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WO1999032539A1 - Polymeres de silicone multicationiques - Google Patents

Polymeres de silicone multicationiques Download PDF

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Publication number
WO1999032539A1
WO1999032539A1 PCT/US1997/023622 US9723622W WO9932539A1 WO 1999032539 A1 WO1999032539 A1 WO 1999032539A1 US 9723622 W US9723622 W US 9723622W WO 9932539 A1 WO9932539 A1 WO 9932539A1
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WO
WIPO (PCT)
Prior art keywords
integer
carbons
alkyl
phenyl
benzyl
Prior art date
Application number
PCT/US1997/023622
Other languages
English (en)
Inventor
Masami Ono
Lonnie Liddell Bryant, Jr.
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP97954197A priority Critical patent/EP1040153A1/fr
Priority to JP51427099A priority patent/JP3297059B2/ja
Priority to AU58039/98A priority patent/AU5803998A/en
Priority to PCT/US1997/023622 priority patent/WO1999032539A1/fr
Priority to BR9714915-2A priority patent/BR9714915A/pt
Publication of WO1999032539A1 publication Critical patent/WO1999032539A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • 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
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • 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
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences

Definitions

  • the present invention relates to a multi-cationic silicone polymer having water-miscible characteristics.
  • the present invention further relates to fabric treatment and hair care compositions comprising the multi-cationic silicone polymer.
  • Silicone polymers are used in various fields of industry due to their general characteristics such as ability to lower surface tension, lubricity, ability to suppress suds, ability to provide glossiness, thermal stability, chemical stability, and very low bioactivity to humans. Silicone polymers with various substituents of a wide range of molecular weight are used for fabric and hard-surface treatment products, cosmetic and toiletry products, and pharmaceutical products. Many of these products are based on solvents and carriers which have high polarity.
  • Silicone polymers which are designed to be miscible with water or suitable for cosmetic and fabric use are known in the art, such as in Kazama et al. "Syntheses and Reactions of Uniform Size Poly(Dimethylsiloxane) with Various Reactive End Groups" Polymer Journal Vol. 19, No. 9, pp1091-1100, issued March 26, 1987, U. S. Patent 4,659,777 issued April 21 , 1987, Japanese Patent Laid-open (Kokai) H2-276824 published November 13, 1990, and Japanese Patent Laid-open (Kokai) H4-85334 and H4-85335 both published March 18, 1992.
  • silicone polymers are difficult to dissolve or mix with solvents having high polarity, particularly water. Based on the foregoing, there is a need for a silicone polymer which is water miscible, and thus suitable for formulating in products based on solvents and carriers which have high polarity. None of the existing art provides all of the advantages and benefits of the present invention.
  • the present invention is directed to a multi-cationic silicone polymer comprising: a) unit (A) and at least one of unit (B) and (C) of the following formulae:
  • ⁇ oxygen, nitrogen, sulfur or methylene
  • X is an integer of 0 to about 20
  • Y is an integer of 0 to about 20
  • Z is an integer of 0 to about 20
  • Q2 is CH2 or any of the following formulae:
  • R1 , R2. R3, and R4 are independently alkyl of 1 to 3 carbons, phenyl, benzyl, or phenethyl;
  • R ⁇ is ethylene or propylene;
  • R ⁇ is hydrogen, alkyl of 1 to 4 carbons, fluorocarbon of 1 to 4 carbons, phenyl, or benzyl;
  • R 7 is alkyl of 1 to about 30 carbons, phenyl, benzyl, or phenethyl;
  • Q 3 is OH, OR 8 , NH2, NHR 9 , SH, SR 10 , COOH, COOR 1 , or a halogen, wherein R 8 , R 9 , R 10 , and R 1 1 are alkyl or alkylene of 1 to about 20 carbons;
  • n is an integer of 1 to about 500; and
  • m is an integer of 1 to about 100;
  • the present invention is further directed to fabric treatment and hair care compositions comprising the multi-cationic silicone polymer.
  • the present invention is still further directed to a suitable method of making the multi-cationic silicone polymer.
  • the multi-cationic silicone polymer of the present invention comprises: a) unit (A) and at least one of unit (B) and (C) of the following formulae:
  • C 1 is oxygen, nitrogen, sulfur or methylene
  • X is an integer of 0 to about 20
  • Y is an integer of 0 to about 20
  • Z is an integer of 0 to about 20
  • Q 2 is CH2 or any of the following formulae:
  • R 1 , R2. R3, and R 4 are independently alkyl of 1 to 3 carbons, phenyl, benzyl, or phenethyl;
  • R5 is ethylene or propylene;
  • R 8 is hydrogen, alkyl of 1 to 4 carbons, fluorocarbon of 1 to 4 carbons, phenyl, or benzyl;
  • R 7 is alkyl of 1 to about 30 carbons, phenyl, benzyl, or phenethyl;
  • Q 8 is OH, OR 8 , NH2, NHR 9 SH, SR , COOH, COOR 1 1 , or a halogen, wherein R 8 , R 9 , R 10 , and R 1 are alkyl or alkylene of 1 to about 20 carbons;
  • n is an integer of 1 to about 500; and
  • m is an integer of 1 to about 100;
  • the multi-cationic silicone polymer of the present invention may comprise units (A) and (C) in a random order and (B) at a terminal, so long as at least one unit of (A) and at least one of either unit (B) or unit (C) are present.
