WO2005103117A1 - Copolymeres blocs de polyether de silicone - Google Patents

Copolymeres blocs de polyether de silicone Download PDF

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WO2005103117A1
WO2005103117A1 PCT/US2005/013082 US2005013082W WO2005103117A1 WO 2005103117 A1 WO2005103117 A1 WO 2005103117A1 US 2005013082 W US2005013082 W US 2005013082W WO 2005103117 A1 WO2005103117 A1 WO 2005103117A1
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gram
siloxane
added
organic group
polyoxyethylene
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Shaow Lin
Kimmai Nguyen
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Dow Silicones Corp
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Dow Corning Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the present invention relates to (AB) n silicone polyethers that are polyorganosiloxane-polyoxyethylene block copolymers having the average formula -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C 2 H 4 O) y ] z - where x and y are greater than A, and x/(x+y) ranges from 0.2 to 0.9, z is greater than 2, R is independently a monovalent organic group, and R 1 is a divalent organic group containing 2 to 30 carbons.
  • the (AB) n silicone polyethers of the present invention can be used to prepare vesicle compositions and stable aqueous dispersions which can be used to entrap, and subsequently deliver after application, a personal, household care, or health care ingredient.
  • Silicone surfactants have been designed for various applications by combining a hydrophobic organopolysiloxane with various hydrophilic moieties.
  • silicone surfactants known as silicone polyethers (SPEs) are based on copolymer structures of polyorganosiloxanes having pendant polyoxyalkylene groups.
  • the copolymer structures of silicone polyethers are the "rake” type, where a predominately linear polyorganosiloxane provides the "backbone" of the copolymer architecture with pendant polyoxyalkylene groups forming the "rake”.
  • "ABA" structures are also common, where a pendant polyoxyalkylene group is at each molecular terminal of a linear polyorganosiloxane.
  • (AB)n silicone polyethers are also known, wherein blocks of a siloxane units and polyether units repeat to form the copolymer.
  • (AB) n SPEs are not as predominant in the art as the rake or ABA silicone polyethers.
  • rake and ABA silicone polyethers there are numerous teachings describing various rake and ABA silicone polyethers structures for applications in many personal, household, and health care compositions as emulsifiers, wetting agents, and general-purpose aqueous surfactants. More recently, the aggregation behavior of rake and ABA silicone polyethers has been reported.
  • AB n silicone polyethers form unique dispersions in aqueous media.
  • certain defined (AB) n SPE structures will form vesicle compositions in aqueous media.
  • certain (AB) n SPE structures form stable dispersions that can be used to create emulsions. These stable dispersions and vesicles can be used to formulate compositions for the delivery of pharmaceutical and personal care actives.
  • the '842 and '941 patents further teach the use of the linear siloxane- polyoxyalkylene (AB) n block copolymers in polyurethane forming compositions, as well as the cured foams and articles produced therefrom.
  • U.S. Patent Nos. 5,472,686 and 5,660,819 by Tsubaki et al. teach cosmetic formulations containing a linear polysiloxane-polyoxyalkylene block copolymer as the main component.
  • the '686 and '819 patents do not teach polysiloxane-polyoxyalkylene block copolymers structures to form vesicles.
  • U.S. Patent 5,767,219 teaches a polysiloxane-polyether block copolymer having excellent heat resistance, which is characterized by the molecular structure consisting of repetition of diorganopolysiloxane units and polyoxyalkylene units having a bisphenol linkage of the formula -O-Pn-CMe 2 -Pn-O- in the unit, Pn being a 1,4-phenylene group and Me is a methyl group.
  • the '219 patent does not teach polysiloxane-polyoxyalkylene block copolymers structures to form vesicles.
  • the (AB) n silicone polyethers of the present invention are polyorganosiloxane- polyoxyethylene block copolymers having the average formula (Formula I); -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C 2 H 4 O) y ] z - where x and y are greater than 4, x/(x+y) ranges from 0.2 to 0.9, z is greater than 2, R is independently a monovalent organic group, and R 1 is a divalent organic group containing 2 to 30 carbons.
  • the (AB) n SPEs of Formula I have a value of x (i.e. the degree of polymerization, DP, of the polysiloxane chain in the siloxane units) that ranges from 20 to 100, alternatively from 30 to 75. These structures form vesicles in aqueous media.
