CN101341156A - Hydrolysis resistant organomodified disiloxane surfactants - Google Patents

Hydrolysis resistant organomodified disiloxane surfactants Download PDF

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Publication number
CN101341156A
CN101341156A CNA2006800470265A CN200680047026A CN101341156A CN 101341156 A CN101341156 A CN 101341156A CN A2006800470265 A CNA2006800470265 A CN A2006800470265A CN 200680047026 A CN200680047026 A CN 200680047026A CN 101341156 A CN101341156 A CN 101341156A
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composition
methyl
phase comprises
alkyl
carbon atom
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CN101341156B (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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General Electric Co
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Priority claimed from US11/300,100 external-priority patent/US7507775B2/en
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

Abstract

Compositions comprising an asymmetric disiloxane surfactant composition comprising 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 related application
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 composition, it demonstrates resistance to hydrolysis in wide pH scope.More specifically, the present invention relates between about pH3～about pH12, have this anti-hydrolysis disiloxane surfactant of resistance to hydrolysis.
Background technology
The local paint of liquid composition is had on the surface of life and inanimate objects to produce the change of expectation, comprise that control is wetting, sprawl, foam, 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 and obtains desired effects.But the trisiloxanes compound only can be used for narrow pH scope, from slightly acidic pH6 alkaline pH 7.5 extremely as mild as a dove.Outside this narrow pH range, the trisiloxanes compound decomposes fast 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 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 satisfy following relation:
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 molar fraction basis under the stoichiometry.
The invention provides sily oxide 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
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 satisfy following relation:
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, 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 the composition of the present invention, wherein its definition and relation limit hereinafter, and it is consistent with the above qualification 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 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 in the mode of routine 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.
The noble metal catalyst that is suitable for preparing the siloxanes of polyethers-replacement 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 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, by with reference to being introduced into the application.Useful in the present invention another kind of platiniferous substance description is in United States Patent (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 determine the significant quantity of platinum catalyst.Usually, significant quantity is about 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 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 composition of the present invention or do not react.Under acidic conditions, composition 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, composition 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, composition 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, composition 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, composition 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, composition 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, composition 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, composition 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 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 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 enter the perviousness of plant epidermis.These auxiliary agents or provide with jar side additive (tank-side additive) are 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 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 used sterilant.The pesticide compound that can use 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, reaching grass ends, amerol, clomazone, fluorine pyridine ketone (fluridone), monometflurazone, dinitraniline, isopropaline,2,6-dinitroN,N-dipropylcumidine, oryzalin, it is logical to kill grass, prodiamine, trifluralin, glyphosate, 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, dimethomorph among the present invention; 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), ether bacterium amine (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 with composition of the present invention, larvacide, miticide and ovicide (ovacide) compound comprises, but be not limited to Bacillus thuringiensis, SPINOSAD 105 (spinosad), avermectin, doramectin (doramectin), lepimectin, pyrethrin, SevinCarbaryl, anti-aphid becomes (pirimicarb), aldicarb, methomyl, U-36059, boric acid, chlordimeform, Rimon (novaluron), two three flufenoxuron (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, four mite piperazines, 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 finished 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 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) 5,674,2 described in 832,2,4-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 nonionogenic tenside, cats product, anion surfactant, 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 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 by with reference to incorporating the application into.
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 thing, 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, 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 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 are for example
Figure A20068004702600121
(Loveland Industries, Greeley, CO) and Quest (Helena Chemical, Collierville, TN), the clay of modification for example
Figure A20068004702600122
(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 " 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, " canned " preparation can 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 can for solidified or dried film, for example the wear resistance of Gai Shaning, adhesion inhibiting properties, wetting ability and hydrophobicity.Coating formulation can be used as solvent-laden coating, aqueous coating and powder coating and 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 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 composition of 85pbw～99pbw.
Organically-modified disiloxane surfactant composition of the present invention can for example reveal and white form 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 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 the application particularly.
The used term " non-water hydroxyl organic compound " of the application is meant that be the organic compound of the hydroxyl of liquid when room temperature for example about 25 ℃ and about 1 normal atmosphere, exemplary have alcohol, dibasic alcohol, polyvalent alcohol and poly-dihydric alcohol and composition thereof.It is the organic compound of the hydroxyl of liquid that the organic hydroxylic solvent of non-water is selected from when room temperature for example about 25 ℃ and about 1 normal atmosphere, 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 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 are to 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 use and comprise by the personal care articles of its deutero-silicon composition of the present invention, 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, the hairdressing 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 added other personal care formulations of organosilicon component usually, 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 comprises 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 the form of monophasic form or 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 among the 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 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 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 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 known component in the 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, 2-hydroxyl-4-methoxyl group-benzophenone, 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 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 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, 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 composition of the present invention, and the hydride intermediate 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 under cooling, keep 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 by gasometric titration (gasiometric titration) the Si-H content of this product is 96cc H 2/ g.