  • the multi- cationic silicone polymers herein include at least one block cationic polyelectrolyte site as included in unit (B) or (C). With such a structure, the multi- cationic silicone polymer of the present invention can possess the characteristics of a silicone polymer as well as water-miscible characteristics of a cationic polymer.
  • the structural design and molecular weight of the multi-cationic silicone polymer of the present invention may be selected by the artisan to obtain those according to the desired product to which the polymer is formulated.
  • the multi-cationic silicone polymer of the present invention may terminate with an additional moiety or include adequate spacers as selected by the artisan to facilitate synthesis.
  • the multi-cationic silicone polymer of the present invention can be terminated with unit (B), or with unit (A) or (C) end-capped with an alkyl or a trimethylsilicon.
  • unit (C) is included, the multi-cationic silicone polymer comprises a branched moiety, whereas when unit (C) is not included, the multi- cationic silicone polymer is linear.
  • the multi-cationic silicone polymer of the present invention may be made only from unit (A) and unit (B).
  • the multi-cationic silicone polymer of the present invention is made of one unit of (A) and 2 units of (B)
  • the polymer includes 2 block cationic polyelectrolyte sites, and preferably takes the following general formula (la):
  • Q ⁇ is oxygen, nitrogen, sulfur or methylene
  • X is an integer of 0 to about 20
  • Y is an integer of 0 to about 20
  • Z is an integer of 0 to about 20
  • R 1 , R 2 , R3, and R 4 are independently alkyl of 1 to 3 carbons, phenyl, benzyl, or phenethyl
  • R5 is ethylene or propylene
  • R 8 is hydrogen, alkyl, or fluorocarbon of 1 to 10 carbons, phenyl, or benzyl
  • R 7 is alkyl of 1 to about 30 carbons or phenyl, benzyl, or phenethyl
  • n is an integer of 1 to about 500
  • m is an integer of 1 to about 100
  • X1 is sulfate, hydrosulfate, methylsulfate, carbonate, bicarbonate, chloride, bromide, iodide, or mixtures thereof.
  • Q 1 is oxygen or methylene;
  • X is an integer of 0 to 5;
  • Y is an integer of 0 to about 5;
  • Z is an integer of 0 to about 10;
  • R 1 , R 2 . R3, and R 4 are the same substituents wherein the substituent is an alkyl of 1 to 3 carbons or a phenyl, more preferably methyl;
  • R 8 is ethylene or propylene;
  • R 8 is hydrogen, methyl, ethyl, phenyl, or benzyl, more preferably methyl or ethyl;
  • R 7 is alkyl of 1 to about 30 carbons, preferably methyl or ethyl;
  • n is an integer of 5 to about 500 more preferably 5 to about 200; and
  • m is an integer of 3 to about 100;
  • X1 is sulfate, hydrosulfate, methylsulfate, carbonate, bicarbonate, chloride, bromide, io
  • silicone polymers of the following general formula (lb):
  • n is an integer of from about 5 to about 100
  • m is an integer of 3 to about 20
  • X 1 is selected from the group consisting of sulfate, hydrosulfate, methylsulfate, carbonate, hydrocarbonate, chloride, bromide, iodide, and mixtures thereof.
  • the multi-cationic silicone polymers of the present invention can be prepared by a synthesis route comprising three stages.
  • the first stage comprises ring-opening polymerization of an activated siloxane.
  • the first stage may further comprise a preliminary stage of preparing an activated siloxane.
  • the activated siloxane is a siloxane compound having its terminals substituted with a sulfonic ester or a halogen, preferably tosyl or mesyl sulfonic ester groups.
  • the starting silicone material to make this activated siloxane can be any linear or branched silicone having hydroxy functionality, wherein any other existing functionality are non-reactive with the below mentioned activating agents, nor the below mentioned cyclic iminoethers.
  • the starting silicone material are those comprising unit (A) mentioned above and at least one of units (B 1 ) and (C 1 ) of the following formulae: R3
  • Ql is oxygen, nitrogen, sulfur or methylene
  • X is an integer of 0 to about 20
  • Y is an integer of 0 to about 20
  • Z is an integer of 0 to about 20
  • R 4 are independently alkyl of 1 to 3 carbons, phenyl, benzyl, or phenethyl.
  • the starting silicone material can be any known in the art so long as at least one of the terminals is hydroxy.
  • the starting silicone material is a hydroxyalkyl-siloxane, hydroxyalkoxyalkyl-siloxane, and polyalkoxyl-siloxane. Examples of commercially available starting silicone materials are; X-22-160AS,
  • the starting silicone material as exemplified by dihydroxy-terminated polyalkylsiloxane as shown by formula (II) is subjected to the reaction with an activating agent to obtain an activated siloxane as shown by formula (III).
  • the activating agent is selected from the group consisting of sulfonic halide, wherein halide is a chloride, bromide, or iodide, P(Hal)3, P(Hal)s and SO2(Hal)2 or mixtures thereof; wherein (Hal) is a halogen selected from chloride, bromide, or iodide.
  • Preferable activating agents are tosyl chloride and mesyl chloride.
  • Mesyl chloride is exemplified as formula (XI).
  • Suitable mediums for carrying out this first stage of synthesis include inert solvents which provide an anhydrous condition.
  • exemplary inert solvents are absolute (hereinafter referred to as “abs.”) tetrahydrofuran (hereinafter referred to as "THF”), abs. benzene, abs. toluene, abs. triethylamine, abs. pyridine, and mixtures thereof.
  • the medium contains a Lewis base.