  • the (AB) n SPEs of Formula I have a value of x (i.e. the degree of polymerization, DP, of the polysiloxane chain in the siloxane units) that ranges from 5 to 19, alternatively from 5 to 15. These structures form stable dispersions in aqueous media having a particle size of less than 10 micrometers.
  • the present invention further provides a process to prepare polyorganosiloxane- polyoxyethylene block copolymers comprising reacting; a) a SiH terminated organopolysiloxane, b) a polyoxyethylene having an unsaturated hydrocarbon group at each molecular terminal, c) a hydrosilylation catalyst, d) optionally a solvent, e) optionally an organic endblocker compound having a mono-terminally unsaturated hydrocarbon group, wherein the mole ratio of the unsaturated hydrocarbon groups to SiH in the reaction is at least
  • SPEs of the present invention can be used to entrap, and subsequently deliver after application, a personal, household care, or health care ingredient.
  • the present invention provides a polyorganosiloxane-polyoxyethylene block copolymer having the average formula; Formula I -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C 2 H 4 O) y ] z -
  • the siloxane block in Formula I is a predominately linear siloxane polymer having the formula (R 2 SiO) x , wherein R is independently selected from a monovalent organic group, x is an integer greater than 4.
  • the value of x i.e. the degree of polymerization, DP, of the polysiloxane chain ranges from 20 to 100, alternatively from 30 to 75.
  • DP degree of polymerization
  • the value of x ranges from 5 to 19, alternatively from 5 to 15.
  • These structures form stable dispersions in aqueous media having a particle size of less than 10 micrometers, also discussed supra.
  • the organic groups represented by R in the siloxane polymer are free of aliphatic unsaturation. These organic groups may be independently selected from monovalent hydrocarbon and monovalent halogenated hydrocarbon groups free of aliphatic unsaturation. These monovalent groups may have from 1 to 20 carbon atoms, alternatively 1 to 10 carbon atoms, and are exemplified by, but not limited to alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, and octadecyl; cycloalkyl such as cyclohexyl; aryl such as phenyl, tolyl, xylyl, benzyl, and 2-phenylethyl; and halogenated hydrocarbon groups such as 3,3,3-trifluoropropyl, 3-chloropropyl, and dichlorophenyl.
  • alkyl groups such as
  • the siloxane block is a predominately linear polydimethylsiloxane having the formula (Me SiO) x , where x is as defined above.
  • the polyoxyethylene block of the silicone polyether is represented by the formula (C 2 H 4 O) y wherein y is greater than 4, alternatively y can range from 5 to 45, or alternatively
  • each polyoxyalkylene block in Formula I is linked to a siloxane block by a divalent organic group, designated R 1 .
  • This linkage is determined by the reaction employed to prepare the (AB) classroom block silicone polyether copolymer.
  • the divalent organic groups of R 1 may be independently selected from divalent hydrocarbons containing 2 to 30 carbons and divalent organofunctional hydrocarbons containing 2 to 30 carbons.
  • Representative, non-limiting examples of such divalent hydrocarbon groups include; ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and the like.
  • Representative, non-limiting examples of such divalent organofunctional hydrocarbons groups include acrylate and methacrylate.
  • R 1 is propylene, (-CH 2 CH CH 2 -).
  • the (AB) n block silicone polyethers are endblocked.
  • the endblocking unit is also determined by the reaction employed to prepare the (AB) n block silicone polyether copolymer, which is generally the residual reactive groups of the reactants used.
  • the (AB) n block silicone polyether copolymers can be prepared by the metal catalyzed hydrosilylation reaction of a diallyl polyether (i.e. an allyl group is present on each molecular terminal end) with a SiH terminated polyorganosiloxane.
  • the resulting (AB) n block silicone polyether copolymer would have polyoxyalkylene blocks linked to the silicone blocks via a propyleneoxy group (-CH 2 CH 2 CH O-), and using a slight molar excess of the allyl polyether would result in an allyl endblock unit (-CH 2 CHCH 2 ).
