0 CH 3
9 (CH 3) 3SiCH 2CH 2- 7.5 0 H
10 (CH 3) 3SiCH 2CH 2- 7.5 0 CH 3
11 (CH 3) 3SiCH 2CH 2- 11 0 H
12 (CH 3) 3SiCH 2CH 2- 5 2.5 H
13 (CH 3) 3SiCH 2CH 2- 6.3 0 H
Table 2 provides the description based on the tensio-active agent of sily oxide of contrast.
The tensio-active agent based on siloxanes of table 2-contrast
Figure S2006800470369D00161
Table 3 provides the description based on the tensio-active agent of organo-siloxane polyethers (organosilicone polyether) of contrast, and it has following general formula:
Figure S2006800470369D00162
Z=-CH wherein 2CH 2CH 2O (CH 2CH 2O) a(CH 2CH (CH 3) O) bR 2
The composition of the organo-siloxane polyethet surfactant of table 3-contrast
Figure S2006800470369D00163
In addition, the sample OPE of contrast (the octyl phenol ethoxylate contains 10 polyoxyethylene units) right and wrong-organosilyl organic surface active agent.This product can be with Triton
Figure S2006800470369D00164
X-100 is from DowChemical Company, Midland, and MI obtains.
Embodiment 8
The present embodiment has confirmed that organically-modified sily oxide composition of the present invention reduces the capillary ability of water, demonstrates the effectiveness as tensio-active agent thus.Use the platinized platinum (platinumblade) of sandblast as sensor, use the Kruss tensiometer to measure surface tension.The solution of the various components of preparation in the deionized water solution of 0.005M NaCl, concentration is 0.1wt%, as the balance auxiliary agent.
Table 4 shows, the solution of these unique combination things makes surface tension significantly reduce with respect to the tensio-active agent of routine.
What composition of the present invention also provided the disiloxane surfactant (A, B, C, D and H) that is similar to TSA (E and F) and contrast sprawls character (spreading properties).In addition, with respect to organic silicon polyether (G) and the conventional organic surface active agent product OPE (table 4) of routine, organically-modified disiloxane surfactant of the present invention provides sprawling of improvement.
Following mensuration is sprawled: the relative humidity 50～70% (at 22～25 ℃), the drop of 10 μ L surfactant solns is applied to poly-acetate membrane (polyacetate film) (USI, " Crystal ClearWrite on Film ") on, and measure and sprawl diameter (mm) after 30 seconds.The volume of drop use aupette to apply solution, so that can reproduce.Prepare surfactant soln with the deionized water that was further purified with the millipore filtration system.
Show the 4-surface tension and sprawl character
Figure S2006800470369D00181
Embodiment 9
Use HPLC to the representational composition measuring stability to hydrolysis of the present invention.In the pH of pH4～pH12 scope, prepare the solution of various compositions with the concentration of 0.5wt%, and with HPLC monitor its through the time decomposition.
Analytical procedure:
Use listed experiment condition in table 5, by reverse-phase chromatography technical Analysis sample.
The solvent gradient of table 5-HPLC method
Figure S2006800470369D00191
Detector: ELSD/LTA (using the evaporat light scattering (Evaporative LightScattering with Low Temperature Adapter) of low temperature adapter)
Condition: 30 ℃, 1.95SLPM N 2
Post: Phenomenex LUNA Cl 8 end caps, 5 microns, 75 * 4.6mm
Flow velocity: 1.0mL/min
Inject volume (Inj.Volume): 10 microlitres
Sample: 0.050g/mL in methyl alcohol
Table 6-16 proves, under similar pH condition, with respect to tensio-active agent siloxanes B and the E based on siloxanes of the contrast of standard, composition of the present invention provides the resistance that hydrolysis is decomposed of improvement.
The siloxanes B of contrast and E＜pH5 and＞demonstrate hydrolysis fast during pH 7, and organically-modified disiloxane surfactant of the present invention has shown higher resistance to hydrolysis under identical condition.