Structural formula 1
Figure A20068004702600161
Preparation embodiment 2
1-(3, the 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 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 fractional columns (Vigreux column) material that fractionation obtains under vacuum (about 30mm Hg), 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 A20068004702600162
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.Find that by gasometric titration the Si-H content of this product is 11cc H 2/ g.
Structural formula 3
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 A20068004702600172
Preparation embodiment 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 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 ℃.Add finish 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 the feed hopper, dropwise add this solution at 40-45 ℃.Add finish after, with reaction mixture reflux 1 hour, make its cooling.At water processing (aqueous workup) (water and moisture NaHCO 3Washing, and at MgSO 4Go up 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 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 packing in 250mL RBF stirs under nitrogen and is warming up to 40 ℃.With the Karstedt ' s catalyzer (Pt in the divinyl tetramethyl disiloxane (0), 40ppm) the feed hopper of packing into of the solution in Dicyclopentadiene (DCPD) (29.8g), dropwise add, the speed of adding make cooling keep down temperature of reaction＜60 ℃ (～0.5g/min).After adding is finished, 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.Find that by gasometric titration the Si-H content of this product is 81cc H 2/ g.
Structural formula 6
Figure A20068004702600182
Preparation embodiment 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 correlated disiloxane surfactant (from embodiment 4 and 6).
Correlated trisiloxanes alcoxylates in addition is by the ordinary method preparation of the hydrosilation reaction of platinum mediation, 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 represented by following general formula:
M*M″
M*=R wherein 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 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 of correlated tensio-active agent based on sily oxide.
The correlated tensio-active agent of table 2-based on siloxanes
Table 3 provides the description of correlated tensio-active agent based on organo-siloxane polyethers (organosilicone polyether), and it has following general formula:
Figure A20068004702600202
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-
Figure A20068004702600203
In addition, correlated sample OPE (the octyl phenol ethoxylate contains 10 polyoxyethylene units) right and wrong-organosilyl organic surface active agent.This product can with
Figure A20068004702600204
X-100 is from DowChemical Company, Midland, and MI obtains.
Embodiment 8
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.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.
Composition 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 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.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
Figure A20068004702600221
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 compositions of prepared at concentrations of 0.5wt%, and with HPLC monitor its through the time decomposition.
Analytical procedure:
Use listed experiment condition in the table 5, by reverse-phase chromatography technical Analysis sample.
The solvent gradient of table 5-HPLC method
Figure A20068004702600231
Detector: ELSD/LTA (using the evaporat light scattering (Evaporative LightScattering with Low Temperature Adapter) of low temperature adapter)
Condition: 30 ℃, 1.95 SLPM N 2
Post: Phenomenex LUNA Cl 8 end caps, 5 microns, 75x4.6mm
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, composition of the present invention provides the resistance to the hydrolysis decomposition of improvement.
Correlated siloxanes B and E≤pH5 and＞demonstrate hydrolysis fast during pH7, 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, described 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 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) after next week in identical condition.
The stability to hydrolysis that table 6-measures by HPLC based on the tensio-active agent of siloxanes
Figure A20068004702600241
The stability to hydrolysis that table 7-measures by HPLC based on the tensio-active agent of siloxanes
The stability to hydrolysis that table 8-measures by HPLC based on the tensio-active agent of siloxanes
Figure A20068004702600243
The stability to hydrolysis that table 9-measures by HPLC based on the tensio-active agent of siloxanes
Figure A20068004702600251
The stability to hydrolysis that table 10-measures by HPLC based on the tensio-active agent of siloxanes
The stability to hydrolysis that table 11-measures by HPLC based on the tensio-active agent of siloxanes
Figure A20068004702600261
The stability to hydrolysis that table 12-measures by HPLC based on the tensio-active agent of siloxanes
Figure A20068004702600262
Annotate: stoste 2.5wt%
The stability to hydrolysis that table 13-measures by HPLC based on the tensio-active agent of siloxanes
The stability to hydrolysis that table 14-measures by HPLC based on the tensio-active agent of siloxanes
Figure A20068004702600271
The stability to hydrolysis that table 15-measures by HPLC based on the tensio-active agent of siloxanes
The stability to hydrolysis that table 16-measures by HPLC based on the tensio-active agent of siloxanes
Figure A20068004702600273
Embodiment 10-12
With under acid and alkaline condition (≤pH5 and 〉=pH9) 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 end capped disiloxane surfactant of correlated trimethyl silyl that contrasts the 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,, 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 embodiment 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 super, have the resistance to hydrolysis of improvement at pH3.As mentioned above, by the monitoring through the time the character of sprawling measure resistance to hydrolysis.Here, 0.4wt% solution prepares at pH3, sprawls according to the step measurements of embodiment 8.
Table 17-sprawls character and the relation of time (h) at pH3
Figure A20068004702600281
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 trisiloxanes ethoxylate (superspreader)).The solution of tensio-active agent (0.4wt%) is in pH4 and pH5 preparation, measure through the time sprawl character.Test condition is listed among the embodiment 8.
Table 18-sprawls character and time relation at pH4 and pH5
Figure A20068004702600282
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.Herein, surfactant soln (0.1wt%) is in pH4, pH5, pH8, pH9 and pH10 preparation, and through the time the character of sprawling measure as described in example 8 above.
This correlated organosilicon E of table 19 explanation demonstrates than No. 5 products at pH4, pH5, pH9 and pH10 and sprawls the character loss faster.
Table 19-sprawls character and time relation
Figure A20068004702600291
Embodiment 13
Other composition to the influence of sprawling by 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 composition 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 mixture 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%, 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 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-
Figure A20068004702600301
Table 21-cosurfactant is sprawled character to blend influence
Figure A20068004702600311
The a=02wt% total surfactant
The b=0.1wt% total surfactant
Previous embodiment only is to explanation of the present invention, is used to illustrate 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 used to illustrate that by selected the embodiment of feature of the present invention limits.Used wording " comprises " and its phraseological variant also means and comprises in logic and for example, but is not limited to the wording of various degree in the claim, " 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 of being made up 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 that at present these variants also should be interpreted as much as possible and be overwritten by the appended claims because the former thereby unexpected equivalence of the inaccuracy of language is replaced the possibility that becomes.The full content of all United States Patent (USP)s (and patent application) of the application institute reference herein by 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 (38)