  • Alternative endblock units can result from the addition of other molecules in the reaction employed to prepare the (AB) n block silicone polyether copolymer that are capable of reacting with the siloxane or polyether block intermediates.
  • the addition of organic compounds having mono-terminated aliphatic unsaturation (such as a mono allyl terminated polyether) will result in the endcapping of the (AB) n block silicone polyether copolymer with that organic compound.
  • the molecular weights of the (AB) n block silicone polyether copolymers will be determined by the number of repeating siloxane and polyoxyethylene blocks, as indicated by the subscript z in Formula I. Typically, the value of z is such to provide weight average molecular weights (Mw) to range from 1,500 to 150,000, alternatively, from 10,000 to 100,000.
  • the (AB) n SPEs of the present invention have a molar ratio of the total siloxane units to the polyoxyethylene units in the (AB) prison block silicone polyether. This molecular parameter is expressed by the value of x/(x+y) in Formula I. The value of x/(x+y) can vary from 0.2 to 0.9, or alternatively from 0.4 to 0.9.
  • the (AB) groove SPEs of the present invention can be prepared by any method known in the art for preparing such block copolymers. Alternatively, the (AB) n SPEs of the present invention are prepared according the methods described infra.
  • the present invention further provides a process to prepare polyorganosiloxane- polyoxyethylene block copolymers comprising reacting; a) a SiH terminated organopolysiloxane, b) a polyoxyethylene having an unsaturated hydrocarbon group at each molecular terminal, c) a hydrosilylation catalyst, d) optionally a solvent, e) optionally an organic endblocker compound having a mono-terminally unsaturated hydrocarbon group, wherein the mole ratio of the unsaturated organic groups to SiH in the reaction is at least 1:1.
  • the SiH terminated organopolysiloxanes useful in the process of the present invention can be represented by the formula M'DM', where "M”' means a siloxane unit of formula R 2 HSiO ⁇ /2 , “D” means a siloxane unit of formula R 2 SiO 2/2 , where R is independently a monovalent organic group as defined above.
  • the SiH terminated organopolysiloxane is a dimethylhydrogensiloxy-terminated polydimethylsiloxane having the average formula Me 2 HSiO(Me 2 SiO) x SiHMe 2 , where x is as defined above.
  • SiH terminated organopolysiloxanes and methods for their preparation are well known in the art.
  • the polyoxyethylene useful in the process of the present invention can be any polyoxyethylene comprising the average formula -(C 2 H 4 O) y - , where y is defined as above, and is terminated at each molecular chain end (i.e. alpha and omega positions) with a unsaturated organic group.
  • the unsaturated organic group can be an unsaturated hydrocarbon group such as alkenyl or alkynyl group.
  • alkynyl groups are shown by the following structures; HC ⁇ C-, HC ⁇ CCH 2 -, HC ⁇ CC(CH 3 ) - , HC ⁇ CC(CH 3 ) 2 - , HC ⁇ CC(CH 3 ) CH 2 - .
  • polyoxyethylenes having an unsaturated hydrocarbon group at each molecular terminal are known in the art, and many are commercially available.
  • the unsaturated organic group can be an organofunctional hydrocarbon such as an acrylate, methacrylate and the like.
  • the SiH terminated organopolysiloxane and polyoxyethylene having an unsaturated organic group at each molecular terminal are reacted in the presence of a hydrosilylation catalyst, which are known in the art.
  • a hydrosilylation catalyst which are known in the art.
  • Such hydrosilylation catalysts are illustrated by any metal-containing catalyst which facilitates the reaction of silicon-bonded hydrogen atoms of the SiH terminated organopolysiloxane with the unsaturated hydrocarbon group on the polyoxyethylene.
  • the metals are illustrated by ruthenium, rhodium, palladium, osmium, iridium, or platinum.
  • Hydrosilylation catalysts are illustrated by the following; chloroplatinic acid, alcohol modified chloroplatinic acids, olefin complexes of chloroplatinic acid, complexes of chloroplatinic acid and divinyltetramethyldisiloxane, fine platinum particles adsorbed on carbon carriers, platinum supported on metal oxide carriers such as Pt(Al2 ⁇ 3), platinum black, platinum acetylacetonate, platinum(divinyltetramethyldisiloxane), platinous halides exemplified by PtCl2, PtCl4, Pt(CN)2, complexes of platinous halides with unsaturated compounds exemplified by ethylene, propylene, and organovinylsiloxanes, styrene hexamethyldiplatinum, and RI1CI3 (Bu2 S)3.