  • Exemplary Lewis bases include those which are liquid and solid such as abs. triethylamine, abs.
  • the medium contains at least a stoichiometric amount to the activating agent of a Lewis base, as it provides good yield. Still preferably, the medium contains: a volatile solvent such as abs. THF, abs. benzene, abs.
  • reaction can be carried out at room temperature at atmospheric pressure.
  • the activated siloxane can be any linear or branched silicone having halogen or epoxy functionalities, wherein any other existing functionalities are non-reactive with the below mentioned cyclic iminoethers.
  • the activated silioxane are those comprising unit (A) mentioned above and at least one of unit (B 2 ) or (C 2 ) of the following formulae:
  • Q ⁇ is oxygen, nitrogen, sulfur or methylene
  • X is an integer of 0 to about 20
  • Y is an integer of 0 to about 20
  • Z is an integer of 0 to about 20
  • R 8 and R 4 are independently alkyl of 1 to 3 carbons, phenyl, benzyl, or phenethyl
  • X 2 is a halide or an epoxy of the following formulae:
  • the activated siloxane can be any known in the art so long as it has at least one halogen or epoxy functionality.
  • the epoxy functionality can be a glycidyl-type or oxirane-type.
  • the activated siloxane has halogen functionalities.
  • these halogen terminated activated siloxane are used directly for ring- opening polymerization, the above mentioned reaction with the activating agents are unnecessary.
  • Examples of commercially available siloxane compounds with halogen functionalities which may be used directly as activated siloxane are; LMS-152 supplied by AZmax Co., Ltd., TSL9236, TSL9276, TSL9226, and TSL9206 supplied by Toshiba Silicone.
  • siloxane compounds having epoxy functionalities are; KF-105, X-22-163A, X-22-163B, X- 22-163C, KF-1001 , KF-101 , X-22-169AS, X-22-169B, KF-102, and X-22-173DX supplied by Shin-Etsu Chemical, SF8411 , SF8413, BY16-855, BY16-855B, BY16-839, SF8421 EG, and BY16-845 supplied by Toray Dow Corning Silicone, YF3965, XF42-A4439, TSF4730, XF42-A4438, XC96-A4462, XC96-A4463, XC96-A4464, XF42-A5041 , TSL9946, TSL9986, and TSL9906 supplied by Toshiba Silicone.
  • the activated siloxane either obtained by the preliminary reaction or obtained commercially is polymerized. through a
  • the cyclic iminoether is selected from the group consisting of 2- substituted-2-oxazoline, 2-substituted-5,6-dihydro-4H1 ,3-oxazine, and mixtures thereof.
  • cyclic iminoethers are 2-Z'-2-oxazoline and 2-Z'-oxazine wherein Z' is a hydrogen, alkyl, or fluorocarbon having 1 to 10 carbons, phenyl and benzyl, still preferable are 2-alkyl-2-oxazoline wherein the alkyl is made of 1 to 3 carbons, as exemplified as formula (XII).
  • the tosyl, mesyl or halide group of the activated siloxane (III) is known to be a leaving group on the attack by various nucleophilic monomers.
  • the tosyl and mesyl groups are preferable leaving groups.
  • the activated siloxane (III) is utilized as a macromolecular initiator for the synthesis of a block copolymer through nucleophilic reaction toward the tosylate or mesylate ester function or halide at the functionality by the cyclic iminoether which acts as a nucleophilic monomer.
  • Suitable mediums for carrying out this first stage of synthesis include inert solvents which provide an anhydrous condition.
  • inert solvents are abs. acetonitrile, abs. THF, abs. benzene, abs. toluene, abs. triethylamine, abs. pyridine, and mixtures thereof.
  • the medium contains a Lewis base.
  • Exemplary Lewis bases include those which are liquid and solid such as abs. triethylamine, abs. pyridine, dimethylamino pyridine (hereinafter referred to as "DMAP"), and 1 ,8-diazabicyclo[5.4.0.]-7-undecene (hereinafter referred to as DMAP)
  • DMAP dimethylamino pyridine
  • the medium contains at least a stoichiometric amount to the activated siloxane (III) of a Lewis base. It has been found that the existence of this amount of Lewis base significantly raises the conversion yield of the activated siloxane (III) to the resulting polyamide siloxane. Thus, the number of amide moieties of the present polymers (number "m" in the structure) can be controlled with significantly improved precision to provide the targeted polymer at high yield. Still preferably, the medium contains: a volatile solvent such as abs. acetonitrile, abs. THF, abs. benzene, abs.
  • toluene and mixtures thereof and a stoichiometric amount to the activating agent of a liquid Lewis base such as abs. triethylamine, abs. pyridine, and mixtures thereof.
  • a highly preferred medium is an acetonitrile solution of at least a stoichiometric amount to the activated siloxane of abs. triethylamine.
  • the reaction can be carried out at room temperature or elevated temperature at around atmospheric pressure.
  • the obtained reactant is treated with an alkali or alkali salt to obtain the polyamide siloxane (IV).
  • alkali or alkali salt include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, amines in an inert solvent, and metal or tetra-alkyl ammonium salts of organic acids.
  • aqueous alkaline such as sodium carbonate
  • the finally obtained polymer will have a hydroxy terminal.
  • the reactant is treated with amines in an inert solve, the finally obtained polymer will have amine or ammonium terminated terminals.
  • the reactant is treated with salts of organic acids, the finally obtained polymer will have carboxylate or ester terminals.