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 the monovalence alkyl and the R of branching with 3～6 carbon atoms 7, R wherein 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 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 satisfy following relation:
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 composition of claim 1, wherein R 1It is sec.-propyl.
3. the composition of claim 1, wherein R 1It is isobutyl-.
4. the composition of claim 1, wherein R 1It is the tertiary butyl.
5. the composition of claim 1, wherein R 1Be R 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 bivalent hydrocarbon radical with 2 carbon atoms.
6. the composition of claim 1, wherein R 15Be hydrogen.
7. the composition of claim 1, wherein R 2It is methyl.
8. the composition of claim 2, wherein R 15Be hydrogen.
9. the composition of claim 2, wherein R 2It is methyl.
10. the composition of claim 3, wherein R 15Be hydrogen.
11. the composition of claim 3, wherein R 2It is methyl.
12. the composition of claim 4, wherein R 15Be hydrogen.
13. the composition of claim 4, wherein R 2It is methyl.
14. the composition of claim 5, wherein R 15Be hydrogen.
15. the composition of claim 5, wherein R 2It is methyl.
16. 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 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 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 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 satisfy following relation:
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, wherein said silicon composition has the resistance to hydrolysis of improvement.
17. the composition of claim 16, wherein R 1It is sec.-propyl.
18. the composition of claim 16, wherein R 1It is isobutyl-.
19. the composition of claim 16, wherein R 1It is the tertiary butyl.
20. the composition of claim 16, wherein R 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 12It is bivalent hydrocarbon radical with 2 carbon atoms.
21. the composition of claim 16, wherein R 15Be hydrogen.
22. the composition of claim 16, wherein R 2It is methyl.
23. the composition of claim 17, wherein R 15Be hydrogen.
24. the composition of claim 17, wherein R 2It is methyl.
25. the composition of claim 18, wherein R 15Be hydrogen.
26. the composition of claim 18, wherein R 2It is methyl.
27. the composition of claim 19, wherein R 15Be hydrogen.
28. the composition of claim 19, wherein R 2It is methyl.
29. the composition of claim 20, wherein R 15Be hydrogen.
30. the composition of claim 20, wherein R 2It is methyl.
31. water miscible liquid, wherein discontinuous phase comprises water, and external phase comprises the composition of claim 1.
32. water miscible liquid, wherein discontinuous phase comprises water, and external phase comprises the composition of claim 16.
33. water miscible liquid, wherein external phase comprises water, and discontinuous phase comprises the composition of claim 1.
34. water miscible liquid, wherein external phase comprises water, and discontinuous phase comprises the composition of claim 16.
35. nonaqueous emulsion, wherein discontinuous phase comprises non-water hydroxylic solvent, and external phase comprises the composition of claim 1.
36. nonaqueous emulsion, wherein discontinuous phase comprises non-water hydroxylic solvent, and external phase comprises the composition of claim 16.
37. nonaqueous emulsion, wherein external phase comprises non-water hydroxylic solvent, and discontinuous phase comprises the composition of claim 1.
38. nonaqueous emulsion, wherein external phase comprises non-water hydroxylic solvent, and discontinuous phase comprises the composition of claim 16.
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CN110352211A (en) * 2018-02-02 2019-10-18 莫门蒂夫性能材料股份有限公司 Trisiloxane alkoxylate composition
CN112138575A (en) * 2020-10-14 2020-12-29 马鞍山健鼎化工有限公司 Stirring device for producing polymeric ferric sulfate and working method

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TW201038684A (en) * 2009-01-09 2010-11-01 Momentive Performance Mat Inc Silane coating compositions containing silicon-based polyether copolymers, methods for coating metal surfaces and articles made therefrom

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CN110352211A (en) * 2018-02-02 2019-10-18 莫门蒂夫性能材料股份有限公司 Trisiloxane alkoxylate composition
CN110352211B (en) * 2018-02-02 2023-04-04 莫门蒂夫性能材料股份有限公司 Trisiloxane alkoxylate compositions
CN112138575A (en) * 2020-10-14 2020-12-29 马鞍山健鼎化工有限公司 Stirring device for producing polymeric ferric sulfate and working method

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