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WO2002006380A2 - Nouveaux polymeres antimicrobiens et composition contenant lesdits polymeres - Google Patents

Nouveaux polymeres antimicrobiens et composition contenant lesdits polymeres Download PDF

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Publication number
WO2002006380A2
WO2002006380A2 PCT/US2000/019579 US0019579W WO0206380A2 WO 2002006380 A2 WO2002006380 A2 WO 2002006380A2 US 0019579 W US0019579 W US 0019579W WO 0206380 A2 WO0206380 A2 WO 0206380A2
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Prior art keywords
polymer
ether
group
providing
independently
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WO2002006380A3 (fr
Inventor
Lonnie Liddell Bryant, Jr.
Gong-Xiang Chen
Ming-Hua Chen
Masami Ono
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to AU2000263528A priority Critical patent/AU2000263528A1/en
Priority to PCT/US2000/019579 priority patent/WO2002006380A2/fr
Publication of WO2002006380A2 publication Critical patent/WO2002006380A2/fr
Publication of WO2002006380A3 publication Critical patent/WO2002006380A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • 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
    • A61K8/90—Block copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/50—Ethers of hydroxy amines of undetermined structure, e.g. obtained by reactions of epoxides with hydroxy amines
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5426—Polymers characterized by specific structures/properties characterized by the charge cationic
    • 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

Definitions

  • the present invention relates to polymers and compositions containing the same. Specifically, the present invention relates to polymers having an antimicrobial activity, and compositions containing the same.
  • Microbes and especially bacteria, are known to cause diseases and/or infections in humans and other organisms with whom they come in contact. To reduce the likelihood that microbes will come in contact with people, it is known to wash items with soap and water. Such washing may reduce the concentration of microbes on the surface of hands, clothing, and the like. Furthermore, it is known that certain substances having an anti-microbial efficacy (e.g. antibiotics) may actually kill microbes, and therefore may be used to help sterilize items, such as surgical equipment, which need to be free of microbes.
  • antibiotics an anti-microbial efficacy
  • anti-microbial substances such as antibiotics have become increasingly common, it has been found that microbes are becoming increasingly resistant to these traditional antibiotics. Recently, bacteria have even developed resistance, and even immunity, to multiple antibiotics.
  • consumer products which remove or kill microbes from everyday items such as clothing, hard surfaces, and skin.
  • consumer products have varying degrees of actual anti-microbial efficacy. Consumers may especially desire both a short-term and a long-term anti-microbial benefit from a product.
  • the need exists for a novel and improved compound which has an anti-microbial effect.
  • the need also exists for an improved consumer product containing such a compound.
  • the present invention relates to a polymer selected from the group of a linear polymer, a branched polymer, and a mixture thereof.
  • the linear polymer has the structure:
  • each R. is independently a C 2 -C 6 alkyl
  • each R 2 is independently a C 6 -C 22 alkyl
  • each R 3 is independently a C r C 12 alkyl.
  • a is from about 1 to about 20
  • b is about 1 to about 20
  • c is about 1 to about 50
  • each X " is an anion.
  • the branched polymer has the structure:
  • each B independently has the structure:
  • each R 4 independently has the structure: -(R,-Y)p-R,-OH
  • Each p is independently from about 1 to about 20, and the total of all p in the branched polymer is from about 2 to about 40.
  • Each X " is an anion, a is from about 1 to about 20, b is about 1 to about 20, c is about 1 to about 50, each d is independently 1 or 2, and e is a number equal to the number of quaternized nitrogens in A and B.
  • the novel polymer described herein may surprisingly provide one or more benefits such as an anti-microbial effect, a hair conditioning benefit, a fabric softening benefit, a moisturizing benefit, and/or a lubrication benefit when included in a consumer product.
  • the polymer herein provides an anti-microbial effect in combination with one or more of the above-mentioned benefits.
  • the polymer herein may be especially useful in a hair care composition, a laundry detergent composition, a hard surface cleaning composition, a deodorizing composition, and/or a sanitizing composition, as the multiple cationically-charged groups provide a strong attraction to negatively- charged surfaces.
  • a hair care composition a laundry detergent composition, a hard surface cleaning composition, a deodorizing composition, and/or a sanitizing composition
  • alkyl means a hydrocarbon moiety which is straight, cyclic, or branched, and saturated or unsaturated. Unless otherwise specified, alkyl moieties are preferably saturated or unsaturated with double bonds, preferably with one or two double bonds.