  • the second stage comprises reduction or hydrolysis of the obtained polyamide siloxane (IV).
  • Reduction can be done, for example, by reacting the polyamide siloxane with a reducing agent such as LiAI(OR) x H4_ x wherein R is methyl, ethyl, or isopropyl, and x is 0 or an integer from 1 to 3; preferably UAIH4 (lithium aluminum hydride) to obtain a reduced polyamide siloxane as exemplified by formula (V) as shown in the following scheme:
  • a reducing agent such as LiAI(OR) x H4_ x wherein R is methyl, ethyl, or isopropyl, and x is 0 or an integer from 1 to 3; preferably UAIH4 (lithium aluminum hydride)
  • Suitable mediums for carrying out such reduction include inert solvents such as abs. THF and abs. diethylether.
  • Reduction can be alternatively done by reacting the polyamide siloxane with an agent such as (C2H5)3 ⁇ + BF4 _ , C SiH, Cl3SiOH, Cl3SiOCH3, Cl3SiOC-2H5, (CH3)3SiCI, or dimethylsulfate in an inert solvent such as n-hexane or CH2CI2, followed by treatment with NaBCNH3or
  • Hydrolysis can be done, for example, by reacting the polyamide siloxane with aqueous and alcohol/aqueous solutions of strong acids and alkalis such as HCI, NaOH, KOH, or NaHC ⁇ 3 to obtain a hydrolyzed polyamide siloxane as exemplified by formula (VI) as shown in the following scheme:
  • Hydrolysis can be alternatively done by reacting the polyamide siloxane with an agent such as (C2H5)3 ⁇ + BF4", C ⁇ SiH, CI3S.OH, CI3S.OCH3, ClsSiOC ⁇ Hs, (CH3)3SiCI, H2N-NH2, or dimethylsulfate in an inert solvent such as abs. THF, diethylether, n-hexane or CH2CI2. followed by treatment with diluted aqueous solutions of acids or alkalis such as HCI, NaOH, KOH, NaHC ⁇ 3, K2CO3, Na2CO3, or KHCO3.
  • an agent such as (C2H5)3 ⁇ + BF4", C ⁇ SiH, CI3S.OH, CI3S.OCH3, ClsSiOC ⁇ Hs, (CH3)3SiCI, H2N-NH2, or dimethylsulfate in an inert solvent such as abs. THF, diethylether, n-
  • the third stage comprises quaternization of the obtained reduced polyamide siloxane (V) or hydrolyzed polyamide siloxane (VI) to obtain a multi- cationic siloxane polymer of the present invention. This can be carried out by adding a quaternizing agent.
  • Quaternizing agents are selected from the group consisting of monomethylsulfuric acid, dimethylsulfate, diethylsulfate, dimethylcarbonate, methylchloride, methyliodide, methylbromide, ethylchloride, ethyliodide, ethylbromide, benzylchloride, benzylbromide, benzyliodide, sulfuric acid, carboxylic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and mixtures thereof.
  • the multi-cationic silicone polymers of the present invention are believed to possess physical properties of both a silicone polymer and a cationic polymer. Specifically, the multi-cationic sites are believed to provide the multi-cationic silicone polymers herein to be water miscible, provide good deposition and/or adhesion to various substrates, and provide antibacterial effects. It is also believed that the multi-cationic silicone polymers herein provide useful characteristics of a silicone polymer.
  • the multi-cationic silicone polymers herein are useful in various field and employed in various products.
  • Non-limiting examples of its useful fields include: consumer products area, medical and pharmaceutical area, fabrics area, and other industrial and chemical areas.
  • the multi-cationic silicone polymers herein are suitable for: treating, conditioning, polishing or providing antibacterial activity to; laundry products, hair care products, skin care products, and hard surface treating products.
  • the multi-cationic silicone polymers herein are suitable for: conditioning, softening, anti-wrinkle, anti-static, anti- bacterial, and soil anti-redeposition of laundry products such as laundry detergents, soaps, fabric cleaners, fabric conditioners, fabric static controlling products, and fabric wrinkle controlling products; conditioning, anti-static, antibacterial, and fixative agents for hair care products such as shampoos, hair conditioners, hair treatments, hair sprays, and hair mousses; lubricating and deodorizing for skin care products such as cosmetics and antiperspirants; polishing, lubricating, and anti-bacterial for hard surface treating products such as furniture treating products, kitchen cleaners, and automobile cleaners or polishers; and for viscosity building or for providing controlled-release of active material or perfumes for any of the above.
  • the multi-cationic silicone polymers herein are useful for adhesive for transdermal delivery of actives, immobilized preparations, dental impressions, and anti-caries agents in dental/oral care formulations.
  • the multi-cationic silicone polymers herein are useful for algicides, anti-mold, anti-microbial, deodorizing, coating, mold-release, anti-friction, anti-foaming, anti-static, and for blending for composites.
  • the multi-cationic silicone polymers of the present invention are particularly useful for products which are based on solvents and carriers of high polarity, particularly water, and which are aimed to deposit on a substrate. Because of their water miscible nature, and multi-cationic sites, the multi-cationic silicone polymers of the present invention are thought to provide good deposition to the surface of substrates such as fabric, hair, skin, and hard-surfaces, particularly fabric and hair. Further, these multi-cationic silicone polymers provide bacteriocide effects to the aqueous formulations to which it is added.
  • the present invention further relates to fabric treatment compositions comprising the multi-cationic silicone polymer.
