CN101341156B - Hydrolysis resistant organomodified disiloxane surfactants - Google Patents

Hydrolysis resistant organomodified disiloxane surfactants Download PDF

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CN101341156B
CN101341156B CN2006800470265A CN200680047026A CN101341156B CN 101341156 B CN101341156 B CN 101341156B CN 2006800470265 A CN2006800470265 A CN 2006800470265A CN 200680047026 A CN200680047026 A CN 200680047026A CN 101341156 B CN101341156 B CN 101341156B
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compsn
phase comprises
alkyl
water
carbon atom
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CN101341156A (en
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马克·D·莱瑟曼
乔治·A·波利塞罗
休尔什·K·拉贾拉曼
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General Electric Co
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Priority claimed from US11/427,913 external-priority patent/US7652072B2/en
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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)
  • Wood Science & Technology (AREA)
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Abstract

Compositions comprising an asymmetric disiloxane surfactant composition comprise an organosilicon composition comprising an organosilicon having the formula MM', where M or M' comprises an alkylpolyalkyleneoxide bearing substituent selected from the group consisting of: R<13>(C2H4O)a(C3H6O)b(C4H8O)cR<14> and R<12>SiR<5>R<6>(R<13>(C2H4O)a(C3H6O)b(C4H8O)cR<14>) exhibit resistance to hydrolysis over a wide pH range.

Description

The organically-modified disiloxane surfactant of anti-hydrolysis
The cross reference of asking in relevant
The application is the part continuation application of the U. S. application sequence number 11/300,100 of submission on December 13rd, 2005, and this U. S. application has required 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 compsn, it demonstrates resistance to hydrolysis in wide pH scope.More specifically, the present invention relates between about pH 3～about pH 12, have this anti-hydrolysis disiloxane surfactant of resistance to hydrolysis.
Background technology
The local paint of liquid compsn is had on the surface of life and inanimate objects to produce the change of expectation, comprise control wetting, sprawl, foam, process such as cleaning.When in the aqueous solution, using when improving active ingredient, have been found that trisiloxanes type compound can be used to make it possible to control these processes and obtains desired effects to the transitivity on the surface that is processed.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 decomposes hydrolytically unstable fast.
Summary of the invention
The present invention provides silicon composition, and 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 the monovalence alkyl and the R of branching with 3～6 carbon atoms 7, and R 7Be selected from R 8R 9R 10SiR 12(R 4R 5R 6) SiR 12
R wherein 8, R 9And R 10Be selected from the monovalence alkyl with 1～6 carbon atom and monovalence aryl or alkane aryl and R independently of one another with 6～13 carbon atoms 12Be bivalent hydrocarbon radical with 1～3 carbon atom,
R 2And R 3Be selected from monovalence alkyl or R independently of one another with 1～6 carbon atom 1, R wherein 4Be to have substituent alkyl polyoxygenated alkene (alkylpolyalkyleneoxide bearing substituent), it is selected from:
R 13(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14With
R 12SiR 5R 6(R 13(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14)
R wherein 13Be to have the divalence straight chain of following structure or the alkyl of branching:
-CH 2-CH(R 15)(R 16) dO-
R wherein 15Be H 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 the monovalence alkyl and the ethanoyl of 1～6 carbon atom, wherein subscript a, b and c are 0 or positive number, and relation below satisfying:
2≤a+b+c≤20, a>=2 wherein,
And R 5And R 6Be selected from monovalence alkyl or R independently of one another with 1～6 carbon atom 4
Embodiment
Among the application under the used stoichiometry target round values be meant molecule thing class, the target non integer value is meant the mixture of the molecule thing class on the molar mass average basis, on the number averaged basis or the x basis under the stoichiometry.
The present invention provides sily oxide compound or its compsn of useful as surfactants, and 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
R wherein 8, R 9And R 10Be selected from monovalence alkyl and monovalence aryl or alkane aryl with 6～13 carbon atoms, R independently of one another with 1～6 carbon atom 12Be bivalent hydrocarbon radical with 1～3 carbon atom,
R 2And R 3Be selected from monovalence alkyl or R independently of one another with 1～6 carbon atom 1, R wherein 4For having substituent alkyl polyoxygenated alkene, it is selected from:
R 13(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14With
R 12SiR 5R 6(R 13(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14)
R wherein 13Be to have the divalence straight chain of following structure or the alkyl of branching:
-CH 2-CH(R 15)(R 16) dO-
R wherein 15Be H 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 the 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 relation below satisfying:
2≤a+b+c≤20, a>=2 wherein,
With, R 5And R 6Be selected from monovalence alkyl or R independently of one another with 1～6 carbon atom 4When subscript a satisfied condition 2≤a≤4, the listed cosurfactant of hereinafter was used in suggestion, to reach the benefit of compsn of the present invention.