  • the amount of hydrosilylation catalyst that is used is not narrowly limited as long as there is a sufficient amount to accelerate a reaction between the polyoxyethylene having an unsaturated hydrocarbon group at each molecular terminal and the SiH terminated organopolysiloxane at room temperature or at temperatures above room temperature.
  • the exact necessary amount of this catalyst will depend on the particular catalyst utilized and is not easily predictable. However, for platinum-containing catalysts the amount can be as low as one weight part of platinum for every one million weight parts of components the polyoxyethylene having an unsaturated hydrocarbon group at each molecular terminal and the SiH terminated organopolysiloxane.
  • the catalyst can be added at an amount 10 to 120 weight parts per one million parts of components the polyoxyethylene having an unsaturated organic group at each molecular terminal and the SiH terminated organopolysiloxane, but is typically added in an amount from 10 to 60 weight parts per one million parts of the polyoxyethylene having an unsaturated organic group at each molecular terminal and the SiH terminated organopolysiloxane.
  • the hydrosilylation reaction can be conducted neat or in the presence of d), a solvent.
  • the solvent can be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol, a ketone such as acetone, methylethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, or ethylene glycol n-butyl ether, a halogenated hydrocarbon such as dichloromethane, 1,1,1- trichloroethane or methylene chloride, chloroform, dimethyl sulfoxide, dimethyl formamide, acetonitrile, te
  • the amount of solvent can be up to 50 weight percent, but is typically from 20 to 50 weight percent, said weight percent being based on the total weight of components in the hydrosilylation reaction.
  • the solvent used during the hydrosilylation reaction can be subsequently removed from the resulting silicone polyether by various known methods.
  • Optional component e) is an organic endblocker compound having a mono-terminally unsaturated organic group. The addition of this component can be used to adjust the molecular weight of the block silicone polyether.
  • these are chosen from polyoxyethylenes comprising the average formula -(C 2 H 4 ⁇ ) y - , where y is defined as above, and is terminated at one molecular chain end with an unsaturated group, such as an alkenyl or alkynyl group.
  • Additional components can be added to the hydrosilylation reaction which are known to enhance such reactions. These components include salts such as sodium acetate which have a buffering effect in combination with platinum catalysts.
  • the (AB) n SPEs of Formula I have a value of x (i.e. the degree of polymerization, DP, of the polysiloxane chain in the siloxane units) that ranges from 20 to 100, alternatively from 30 to 75. These structures form vesicles in aqueous media.
  • vesicle compositions can be prepared by mixing the (AB) compliment SPEs with water using any technique known common in the state of the art for creating vesicle compositions. The type and extent of the mixing technique will depend on the specific structure of the (AB) jam SPE chosen.
  • the vesicle compositions are prepared using a process comprising; I) combining, A) a (AB) n silicone polyether copolymer having the average formula; -[R 1 (R 2 SiO) x (R 2 SiR 1 O)(C 2 H 4 O) y ] z - where x and y are greater than 4, and x/(x+y) ranges from 0.2 to 0.9, z is greater than 2, R is independently a monovalent organic group, and R 1 is a divalent organic group containing 2 to 30 carbons.
  • Optional component B) is a water-miscible volatile solvent.
  • water-miscible means the solvent forms a dispersion with water at room temperature for at least several hours.
  • Volatile means the solvent has a higher vapor pressure than water at various temperatures.
  • Suitable water-miscible volatile solvents for vesicle dispersion preparation include organic solvents such as alcohols, ethers, glycols, esters, acids, halogenated hydrocarbons, diols.
  • organic solvents should be miscible with water at the proportion and lower in order to effectively disperse silicones and maintain stable and uniform dispersion overtime.
  • water-miscible alcohols include method, ethanol, propanol, isopropanol, butanol, and higher hydrocarbon alcohols; ethers include gylcol ethers, methyl- ethyl ether, methyl isobutyl ether (MIBK), etc; glycols include propylene glycols, esters include esters of triglycerol, the esterification products of acid and alcohol; halogenated hydrocarbons include chloroform.