  • the multi-cationic silicone polymer of the present invention is useful for fabric treatment compositions, particularly those which comprise water as a carrier.
  • These fabric treatment compositions preferably comprise about 0.01 % to about 30% of the multi-cationic silicone polymer, and a suitable carrier.
  • Suitable carriers include water, ethanol, isopropanol, 1,2-propanediol, 1 ,3-propanediol, propylene carbonate, and mixtures thereof.
  • the fabric treatment compositions of the present invention provide anti-wrinkle benefit, softness, and antistatic benefit to the fabric which is treated.
  • the present invention further relates to hair care compositions comprising the multi-cationic silicone polymer.
  • the multi-cationic silicone polymer of the present invention is useful for hair care compositions, particularly those which comprise water as a carrier.
  • the hair care compositions preferably comprise about 0.01% to about 30% of the multi-cationic silicone polymer, and a suitable carrier.
  • Suitable carriers include water, lower alkyl alcohols, polyhydric alcohols, and mixtures thereof.
  • the lower alkyl alcohols useful herein are C-
  • the preferred lower alkyl alcohol is ethyl alcohol, isopropyl alcohol, and mixtures thereof.
  • the polyhydric alcohols useful herein include, for example, propylene glycol, hexylene glycol, glycerin, and propane diol, and mixtures thereof.
  • the hair care composition of the present invention may further comprise an additional hair care active such as detersive surfactants, conditioning agents, and fixative polymers.
  • the multi- cationic silicone polymer is particularly useful for making hair conditioning compositions further containing an additional conditioning agent selected from the group consisting of solid and liquid fatty compounds such as fatty alcohols, fatty acids, fatty acid derivatives, fatty alcohol derivatives, and steroids, solid and liquid hydrocarbons, cationic surfactants, other cationic polymers, and other silicone compounds.
  • the hair care compositions of the present invention provide conditioning benefit and antistatic benefit to the hair which is treated.
  • the polymer with formula (le) is suitably obtained by a synthesis route as shown in the following scheme:
  • X 8 " mixture of anions selected from the group consisting of SO4 2- , HSO4-, and CH3SO4-
  • a 60 mmole portion of mesyl chloride (1.5 equivalent) is added dropwise to an ice-cooled stirring solution of 20 mmole dihydroxy polysiloxane having an average 90 to 110 units (XXI) and 60 mmole triethylamine (1.5 equivalent) in 120 ml of abs. THF.
  • the reaction mixture is stirred for 1 hour under ice-cooling and for 1 day at room temperature. Removal of THF in vacuo after filtration is followed by the addition of 100 ml of ice water to the residue. This mixture is extracted with chloroform and the chloroform extract is washed with aq. sat. NaHC ⁇ 3 and dried with anhydrous sodium sulfate.
  • This syrup is further treated according to common treatment to obtain a mesyl derivative of polysiloxane (XXII).
  • Rinq-openin ⁇ polymerization A sealed reaction mixture of a 5.440 g portion of the obtained mesyl siloxane (XXII) (5 mmole), 100 mmole distilled 2-methyl-2-oxazoline and 10 mmole triethylamine in 50 ml of anhydrous acetonitrile in a sealed tube is stirred at 80°C for 24 hours. The reaction mixture is then cooled to room temperature and 20 ml of 10% sodium carbonate is added with stirring. The mixture is stirred for 2 hours, then the mixture is concentrated in vacuo. The mixture is extracted with chloroform and the chloroform extract is dried with anhydrous sodium sulfate. This syrup is further treated according to common treatment to obtain a polyamide siloxane (XXIII). Reduction
  • N-alkyl polyethyleneimino siloxane (XXIV). Quaternization A 8.1 g portion of the obtained N-alkyl polyethyleneimino siloxane (XXIV) is dissolved in 50 ml hexane and is treated with 3.2 g sodium hydrogen carbonate and 20 ml of water in ice bath cooling. To this mixture is added 4.4 g of dimethyl sulfate dropwise over a period of twenty minutes at 0°C. After the addition is complete the reaction mixture is stirred in ice bath for an additional hour, then the temperature is increased gradually until the reaction mixture reaches reflux, then continued stirring under reflux overnight.
  • XXIV N-alkyl polyethyleneimino siloxane
  • the polymer with formula (If) is suitably obtained using the polyamide siloxane XXIII as shown in Example 1 by a synthesis route as shown in the following scheme:
  • the polymer with formula (Ig) is suitably obtained by a synthesis route as shown in the following scheme:
  • X 8 " mixture of anions selected from the group consisting of SO4 2 ", HSO4" and CH3SO4- WO 99/32539 textbook., PCT/US97/23622
  • a 90 mmole portion of mesyl chloride (1.5 equivalent) is added dropwise to an ice-cooled stirring solution of 20 mmole branched carbinol polysiloxane having an average 50 to 70 units (structure XXXI) and 90 mmole triethylamine (1.5 equivalent) in 120 ml of abs. THF.
  • the reaction mixture is stirred for 1 hour under ice-cooling and for 1 day at room temperature. Removal of THF in vacuo after filtration is followed by the addition of the 100 ml of ice water to the residue.
  • a sealed reaction mixture of a 5 mmole portion of the obtained mesyl siloxane (XXXII), 150 mmole distilled 2-methyl-2-oxazoline and 15 mmole triethylamine in 50 ml of anhydrous acetonitrile in a sealed tube is stirred at 80°C for 24 hours.