  • anti-microbial means that the indicated substance decreases the concentration of microbes, either immediately, or over a period of time. This may occur, for example, by killing existing microbes, by reducing microbe numbers below the level required for a sustainable population, and/or by inhibiting microbial growth and/or reproduction.
  • microbe indicates a bacteria, a fungus, a protozoa and/or other microorganisms, especially bacteria and fungus, and more especially gram negative bacteria and gram positive bacteria.
  • the novel polymer herein is either a linear polymer, a branched polymer, or a mixture thereof.
  • the polymer has a plurality of quaternized nitrogen moieties, wherein at least two nitrogen moieties are separated by at least one alkoxy group.
  • linear polymer means that any side groups attached to the main polymer chain are unsubstituted alkyl groups, such as R 2 and R 3 , which are described below.
  • the linear polymer useful herein has the formula:
  • each R. is independently a C 2 -C 6 alkyl, preferably a C 2 -C 4 alkyl, and more preferably a C 2 H 4 alkyl, or a straight-chain C 3 H 6 alkyl.
  • Each R 2 is independently a C 6 -C 22 alkyl, preferably a C 6 -C 18 alkyl.
  • each R 3 is independently a C r C 12 alkyl, preferably a C r C 12 straight chain alkyl, and more preferably a saturated C r C 4 straight chain alkyl.
  • a "linear polymer" as defined herein may contain unsubstituted alkyl groups such as R 2 and R 3 which are attached to a quaternized nitrogen moiety.
  • a is from about 1 to about 20, preferably from about 1 to about 10, and more preferably from about 3 to about 7; b is about 1 to about 20, preferably from about 1 to about 10, and more preferably from about 3 to about 7; c is about 1 to about 50, preferably from about 1 to about 25, and more preferably from about 1 to about 20; and each X " is an anion, where the total charge of all X " is sufficient to balance the charge of the molecule.
  • X " may be one or more anions, which have a single negative charge, or one or more multiply-valent anions.
  • X " is a halide, a sulfate, an organosulfate, or a mixture thereof, and more preferably a chloride, a bromide, a methylsulfate, or a mixture thereof.
  • the number quaternized nitrogens in the linear polymer (as represented by a + b) is from about 6 to about 14, as such linear polymers are more easily formed by the processes described herein.
  • the branched polymer useful herein has the formula:
  • each B independently has the structure:
  • each R 4 independently has the structure:
  • Each Y is independently a nitrogen or an oxygen. If Y is a nitrogen, it may be a charged or uncharged, substituted and/or quaternized nitrogen. Any substitutions on a Y which is a nitrogen are selected from the group consisting of H, R 3 , and R 4 , wherein R 3 is defined as above in the linear polymer.
  • Each p is independently from about 1 to about 20, preferably from about 1 to about 10, and more preferably form about 1 to about 8, while the total of all p in the branched polymer is from about 2 to about 40, preferably from about 2 to about 20.
  • At least one nitrogen in A there is at least one nitrogen in A, and at least one nitrogen in B. Furthermore, at least one nitrogen in A is quaternized and at least one nitrogen in B is quaternized, preferably from about 50% to about 100% of the nitrogens in A are quaternized and from about 50% to about 100% of the nitrogens in B are quaternized, and more preferably from about 100% of the nitrogens in A are quaternized and from about 100% of the nitrogens in B are quaternized.
  • Each R n ⁇ X " , a, b, and c is defined as described above for the linear polymer, while each d is independently 1 or 2.
  • such a polymer may be described as a polyamine ether block polymer containing a plurality of quaternized nitrogen groups.
  • at least one R 4 group has the structure:
  • R ⁇ — Y — (R ⁇ — Y)p— ⁇ — OH and preferably at least one R 4 group in A and at least one R 4 group in B has the structure:
  • the branched polymer herein must contain at least one quaternized nitrogen in A and at least one quaternized nitrogen in B, it is recognized that not all nitrogens need to be quaternized.
  • the branched polymer may comprise a mixture of quaternized nitrogens and unquatemized nitrogens. Specifically, the ratio of quaternized nitrogens to unquatemized nitrogens may be adjusted as desired via, for example, adjusting the amount of quatemizing agent employed in the process described herein. In a highly preferred embodiment, the branched polymer has from about 2 to about 20 quaternized nitrogens therein.