  • water-miscible organic solvents are solvents with relatively low boiling points ( ⁇ 100°C) or high evaporation rate, so they may be removed under vacuum with ease.
  • the most preferred water-miscible organic solvents for this invention are volatile alcohols including methanol, ethanol, isopropanol, and propanol. These alcohols can be removed from aqueous mixtures containing silicone vesicle dispersions via vacuum stripping at ambient temperature.
  • the order of mixing components A), B), and C) is not critical, but typically A) and B) are first mixed and then water added to the mixture. There are no special requirements or conditions needed for effecting the mixing of components A), B), and C).
  • the mixing can be conducted in a batch, semi-continuous, or continuous process.
  • the amount of components A), B), and C) can vary in the process, but typically range as follows; A) 2 to 50 wt%, alternatively 2 to 25 wt %, or alternatively 2 to 15 wt%, B) 0 to 50 wt%, alternatively 2 to 25 wt %, or alternatively 2 to 15 wt%, C) sufficient amount to provide the sum of the wt% of A), B), and C) to equal 100% [0042]
  • the amount of B) water-miscible volatile solvent used to disperse the (AB) n SPEs depends on the type of organopolysiloxane and how much hydrophilic groups are present.
  • the aqueous mixture to effective disperse silicones comprises of 5 to 80 parts of solvent and 20 to 95 parts of water; alternatively 5 to 50 parts of water, or alternatively 10 to 40 parts water.
  • the (AB) n SPEs of Formula I have a value of x (i.e. the degree of polymerization, DP, of the polysiloxane chain in the siloxane units) that ranges from 5 to 19, alternatively from 5 to 10. These structures form stable dispersions in aqueous media having a particle size of less than 10 micrometers.
  • the stable aqueous dispersions are prepared by mixing the (AB) n SPEs of the second embodiment with water.
  • the mixing technique is not critical, as the (AB) n SPEs of the second embodiment easily form stable dispersions from simply mixing the SPEs as defined with water.
  • the vesicle compositions and stable aqueous dispersions prepared from the (AB) n SPEs of the present invention can be used to entrap, and subsequently deliver after application, a personal, household care, or health care ingredient.
  • a personal, household, or health care ingredient A listing of possible personal, household, or health care ingredients is taught in WO 03/101412, which is incorporated herein by reference.
  • the personal or health care ingredient can also be selected from a personal or health care "active", that is, any compound known to have either cosmetic and/or pharmaceutical activity.
  • a representative listing of such personal or health care actives are disclosed in US Patent 6,168,782, which is hereby incorporated by reference.
  • compositions prepared according to the invention can be used in various over-the- counter (OTC) personal care compositions, health care compositions, and household care compositions, but especially in the personal care arena.
  • OTC over-the- counter
  • they can be used in antiperspirants, deodorants, skin creams, skin care lotions, moisturizers, facial treatments such as acne or wrinkle removers, personal and facial cleansers, bath oils, perfumes, colognes, sachets, sunscreens, pre-shave and after-shave lotions, liquid soaps, shaving soaps, shaving lathers, hair shampoos, hair conditioners, hair sprays, mousses, permanents, depilatories, hair cuticle coats, make-ups, color cosmetics, foundations, blushes, lipsticks, lip balms, eyeliners, mascaras, oil removers, color cosmetic removers, nail polishes, and powders.
  • Representative (AB) n silicone polyethers herein designated as (AB) n SPEs, were prepared by the hydrosilylation of alpha-omega alkenyl-terminated polyethers and dimethylhydrogen-terminated siloxane of varying degrees of polymerization (designated as M'D x M*), in the presence of a platinum catalyst.
  • M'D X M' siloxanes - a series of dimethyl-hydrogen terminated (Me 2 HSiO) linear polydimethylsiloxanes of varying degree of polymerizations (as designated by x) were prepared using well known siloxane polymerization techniques. The average formulas for this series of siloxanes are summarized in Table 1.
  • a 2000 ml three neck round bottom flash equipped with temperature probe, electrical stirrer, and condenser was charged with 187 gram of Polyglycol AAl 200 polyethylene glycol diallyl ether (Clariant Corp., Mt. Holly, NC), 52 gram of xylene and 0.25 gram of sodium acetate.