A kind of method for preparing compsn 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 hydrogenate precursor of M ' structural unit in the compsn of the present invention; Wherein its definition and relation limit hereinafter; And consistent with the above qualification of making, said olefin-modified polyoxygenated alkene is the allyloxy polyoxyethylene glycol for example, or first is for allyloxy polyoxygenated alkene; These compounds are referred among the application as an example, are not to limit other possible olefin-modified oxyalkylene component.The used term " olefin-modified polyoxygenated alkene " of the application is defined as the molecule with the one or more oxyalkylene groups that contain one or more terminal carbon-carbon double bonds or side carbon-carbon double bond.Polyethers is olefin-modified polyoxygenated alkene (hereinafter being called " polyethers "), is represented by following general formula:
CH 2＝CH(R 15)(R 16) dO(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14
Wherein
R 15Be H 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 made up of blended oxyalkylene group (oxyalkyleneoxide group) (being ethylene oxide, propylene oxide and oxybutylene), 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(CH 2CH(CH 2CH 3)O) 2H
Prepare polyether-modified siloxanes with the mode of routine through using hydrosilylation reactions olefin-modified (being vinyl, allyl group or methylallyl) polyoxygenated alkene to be grafted on hydrogenate (SiH) midbody of sily oxide of the present invention.
The noble metal catalyst that is suitable for preparing polyethers-substituted siloxanes also is known in the art, comprises the mixture of rhodium, ruthenium, palladium, osmium, iridium and/or platinum.The platinum catalyst that is used for this SiH alkene addition reaction of many types is known, and this platinum catalyst can be used for producing compsn of the present invention.Platinic compound can be selected from has formula (PtCl 2Alkene) and H (PtCl 3Alkene) those like USP 3,159, described in 601, are introduced into the application through 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, like USP 3,220, described in 972, through with reference to being introduced into the application.Useful in the present invention another kind of platiniferous substance description is in USP 3,715,334; In 3,775,452 and 3,814,730 (Karstedt).The background about prior art in addition can find in following 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 confirm the significant quantity of platinum catalyst.Usually, significant quantity is about 0.1～50ppm of all organically-modified sily oxide compsn.
Compsn 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 through multiple test; But the resistance to hydrolysis of the raising of using among the application is meant after the pH that is exposed to solution is lower than 6 aqueous acidic condition 24 hours or the pH that is being exposed to solution greater than after 7.5 the aqueous alkaline condition 24 hours, 50mol% or above resistance to hydrolysis remaining unchanged of compsn of the present invention or do not react.Under acidic conditions, compsn of the present invention is 5 or following maintenance when surpassing 48 hours time at pH, demonstrates remaining rate (survival) and is the 50mol% of starting point concentration or bigger; Particularly, compsn of the present invention is 5 or following maintenance when surpassing the time in 2 weeks at pH, and demonstrating resistates is 50mol% or bigger; More specifically, compsn of the present invention is 5 or following maintenance when surpassing 1 month time at pH, and demonstrating resistates is 50mol% or bigger; The most particularly, compsn of the present invention is 5 or following maintenance when surpassing 6 months time at pH, and demonstrating resistates is 50mol% or bigger.Under alkaline condition, compsn of the present invention is 8 or above maintenance when surpassing the time in 2 weeks at pH, and demonstrating resistates is 50mol% or bigger; Particularly, compsn of the present invention is 8 or above maintenance when surpassing the time in 4 weeks at pH, and demonstrating resistates is 50mol% or bigger; More specifically, compsn of the present invention is 8 or above maintenance when surpassing 6 months time at pH, and demonstrating resistates is 50mol% or bigger; The most particularly, compsn of the present invention is 8 or above maintenance when surpassing the time in 1 year at pH, and demonstrating resistates is 50mol% or bigger.
