WO2020252566A1 - Mélanges antimicrobiens à base de matière plastique, procédés pour leur préparation et leurs utilisations - Google Patents

Mélanges antimicrobiens à base de matière plastique, procédés pour leur préparation et leurs utilisations Download PDF

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WO2020252566A1
WO2020252566A1 PCT/CA2020/050800 CA2020050800W WO2020252566A1 WO 2020252566 A1 WO2020252566 A1 WO 2020252566A1 CA 2020050800 W CA2020050800 W CA 2020050800W WO 2020252566 A1 WO2020252566 A1 WO 2020252566A1
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lignin
plastic
quaternary ammonium
antimicrobial
blend
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PCT/CA2020/050800
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English (en)
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Minh Tan TON-THAT
Hongbo Li
Chi Woon Leung
Edmond Lam
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National Research Council Of Canada
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/201—Pre-melted polymers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2497/00—Characterised by the use of lignin-containing materials

Definitions

  • TITLE ANTIMICROBIAL PLASTIC BLENDS, PROCESSES FOR THE PREPARATION THEREOF AND USES THEREOF
  • the present application relates to antimicrobial plastic blends, to processes for preparing such blends and to uses of such blends, for example, as a surface for killing and/or inhibiting the growth of a microbe.
  • Antimicrobial plastics are a growing market due, for example, to consumer concerns with health and safety. They may be useful, for example, in combatting the transmission of infectious diseases, the degradation of materials by microorganisms, and/or the formation of odor and discoloration.
  • the dominant bacteria present are from the genus Staphylococcus , where 22.6% of the bacterial population are resistant to the antibiotic methicillin. 1
  • lignin As the second most abundant natural polymer after cellulose, lignin is generally more economically competitive and eco-friendly than existing organic and organometallic antimicrobial agents. Phenolic lignin fragments have been disclosed to have antimicrobial properties. For example, Zemak and co-workers 2 tested different lignin fragments against a variety of microbes including E. coli , S. cerevisae, C. albicans , B. licheniformis , M. luteus and A. niger (filamentous fungi).
  • lignin does not exhibit broad-spectrum antimicrobial activity.
  • Gram negative bacteria such as E. coli and S. enteriditis
  • caustic-extracted lignins 4 are not affected by caustic-extracted lignins 4 .
  • Lignin-gelatin 5 showed no antimicrobial activity over a broad spectrum of 26 bacteria, yeast and molds.
  • Antimicrobial activity for Escherichia coli and Staphylococcus aureus was reported by Gregorov and co-workers 6 for 2 wt% nano-Bjorkman lignin in polyethylene but the material was prepared via a solvent process, which is not cost-effective for industrial applications.
  • Ma et al. 7 have prepared a membrane with antifouling and antibacterial abilities from trimethyl quaternary ammonium salt grafted lignin (QAL) and polystyrene (PS).
  • QAL was prepared by grafting varying degrees of trimethyl quaternary ammonium ion monomer (prepared from the reaction of trimethylamine and epichlorohydrin) onto alkali lignin.
  • the membranes were prepared from a solvent process comprising adding a solution of PS dissolved in dichloromethane to a solution of QAL dissolved in dichloromethane to yield precipitates which were collected by filtration, washed with deionized water and then cast following the addition of 15% acetone. Cross-sections of the membranes were imaged by scanning electron microscopy (SEM) which showed increasing QAL content inside the membrane.
  • SEM scanning electron microscopy
  • Blends comprising quaternary ammonium-modified, lignin- containing materials dispersed in a polypropylene resin were prepared by a process comprising compounding the components in an extruder to form a plastic compound and injection molding of the resulting plastic compound.
  • a fine and homogenous dispersion of dimethyldioctadecylammonium (DMDOA)-modified Kraft lignin was present throughout the polymeric matrix and advantageously on the polypropylene polymer surface.
  • DDOA dimethyldioctadecylammonium
  • the present application includes a process for preparing a plastic compound for use in forming an antimicrobial plastic blend, the process comprising:
  • the present application also includes a process for preparing an antimicrobial plastic blend, the process comprising:
  • the present application further includes a process for preparing an antimicrobial plastic blend, the process comprising:
  • plastic compounding a plastic and a quaternary ammonium-modified, lignin-containing material to obtain a plastic compound
  • the present application also includes an antimicrobial plastic blend comprising a quaternary ammonium-modified, lignin-containing material dispersed in a plastic.
  • the present application further includes a use of an antimicrobial plastic blend of the present application as a surface for killing and/or inhibiting the growth of a microbe as well as a method of killing and/or inhibiting the growth of a microbe, the method comprising contacting the microbe with a surface of an antimicrobial plastic blend of the present application.