  • the flask was heated to 100°C.
  • About 329.76 gram of dimethylhydrogen endblocked polydimethyl siloxane with a number average degree polymerization of 30 DP (SiH @ 1050 ppm) was added dropwise via an addition funnel.
  • a 2000 ml three neck round bottom flash equipped with temperature probe, electrical stirrer, and condenser was charged with 150 gram of Polyglycol AAl 200 polyethylene glycol diallyl ether, 111 gram of xylene and 0.33 gram of sodium acetate.
  • the flask was heated to 100 °C.
  • a 2000 ml three neck round bottom flash equipped with temperature probe, electrical stirrer, and condenser was charged with 453 gram of Polyglycol AAl 200 polyethylene glycol diallyl ether, 50 gram of xylene and 0.5 gram of sodium acetate.
  • the flask was heated to 100°C.
  • a 2000 ml three neck round bottom flash equipped with temperature probe, electrical stirrer, and condenser was charged with 601.6 gram of Polyglycol AA2000 polyethylene glycol diallyl ether (Clariant, Mt. Holly, NC), 54.9 gram of toluene.
  • the flask was heated to 100°C.
  • About 398.4 gram of dimethylhydrogen endblocked polydimethyl siloxane with a number average degree polymerization of 15 DP (SiH @ 1730 ppm) was added dropwise via an addition funnel.
  • a 2000 ml three neck round bottom flash equipped with temperature probe, electrical stirrer, and condenser was charged with 150.4 gram of Polyglycol AA2000 polyethylene glycol diallyl ether, 50 gram of toluene.
  • the flask was heated to 100°C.
  • About 99.6 gram of dimethylhydrogen endblocked polydimethyl siloxane with a number average DP of 15 was added dropwise via an addition funnel.
  • about 0.5 gram of platinum catalyst (l,3-diethenyl-l,l,3,3-tetramethyldisiloxane platinum complex in dimethyl siloxane) was added to the mixture.
  • Example 9 A similar procedure to Example 8 was followed to prepare two other (AB) abuse SPEs, labeled as Example 9 and Example 10.
  • a 3000 ml three neck round bottom flash equipped with temperature probe, electrical stirrer, and condenser was charged with 199 gram of Polyglycol AAl 200 polyethylene glycol diallyl ether, .4 gram of sodium acetate, 84.5 gram of isopropanol alcohol. Also added to the flask was about 647 gram of dimethylhydrogen endblocked polydimethyl siloxane with a number average DP of 50. The flask was heated to 85°C. Half of the Pt was added, about 0.76 gram, to initiate the reaction. About 10 minutes later, the remaining Pt was added. The reaction mixture was allowed to mixed for about 1 hour to allow for the polymer to grow.
  • Examples 12 & 13 Vesicle Compositions containing Vitamin A Palmitate from the (AB) register SPEs of Examples 9 & 11 [0060] The following procedure was used to prepare the vesicle compositions summarized in Table 3 as Examples 12 and 13. [0061] Ethanol (EtOH) was added to (AB)neig SPE of Example 9, a (AB)n block copolymer of M'D 50 M' siloxane and polyglycol AA1200 polyether, having a weight-average molecular weight Mw of 43,105 g/mole), to provide a homogeneous mixture. With continuous mixing, water was added slowly to form a homogeneous dispersion.
  • Example 12 The mixture was subsequently homogenized to a mixture having an average particle size of 0.214 ⁇ m.
  • the EtOH in the dispersion was then removed using a Rotovapor under vacuum at ambient temperature, to yield an alcohol-free, homogeneous dispersion having an average particle size of 0.359 ⁇ m, designated as Example 12.
  • Example 9 A vesicle composition using (AB) friendship SPE of Example 9 was also made following the same procedure and summarized as Example 13.