The purposes of compsn 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 on the blade face, to provide wetting and to sprawl.Auxiliary agent usually is a tensio-active agent, and it can have various functions, for example increases spray droplet at the confining force that is difficult on the wetting blade face, improves and sprawls to improve the fraction of coverage of spraying, perhaps provides weedicide to get into the perviousness of plant epidermis.These auxiliary agents perhaps provide with jar side additive (tank-side additive), perhaps as the component in the 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; Organically-modified disiloxane surfactant wherein of the present invention exists with the form as enriched material in the bucket mix formulation or dilution, and the concentration that the amount of existence is enough to when final the use provides 0.005%～2%.Randomly, insecticides can comprise vehicle, cosurfactant, solvent, foam control agent, deposition aid, stop-off gent (driftretardants), biotechnological formulation, micro-nutrients, fertilizer etc.The term sterilant is meant any compound that is used to eliminate 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 suppressor factor, mitotic division disruption agent (mitotic disrupter), lipid biosynthesis inhibitor (lipid biosynthesis inhibitors), cell walls suppressor factor and membranolysis agent (cell membranedisrupter).The amount of the sterilant that in compsn of the present invention, uses changes along with the type of used sterilant.The pesticide compound that can use with compsn of the present invention instance 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, substituted urea, uridylic, bentazone, different phenmedipham, methazole, phenmedipham, reach that grass ends, amerol, clomazone, fluorine pyridine ketone (fluridone), monometflurazone, dinitraniline, isopropaline,2,6-dinitroN,N-dipropylcumidine, oryzalin, kill that grass is logical, prodiamine, trifluralin, Glyphosate 62 IPA Salt, sulfonylurea, imidazolone, clethodim, chloroformate grass 、 oxazole diclofop-methyl, efficient fluazifop, haloxyfopPmethyl, quizalofopethyl (quizalofop), sethoxydim, Niagara 5006, isoxaben and dipyridyl (bipyridylium) compound.
Spendable fungicide composition can include, but not limited to aldimorph, tridemorph, dodemorfe, HSDB 6915 among the present invention; Fluzilazol, penta ring azoles, cyproconazole, oxole bacterium, furconazole, Wocosin 50TK, tebuconazole etc.; IMAZALIL, mildethane, F-1991, derosal, m-tetrachlorophthalodinitrile (chlorothialonil), dicloran, oxime bacterium ester (trifloxystrobin), fluoxastrobin (fluoxystrobin), ether bacterium amine (dimoxystrobin), nitrile ICIA 5504 (azoxystrobin), sterilization amine (furcaranil), Prochloraz, flusulfamide, Famoxate (famoxadone), Vancide 89, MANEB 20WP, zinc manganese ethylenebisdithiocarbamate, oppose bacterium, dodine more, and metaxanin.
Can comprise with sterilant, larvacide, miticide and ovicide (ovacide) compound that compsn of the present invention uses; But be not limited to, Bacillus thuringiensis, Tracer Naturalyte 105 (spinosad), avermectin, doramectin (doramectin), lepimectin, pyrethrin, SevinCarbaryl, PP-062 (pirimicarb), aldicarb, methomyl, U-36059, boric acid, chlordimeform, Rimon (novaluron), two three WL 115110s (bistrifluron), desinsection are 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, four mite piperazines, cyhalothrin, WL 43479, bifenthrin, PP-383 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, Marinco H, 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 accomplished this function.
The agricultural vehicle:
Damping fluid known in the art, sanitas and other standard excipients also can be included in the said composition.
Solvent also can be included in the compsn of the present invention.These solvents are liquid in room temperature.Instance comprises lower alkyl esters, lipid acid, ketone, glycol, polyoxyethylene glycol, glycol, paraffin of water, alcohol, aromatic solvent, oils (being MO, vegetables oil, silicone oil etc.), vegetables oil etc.Concrete solvent can be like USP 5,674,2 described in 832; 2,4-trimethylammonium-1,3-pentane diol and oxyalkylated (especially ethoxylation) variant thereof; Or N-methyl-pyrrolidone (n-methyl-pyrrilidone), said USP is incorporated this paper into through reference.
Cosurfactant:
The useful cosurfactant of the application comprises nonionogenic tenside, cats product, anionic surface is alive gives birth to agent, amphoterics, zwitterionics, polymeric tensio-active agent, 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 ultra short chain hydrophobic grouping of sprawling (superspreading), and like USP 5,558, described in 806, said USP is through with reference to incorporating the application into.
Useful tensio-active agent comprises the alcoxylates that contains segmented copolymer, ethoxylate especially, and said segmented copolymer comprises the multipolymer of oxyethane, propylene oxide, butylene oxide ring and composition thereof; Alkylaryl alcoxylates, especially ethoxylate or propoxylated glycerine, and their verivate comprise alkyl phenol ethoxylate; Aryl alkoxy aryl thing, especially ethoxylate or propoxylated glycerine, and their verivate; Amine alcoxylates, especially amine ethoxylate; Fatty acid alkoxylates; Fatty alcohol alkoxy compound; AS; Korenyl 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 instance 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, 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 surfactants 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 MO, the seed oil that methylates (being methyl soybean fat acid metal salt (methylsoyate) or methyl Canola oil metal-salt (methylcanolate)), vegetables oil (for example VT 18 and Canola oil), water conditioner be Choice
Figure S2006800470265D00081
(Loveland Industries for example; Greeley; CO) and Quest (Helena Chemical; Collierville; TN), the clay of modification Surround
Figure S2006800470265D00082
(Englehard Corp. for example;), foam control agent, tensio-active agent, wetting agent, dispersion agent, emulsifying agent, deposition aid, antidrip component (antidriftcomponent), and water.