  • Figure 1 shows exemplary scanning electron microscopy (SEM) images of an injection-molded blend of IndulinTM AT lignin and polypropylene according to a comparative example of the present application (upper image) and an injection-molded blend of a modified Indulin AT lignin dispersed in polypropylene according to an embodiment of the present application. Scale bars show 100 pm.
  • Figure 2 shows exemplary SEM images of a melt compounded blend of ProtobindTM P1000 lignin and polypropylene according to a comparative example of the present application (upper left image) and melt compounded blends of ProtobindTM lignin modified with varying amounts (10, 50 and 100% mol/mol PhOH) of dehydrogenated tallow)dimethylammonium cation according to embodiments of the present application (upper right image, lower left image and lower right image, respectively). Scale bars show 20 pm.
  • the term “comprising” and its derivatives, as used herein, are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and/or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and/or steps.
  • the foregoing also applies to words having similar meanings such as the terms, “including”, “having” and their derivatives.
  • the term“consisting” and its derivatives, as used herein, are intended to be closed terms that specify the presence of the stated features, elements, components, groups, integers, and/or steps, but exclude the presence of other unstated features, elements, components, groups, integers and/or steps.
  • alkyl as used herein, whether it is used alone or as part of another group, means linear or branched chain, saturated alkyl groups. The number of carbon atoms that are possible in the referenced alkyl group are indicated by the numerical prefix“CniV.
  • Ci-4alkyl means an alkyl group having 1 , 2, 3 or 4 carbon atoms.
  • alkenyl as used herein, whether it is used alone or as part of another group, means linear or branched chain, unsaturated alkenyl groups.
  • the number of carbon atoms that are possible in the referenced alkyl group are indicated by the numerical prefix“CniV.
  • C2- 30 alkenyl means an alkenyl group having 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29 or 30 carbon atoms and at least one double bond, for example 1 to 3, 1 to 2 or one double bond.
  • the expression“proceed to a sufficient extent” as used herein with reference to the reactions or process steps disclosed herein means that the reactions or process steps proceed to an extent that conversion of the starting material or substrate to product is maximized. Conversion may be maximized when greater than about 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95 or 100% of the starting material or substrate is converted to product.
  • lignin refers to a class of branched phenolic polymers that can bond or embed with other biopolymers (typically cellulose and/or hemicellulose) in plant cell walls.
  • the composition of lignin can vary depending on the biological species but typically is a copolymer derived from varying ratios of the phenyl-propanoid units p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol often referred to as monolignols.
  • p-coumaryl alcohol refers to a compound having the following structure:
  • phenolic group refers to a group comprising a hydroxyl group bound to a phenyl ring in the lignin; i.e. it includes p-hydroxyphenyl, guaiacyl and syringyl groups.
  • lignin-containing material refers to any material comprising lignin and includes lignin as well as lignocellulose.
  • quaternary ammonium-modified as used herein in reference to a lignin-containing material means that quaternary ammonium cations are ionically bonded to phenolate anions in the lignin-containing material, the phenolate anions being the conjugate bases of phenolic groups in the lignin.
  • Modified lignins can be compounded usefully with plastics such as polyolefins, polyesters, styrene-containing polymers or polyvinyls by extrusion at up to about 15-40% (w/w) with useful mechanical characteristics.
  • plastics such as polyolefins, polyesters, styrene-containing polymers or polyvinyls
  • polymer blends comprising quaternary ammonium-modified, lignin-containing materials dispersed in a polypropylene polymer resin were prepared by a process comprising compounding the components in an extruder to form a plastic compound and injection molding of the resulting plastic compound.
  • the present application includes a process for preparing a plastic compound for use in forming an antimicrobial plastic blend, the process comprising:
  • plastic compounding a plastic and a quaternary ammonium-modified, lignin-containing material to obtain the plastic compound.
  • the lignin-containing material can be any suitable lignin-containing material.
  • the lignin-containing material is lignin, lignocellulose or combinations thereof.
  • the lignin-containing material is lignin.
  • the lignin can be any suitable lignin.
  • the lignin is selected from Kraft lignin, soda lignin, organosolv lignin, a lignin obtained from a biorefinery process and combinations thereof.
  • the lignin is Kraft lignin.
  • the lignin is soda lignin.
  • the source of the lignin can be any suitable source.
  • the lignin is softwood lignin, hardwood lignin, a lignin from an agricultural source (e.g. wheat straw) or combinations thereof.
  • the lignin is softwood lignin or a wheat straw lignin.
  • the lignin is softwood lignin.
  • the lignin is hardwood lignin.
  • the lignin is softwood Kraft lignin, hardwood Kraft lignin or combinations thereof.
  • the lignin is softwood Kraft lignin.
  • the lignin is hardwood Kraft lignin.
  • the lignin is a pine Kraft lignin.
  • the lignin is a wheat straw soda lignin.
  • the quaternary ammonium cation is any suitable quaternary ammonium cation or mixtures thereof.