  • the polymer herein may provide one or more benefits when included in a consumer product, such as, for example, an anti-microbial effect, and/or a fiber (e.g., hair or fabric fibers) conditioning or softening benefit.
  • a fiber e.g., hair or fabric fibers
  • the present polymer may provide an especially effective anti-microbial effect against a microbe, such as a gram-positive bacteria, a gram-negative bacteria, a fungus, a protozoa, and/or a mixture thereof, preferably a gram-positive bacteria, a gram-negative bacteria and/or a fungus, and more preferably a gram-positive bacteria, a gram-negative bacteria.
  • a microbe such as a gram-positive bacteria, a gram-negative bacteria and/or a fungus, and more preferably a gram-positive bacteria, a gram-negative bacteria.
  • the linear polymer and the branched polymer herein provide such an anti-microbial effect by one or more mechanisms such as disruption of cell membranes and/or disruption of cell processes by penetrating the cell membrane and/or the cell. This in turn may kill existing microbes, reduce microbe numbers below the level required for a sustainable population, and/or inhibit microbial growth and/or reproduction.
  • a fiber conditioning or softening benefit may result from, for example, a moisturizing or lubricating effect when the polymer is applied to a fiber, such as a fabric and/or hair.
  • the polymers by virtue of their quaternized nitrogen groups and/or their ether group(s), have a particularly strong affinity towards such fibers, and especially negatively charged fibers.
  • the polymer may therefore be attracted to, or even penetrate fibers to provide a conditioning or lubricating benefit; i.e., the polymer may provide a lubricating effect by smoothening the surface of the fiber.
  • the polymers In addition to being attracted to the fibers, the polymers, especially those having a plurality of ether groups, also have a strong affinity towards water. Thus, the polymers may serve to bind water to the fiber to provide a noticeable moisturizing benefit.
  • the polymer may also reduce wrinkling by disrupting inter-fiber hydrogen bonds in, for example, a fabric article.
  • the polymer may also reduce or negate the static charge of a fiber to reduce static cling, and/or fly-away hair, which in turn makes the fabric/hair more manageable.
  • the polymer may be included in a consumer product composition in an effective amount.
  • the term "effective amount" varies according to many factors such as product category, the desired benefit sought, the method for applying the polymer to achieve the desired benefit, etc.
  • an effective amount of polymer to provide one or more desirable benefits will be at least about 0.001%, preferably from about 0.001% to about 50%, more preferably from about 0.01% to about 30%, and even more preferably from about 0.05% to about 15%, by weight of the final consumer product composition. It is recognized that a consumer product compositions for direct application typically requires a lower amount of the polymer to achieve the desired benefit, while a consumer product composition which is applied indirectly, or in a diluted form typically requires a higher amount of the polymer to achieve the desired benefit.
  • the polymer herein is stable under typical consumer product manufacturing, and storage conditions (e.g., temperature, humidity), and may therefore provide benefits over an extended period of time.
  • the polymer herein may be especially useful in conditions where other ingredients are inadequate, for example, in a liquid composition.
  • the polymer herein is typically compatible with a wide variety of ingredients typically found in a consumer product composition.
  • a non-limiting example of a preferred consumer product composition includes an antiseptic or disinfecting composition, a fabric detergent and/or fabric conditioner, a fabric treatment composition, a hair shampoo and/or hair conditioner, a hand, body, and/or toilet soap, a hard surface cleaner, etc.
  • a consumer product composition is not limited by any particular physical form, and thus may be a liquid, a gel, a spray, a foam, a solid, a powder, or even an aerosol, as appropriate.
  • a carrier is present in the consumer product composition to deliver the polymer to the intended target and/or surface.
  • the term "carrier” indicates any substance or composition which is not the polymer herein, and which provides a delivery mechanism to apply the polymer, either directly or indirectly, to the targeted surface and/or item.
  • the carrier may contain additional active ingredients which provide additional benefits, or may be completely inert, as desired.
  • the carrier may be in any physical form, as appropriate.
  • the polymer may be included in addition to, and/or in place of, any already-present anti- microbially-effective agent(s) and/or conditioning compounds within the carrier.