Suitable agricultural chemical composition gets through combination system with mode known in the art, for example, and through 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 " is meant when being about to use at least a agrochemicals is added to the spraying medium, for example in water or the oil.Term " canned " is meant preparation or the enriched material that contains at least a agrochemicals component.Then, when being about to use, can " canned " preparation be diluted to working concentration, 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 solidified or dried film.Coating formulation can be used as solvent-laden coating, aqueous coating and powder coating and exists.
Coating composition can be used as: trade sales 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; Based on the personal care articles compsn of per 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 compsn of 85pbw～99pbw.
Organically-modified disiloxane surfactant compsn of the present invention can for example reveal with the form of frost and use with the personal care articles emulsion.As known, emulsion comprises at least two immiscible phases, one of them is a successive, another is discontinuous.Other emulsion can be the liquid or solid of the viscosity with variation.In addition, it is microemulsion that the granularity of emulsion can make emulsion, and when enough hour, microemulsion can be transparent.Also possibly 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 USP 6,060,546 with USP 6,271,295 in, their content is through with reference to introducing the application particularly.
The used term " non-water hydroxyl organic compound " of the application is meant that in room temperature for example about 25 ℃ is the organic cpds of the hydroxyl of liquid during with about 1 normal atmosphere, and exemplary have alcohol, divalent alcohol, polyvalent alcohol and poly-dihydric alcohol and composition thereof.It is the organic cpds of the hydroxyl of liquid during with about 1 normal atmosphere that the organic hydroxylic solvent of non-water is selected from room temperature for example about 25 ℃, and it comprises alcohol, divalent alcohol, polyvalent alcohol and poly-dihydric alcohol and composition thereof.Preferably, non-water hydroxyl organic solvent is selected from terepthaloyl moietie, ethanol, propyl alcohol, Virahol, Ucar 35, DPG, tripropylene glycol, butyleneglycol, different-butyleneglycol, methylpropane glycol, glycerine, Sorbitol Powder, polyoxyethylene glycol, W 166 monoalky lether, polyoxyalkylene multipolymer and composition thereof.
In case obtain the form of expectation; No matter be 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 all usually be have improvement deposit properties and good touch characteristic frost or reveal.Can it 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 use and include, but not limited to reodorant by the personal care articles of its deutero-silicon composition of the present invention; 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, hairdressing spray, hair dye, hair dyeing product, bleached hair agent, hair-waving product, straighter, and the product of having a manicure is such as nail varnish, enamel remover, nail frost and dew, stratum corneum tenderizer, and 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 added other personal care formulations of organosilicon component usually, and the drug delivery system of topical application that is used for being applied to the medicinal compositions of skin.
In preferred embodiment, personal care articles compsn 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, tinting material, spices, biocide, sanitas, inhibitor, biocide, anti-mycotic agent, antiperspirant, keratoderma stripper (exfoliant), hormone, enzyme, medicinal compound, VITAMINs, 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 pyrogenic silica or hydrated SiO 2, the particulate filler for example wilkinite and the organically-modified clay of talcum, kaolin, starch, modified starch, mica, nylon, clay for example for example of pearl white and titanium dioxide-coated of pearly pigment.
Suitable personal care articles compsn for example, makes through one or more said components are mixed with described organically-modified disiloxane surfactant through getting with mode combination system known in the art.Suitable personal care articles compsn can be the form of monophasic form or emulsion; Said 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 among the 1993 Monograph onantiperspirant drug products for over-the-counter human use; For example aluminum halide, hydroxyhalides (aluminum hydroxyhalide) are like Wickenol CPS 325 (aluminum chlorohydrate); And with the 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 glycocoll mixture (aluminum zirconiumglycine complexe) is like aluminum zirconium tetrachlorohydrate glycocoll mixture (aluminum zirconiumtetrachlorohydrex gly).
In another useful embodiment, skin care compsns comprises organically-modified disiloxane surfactant and carrier for example silicone oil or organic oil.Skin care compsns can randomly also comprise tenderizer; Triglyceride level for example; Wax ester (wax ester), the alkyl or alkenyl ester of lipid acid, or polyol ester; Be generally used for the known component in the skin care compsns with one or more; Pigment for example, VITAMINs such as vitamin A, vitamins C and vitamin E, opalizer or sun screening compound (sunblockcompound) be titanium oxide, zinc oxide, 2-hydroxyl-4-methoxyl group-UVNUL MS-40, octyl methoxycinnamate, butyl methoxydibenzoylmethise, para-amino benzoic acid and octyldimethyl para-amino benzoic acid (octyl dimethyl-p-aminobenzoic acid) for example.