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Abstract

L'invention concerne des polyéthers de silicone (AB)n constituant des copolymères blocs de polyorganosiloxane-polyoxéthylène représentés par la formule moyenne -[R1(R2SiO)x(R2SiR1O)(C2H4O)y]z-, dans laquelle x et y sont supérieurs à 4, et x/(x+y) varie de 0,2 à 0,9, z est supérieur à 2, R est indépendamment un groupe organique monovalent, et R1 est un groupe organique divalent contenant de 2 à 12 carbones. Lesdits polyéthers de silicone (AB)n sont utilisés pour préparer des compositions de vésicules et des dispersions aqueuses stables pouvant être utilisées pour piéger, et ensuite libérer après son application, un ingrédient personnel, ménager, ou médical.
PCT/US2005/013082 2004-04-20 2005-04-19 Copolymeres blocs de polyether de silicone Ceased WO2005103117A1 (fr)

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US61122904P 2004-09-17 2004-09-17
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WO2007021486A1 (fr) * 2005-08-17 2007-02-22 Dow Corning Corporation Cristaux liquides et vésicules lyotropiques
WO2008127519A1 (fr) * 2007-04-11 2008-10-23 Dow Corning Corporation Copolymères bloc de polyéther de silicone possédant des groupes organofonctionnels de blocage d'extrémité
US7678301B2 (en) 2004-04-20 2010-03-16 Dow Corning Corporation Vesicles of high molecular weight silicone polyethers
US7754800B2 (en) 2005-04-06 2010-07-13 Dow Corning Europe Sa Organosiloxane compositions
WO2010047993A3 (fr) * 2008-10-22 2010-09-16 Dow Corning Corporation Copolymères de polyéther-silicone à fonctions amino terminales bloquées utiles dans des compositions de soins personnels
US7887834B2 (en) 2004-04-20 2011-02-15 Dow Corning Corporation Aqueous dispersions of silicone polyether block copolymers
US8487037B2 (en) 2009-03-26 2013-07-16 Dow Corning Corporation Preparation of organosiloxane polymers
US8735493B2 (en) 2009-03-26 2014-05-27 Dow Corning Corporation Preparation of organosiloxane polymers
WO2016014609A1 (fr) * 2014-07-23 2016-01-28 Dow Corning Corporation Émulsions de silicone
US10441527B2 (en) 2015-04-08 2019-10-15 Dow Silicones Corporation Fluid compositions and personal care
US11168213B2 (en) 2017-07-31 2021-11-09 Dow Silicones Corporation Moisture curable compositions
US11319446B2 (en) 2017-07-31 2022-05-03 Dow Silicones Corporation Moisture curable compositions
CN114672029A (zh) * 2022-04-27 2022-06-28 四川大学 一种非离子有机硅表面活性剂的制备方法
US11383182B2 (en) 2019-06-24 2022-07-12 Dow Silicones Corporation Linear silicone polyether foam control agent
WO2022255356A1 (fr) 2021-06-04 2022-12-08 ダウ・東レ株式会社 Procédé de fabrication d'une composition de copolymère séquencé de polyéther-polysiloxane, composition de copolymère séquencé de polyéther-polysiloxane et son utilisation
JP2022186643A (ja) * 2021-06-04 2022-12-15 ダウ・東レ株式会社 ポリエーテル－ポリシロキサンブロック共重合体組成物の製造方法
KR20240028338A (ko) 2021-06-04 2024-03-05 다우 도레이 캄파니 리미티드 향상된 발포 특성을 갖는 폴리에테르-폴리실록산 블록 공중합체 함유 조성물, 이의 용도 및 이의 제조 방법

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US7678301B2 (en) 2004-04-20 2010-03-16 Dow Corning Corporation Vesicles of high molecular weight silicone polyethers
US7887834B2 (en) 2004-04-20 2011-02-15 Dow Corning Corporation Aqueous dispersions of silicone polyether block copolymers
US8067519B2 (en) 2005-04-06 2011-11-29 Dow Corning Corporation Organosiloxane compositions