  • the antiseptic or disinfecting composition which may act as a carrier herein is typically either alcohol- or water-based, and typically also contains a surfactant, a dye, a perfume, etc.
  • Preferred examples of the antiseptic or disinfecting composition which may act as a carrier for the polymer herein are described in, for example, U.S. Patent No. 6,048,836 to Romano, et al., issued on April 11, 2000; U.S. Patent No. 5,403,587 to McCue and Smialowicz, issued on April 4, 1995; U.S. Patent No. 5,174,990 to Douglas, Issued December 29, 1992; U.S. Patent No. 5,135,623 to Dziabo and Ripley, issued on August 4, 1992; U.S. Patent No.
  • a fabric detergent composition typically contains one or more anionic, nonionic, cationic, or amphoteric surfactants, a builder, a chelant, a perfume, a soil-dispersing aid, an anti-redeposition aid, a dye-transfer inhibitor, and/or other ingredients known in the art.
  • a fabric conditioner may also contain similar ingredients, as well as a fabric softening active, an anti-static active, etc. Examples of such a fabric detergent and/or a fabric conditioner are described in, for example, PCT Patent Application No. U.S.
  • Preferred examples of the fabric treatment composition which may act as a carrier for the polymer herein include a bleaching composition, a finishing composition, etc.
  • a bleaching composition typically contains either a chlorine bleach and/or an oxygen bleach, and is typically added to a fabric article in diluted form.
  • Highly preferred examples of a bleaching composition useful herein are described in, for example, U.S. Patent. No. 5,559,090 to Scialla and Cardola, issued on September 24, 1996; U.S. Patent. No. 5,536,438 to Scialla, et al., issued on July 16, 1996; WO 95/21122 to Rapisarda, et al., published on August 10, 1995; U.S. Patent No.
  • the finishing composition which may act as a carrier for the polymer herein is typically applied to a fabric article as one of the last steps prior to use (e.g., wearing) and/or in-between uses.
  • the finishing composition provides the fabric article with one or more desirable properties such as crispness, wrinkle reduction, shape maintenance, color enhancement, whiteness enhancement, improved in-wear comfort, malodor reduction/prevention, stain protection, a desirable scent, fiber integrity maintenance, etc.
  • the finishing composition is typically an ironing composition, a fabric styling composition, a wrinkle reduction composition, a stain prevention composition, or a combination thereof.
  • Preferred finishing compositions useful herein include those described in U.S. Patent No. 6,033,679 to Woo, et al., issued on March 7, 2000; U.S. Patent No.
  • the finishing composition acts as a fabric refresher composition and/or a home dry cleaning composition which, respectively, reduces odors, and/or reduces the need for dry cleaning of the fabric article.
  • Highly preferred fabric refresher compositions are include those described in, U.S. Patent No. 5,714,137 to Trinh, et al., issued on February 3, 1998; U.S. Patent No. 5,593,670 to Trinh, et al., issued January 14, 1997; and U.S. Patent No. 5,939,060 to Trinh, et al., issued on August 17, 1999.
  • the polymer herein may also be included in a home dry cleaning apparatus or kit as described in, for example, U.S. Patent No.
  • a hair shampoo typically contains a surfactant, preferably an anionic and/or nonionic surfactant, a humectant, a perfume, water, a dye, and/or other optional ingredients.
  • a hair conditioner typically contains a silicone and/or cationic hair conditioning compound, in addition to any of the ingredients described for a hair shampoo.
  • a preferred hair shampoo and/or hair conditioner which may act as a carrier for the polymer herein is described in, for example, U.S. Patent No. 5,955,066 to Sako, et al., issued on September 21 , 1999; and PCT Publication WO 97/31616 A1 to Mitsumatsu and Nakamura, published on September 4, 1997.
  • a hand, body, and/or toilet soap and/or wipe is typically formulated for mild cleaning of the human body, and thus contains a mild surfactant, typically an anionic surfactant, a moisturizing agent, and other typical ingredients.
  • a mild surfactant typically an anionic surfactant, a moisturizing agent, and other typical ingredients.
  • a preferred hand, body, and/or toilet soap and/or wipe which may act as a carrier for the polymer herein is described in, for example, U.S. Patent No.
  • a hard surface cleaner typically contains a surfactant, and may contain an abrasive for cleaning dishes, ceramic, wood, flooring, walls, windows, etc.