  • the reaction mixture is then cooled to room temperature and 20 ml of 10% sodium carbonate is added with stirring.
  • the mixture is stirred for 2 hours, then the mixture is concentrated in vacuo.
  • the mixture is extracted with chloroform and the chloroform extract is dried with anhydrous sodium sulfate.
  • This syrup is further treated according to common treatment to obtain a polyamide siloxane (XXXIII).
  • N-alkyl polyethyleneimino siloxane (XXXIV) is dissolved in 50 ml hexane and is treated with 3.2 g of sodium hydrogen carbonate and 20 ml of water in ice bath cooling. To this mixture is added 4.4 g of dimethyl sulfate dropwise over a period of twenty minutes at 0°C. After the addition is complete the reaction mixture is stirred in ice bath for an additional hour, then the temperature is increased gradually until the reaction mixture reaches reflux, then continued stirring under reflux overnight. The reaction mixture is then cooled to room temperature and the hexane layer is separated and washed with sat. aq. NaHCO3 and water 3 times.
  • the polymer with formula (Ih) is suitably obtained by a synthesis route as shown in the following scheme prepared by starting material (XLI) and the same reacting agents, solvents, and conditions as described in Example 3 above.
  • X 8 - mixture of anions selected from the group consisting of SO4 2 -, HSO4-, and CH3SO4-
  • the multi-cationic silicone polymer embodiments disclosed and represented by the previous examples have many advantages. For example, they provide good deposition to the surface of fabric and hair, and provide bacteriocide effects when included in aqueous compositions. When incorporated in fabric treatment compositions, they provide anti-wrinkle benefit, softness, and anti-static benefit. When incorporated in hair conditioner compositions, they provide conditioning benefit and anti-static benefit.

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Abstract

L'invention concerne des polymères de silicone comprenant a) un motif (A) et au moins l'un des motifs (B) et (C) de formules (A) (B) (C), dans lesquelles Q1 désigne l'oxygène, l'azote, le soufre ou un méthylène; X est un nombre entier compris entre 0 et environ 20; Y est un nombre entier compris entre 0 et environ 20; Z est un nombre entier compris entre 0 et environ 20; Q2 désigne CH¿2? ou correspond à l'une des formules (a), (b), (c) ou (d), R?1, R2, R3 et R4¿ désignent, indépendamment, un alkyle de 1 à 3 carbones, un phényle, benzyle ou phénéthyle; R5 désigne l'éthylène ou le propylène; R6 désigne l'hydrogène, un alkyle de 1 à 4 carbones, un fluorocarbone de 1 à 4 carbones, un phényle ou un benzyle; R7 désigne un alkyle de 1 à environ 30 carbones, un phényle, benzyle ou phénéthyle; Q3 désigne un OH, OR8, NH2, NHR9, SH, SR10, COOH, COOR11 ou un halogène, où R?8, R9, R10 et R11¿ désignent un alkylène de 1 à environ 20 carbones; n est un nombre entier compris entre 1 et environ 500; et m est un nombre entier compris entre 1 et environ 100; et b) une quantité stoechiométrique d'un anion choisi dans le groupe comprenant les formes anioniques de sulfate, hydrosulfate, carbonate, bicarbonate, chlorure, bromure, iodure et mélanges de ceux-ci. L'invention concerne en outre des compositions pour le traitement de tissus et pour soins capillaires renfermant les polymères de silicone multicationiques précités. L'invention concerne également des procédés appropriés de fabrication desdits polymères de silicone.
PCT/US1997/023622 1997-12-19 1997-12-19 Polymeres de silicone multicationiques WO1999032539A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP97954197A EP1040153A1 (fr) 1997-12-19 1997-12-19 Polymeres de silicone multicationiques
JP51427099A JP3297059B2 (ja) 1997-12-19 1997-12-19 多価カチオン性シリコーンポリマー
AU58039/98A AU5803998A (en) 1997-12-19 1997-12-19 Multi-cationic silicone polymers
PCT/US1997/023622 WO1999032539A1 (fr) 1997-12-19 1997-12-19 Polymeres de silicone multicationiques
BR9714915-2A BR9714915A (pt) 1997-12-19 1997-12-19 Polìmero de silicone, composição de tratamento de tecido, composição de tratamento de cabelo e processo para produzir o polìmero de silicone

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PCT/US1997/023622 WO1999032539A1 (fr) 1997-12-19 1997-12-19 Polymeres de silicone multicationiques

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Cited By (30)

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DE10004321A1 (de) * 2000-02-01 2001-08-09 Wacker Chemie Gmbh Quarternäre Ammonium- und tertiäre Aminogruppen enthaltende Organosiliciumverbindungen, deren Herstellung und Verwendung
WO2002018528A1 (fr) * 2000-08-28 2002-03-07 The Procter & Gamble Company Compositions pour traitement de tissus renfermant des silicones cationiques et procedes utilisant celles-ci