  • the groups on the quaternary ammonium cation or mixtures thereof are selected from alkyl groups, alkenyl groups and combinations thereof.
  • the quaternary ammonium cation is one or more quaternary ammonium cations of Formula I:
  • R 3 wherein R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-3oalkyl and C2-3oalkenyl.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-3oalkyl.
  • two or three of R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-4alkyl and the remaining one or two of R 1 , R 2 , R 3 and R 4 are each independently selected from Cio-3oalkyl or Cio- 3oalkenyl.
  • two or three of R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-4alkyl and the remaining one or two of R 1 , R 2 , R 3 and R 4 are each independently selected from Cio-3oalkyl.
  • two or three of R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-4alkyl and the remaining one or two of R 1 , R 2 , R 3 and R 4 are each independently selected from Ci2-24alkyl, optionally linear Ci2-24alkyl.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-4alkyl and the remaining one or two of R 1 , R 2 , R 3 and R 4 are each independently selected from Ci4-2oalkyl, optionally linear Ci4-2oalkyl.
  • the Ci-4alkyl is methyl.
  • R 1 and R 2 are each independently selected from Ci-4alkyl and R 3 and R 4 are each independently selected from Cio-3oalkyl.
  • R 1 and R 2 are each independently selected from Ci- 4alkyl and R 3 and R 4 are each independently selected from Ci2-24alkyl, optionally linear Ci2-24alkyl.
  • R 1 and R 2 are each independently selected from Ci-4alkyl and R 3 and R 4 are each independently selected from Ci4-2oalkyl, optionally linear Ci4-2oalkyl.
  • R 1 and R 2 are each independently selected from Ci- 4alkyl and R 3 and R 4 are each n-octadecyl.
  • the Ci-4alkyl is methyl.
  • R 1 and R 2 are each methyl and R 3 and R 4 are each n-octadecyl; i.e. the alkyl quaternary ammonium cation of Formula I is DMDOA cation.
  • R 1 , R 2 and R 3 are each independently selected from Ci-4alkyl and R 4 is Cio-3oalkyl. In another embodiment, R 1 , R 2 and R 3 are each independently selected from Ci-4alkyl and R 4 is Ci2-24alkyl, optionally linear Ci2-24alkyl. In a further embodiment, R 1 , R 2 and R 3 are each independently selected from Ci-4alkyl and R 4 is Ci4-2oalkyl, optionally linear Ci4- 2oalkyl. In a further embodiment, R 1 , R 2 and R 3 are each independently selected from Ci-4alkyl and R 4 is n-hexadecyl. In an embodiment, the Ci-4alkyl is methyl.
  • R 1 , R 2 and R 3 are each methyl and R 4 is n-hexadecyl; i.e. the alkyl quaternary ammonium cation of Formula I is cetyltrimethylammonium cation.
  • the quaternary ammonium is a mixture of quaternary ammonium cations of Formula I, wherein each R 1 and R 2 are independently selected from Ci-4alkyl and each R 3 and R 4 are independently selected from Cio-3oalkyl and Cio-3oalkenyl.
  • the quaternary ammonium is a mixture of quaternary ammonium cations of Formula I
  • each R 1 and R 2 are independently selected from Ci-4alkyl and each R 3 and R 4 are independently selected from Ci2-24alkyl and Ci2-24alkenyl, optionally linear Ci2-24alkyl or Ci2-24alkenyl.
  • the quaternary ammonium is a mixture of quaternary ammonium cations of Formula I, wherein each R 1 and R 2 are independently selected from Ci-4alkyl and each R 3 and R 4 are independently selected from Ci2-2oalkyl, optionally linear Ci2-2oalkyl.
  • the quaternary ammonium is a mixture of quaternary ammonium cations of Formula I, wherein each R 1 and R 2 are independently selected from Ci-4alkyl and each R 3 and R 4 are selected from linear Ci2-2oalkyl, wherein the alkyl chain length distribution is: no more than 2% Ci2, from 1-5% Ci4, from 25-35% Ci6, from 60-70% Cie and no more than 2% C20.
  • the Ci-4alkyl is methyl.
  • R 1 and R 2 are each methyl and R 3 and R 4 are linear Ci2-2oalkyl, wherein the alkyl chain length distribution is: no more than 2% C12, from 1-5% C14, from 25-35% C16, from 60-70% Cie and no more than 2% C20.; i.e. the mixture of alkyl quaternary ammonium cations of Formula I is a dehydrogenated tallow)dimethylammonium cation. Suitable sources of dehydrogenated tallow)dimethylammonium cation are commercially available. For example, di(hydrogenated tallow)dimethylammonium chloride (CAS No. 61789-80-8) is available from commercial sources.
  • the bromide form of the onium ion may also be available commercially.