  • a preferred hard surface cleaner which may act as a carrier for the polymer herein is described in, for example, U.S. Patent No. 5,562,850 to Woo, et al., issued on October 8, 1996; WO 97/44417 A1 to Askew, et al., published on November 27, 1997; and WO 97/25396 to Cardola, et al., published on July 17, 1997.
  • polymers of the present invention may be prepared by a variety of synthetic routes; preferably the polymer is prepared according to one of the two synthetic routes described, below.
  • an activated ether preferably an activated polyether
  • the activated ether is an ether compound containing a sulfonic ester group, a halogen group, and/or an epoxy group which has been substituted for a hydroxyl group.
  • the activated ether is an ether compound having its terminal hydroxyl group, or at least one pendant hydroxyl group, preferably its terminal hydroxyl group, substituted with a sulfonic ester or a halogen, preferably a tosyl or a mesyl sulfonic ester group.
  • the activated ether may be any linear or branched ether compound having a halogen group and/or an epoxy group, wherein any other existing functional groups are non-reactive with the below-mentioned cyclic iminoether.
  • the epoxy group is preferably a glycidyl-type epoxy group or an oxirane-type epoxy group.
  • the activated ether useful herein may be either purchased, or synthesized.
  • activated ethers examples include 2-chloroethyl methane sulfonate, available from Aldrich (Milwaukee, Wisconsin, USA; CAS # [3570-58-9]; Aldrich Catalog No. C4, 170-3) and bis-2-chloroethyl ether (Milwaukee, Wisconsin, USA; CAS # [111-44-4]; Aldrich Catalog No. C4.113-4).
  • the activated ether may be synthesized by providing an ether compound (either linear or branched), preferably a polyether compound, which contains at least one reactive hydroxyl group, preferably a terminal, reactive hydroxyl group, a halogen group, and/or an epoxy group.
  • any other existing functional groups should be non-reactive with the below-mentioned activating agents, and the below-mentioned cyclic iminoethers in the synthesis conditions described.
  • Preferred ether compounds useful herein include commonly available dihydroxy-terminated poly(oxyalkylene)ethers.
  • An activating agent is also provided which is selected from the group consisting of R-S0 3 (hal), R-P(hal) 3 , R-P(hai) 5 , and R-S0 2 (hal) 2 or mixtures thereof, wherein R is an alkyl group, and each hal is a halide independently selected from chloride, bromide, and iodide.
  • Preferable activating agents are tosyl chloride and mesyl chloride.
  • An anhydrous, inert solvent is also provided.
  • a preferred anhydrous, inert solvent is absolute (hereinafter referred to "abs.") tetrahydrofuran (hereinafter referred to as "THF”), abs. benzene, abs. toluene, abs. triethylamine, abs. pyridine, and a mixture thereof.
  • the anhydrous, inert solvent further contains a Lewis base.
  • a highly preferred Lewis base includes abs. triethylamine, abs. pyridine, dimethylamino pyridine, and 1,8-diazabicyclo[5.4.0]- 7-undecene. Absolute triethylamine and abs.
  • the absolute, inert solvent contains a Lewis base at a level at least equal to the stoichiometric amount of the activating agent, as it provides a significantly improved yield.
  • the anhydrous, inert solvent contains: a volatile solvent such as abs. benzene, abs. toluene, abs. THF and mixtures thereof, and a Lewis base, such as abs. triethylamine, abs. pyridine, and mixtures thereof, at a level at least equal to the stoichiometric amount of the activating agent.
  • the ether compound is then activated with the activating agent in the anhydrous, inert solvent, with or without the optional Lewis base, to form an activated ether, preferably an activated polyether.
  • the activation reaction is typically carried out at from about 5 °C to about 40 °C, and at atmospheric pressure.
  • the activated ether comprises a terminal halogen.
  • the activated ether comprising a terminal halogen may be used directly in a ring-opening polymerization reaction, without the need for an activating agent.
  • the activated ether preferably the activated polyether, is preferably polymerized through a ring-opening polymerization reaction. This may be accomplished by providing a cyclic iminoether and reacting the activated ether with the cyclic iminoether to form a polyamide ether.