Although contrast D demonstrates similar resistance to hydrolysis, it does not provide the character of sprawling of raising, described raising to sprawl character relevant to organically-modified disiloxane surfactant of the present invention.For example contrast the diameter of sprawling that D has 6mm (0.4%) only, and HPLC is presented at pH4 and has 82% product residue after 48h, and the diameter of sprawling of described organically-modified disiloxane surfactant product 10 is 34mm, and remains 75% product (table 4,11 and 16) in identical condition after next week.
The stability to hydrolysis based on the tensio-active agent of siloxanes that table 6-measures by HPLC
Figure S2006800470369D00201
The stability to hydrolysis based on the tensio-active agent of siloxanes that table 7-measures by HPLC
Figure S2006800470369D00202
The stability to hydrolysis based on the tensio-active agent of siloxanes that table 8-measures by HPLC
The stability to hydrolysis based on the tensio-active agent of siloxanes that table 9-measures by HPLC
Figure S2006800470369D00211
The stability to hydrolysis based on the tensio-active agent of siloxanes that table 10-measures by HPLC
Figure S2006800470369D00212
The stability to hydrolysis based on the tensio-active agent of siloxanes that table 11-measures by HPLC
Figure S2006800470369D00221
The stability to hydrolysis based on the tensio-active agent of siloxanes that table 12-measures by HPLC
Figure S2006800470369D00222
Annotate: stoste 2.5wt%
The stability to hydrolysis based on the tensio-active agent of siloxanes that table 13-measures by HPLC
The stability to hydrolysis based on the tensio-active agent of siloxanes that table 14-measures by HPLC
Figure S2006800470369D00231
The stability to hydrolysis based on the tensio-active agent of siloxanes that table 15-measures by HPLC
Figure S2006800470369D00232
The stability to hydrolysis based on the tensio-active agent of siloxanes that table 16-measures by HPLC
Figure S2006800470369D00233
Embodiment 10-12
From under acid and alkaline condition (≤pH 5 and 〉=pH 9) to experience the tensio-active agent based on siloxanes of routine of fast hydrolyzing different, trisiloxanes alcoxylates (contrast E and F) with respect to routine, and by the disiloxane surfactant of the trimethyl silyl end-blocking of the contrast of contrast B representative, organically-modified disiloxane surfactant of the present invention provides the resistance to hydrolysis of increase.Along with super spreadability through the time reduce, observe hydrolysate.Therefore, with working concentration and the pH of expectation, prepared the solution of organically-modified disiloxane surfactant of the present invention, and the tensio-active agent of contrast.Mensuration is sprawled with the relation of time with the explanation resistance to hydrolysis.
Embodiment 10
Table 17 is illustrative embodiment of organically-modified disiloxane surfactant, and wherein No. 10 products are sprawled tensio-active agent (product E) with respect to the trisiloxane ethoxylate of routine is super, have the resistance to hydrolysis of improvement at pH 3.As mentioned above, by the monitoring through the time the character of sprawling measure resistance to hydrolysis.Here, 0.4wt% solution is sprawled according to the step measurements of embodiment 8 in pH 3 preparations.
Table 17-sprawls character and the relation of time (h) at pH 3
Figure S2006800470369D00241
Embodiment 11
In another embodiment, the of the present invention organically-modified disiloxane surfactant proof of No. 6 and No. 11 product representatives has the resistance to hydrolysis (table 18) of improvement with respect to product F (the super spreading agent of trisiloxane ethoxylate (superspreader)).The solution of tensio-active agent (0.4wt%) is in pH 4 and pH 5 preparations, measure through the time sprawl character.Test condition is listed in embodiment 8.
Table 18-is in the relation of sprawling character and time of pH 4 and pH 5
Figure S2006800470369D00242
Embodiment 12
In another embodiment, the of the present invention organically-modified disiloxane surfactant of No. 5 product representatives demonstrates the resistance to hydrolysis of improvement with respect to the product E of contrast.Herein, surfactant soln (0.1wt%) is in pH 4, pH 5, pH 8, pH 9 and pH 10 preparations, and through the time the character of sprawling measure as described in example 8 above.
The organosilicon E of this contrast of table 19 explanation demonstrates than No. 5 products at pH 4, pH 5, pH 9 and pH 10 and sprawls faster the character loss.