  • suitable sources of di(hydrogenated tallow)dimethylammonium cation can be obtained by reacting tallow fatty acids with NH3 and dehydrating to obtain an intermediate fatty acid nitrile which is then reduced to obtain a secondary amine, methylated with formaldehyde and quaternized with a suitable methyl halide such as methylchloride (see, for example: European Centre for Ecotoxicology and Toxicology of Chemicals (ECETOC), Technical Report No. 53, DHTDMAC:- Aquatic and Terrestrial Hazard Assessment CAS No. 61789-80-8, February 1993, ISSN-0773-8072- 53).
  • the molar ratio between phenolic groups in the lignin-containing material and the quaternary ammonium cation is from about 1 : 1 to about 1 : 0.05. In another embodiment, the molar ratio between phenolic groups in the lignin-containing material and the quaternary ammonium cation is from about 1 : 1 to about 1 : 0.1 . In another embodiment of the present application, the molar ratio between phenolic groups in the lignin-containing material and the quaternary ammonium cation is about 1 : 1 to about 1 : 0.25.
  • the molar ratio between phenolic groups in the lignin- containing material and the quaternary ammonium cation is from about 1 : 0.5 to about 1 : 0.25. In another embodiment, the molar ratio between phenolic groups in the lignin-containing material and the quaternary ammonium cation is from about 1 : 0.2 to about 1 : 0.3. In another embodiment, the molar ratio between phenolic groups in the lignin-containing material and the quaternary ammonium cation is about 1 : 0.25.
  • the plastic is any suitable plastic.
  • suitable plastics may be obtained from petroleum-based and/or renewable resources.
  • the plastic is a thermoplastic, a thermoset, an elastomer or combinations thereof.
  • the plastic is a thermoplastic.
  • the plastic is a thermoset.
  • the plastic is an elastomer.
  • the plastic comprises, consists essentially of or consists of a polypropylene, a propylene copolymer, a polyethylene, an ethylene copolymer, polybutylene succinate, a styrene-containing polymer, a polyvinyl or a polylactide resin.
  • the plastic comprises, consists essentially of or consists of a polypropylene.
  • the quaternary ammonium-modified, lignin- containing material is prepared by a process comprising reacting an alkaline aqueous solution comprising the lignin-containing material with an aqueous solution comprising the quaternary ammonium cation for a time and at a temperature for the conversion of the lignin-containing material and the quaternary ammonium cation to the quaternary ammonium-modified, lignin- containing material to proceed to a sufficient extent.
  • the quaternary ammonium cation in the aqueous solution comprising the quaternary ammonium cation is in the form of a suitable salt such as a chloride or bromide salt.
  • the alkaline aqueous solution comprising the lignin-containing material has a lignin concentration of from about 2% (w/v) to about 40% (w/v), about 15% (w/v) to about 40% (w/v), about 15% (w/v) to about 25% (w/v), about 20% (w/v) or about 15% (w/v).
  • the amount of base e.g.
  • NaOH NaOH
  • water is chosen in light of the desired stoichiometric ratio between the hydroxide ion of the base and the phenolic groups of the lignin in the lignin-containing material and is typically from about 10% to about 100%.
  • the molar ratio between the NaOH : phenolic groups in the lignin-containing material : the quaternary ammonium cation is from about 0.20 : 1 : 0.20 to about 0.30 : 1 : 0.30 or about 0.25 : 1 : 0.25.
  • the aqueous solution comprising the quaternary ammonium cation has a concentration of about 0.01 M to about 0.25 M, about 0.08 M or about 0.14 M.
  • the lignin-containing material and the quaternary ammonium cation are reacted for a time of at least about 5 minutes at a temperature of about 10°C to about 100°C or about 50°C to about 60°C.
  • the means for compounding is any suitable means.
  • the compounding comprises extruding the molten plastic comprising the quaternary ammonium-modified, lignin-containing material and optionally the additives, if present.
  • the compounding comprises mixing the plastic, the quaternary ammonium-modified, lignin- containing material and optionally the additive(s), if present, in the molten stage of the plastic in a twin-screw extruder and optionally further comprises extruding the molten plastic comprising the quaternary ammonium-modified, lignin- containing material and optionally the additive(s), if present as an extrudate.
  • the conditions for compounding may depend, for example, on the identity of the plastic.
  • the plastic is a polypropylene resin (for example, a polypropylene resin having a melt flow index of about 12 g/ 10 min such as polypropylene Pro-fax 6323) and the conditions comprise a temperature of from about 170°C to about 220°C or about 180°C, and a screw speed of from about 50 rpm to about 300 rpm or about 100 rpm.
  • the process may further comprise cooling the extrudate and forming the extrudate into pellets.
  • the means for cooling and/or forming extrudate into pellets can be any suitable means, the selection of which can be made by the person skilled in the art.