  • the preferred cyclic iminoether useful herein is selected from the group consisting of 2-substituted-2- oxazoline, 2-substituted-5,6-dihydro-1 ,3-oxazine, and a mixture thereof, more preferably 2-Z'-2-oxazoline, 2-Z'-oxazine, and a mixture thereof, wherein Z' is a hydrogen, alkyl, or fluorocarbon having 1 to 10 carbons, phenyl and benzyl; even more preferably 2-alkyl-2-oxazoline, and a mixture thereof, wherein the alkyl contains from 1 to 3 carbons.
  • the tosyl group, mesyl group, and/or halide group of the activated ether is a known leaving group which is dislodged upon attack by various nucleophilic monomers.
  • the activated ether is used as a macromolecular initiator for the synthesis of a block copolymer through nucleophilic reaction toward the tosylate or mesylate ester group and/or the halide group by the cyclic iminoether which acts as a nucleophilic monomer.
  • the polyamide ether is thus obtained by a nucleophilic-substitution reaction which concentrates polyamide moieties at the locations on the polymer which were previously occupied by the above- mentioned leaving group(s).
  • the polyamide ether is a polyamide polyether.
  • Suitable mediums for carrying out this synthesis include anhydrous, inert solvent described above.
  • the anhydrous, inert solvent contains a Lewis base therein to facilitate the reaction, and/or to improve yields. More preferably, the medium contains Lewis base at a level at least equal to the stoichiometric amount of the activated ether. It has been found that the presence of this amount of Lewis base significantly raises the conversion yield of the activated ether to the desired polyamide ether. Thus, the number of amide moieties of the present polymers may be controlled with significantly improved precision to provide the targeted polymer in a relatively high yield.
  • the anhydrous, inert solvent contains: a volatile solvent such as abs. acetonitrile, abs.
  • THF triethylamine
  • pyridine a Lewis base
  • a highly preferred anhydrous, inert solvent is an acetonitrile containing abs. triethylamine in an amount at least equal to the stoichiometric amount of the activated ether.
  • the activated ether is reacted with the cyclic iminoether in the anhydrous, inert solvent to complete the ring-opening polymerization reaction.
  • This reaction may be carried out at room temperature or elevated temperature, and at around atmospheric pressure.
  • the obtained material is preferably, but not necessarily, treated with an alkali or alkali salt to stop the reaction and to obtain the polyamide ether.
  • Alkali and alkali salts useful herein include sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, an amine in an anhydrous, inert solvent, and/or a metal or tetra-alkyl ammonium salts of an organic acid.
  • the obtained material When the obtained material is treated with an amine in an anhydrous, inert solvent, the resulting polyamide ether will have amine terminus or ammonium terminus. When the obtained material is treated with a salt of an organic acid, the obtained polyamide ether will have a carboxylate terminus or an ester terminus.
  • a reducing agent and/or a hydrolyzing agent is optionally provided to react with the polyamide ether to form a polyamine ether.
  • reducing agents are known in the art, a preferred reducing agent includes LiAI(OR) x H 4 wherein R is methyl, ethyl, or isopropyl, and x is an integer from 0 to 3; preferably LiAIH 4 (lithium aluminum hydride) in the presence of an anhydrous, inert solvents such as abs. THF and abs. diethylether.
  • Reduction may also be accomplished by reacting the polyamide ether with an agent such as (C 2 H 5 ) 3 0 + BF 4 " , CI 3 SiH, CI 3 SiOH, CI 3 SiOCH 3 , CI 3 SiOC 2 H 5 , (CH 3 ) 3 SiCI or dimethylsulfate in an inert solvent such as n-hexane or CH 2 CI 2 , followed by treatment with NaB(CN)H 3 or NaBH 4 in diethylether, ethanol, or THF.
  • an agent such as (C 2 H 5 ) 3 0 + BF 4 " , CI 3 SiH, CI 3 SiOH, CI 3 SiOCH 3 , CI 3 SiOC 2 H 5 , (CH 3 ) 3 SiCI or dimethylsulfate in an inert solvent such as n-hexane or CH 2 CI 2 , followed by treatment with NaB(CN)H 3 or NaBH 4 in diethylether, ethanol, or THF
  • a hydrolyzing agent may be provided with which to hydrolyze the polyamide ether.
  • a preferred hydrolyzing agent useful herein is an aqueous or an aqueous-alcohol solution of a strong acid or an alkali such as HCI, NaOH, KOH, or NaHC0 3 . Hydrolysis may be accomplished, for example, by reacting the polyamide ether with the hydrolyzing agent to obtain a polyamine ether.