Table 19-sprawls the relation of character and time
Figure S2006800470369D00251
Embodiment 13
Other composition on the impact of sprawling by organo-siloxane disiloxane surfactant of the present invention is mixed to measure based on organic cosurfactant with conventional.Cosurfactant is described in table 20.
Blend is prepared as physical mixture, and wherein organosilyl weight fraction is represented by α, and the expression cosurfactant has been supplied the surplus of blend ratio.For example when α=0, this shows that composition contains 0% organosilicon component, and 100% cosurfactant, and α=1.0 show that said composition contains 100% organosilicon, there is no (0%) cosurfactant.The mixture of these two kinds of components represents by weight fraction α, and wherein α changes in following scope: 0＜α＜1.0.For example, when α=0.25, this shows that surfactant mixture is comprised of 25% organosilicon and 75% cosurfactant.Then these blends are diluted in water be used to sprawling and estimate desirable concentration.
When the total surfactant of 0.1wt% or 0.2wt%, measure as described in example 8 above and sprawl.
Table 21 proof, the representative example of cosurfactant of the present invention provides the favourable result of sprawling, and unforeseeable collaborative increase is provided in some cases, and wherein mixture sprawls diameter over the diameter of sprawling of single component.
The description of the conventional cosurfactant of table 20-
ID describes
IDA-5 isodecyl alcohol ethoxylate (4-5EO)
IDA-6 isodecyl alcohol ethoxylate (5-6EO)
TMN-6 Exxal 12 ethoxylate (6EO)
Oxo-TDA-5 oxo-tridecyl alcohol ethoxylate (5EO)
Oxo-TDA-6 oxo-tridecyl alcohol ethoxylate (6EO)
APG C 8-10Alkyl poly glucoside
Table 21-cosurfactant is sprawled the impact of character on blend
Figure S2006800470369D00271
The a=02wt% total surfactant
The b=0.1wt% total surfactant
Previous embodiment is only to explanation of the present invention, is used for illustrating only some features of the present invention.The claimed wide as far as possible the present invention who has expected of claims intention, the embodiment that described the application's embodiment explanation is selected from various all possible embodiment.Therefore, the applicant is intended that, and claims are not limited by selected embodiment be used to feature of the present invention is described.In claim, wording used " comprises " and its phraseological variant also means and comprise the wording of various degree in logic, such as, but not limited to, " basically by ... form " and " by ... form ".In the time of necessary, provide scope; Those scopes comprise subranges all between them.This scope can be regarded a Ma Kushi group or a plurality of Ma Kushi group that is comprised of different paired digital boundaries as, described Ma Kushi group or a plurality of Ma Kushi group are limited by its lower limit and the upper limit fully, increase in number from lower limit to the upper limit in normal mode.Expectation those skilled in the art should be able to expect the variation of these scopes, if do not offer to the public, these variations also should be interpreted as much as possible and be overwritten by the appended claims.Also expectation is, scientific-technical progress will make at present the former thereby unexpected possibility that becomes of replacing of equal value due to the inaccuracy of language, and these variants also should be interpreted as much as possible and be overwritten by the appended claims.The full content of all United States Patent (USP)s (and patent application) of the application institute reference is all incorporated the application into by reference herein, just looks like that they put down in writing the same in this application in full.

Claims (39)

1. silicon composition, it comprises the organosilicon with following formula:
MM′
Wherein
M＝R 1R 2R 3SiO 1/2；
M′＝R 4R 5R 6SiO 1/2；
R wherein 1Be selected from monovalence alkyl and the R of the branching with 3～6 carbon atoms 7, R wherein 7Be selected from R 8R 9R 10SiR 12(R 4R 5R 6) SiR 12(Si (R 2R 3) SiO 1/2)
R wherein 8, R 9And R 10Be selected from independently of one another the monovalence alkyl with 1～6 carbon atom, R 12The bivalent hydrocarbon radical with 1～3 carbon atom,
R 2And R 3Be selected from independently of one another monovalence alkyl or R with 1～6 carbon atom 7, R wherein 4The alkyl polyoxygenated alkene with following general formula:
R 13(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14
R wherein 13To have the divalence straight chain of following structure or the alkyl of branching:
-CH 2-CH(R 15)(R 16) dO-
R wherein 15H or methyl; R 16Be the divalent alkyl with 1～6 carbon atom, wherein subscript d can be 0 or 1;
R 14Be selected from H or have the monovalence alkyl of 1～6 carbon atom, wherein subscript a, b and c are 0 or positive number, and satisfy following relation:
2＜a+b+c＜20, and a＞2,
And R 5And R 6Be selected from independently of one another the monovalence alkyl with 1～6 carbon atom.