  • the present application also includes a use of a plastic blend of the present application in forming an antimicrobial plastic blend. Accordingly, the present application further includes a process for preparing an antimicrobial plastic blend, the process comprising:
  • the plastic compound of the present application is obtained from a process for preparing a plastic compound for use in forming an antimicrobial plastic blend of the present application. Accordingly, the present application further includes a process for preparing an antimicrobial plastic blend, the process comprising:
  • plastic compounding a plastic and a quaternary ammonium-modified, lignin-containing material to obtain a plastic compound
  • the means for forming is any suitable means.
  • the forming comprises injection molding, extrusion, blowing, casting, calendaring, thermoforming or compression.
  • the forming comprises injection molding.
  • the conditions for forming may depend, for example, on the identity of the plastic and can be readily selected by a person skilled in the art.
  • the plastic is a polypropylene resin (for example, a polypropylene resin having a melt flow index of about 12 g/ 10 min such as polypropylene Pro-fax 6323) and the conditions comprise injection molding at a temperature of from about 170°C to about 220°C or about 180°C.
  • the antimicrobial plastic blend or plastic compound comprises from about 1 % (w/w) to about 50% (w/w) of the quaternary ammonium-modified, lignin-containing material, based on the total weight of the antimicrobial plastic blend or plastic compound, as the case may be. In another embodiment, the antimicrobial plastic blend or plastic compound comprises from about 5% (w/w) to about 30% (w/w) of the quaternary ammonium-modified, lignin-containing material, based on the total weight of the antimicrobial plastic blend or plastic compound, as the case may be.
  • the antimicrobial plastic blend or plastic compound comprises from about 10% (w/w) to about 20% (w/w) of the quaternary ammonium-modified, lignin-containing material, based on the total weight of the antimicrobial plastic blend or plastic compound, as the case may be. In another embodiment, the antimicrobial plastic blend or plastic compound comprises from about 15% (w/w) to about 25% (w/w) of the quaternary ammonium-modified, lignin-containing material, based on the total weight of the antimicrobial plastic blend or plastic compound, as the case may be.
  • the antimicrobial plastic blend or plastic compound further comprises one or more additives such as but not limited to a compatibilizer, a filler, a processing aid, a flame retardant, a reinforcement, an impact modifier or combinations thereof.
  • a compatibilizer such as but not limited to a filler, a processing aid, a flame retardant, a reinforcement, an impact modifier or combinations thereof.
  • the person skilled in the art would be able to select suitable conditions for compounding such additives with the plastic and the quaternary ammonium-modified, lignin-containing material to obtain the antimicrobial plastic blend or plastic compound, as the case may be, comprising such additives.
  • the term“compatibilizer” as used herein refers to an additive that when added to a blend of immiscible materials during extrusion, modifies the interfacial properties of the materials and stabilizes the melt blend.
  • the compatibilizer when present, can be any suitable compatibilizer.
  • the compatibilizer comprises, consists essentially of or consists of a suitable maleic hydride grafted polypropylene, acrylic acid grafted polypropylene, maleic hydride grafted polyethylene, acrylic acid grafted polyethylene, maleic hydride grafted propylene copolymer, acrylic acid grafted propylene copolymer, maleic hydride grafted ethylene copolymer, acrylic acid grafted ethylene copolymer or combinations thereof.
  • the compatibilizer comprises, consists essentially of or consists of a maleic hydride grafted polypropylene.
  • the antimicrobial plastic blend or the plastic compound as the case may be, consists of or consists essentially of the plastic and the quaternary ammonium-modified, lignin-containing material.
  • exemplary DMDOA-modified lignin- polypropylene blends were found to be useful against both Gram-positive and Gram-negative bacteria.
  • a blend of polypropylene containing modified lignin tested according to ISO 22196:2007 International Standard for Measurement of Antibacterial Activity on Plastics Surfaces
  • the present application also includes an antimicrobial plastic blend comprising a quaternary ammonium-modified, lignin- containing material dispersed in a plastic.
  • the antimicrobial plastic blend is prepared according to a process for preparing an antimicrobial plastic blend of the present application.
  • the present application also includes a plastic compound for use in forming an antimicrobial plastic blend, the plastic compound comprising a plastic and a quaternary ammonium- modified, lignin-containing material.
  • the plastic compound is prepared according to a process for preparing a plastic compound for use in forming an antimicrobial plastic blend of the present application.
  • the lignin-containing material can be any suitable lignin-containing material.
  • the lignin-containing material is lignin, lignocellulose or combinations thereof.
  • the lignin-containing material is lignin.
  • the lignin can be any suitable lignin.
  • the lignin is selected from Kraft lignin, soda lignin, organosolv lignin, a lignin obtained from a biorefinery process and combinations thereof.
  • the lignin is Kraft lignin.
  • the lignin is soda lignin.
  • the source of the lignin can be any suitable source.