  • the polyamide ether may be both reduced and hydrolyzed by reducing the polyamide ether with a reducing agent such as (C 2 H 5 ) 3 0 + BF 4 " , CI 3 SiH, CI 3 SiOH, CI 3 SiOCH 3) CI 3 SiOC 2 H 5 , (CH 3 ) 3 SiCI and/or dimethylsulfate in an inert solvent such as n-hexane or CH 2 CI 2 , followed by treatment with a hydrolyzing agent such as a diluted aqueous solution of an acid or an alkali such as HCI, NaOH, KOH, NaHC0 3 , K 2 C0 3 , Na 2 C0 3 , KHC0 3 , and/or an aqueous solution of an inorganic salt such as NaCI, KCI, and/or NH 4 CI.
  • the polyamide ether is preferably a polyamide polyether and the polyamine ether is preferably a polyamine polyether.
  • the polyamine ether preferably the polyamine polyether, is then typically quaternized to obtain the polymer of the present invention.
  • the quaternizing agent useful herein is selected from the group consisting of monomethylsulfuric acid, dimethylsulfate, diethylsulfate, dimethylcarbonate, alkyl halides such as methylchloride, methyliodide, methylbromide, ethylchloride, ethyliodide, ethylbromide, benzylchloride, benzylbromide, benzyliodide; sulfuric acid, carboxylic acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and a mixture thereof.
  • the quaternized site is pH-dependent.
  • the quaternizing agent may be selected according to the desired characteristic of the polymer having a plurality of cationic moieties.
  • the polymer herein may also be prepared by a simplified two-step procedure reacting the activated ether described above directly with a polyamine via nucleophilic substitution, followed by quaternization with a quaternizing agent.
  • the activated ether described above may also be employed in nucleophilic substitution reactions with polyamines.
  • the nucleophilic sites are those nitrogen centers of the polyamines which displace the leaving groups of the preferred and previously described halide, tosyl ester, and/or mesyl ester derivatives of the activated ether.
  • the polyamine useful herein may have repeating C 2 -C 6 alkoxy units, either as straight-chain or branched, cyclic or aromatic moieties.
  • the degree of polymerization for a linear polyamine may range from about 2 to about 40, while the degree of polymerization of a branched polyamine (to form the branched polymer) may range from about 4 to about 80.
  • the polyamine may be either linear or branched. As this is a substitution reaction, a preferred leaving group includes a tosyl group and a mesyl group.
  • the activated ether is used as a macromolecular initiator for the synthesis of a block copolymer through a nucleophilic reaction toward the tosylate ester group, the mesylate ester group, or the halide group at any amine site of the polyamine.
  • the resultant polyamine ether (sometimes described as a polyamine ether block copolymer) may be linear or branched, as desired.
  • the quaternization will typically take place in a polar solvent, preferably in an alcohol, or an alcohol solution, and more preferably in ethanol or an ethanol solution.
  • the quaternization reaction may be carried out at around atmospheric pressure, and at either room temperature or elevated temperature.
  • the polymer herein may be identified by methods known in the art, such as nuclear magnetic resonance (hereinafter, "NMR").
  • a polyethylene oxide-block-poly (N, N'-dilauryl ethyleneimine) polymer according to the present invention is prepared according to the following process. Preparation of Mesyl Polyethylene Oxide
  • mesyl chloride (17.2 g; 0.15 mol) is added via an addition funnel to a stirred (magnetic) solution of polyethylene oxide-600 (30g; 0.05 mol) in 150 mL dried THF and triethylamine (15.2g; 0.15 mol) while cooling with ice water.
  • the reaction mixture is stirred while cooling in an ice bath for 2 hours, and then at room temperature for 24 hours. Then mixture is filtered and the precipitate is washed with abs. THF.
  • 100 mL NaHC0 3 saturated solution
  • the solution is extracted 3 times with 100 mL chloroform.
  • the mesyl polyethylene oxide formed above (30.3 g; 0.04 mol), 2-methyl-2-oxazoline (68 g; 0.8 mol), triethylamine (8.1 g; 0.08 mol) and acetonitrile (60 mL) are added in the presence of a N 2 atmosphere.
  • the tube was sealed and the mixture stirred under 80 °C for 24 hours.