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, compsn of the present invention is used in combination 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 compsn of the present invention is the organosilyl compound that contains that discharges fragrance, like 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 through reference.
The purposes of compsn of the present invention is not limited to the personal care articles compsn, also can expect with the other products of compositions-treated of the present invention for example wax, lustering agent and textiles.
D. home care article
The home care article are used and are comprised laundry detergent and fabric softener, dishwashing detergent liquid, 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 compsn of the present invention, and the hydrogenate midbody of comparative composition prepares according to described in following examples.
Preparation embodiment 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 100ppm), stirs under nitrogen, and is warming up to 60 ℃.With trimethyl-ethylene base silane (25.6g) feed hopper of packing into, dropwise add, the speed of adding make cooling down maintenance temperature of reaction＜70 ℃ (～1g/min).To be reflected at 65 ℃ and keep 1 hour, sampling is used for GC then; Find remaining tetramethyl disiloxane and M ' M of 94: 6 R: M RM RThe material that fractionation obtains under vacuum (about 30mm Hg) obtains 51.6g M ' M RProduct, 99.1%GC purity.Find that through gasometric titration (gasiometric titration) the Si-H content of this product is 96cc H 2/ g.
Structural formula 1
Figure S2006800470265D00121
Preparation embodiment 2
1-(3, the 3-dimethylbutyl)-1,1,3,3-tetramethyl disiloxane (structural formula 2).The tetramethyl disiloxane (46.1g) of in the 250mL round-bottomed flask, packing into 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 the feed hopper, dropwise add, the speed of adding make cooling keep down temperature of reaction＜40 ℃ (～0.5g/min).To be reflected at 50 ℃ and keep 1 hour, sampling is used for GC then; Find remaining tetramethyl disiloxane, M ' M RProduct and M RM RBy product (32: 53: 9).Use 25-cm dimension lattice Lou separation columns (Vigreux column) material that fractionation obtains under vacuum (about 30mm Hg), obtain 25.0gM ' M RProduct,＞98.1%GC purity.The Si-H content of finding this product through gasometric titration is 100cc H 2/ g.
Structural formula 2
Figure S2006800470265D00122
Preparation embodiment 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 80mL Fischer-Porter bomb 3) 3RhCl 40ppm), stirs, and is 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 reaction sampling is used for GC analyzes; Find remaining tetramethyl disiloxane, M ' M RProduct and M RM RBy product (2: 95: 3).Under 40 ℃, vacuum (about 150mm Hg), the material that obtains is carried out stripping,, use diatomite filtration then, obtain 21.3g M ' M to remove alkene and M ' M ' RProduct/toluene solution, 94%GC purity.The Si-H content of finding this product through gasometric titration is 11cc H 2/ g.
Structural formula 3
Figure S2006800470265D00131
Preparation embodiment 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 80mL Fischer-Porter bomb 3) 3RhCl 40ppm), stirs and is 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 reaction sampling is used for GC analyzes; 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 S2006800470265D00132
Preparation embodiment 5
The 1-tertiary butyl-1,1,3,3-tetramethyl disiloxane (structural formula 5).In the 1L round-bottomed flask, pack into water (95g) and DIPE (50g) and stir.The solution of tert-butyldimethylsilyl chloride thing (39.5g) in isopropyl ether (50g) is packed in the feed hopper, dropwise join in water/IPE mixture, the speed of adding makes and keeps temperature of reaction between 30-35 ℃.After add accomplishing, 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 the feed hopper, dropwise add this solution at 40-45 ℃.After add accomplishing,, make its cooling with reaction mixture reflux 1 hour.At water processing (aqueous workup) (water and moisture NaHCO 3Washing, and at MgSO 4Go up dry organic fraction) afterwards, come separated product through fractionation under vacuum, obtain 39.2g M (R) M ' product/isopropyl ether solution (it is 70%/20% that GC analyzes).The Si-H content of finding this product through gasometric titration is 79cc H 2/ g.
Structural formula 5
Figure S2006800470265D00141
Preparation embodiment 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 in 250mL RBF, packing into stirs and is warming up to 40 ℃ under nitrogen.With Karstedt ' s catalyzer (Pt in the divinyl tetramethyl disiloxane (0), the 40ppm) feed hopper of packing into of the solution in Dicyclopentadiene (DCPD) (29.8g) dropwise adds, the speed of adding make cooling keep down temperature of reaction＜60 ℃ (～0.5g/min).Add after the completion, will be reflected 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.The Si-H content of finding this product through gasometric titration is 81cc H 2/ g.