  • the lignin is softwood lignin, hardwood lignin, a lignin from an agricultural source (e.g. wheat straw) or combinations thereof.
  • the lignin is softwood lignin or a wheat straw lignin.
  • the lignin is softwood lignin.
  • the lignin is hardwood lignin.
  • the lignin is softwood Kraft lignin, hardwood Kraft lignin or combinations thereof.
  • the lignin is softwood Kraft lignin.
  • the lignin is hardwood Kraft lignin.
  • the lignin is a pine Kraft lignin.
  • the lignin is a wheat straw soda lignin.
  • the quaternary ammonium cation is any suitable quaternary ammonium cation or mixtures thereof.
  • the groups on the quaternary ammonium cation or mixtures thereof are selected from alkyl groups, alkenyl groups and combinations thereof.
  • the quaternary ammonium cation is one or more quaternary ammonium cations of Formula I:
  • R 3 wherein R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-3oalkyl and C2-3oalkenyl.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-3oalkyl.
  • two or three of R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-4alkyl and the remaining one or two of R 1 , R 2 , R 3 and R 4 are each independently selected from Cio-3oalkyl or C10- 3oalkenyl.
  • two or three of R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-4alkyl and the remaining one or two of R 1 , R 2 , R 3 and R 4 are each independently selected from Cio-3oalkyl.
  • two or three of R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-4alkyl and the remaining one or two of R 1 , R 2 , R 3 and R 4 are each independently selected from Ci2-24alkyl, optionally linear Ci2-24alkyl.
  • R 1 , R 2 , R 3 and R 4 are each independently selected from Ci-4alkyl and the remaining one or two of R 1 , R 2 , R 3 and R 4 are each independently selected from Ci4-2oalkyl, optionally linear Ci4-2oalkyl.
  • the Ci-4alkyl is methyl.
  • R 1 and R 2 are each independently selected from Ci-4alkyl and R 3 and R 4 are each independently selected from Cio-3oalkyl.
  • R 1 and R 2 are each independently selected from Ci- 4alkyl and R 3 and R 4 are each independently selected from Ci2-24alkyl, optionally linear Ci2-24alkyl.
  • R 1 and R 2 are each independently selected from Ci-4alkyl and R 3 and R 4 are each independently selected from Ci4-2oalkyl, optionally linear Ci4-2oalkyl.
  • R 1 and R 2 are each independently selected from Ci- 4alkyl and R 3 and R 4 are each n-octadecyl.
  • the Ci-4alkyl is methyl.
  • R 1 and R 2 are each methyl and R 3 and R 4 are each n-octadecyl; i.e. the alkyl quaternary ammonium cation of Formula I is DMDOA cation.
  • R 1 , R 2 and R 3 are each independently selected from Ci-4alkyl and R 4 is Cio-3oalkyl. In another embodiment, R 1 , R 2 and R 3 are each independently selected from Ci-4alkyl and R 4 is Ci2-24alkyl, optionally linear Ci2-24alkyl. In a further embodiment, R 1 , R 2 and R 3 are each independently selected from Ci-4alkyl and R 4 is Ci4-2oalkyl, optionally linear Ci4- 2oalkyl. In a further embodiment, R 1 , R 2 and R 3 are each independently selected from Ci-4alkyl and R 4 is n-hexadecyl. In an embodiment, the Ci-4alkyl is methyl.
  • R 1 , R 2 and R 3 are each methyl and R 4 is n-hexadecyl; i.e. the alkyl quaternary ammonium cation of Formula I is cetyltrimethylammonium cation.
  • the quaternary ammonium is a mixture of quaternary ammonium cations of Formula I, wherein each R 1 and R 2 are independently selected from Ci-4alkyl and each R 3 and R 4 are independently selected from Cio-3oalkyl and Cio-3oalkenyl.
  • the quaternary ammonium is a mixture of quaternary ammonium cations of Formula I, wherein each R 1 and R 2 are independently selected from Ci-4alkyl and each R 3 and R 4 are independently selected from Ci2-24alkyl and Ci2-24alkenyl, optionally linear Ci2-24alkyl or Ci2-24alkenyl.
  • the quaternary ammonium is a mixture of quaternary ammonium cations of Formula I, wherein each R 1 and R 2 are independently selected from Ci-4alkyl and each R 3 and R 4 are independently selected from Ci2-2oalkyl, optionally linear C12- 2oalkyl.
  • the quaternary ammonium is a mixture of quaternary ammonium cations of Formula I, wherein each R 1 and R 2 are independently selected from Ci-4alkyl and each R 3 and R 4 are selected from linear Ci2-2oalkyl, wherein the alkyl chain length distribution is: no more than 2% C12, from 1 -5% C14, from 25-35% C16, from 60-70% C18 and no more than 2% C20.
  • the Ci-4alkyl is methyl.