  • the mixture is then cooled to room temperature and then poured into 20 ml aqueous Na 2 C0 3 (10% wt), and stirred for 2 hours.
  • the poly(ethylene oxide)-block- poly(N-acyl ethylene imine) (69 g; 0.6 mol acyl ethylene imine moieties) is dissolved in 180 mL water.
  • An aqueous solution of NaOH (36 g; 0.9 mol) in water 180 mL is added while stirring. The mixture is stirred at 100 °C for 24 hours. After cooling to room temperature, the insoluble product was isolated by filtration, and extracted with 100% methanol.
  • a polyethylene oxide-block-poly (N-lauryl, N'-methyl ethyleneimine) polymer according to the present invention is prepared according to the process of Example 1 , except that at the quaternization stage is replaced by the following.
  • polyethylene oxide-polyethylene imine (10 g, 0.097 mol amine units)
  • ethanol 80 mL
  • sodium carbonate (12.8 g, 0.12 mol
  • lauryl bromide (24.2 g, 0.097 mol).
  • the product is then dried in vacuum at 60 °C for 12 hours to obtain 19.6 g product.
  • This product is determined by NMR to be a polyethylene oxide-block-poly (N-lauryl, N'-methyl ethylene imine) polymer, corresponding to the following formula:
  • EXAMPLE 3 The following linear polymer of Example 2 is synthesized according to the process herein. This polymer has the structure:
  • MIC Minimum Inhibitory Concentration
  • the polymer has a significant anti-microbial efficacy across a wide range of microorganisms.
  • the polymers A and B are significantly more effective against a wide variety of microbes, than the comparative polymers C and D. While the data of this table that of the table in
  • Example 3 show slight differences, the values are within an acceptable error range (i.e., about a 4-fold difference). Furthermore, the compound of Example 2
  • a hair conditioning composition is prepared according to the following
  • An antimicrobial fabric conditioning composition is prepared according to the following formula (all levels are percentages, by weight of the final com osition :
  • EXAMPLE 7 An antimicrobial hard surface cleaning composition, especially for cleaning toilets, is prepared according to the following formulas (all levels are percentages, b wei ht of the final com osition :

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Abstract

L'invention concerne un nouveau polymère linéaire ou ramifié le cas échéant, comprenant une pluralité de groupes d'azote quaternaires. Ce nouveau polymère peut présenter un effet anti-microbien, et être bénéfique pour revitaliser les cheveux, adoucir un tissu, humidifier, et/ou lubrifier lorsqu'il est inclus dans un produit de consommation. Ce nouveau polymère peut être produit au moyen d'un ou plusieurs procédé(s), selon le désir.
PCT/US2000/019579 2000-07-18 2000-07-18 Nouveaux polymeres antimicrobiens et composition contenant lesdits polymeres Ceased WO2002006380A2 (fr)

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AU2000263528A AU2000263528A1 (en) 2000-07-18 2000-07-18 Novel, anti-microbial polymers and composition containing same
PCT/US2000/019579 WO2002006380A2 (fr) 2000-07-18 2000-07-18 Nouveaux polymeres antimicrobiens et composition contenant lesdits polymeres

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003068898A1 (fr) * 2002-02-12 2003-08-21 Creavis Gesellschaft Für Technologie Und Innovation Mbh Formulations pour le lavage et le nettoyage contenant des polymeres antimicrobiens
WO2008127416A3 (fr) * 2006-11-08 2008-12-11 Massachusetts Inst Technology Enduits polymères inactivant les virus et les bactéries

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4206295A (en) * 1973-06-11 1980-06-03 Merck & Co., Inc. Process of preparing poly[{alkyl-(3-ammoniopropyl)iminio}trimethylene dihalides]
CH599389B5 (fr) * 1975-12-23 1978-05-31 Ciba Geigy Ag
US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
DE19615286B4 (de) * 1996-04-18 2005-05-19 Cognis Deutschland Gmbh & Co. Kg Antimikrobielle Wirkstoffkonzentrate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003068898A1 (fr) * 2002-02-12 2003-08-21 Creavis Gesellschaft Für Technologie Und Innovation Mbh Formulations pour le lavage et le nettoyage contenant des polymeres antimicrobiens
WO2008127416A3 (fr) * 2006-11-08 2008-12-11 Massachusetts Inst Technology Enduits polymères inactivant les virus et les bactéries

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