2. the composition of claim 1, wherein R 2And R 3Be selected from independently of one another the monovalence alkyl of the branching with 3～6 carbon atoms.
3. claim 1 or 2 composition, wherein R 1It is sec.-propyl.
4. claim 1 or 2 composition, wherein R 1It is isobutyl-.
5. claim 1 or 2 composition, wherein R 1It is the tertiary butyl.
6. claim 1 or 2 composition, wherein R 1R 7, R wherein 7Have following formula:
R 8R 9R 10SiR 12, R wherein 8, R 9And R 10The methyl of respectively doing for oneself, R 12It is the bivalent hydrocarbon radical with 2 carbon atoms.
7. claim 1 or 2 composition, wherein R 15Hydrogen.
8. claim 1 or 2 composition, wherein R 2It is methyl.
9. the composition of claim 3, wherein R 15Hydrogen.
10. the composition of claim 3, wherein R 2It is methyl.
11. the composition of claim 4, wherein R 15Hydrogen.
12. the composition of claim 4, wherein R 2It is methyl.
13. the composition of claim 5, wherein R 15Hydrogen.
14. the composition of claim 5, wherein R 2It is methyl.
15. the composition of claim 6, wherein R 15Hydrogen.
16. the composition of claim 6, wherein R 2It is methyl.
17. the silicon composition of claim 1 or 2, wherein said silicon composition has the resistance to hydrolysis of improvement.
18. the composition of claim 17, wherein R 1It is sec.-propyl.
19. the composition of claim 17, wherein R 1It is isobutyl-.
20. the composition of claim 17, wherein R 1It is the tertiary butyl.
21. the composition of claim 17, wherein R 1R 7, R wherein 7Have following formula:
R 8R 9R 10SiR 12, R wherein 8, R 9And R 10The methyl of respectively doing for oneself, R 12It is the bivalent hydrocarbon radical with 2 carbon atoms.
22. the composition of claim 17, wherein R 15Hydrogen.
23. the composition of claim 17, wherein R 2It is methyl.
24. the composition of claim 18, wherein R 15Hydrogen.
25. the composition of claim 18, wherein R 2It is methyl.
26. the composition of claim 19, wherein R 15Hydrogen.
27. the composition of claim 19, wherein R 2It is methyl.
28. the composition of claim 20, wherein R 15Hydrogen.
29. the composition of claim 20, wherein R 2It is methyl.
30. the composition of claim 21, wherein R 15Hydrogen.
31. the composition of claim 21, wherein R 2It is methyl.
32. water miscible liquid, wherein discontinuous phase comprises water, and external phase comprises the composition of claim 1 or 2.
33. water miscible liquid, wherein discontinuous phase comprises water, and external phase comprises the composition of claim 17.
34. water miscible liquid, wherein external phase comprises water, and discontinuous phase comprises the composition of claim 1 or 2.
35. water miscible liquid, wherein external phase comprises water, and discontinuous phase comprises the composition of claim 17.
36. nonaqueous emulsion, wherein discontinuous phase comprises non-water hydroxylic solvent, and external phase comprises the composition of claim 1 or 2.
37. nonaqueous emulsion, wherein discontinuous phase comprises non-water hydroxylic solvent, and external phase comprises the composition of claim 17.
38. nonaqueous emulsion, wherein external phase comprises non-water hydroxylic solvent, and discontinuous phase comprises the composition of claim 1 or 2.
39. nonaqueous emulsion, wherein external phase comprises non-water hydroxylic solvent, and discontinuous phase comprises the composition of claim 17.
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CN1358110A (en) * 1999-06-25 2002-07-10 克鲁普顿公司 Hydrolyzable silane emulsions and method for preparing the same

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