Structural formula 6
Figure S2006800470265D00142
Preparation embodiment 7
Hydrogenate midbody with the further modification embodiment of various allyl group polyoxygenated alkene 1-6; Obtain organically-modified sily oxide compsn of the present invention (from embodiment 1,2,3 and 5), and correlated disiloxane surfactant (from embodiment 4 and 6).
Correlated trisiloxanes alcoxylates in addition is through the ordinary method preparation of the hydrosilation reaction of platinum mediation, and like the USP 3,299 of Bailey, described in 112, this patent is incorporated the application into through reference.
Table 1 provides the description of compsn of the present invention.These compsns are represented by following general formula:
M *M″
M wherein *=R 1Si (CH 3) 2O 0.5M "=O 0.5Si (CH 3) 2Q
R wherein 1Be described in the table 2;
Q＝-CH 2CH 2CH 2O(CH 2CH 2O) a(CH 2CH(CH 3)O) bR 2
The description of the disiloxane surfactant compsn 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 of correlated tensio-active agent based on sily oxide.
The correlated tensio-active agent of table 2-based on siloxanes
Figure S2006800470265D00161
Table 3 provides the description of correlated tensio-active agent based on organo-siloxane polyethers (organosilicone polyether), and it has following general formula:
Figure S2006800470265D00162
Z=-CH wherein 2CH 2CH 2O (CH 2CH 2O) a(CH 2CH (CH 3) O) bR 2
The composition of the correlated organo-siloxane polyethet surfactant of table 3-
In addition, correlated sample OPE (the octyl phenol ethoxylate contains 10 polyoxyethylene units) right and wrong-organosilyl organic surface active agent.This product can be with Triton
Figure S2006800470265D00164
X-100 from DowChemical Company; Midland, MI obtains.
Embodiment 8
Present embodiment has confirmed that organically-modified sily oxide compsn of the present invention reduces the capillary ability of water, demonstrates the effectiveness as tensio-active agent thus.The platinized platinum (platinumblade) that uses sandblast uses the Kruss tensiometer to measure surface tension as transmitter.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 that the solution of these unique combination things makes surface tension significantly reduce with respect to the tensio-active agent of routine.
Compsn of the present invention also provide be similar to TSA (E and F) and correlated disiloxane surfactant (A, B, C, D and H) sprawl character (spreading properties).In addition, with respect to the 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 sprawled: the relative humidity 50～70% (at 22～25 ℃); The drop of 10 μ L surfactant solns is applied to gathers 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.Use the deionized water that was further purified with the millipore filtration system to prepare surfactant soln.
Show the 4-surface tension and sprawl character
Embodiment 9
Use HPLC to the representational composition measuring stability to hydrolysis of the present invention.In the pH of pH4～pH12 scope, with the solution of the various compsns of prepared at concentrations of 0.5wt%, and with the HPLC monitoring its through the time decomposition.
Analytical procedure:
Use listed experiment condition in the table 5, through reverse-phase chromatography technical Analysis sample.
The solvent gradient of table 5-HPLC method
Figure S2006800470265D00191
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 C18 end cap, 5 microns, 75 * 4.6mm
Flow velocity: 1.0mL/min
Inject volume (Inj.Volume): 10 microlitres
Sample: 0.050g/mL in the methyl alcohol
Table 6-16 proves that under similar pH condition, with respect to correlated the tensio-active agent siloxanes B and the E based on siloxanes of standard, compsn of the present invention provides the resistance to the hydrolysis decomposition of improvement.
Correlated siloxanes B and E demonstrate hydrolysis fast at≤pH5 during with＞pH 7, and organically-modified disiloxane surfactant of the present invention has shown higher resistance to hydrolysis under identical condition.
Though contrast D demonstrates similar resistance to hydrolysis, it does not provide the character of sprawling of raising, said raising to sprawl character relevant with 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 after 48h, has 82% product residue; And the diameter of sprawling of said organically-modified disiloxane surfactant product 10 is 34mm, and remains 75% product (table 4,11 and 16) after next week in identical condition.