WO2003066708A1 (fr) * 2002-02-05 2003-08-14 Ciba Spezialitätenchemie Pfersee GmbH Polysiloxanes contenant des groupes quaternaires a atomes d'azote
WO2003012020A3 (fr) * 2001-07-27 2003-10-30 Procter & Gamble Systeme de soins pour tissus permettant de conferer a un tissu des qualites anti-froissement
US6785924B1 (en) 2000-09-20 2004-09-07 The Procter & Gamble Company Method of orienting shoes in a washing machine and devices for aligning shoes in a washing machine
US6808701B2 (en) 2000-03-21 2004-10-26 Johnson & Johnson Consumer Companies, Inc. Conditioning compositions
DE10036533B4 (de) * 2000-07-27 2005-02-03 Ge Bayer Silicones Gmbh & Co. Kg Verwendung von polyquarternären Polysiloxanen als waschbeständige hydrophile Weichmacher
EP1565512A1 (fr) 2002-11-04 2005-08-24 GE Bayer Silicones GmbH & Co. KG Copolymeres polyamino-polysiloxane et/ou polyammonium-polysiloxane lineaires i
US6942818B2 (en) 2000-10-13 2005-09-13 Ciba Specialty Chemicals Corporation Polysiloxanes with quarternary groups featuring nitrogen atoms
DE10066215B4 (de) * 2000-07-27 2007-03-22 Ge Bayer Silicones Gmbh & Co. Kg Verwendung von polyquarternären Polysiloxanen als waschbeständige hydrophile Weichmacher von Textilien
US7211243B2 (en) 2001-05-14 2007-05-01 The Procter & Gamble Company Terminal aminofunctional polysiloxane hair conditioning compositions and their use in hair coloring compositions
WO2009130144A3 (fr) * 2008-04-23 2010-04-01 Basf Se Délivrance d’agents bénéfiques hydrophobes de savons pour le corps et analogues sur un substrat kératinique
US8378038B2 (en) 2007-02-06 2013-02-19 Basf Se Polysiloxane block copolymers
US8609077B2 (en) 2002-03-21 2013-12-17 Basf Se Polysiloxane compositions
US20150140052A1 (en) * 2013-07-29 2015-05-21 The Procter & Gamble Company Consumer Product Compositions Comprising Organopolysiloxane Emulsions
US20150147286A1 (en) * 2013-07-29 2015-05-28 The Procter & Gamble Company Consumer Product Compositions Comprising Organopolysiloxane Conditioning Polymers
JP2015531011A (ja) * 2012-07-27 2015-10-29 ザ プロクター アンド ギャンブルカンパニー オルガノポリシロキサンコンディショニングポリマーを含む消費者製品組成物
WO2015166038A1 (fr) * 2014-05-01 2015-11-05 Aquaporin A/S Procédé de synthèse d'un copolymère séquencé et ses utilisations
US9198849B2 (en) 2013-07-03 2015-12-01 The Procter & Gamble Company Shampoo composition comprising low viscosity emulsified silicone polymers
US9487736B2 (en) 2012-02-16 2016-11-08 Dow Corning Corporation Granulated foam control agent for the rinse cycle using siloxane wax
US9540489B2 (en) 2013-07-29 2017-01-10 The Procter & Gamble Company Blocky cationic organopolysiloxane
US9611362B2 (en) 2013-07-29 2017-04-04 The Procter & Gamble Company Cationic organopolysiloxanes
US9913795B2 (en) 2013-08-09 2018-03-13 Dow Corning Corporation Cosmetic compositions containing silicones
US9963470B2 (en) 2013-07-29 2018-05-08 The Procter & Gamble Company Branched blocky cationic organopolysiloxane
US9994795B2 (en) 2013-08-13 2018-06-12 Dow Silicones Corporation Method of forming an antifoam granule comprising a silicone polyether
US9993418B2 (en) 2013-07-29 2018-06-12 The Procter & Gamble Company Benefit agent emulsions and consumer products containing such emulsions
US10005110B2 (en) 2011-02-16 2018-06-26 Dow Silicones Corporation Foam control composition
US10081910B2 (en) 2013-07-29 2018-09-25 The Procter & Gamble Company Absorbent articles comprising organopolysiloxane conditioning polymers
US10363211B2 (en) 2013-09-27 2019-07-30 The Procter And Gamble Company Hair conditioning compositions comprising low viscosity emulsified silicone polymers
US10414873B2 (en) 2013-07-29 2019-09-17 The Procter & Gamble Company Organopolysiloxane polymers

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Cited By (42)

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Publication number Priority date Publication date Assignee Title
DE10004321A1 (de) * 2000-02-01 2001-08-09 Wacker Chemie Gmbh Quarternäre Ammonium- und tertiäre Aminogruppen enthaltende Organosiliciumverbindungen, deren Herstellung und Verwendung
US6808701B2 (en) 2000-03-21 2004-10-26 Johnson & Johnson Consumer Companies, Inc. Conditioning compositions
DE10066215B4 (de) * 2000-07-27 2007-03-22 Ge Bayer Silicones Gmbh & Co. Kg Verwendung von polyquarternären Polysiloxanen als waschbeständige hydrophile Weichmacher von Textilien
DE10036533B4 (de) * 2000-07-27 2005-02-03 Ge Bayer Silicones Gmbh & Co. Kg Verwendung von polyquarternären Polysiloxanen als waschbeständige hydrophile Weichmacher
WO2002018528A1 (fr) * 2000-08-28 2002-03-07 The Procter & Gamble Company Compositions pour traitement de tissus renfermant des silicones cationiques et procedes utilisant celles-ci
CN100422300C (zh) * 2000-08-28 2008-10-01 宝洁公司 含有阳离子聚硅氧烷的织物护理组合物及其使用方法