US8344087B2 (en) 2005-04-06 2013-01-01 Dow Corning Corporation Hydrosilylation cured organosiloxanes having diluent therein
US7754800B2 (en) 2005-04-06 2010-07-13 Dow Corning Europe Sa Organosiloxane compositions
US8153724B2 (en) 2005-04-06 2012-04-10 Dow Corning Corporation Organosiloxane compositions
US8088857B2 (en) 2005-04-06 2012-01-03 Dow Corning Corporation Organosiloxane compositions
US8084535B2 (en) 2005-04-06 2011-12-27 Dow Corning Corporation Organosiloxane compositions
US8076411B2 (en) 2005-04-06 2011-12-13 Dow Corning Corporation Organosiloxane compositions
US8022162B2 (en) 2005-04-06 2011-09-20 Dow Corning Corporation Organosiloxane compositions
US7781556B2 (en) 2005-08-17 2010-08-24 Dow Corning Corporation Lyotropic liquid crystals and vesicles
WO2007021486A1 (fr) * 2005-08-17 2007-02-22 Dow Corning Corporation Cristaux liquides et vésicules lyotropiques
US8013097B2 (en) 2007-04-11 2011-09-06 Dow Corning Corporation Silicone polyether block copolymers having organofunctional endblocking groups
WO2008127519A1 (fr) * 2007-04-11 2008-10-23 Dow Corning Corporation Copolymères bloc de polyéther de silicone possédant des groupes organofonctionnels de blocage d'extrémité
KR20110075026A (ko) * 2008-10-22 2011-07-05 다우 코닝 코포레이션 퍼스널 케어 조성물 중의 아미노작용성 말단블록킹된 실리콘 폴리에테르 코폴리머
WO2010047993A3 (fr) * 2008-10-22 2010-09-16 Dow Corning Corporation Copolymères de polyéther-silicone à fonctions amino terminales bloquées utiles dans des compositions de soins personnels
US8734767B2 (en) 2008-10-22 2014-05-27 Dow Corning Corporation Aminofunctional endblocked silicone polyether copolymers in personal care compositions
KR101632609B1 (ko) 2008-10-22 2016-06-23 다우 코닝 코포레이션 퍼스널 케어 조성물 중의 아미노작용성 말단블록킹된 실리콘 폴리에테르 코폴리머
US8487037B2 (en) 2009-03-26 2013-07-16 Dow Corning Corporation Preparation of organosiloxane polymers
US8735493B2 (en) 2009-03-26 2014-05-27 Dow Corning Corporation Preparation of organosiloxane polymers
US10385212B2 (en) 2014-07-23 2019-08-20 Dow Silicones Corporation Silicone emulsions
WO2016014609A1 (fr) * 2014-07-23 2016-01-28 Dow Corning Corporation Émulsions de silicone
US10441527B2 (en) 2015-04-08 2019-10-15 Dow Silicones Corporation Fluid compositions and personal care
US11168213B2 (en) 2017-07-31 2021-11-09 Dow Silicones Corporation Moisture curable compositions
US11319446B2 (en) 2017-07-31 2022-05-03 Dow Silicones Corporation Moisture curable compositions
US11383182B2 (en) 2019-06-24 2022-07-12 Dow Silicones Corporation Linear silicone polyether foam control agent
JP2022186643A (ja) * 2021-06-04 2022-12-15 ダウ・東レ株式会社 ポリエーテル－ポリシロキサンブロック共重合体組成物の製造方法
WO2022255356A1 (fr) 2021-06-04 2022-12-08 ダウ・東レ株式会社 Procédé de fabrication d'une composition de copolymère séquencé de polyéther-polysiloxane, composition de copolymère séquencé de polyéther-polysiloxane et son utilisation
KR20240016412A (ko) 2021-06-04 2024-02-06 다우 도레이 캄파니 리미티드 폴리에테르-폴리실록산 블록 공중합체 조성물의 제조방법, 폴리에테르-폴리실록산 블록 공중합체 조성물 및 그의 용도
CN117597399A (zh) * 2021-06-04 2024-02-23 陶氏东丽株式会社 聚醚-聚硅氧烷嵌段共聚物组合物的制造方法、聚醚-聚硅氧烷嵌段共聚物组合物及其用途
KR20240028338A (ko) 2021-06-04 2024-03-05 다우 도레이 캄파니 리미티드 향상된 발포 특성을 갖는 폴리에테르-폴리실록산 블록 공중합체 함유 조성물, 이의 용도 및 이의 제조 방법
CN114672029A (zh) * 2022-04-27 2022-06-28 四川大学 一种非离子有机硅表面活性剂的制备方法

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