  • R 1 and R 2 are each methyl and R 3 and R 4 are linear Ci2-2oalkyl, wherein the alkyl chain length distribution is: no more than 2% C12, from 1-5% Ci 4, from 25-35% C16, from 60-70% C18 and no more than 2% C20.; i.e. the mixture of alkyl quaternary ammonium cations of Formula I is a dehydrogenated tallow)dimethylammonium cation.
  • the molar ratio between phenolic groups in the lignin-containing material and the quaternary ammonium cation is from about 1 : 1 to about 1 : 0.05. In another embodiment, the molar ratio between phenolic groups in the lignin-containing material and the quaternary ammonium cation is from about 1 : 1 to about 1 : 0.1 . In another embodiment of the present application, the molar ratio between phenolic groups in the lignin-containing material and the quaternary ammonium cation is about 1 : 1 to about 1 : 0.25.
  • the molar ratio between phenolic groups in the lignin- containing material and the quaternary ammonium cation is from about 1 : 0.5 to about 1 : 0.25. In another embodiment, the molar ratio between phenolic groups in the lignin-containing material and the quaternary ammonium cation is from about 1 : 0.2 to about 1 : 0.3. In another embodiment, the molar ratio between phenolic groups in the lignin-containing material and the quaternary ammonium cation is about 1 : 0.25.
  • the plastic is any suitable plastic.
  • suitable plastics may be obtained from petroleum-based and/or renewable resources.
  • the plastic is a thermoplastic, a thermoset, an elastomer or combinations thereof.
  • the plastic is a thermoplastic.
  • the plastic is a thermoset.
  • the plastic is an elastomer.
  • the plastic comprises, consists essentially of or consists of a polypropylene, a propylene copolymer, a polyethylene, an ethylene copolymer, polybutylene succinate, a styrene-containing polymer, a polyvinyl or a polylactide resin.
  • the plastic comprises, consists essentially of or consists of a polypropylene.
  • the antimicrobial plastic blend or plastic compound comprises from about 1 % (w/w) to about 50% (w/w) of the quaternary ammonium-modified, lignin-containing material, based on the total weight of the antimicrobial plastic blend or plastic compound, as the case may be. In another embodiment, the antimicrobial plastic blend or plastic compound comprises from about 5% (w/w) to about 30% (w/w) of the quaternary ammonium-modified, lignin-containing material, based on the total weight of the antimicrobial plastic blend or plastic compound, as the case may be.
  • the antimicrobial plastic blend or plastic compound comprises from about 10% (w/w) to about 20% (w/w) of the quaternary ammonium-modified, lignin-containing material, based on the total weight of the antimicrobial plastic blend or plastic compound, as the case may be. In another embodiment, the antimicrobial plastic blend or plastic compound comprises from about 15% (w/w) to about 25% (w/w) of the quaternary ammonium-modified, lignin-containing material, based on the total weight of the antimicrobial plastic blend or plastic compound, as the case may be.
  • the antimicrobial plastic blend or plastic compound further comprises one or more additives such as but not limited to a compatibilizer, a filler, a processing aid, a flame retardant, a reinforcement, an impact modifier or combinations thereof.
  • a compatibilizer when present, can be any suitable compatibilizer.
  • the compatibilizer comprises, consists essentially of or consists of a suitable maleic hydride grafted polypropylene, acrylic acid grafted polypropylene, maleic hydride grafted polyethylene, acrylic acid grafted polyethylene, maleic hydride grafted propylene copolymer, acrylic acid grafted propylene copolymer, maleic hydride grafted ethylene copolymer, acrylic acid grafted ethylene copolymer or combinations thereof.
  • the compatibilizer comprises, consists essentially of or consists of a maleic hydride grafted polypropylene.
  • the antimicrobial plastic blend or plastic compound consists of or consists essentially of the plastic and the quaternary ammonium- modified, lignin-containing material.
  • the quaternary ammonium-modified, lignin- containing material is homogeneously dispersed throughout the plastic and on the surface of the antimicrobial plastic blend.
  • the antimicrobial plastic blend is an antibacterial plastic blend (i.e. kills and/or inhibits the growth of bacteria), an antifungal plastic blend (i.e. kills and/or inhibits the growth of fungi) or a combination thereof.
  • the antimicrobial plastic is an antibacterial plastic blend.
  • the antimicrobial plastic blend has antibacterial activity against Gram-negative bacteria, Gram-positive bacteria or a combination thereof.
  • the antimicrobial plastic blend has antibacterial activity against Gram-negative bacteria and Gram-positive bacteria.
  • the Gram-negative bacteria is Escherichia coli.
  • the Gram-positive bacteria is Staphylococcus aureus.
  • the Gram-negative bacteria is Escherichia coli and the Gram-positive bacteria is Staphylococcus aureus.