US7384903B2 (en) 2000-08-28 2008-06-10 The Procter & Gamble Company Fabric care and perfume compositions and systems comprising cationic silicones and methods employing same
AU2001286709B2 (en) * 2000-08-28 2005-10-06 The Procter & Gamble Company Fabric care compositions comprising cationic silicones and methods employing same
US6785924B1 (en) 2000-09-20 2004-09-07 The Procter & Gamble Company Method of orienting shoes in a washing machine and devices for aligning shoes in a washing machine
US6942818B2 (en) 2000-10-13 2005-09-13 Ciba Specialty Chemicals Corporation Polysiloxanes with quarternary groups featuring nitrogen atoms
US7211243B2 (en) 2001-05-14 2007-05-01 The Procter & Gamble Company Terminal aminofunctional polysiloxane hair conditioning compositions and their use in hair coloring compositions
US7196048B2 (en) 2001-07-27 2007-03-27 The Procter & Gamble Co. Fabric care systems for providing anti-wrinkle benefits to fabric
US6818610B2 (en) 2001-07-27 2004-11-16 Procter & Gamble Company Fabric care systems for providing anti-wrinkle benefits to fabric
WO2003012020A3 (fr) * 2001-07-27 2003-10-30 Procter & Gamble Systeme de soins pour tissus permettant de conferer a un tissu des qualites anti-froissement
WO2003066708A1 (fr) * 2002-02-05 2003-08-14 Ciba Spezialitätenchemie Pfersee GmbH Polysiloxanes contenant des groupes quaternaires a atomes d'azote
US8609077B2 (en) 2002-03-21 2013-12-17 Basf Se Polysiloxane compositions
EP1565512A1 (fr) 2002-11-04 2005-08-24 GE Bayer Silicones GmbH & Co. KG Copolymeres polyamino-polysiloxane et/ou polyammonium-polysiloxane lineaires i
EP1565512B1 (fr) * 2002-11-04 2018-07-04 Momentive Performance Materials GmbH Copolymères polyamino-polysiloxane et/ou polyammonium-polysiloxane linéaires i
US8378038B2 (en) 2007-02-06 2013-02-19 Basf Se Polysiloxane block copolymers
US9669243B2 (en) 2008-04-23 2017-06-06 Basf Se Delivery of hydrophobic benefit agents from bodywashes and the like onto a keratinous substrate
WO2009130144A3 (fr) * 2008-04-23 2010-04-01 Basf Se Délivrance d’agents bénéfiques hydrophobes de savons pour le corps et analogues sur un substrat kératinique
US10005110B2 (en) 2011-02-16 2018-06-26 Dow Silicones Corporation Foam control composition
US9487736B2 (en) 2012-02-16 2016-11-08 Dow Corning Corporation Granulated foam control agent for the rinse cycle using siloxane wax
RU2606390C2 (ru) * 2012-07-27 2017-01-10 Дзе Проктер Энд Гэмбл Компани Полиорганосилоксановые полимеры
JP2015531011A (ja) * 2012-07-27 2015-10-29 ザ プロクター アンド ギャンブルカンパニー オルガノポリシロキサンコンディショニングポリマーを含む消費者製品組成物
RU2606393C2 (ru) * 2012-07-27 2017-01-10 Дзе Проктер Энд Гэмбл Компани Полиорганосилоксановые полимеры
US9198849B2 (en) 2013-07-03 2015-12-01 The Procter & Gamble Company Shampoo composition comprising low viscosity emulsified silicone polymers
US20150140052A1 (en) * 2013-07-29 2015-05-21 The Procter & Gamble Company Consumer Product Compositions Comprising Organopolysiloxane Emulsions
US10081910B2 (en) 2013-07-29 2018-09-25 The Procter & Gamble Company Absorbent articles comprising organopolysiloxane conditioning polymers
US9611362B2 (en) 2013-07-29 2017-04-04 The Procter & Gamble Company Cationic organopolysiloxanes
US20150147286A1 (en) * 2013-07-29 2015-05-28 The Procter & Gamble Company Consumer Product Compositions Comprising Organopolysiloxane Conditioning Polymers
US9701929B2 (en) 2013-07-29 2017-07-11 The Procter & Gamble Company Consumer product compositions comprising organopolysiloxane emulsions
US9963470B2 (en) 2013-07-29 2018-05-08 The Procter & Gamble Company Branched blocky cationic organopolysiloxane
US9580670B2 (en) 2013-07-29 2017-02-28 The Procter & Gamble Company Consumer product compositions comprising organopolysiloxane conditioning polymers
US9993418B2 (en) 2013-07-29 2018-06-12 The Procter & Gamble Company Benefit agent emulsions and consumer products containing such emulsions
US9540489B2 (en) 2013-07-29 2017-01-10 The Procter & Gamble Company Blocky cationic organopolysiloxane
US10414873B2 (en) 2013-07-29 2019-09-17 The Procter & Gamble Company Organopolysiloxane polymers
US9913795B2 (en) 2013-08-09 2018-03-13 Dow Corning Corporation Cosmetic compositions containing silicones
US9994795B2 (en) 2013-08-13 2018-06-12 Dow Silicones Corporation Method of forming an antifoam granule comprising a silicone polyether
US10689601B2 (en) 2013-08-13 2020-06-23 Dow Silicones Corporation Method of forming an antifoam granule containing a silicone polyether
US10363211B2 (en) 2013-09-27 2019-07-30 The Procter And Gamble Company Hair conditioning compositions comprising low viscosity emulsified silicone polymers
WO2015166038A1 (fr) * 2014-05-01 2015-11-05 Aquaporin A/S Procédé de synthèse d'un copolymère séquencé et ses utilisations

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