The stability to hydrolysis that table 6-measures through HPLC based on the tensio-active agent of siloxanes
Figure S2006800470265D00201
The stability to hydrolysis that table 7-measures through HPLC based on the tensio-active agent of siloxanes
The stability to hydrolysis that table 8-measures through HPLC based on the tensio-active agent of siloxanes
Figure S2006800470265D00203
The stability to hydrolysis that table 9-measures through HPLC based on the tensio-active agent of siloxanes
The stability to hydrolysis that table 10-measures through HPLC based on the tensio-active agent of siloxanes
Figure S2006800470265D00212
The stability to hydrolysis that table 11-measures through HPLC based on the tensio-active agent of siloxanes
Figure S2006800470265D00221
The stability to hydrolysis that table 12-measures through HPLC based on the tensio-active agent of siloxanes
Figure S2006800470265D00222
Annotate: stoste 2.5wt%
The stability to hydrolysis that table 13-measures through HPLC based on the tensio-active agent of siloxanes
Figure S2006800470265D00223
The stability to hydrolysis that table 14-measures through HPLC based on the tensio-active agent of siloxanes
Figure S2006800470265D00231
The stability to hydrolysis that table 15-measures through HPLC based on the tensio-active agent of siloxanes
The stability to hydrolysis that table 16-measures through HPLC based on the tensio-active agent of siloxanes
Figure S2006800470265D00233
Embodiment 10-12
With under acid and alkaline condition (≤pH 5 with>=pH 9) to experience the tensio-active agent based on siloxanes of routine of quick hydrolysis different; Trisiloxanes alcoxylates (contrast E and F) with respect to routine; And by the disiloxane surfactant of the correlated trimethylsilyl-terminated of contrast B representative, organically-modified disiloxane surfactant of the present invention provides the resistance to hydrolysis of increase.Along with ultra spreadability through the time reduce, observe hydrolysate.Therefore,, prepared the solution of organically-modified disiloxane surfactant of the present invention with the working concentration and the pH of expectation, and correlated tensio-active agent.Mensuration sprawl with time relation with the explanation resistance to hydrolysis.
Embodiment 10
Table 17 is illustrative example of organically-modified disiloxane surfactant, and wherein No. 10 products are sprawled tensio-active agent (product E) with respect to the trisiloxanes ethoxylate of routine is ultra, have the resistance to hydrolysis of improvement at pH 3.As stated, through 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 S2006800470265D00241
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 ultra spreading agent of trisiloxanes 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 among the embodiment 8.
Table 18-sprawls character and time relation pH 4 and pH's 5
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 correlated product E.Here, surfactant soln (0.1wt%) is in pH 4, pH 5, pH 8, pH 9 and pH 10 preparations, and through the time sprawl described in character such as the embodiment 8 and measure.
This correlated organosilicon E of table 19 explanation demonstrates than No. 5 products at pH 4, pH 5, pH 9 and pH 10 and sprawls the character loss faster.
Table 19-sprawls character and time relation
Figure S2006800470265D00251
Embodiment 13
Other composition to the influence of sprawling through organo-siloxane disiloxane surfactant of the present invention and conventional mixing based on organic cosurfactant are measured.Cosurfactant is described in the table 20.
Blend is prepared as physical mixture, and wherein organosilyl weight fraction is represented that by α the expression cosurfactant has been supplied the surplus of blend ratio.For example when α=0, this shows that compsn contains 0% organosilicon component and 100% cosurfactant, and α=1.0 show that said composition contains 100% organosilicon, do not have (0%) cosurfactant.The mixture of these two kinds of components is represented that by weight fraction α wherein α changes in following scope: 0≤α≤1.0.For example, when α=0.25, this shows that surfactant mixt is made up of 25% organosilicon and 75% cosurfactant.Then these blends are diluted in water and are used to sprawl the desirable concentration of evaluation.
When the total surfactant of 0.1wt% or 0.2wt%, described in embodiment 8, measure and sprawl.
Table 21 proof, the representative example of cosurfactant of the present invention provides the favourable result that sprawls, and unforeseeable collaborative increase is provided in some cases, and wherein mixture sprawls the diameter of sprawling that diameter surpasses single component.
The description of the conventional cosurfactant of table 20-
ID describes
IDA-5 isodecyl alcohol ethoxylate (4-5 EO)
IDA-6 isodecyl alcohol ethoxylate (5-6 EO)
TMN-6 Exxal 12 ethoxylate (6 EO)
Oxo-TDA-5 oxo-tridecyl alcohol ethoxylate (5 EO)
Oxo-TDA-6 oxo-tridecyl alcohol ethoxylate (6 EO)
APG C 8-10Alkyl poly glucoside
Table 21-cosurfactant is sprawled The properties to blend
Figure S2006800470265D00271
The a=0.2wt% total surfactant
The b=0.1wt% total surfactant
Previous embodiment only is to explanation of the present invention, is used to explain only some characteristics of the present invention.Wide as far as possible the present invention that the accompanying claims intention requires protection to expect, the embodiment that described the application's embodiment explanation is selected from various all possible embodiment.Therefore, applicant's intention is that accompanying claims is not used to explain that by selected the embodiment of characteristic of the present invention limits.Used wording " comprises " and also means and comprise in logic with its phraseological variant and for example, but be not limited to the wording of various degree in the claim, " basically by ... form " with " by ... form ".In the time of necessary, scope is provided; Those scopes comprise subranges all between them.This scope can be regarded a Ma Kushi group or a plurality of Ma Kushi group of being made up of different paired digital boundaries as; Described Ma Kushi group or a plurality of Ma Kushi group are limited its lower limit and the upper limit fully, increase in number from lower limit to the upper limit with 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 by accompanying claims as much as possible and cover.Also expectation is, scientific-technical progress will make that at present these variants also should be interpreted as by accompanying claims as much as possible and cover because the former thereby unexpected equivalence of the inaccuracy of language is replaced the possibility that becomes.The full content of all USPs (and patented claim) of the application institute reference herein through with reference to incorporating the application into, just looks like that they put down in writing the same in this application in full all.

Claims (14)

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 R 7, R wherein 7Has following formula
R 8R 9R 10SiR 12
R wherein 8, R 9And R 10The methyl of respectively doing for oneself, R 12Be bivalent hydrocarbon radical with 2 carbon atoms,
R 2And R 3Be selected from monovalence alkyl or R independently of one another with 1～6 carbon atom 1, R wherein 4Be to have substituent alkyl polyoxygenated alkene, it is selected from:
R 13(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14With
R 12SiR 5R 6(R 13(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14)
R wherein 13Be to have the divalence straight chain of following structure or the alkyl of branching:
-CH 2-CH(R 15)(R 16) dO-
R wherein 15Be H 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 the monovalence alkyl and the ethanoyl of 1～6 carbon atom, wherein subscript a, b and c are 0 or positive number, and relation below satisfying:
2≤a+b+c≤20, a>=2 wherein,
And, R 5And R 6Be selected from monovalence alkyl or R independently of one another with 1～6 carbon atom 4
2. the compsn of claim 1, wherein R 15Be hydrogen.
3. the compsn of claim 1, wherein R 2It is methyl.
4. 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 R 7, and R 7Have following formula:
R 8R 9R 10SiR 12
R wherein 8, R 9And R 10The methyl of respectively doing for oneself, R 12Be bivalent hydrocarbon radical with 2 carbon atoms,
R 2And R 3Be selected from monovalence alkyl or R independently of one another with 1～6 carbon atom 1, R wherein 4Be to have substituent alkyl polyoxygenated alkene, it is selected from:
R 13(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14With
R 12SiR 5R 6(R 13(C 2H 4O) a(C 3H 6O) b(C 4H 8O) cR 14)
R wherein 13Be to have the divalence straight chain of following structure or the alkyl of branching:
-CH 2-CH (R 15) (R 16) dO-, wherein R 15Be H 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 the monovalence alkyl and the ethanoyl of 1～6 carbon atom, wherein subscript a, b and c are 0 or positive number, and relation below satisfying:
2≤a+b+c≤20, a>=2 wherein,
And, R 5And R 6Be selected from monovalence alkyl or R independently of one another with 1～6 carbon atom 4Wherein said silicon composition has the resistance to hydrolysis of improvement; The resistance to hydrolysis of this improvement be meant be exposed to pH be lower than 6 aqueous acidic condition 24 hours after or be exposed to pH greater than 7.5 aqueous alkaline condition 24 hours after, 50mol% or above said remaining unchanged of compsn or do not react.
5. the compsn of claim 4, wherein R 15Be hydrogen.
6. the compsn of claim 4, wherein R 2It is methyl.
7. water miscible liquid, wherein discontinuous phase comprises water, external phase comprises the compsn of claim 1.
8. water miscible liquid, wherein discontinuous phase comprises water, external phase comprises the compsn of claim 4.
9. water miscible liquid, wherein external phase comprises water, discontinuous phase comprises the compsn of claim 1.
10. water miscible liquid, wherein external phase comprises water, discontinuous phase comprises the compsn of claim 4.
11. nonaqueous emulsion, wherein discontinuous phase comprises non-water hydroxylic solvent, and external phase comprises the compsn of claim 1.
12. nonaqueous emulsion, wherein discontinuous phase comprises non-water hydroxylic solvent, and external phase comprises the compsn of claim 4.
13. nonaqueous emulsion, wherein external phase comprises non-water hydroxylic solvent, and discontinuous phase comprises the compsn of claim 1.
14. nonaqueous emulsion, wherein external phase comprises non-water hydroxylic solvent, and discontinuous phase comprises the compsn of claim 4.
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