  • the present application also includes a use of the antimicrobial plastic blend of the present application for killing and/or inhibiting the growth of a microbe.
  • the microbe is bacteria, fungi or a combination thereof.
  • the microbe is bacteria.
  • the bacteria are Gram-negative, Gram-positive or combinations thereof.
  • the bacteria are Gram-negative.
  • the bacteria are Gram-positive.
  • the bacteria are a combination of Gram-negative bacteria and Gram-positive bacteria.
  • the Gram-negative bacteria is Escherichia coli.
  • the Gram-positive bacteria is Staphylococcus aureus.
  • the Gram-negative bacteria is Escherichia coli and the Gram-positive bacteria is Staphylococcus aureus.
  • the present application also includes a method of killing and/or inhibiting the growth of a microbe, the method comprising contacting the microbe with a surface of an antimicrobial plastic blend of the present application.
  • the microbe is bacteria, fungi or a combination thereof.
  • the microbe is bacteria.
  • the bacteria are Gram-negative, Gram-positive or combinations thereof.
  • the bacteria are Gram-negative.
  • the bacteria are Gram-positive.
  • the bacteria are a combination of Gram-negative bacteria and Gram-positive bacteria.
  • the Gram-negative bacteria is Escherichia coli. In a further embodiment, the Gram-positive bacteria is Staphylococcus aureus. In another embodiment, the Gram-negative bacteria is Escherichia coli and the Gram-positive bacteria is Staphylococcus aureus.
  • Such methods and uses may have applications in fields such as but not limited to transportation, household products, food, healthcare, agriculture, and/or construction, where controlling microbes such as bacteria is desirable.
  • Example 1 Grafting of lignin with alkyl quaternary ammonia cations
  • alkaline Kraft lignin (AKL): Alkaline solutions (0.2 mol/L, pH about 12.90) were prepared by adding in a 1000 ml_ beaker, 8 g of NaOH in 1000 ml_ of deionized water. The pH of the alkaline solutions was measured using a pH-meter. The amount of NaOH dissolved in water was chosen to respect the stoichiometric ratio between NaOH and the phenolic group of lignin (about 2 mmol/g).
  • Kraft lignin solutions (KL10%) (100 g/L) were then prepared by dissolving in a 250 ml_ beaker, 10 g of the Kraft lignin in 100 ml_ of the prepared alkaline solution. The dissolution of the Kraft lignin in the alkaline solution was performed while stirring at 350 rpm at 60°C for 30 minutes.
  • Ionic solutions 50 g/L were prepared by adding a known mass of each alkyl quaternary ammonium salt (onium ion) in a 500 mL beaker containing a known volume of deionized water. The solution was mechanically stirred progressively from 1300 to 1700 rpm at 60°C for 30 minutes. The pH of the solution was measured using a pH meter.
  • the onium ion to NaOH molar ratio was the parameter varied (0.75:0.75, 0.5:0.5 and 0.25:0.25 for 1 mole phenolic of lignin).
  • Precipitation may take place as the result of the ionic exchange reaction.
  • the pH of the mixture at the end of the reaction was measured.
  • the precipitated complexes were separated from the supernatant solution by centrifugation at 4700 rpm for 30 minutes.
  • the precipitate was first washed with alkaline solution then centrifuged at 4700 rpm for 30 minutes to remove unreacted lignin.
  • the supernatant from the second centrifugation was added to the one obtained from the first centrifugation.
  • the precipitate was then rinsed with warm deionized water (50°C) and then centrifuged at 4700 rpm for 20 minutes 3 times.
  • the precipitate was dried to constant mass at 60°C for 48 hours.
  • the precipitate was then weighed and the yield of the complex formation was measured. Samples were ground for further tests.
  • Pre dry blend
  • PP polypropylene
  • Eastman Epolene 43 (E-43), a maleic anhydride grafted PP, was used as a compatibilizer in 1 case.
  • the pre (dry-blend) was fed into a LabTech twin-screw extruder with the configuration and parameters as follows: T emperature: 180°C in all zones, Screw speed: 100 rpm, Output: 2 kg/h.
  • the blends can also be prepared by feeding directly the lignin and the PP into the extruder at the beginning of the extruder. Alternatively, the lignin can also be fed into the extruder by side feeding.
  • Injection molding The blends at ratios indicated hereinbelow were injected in an injection-molding machine (Boy machines Inc., USA) at 180°C in all zones. Dog-bones, bars and disks were obtained.
  • Figure 1 shows a comparison between an unmodified Indulin AT- polypropylene blend and a DMDOA-modified Indulin AT-polypropylene blend (NaOH : PhOH : onium ion ratio of 0.25 : 1 : 0.25).
  • the dispersion of the modified Indulin AT in polypropylene was excellent in contrast to the poor dispersion of the unmodified Indulin AT in polypropylene.
  • Table 1 provides an overview of the mechanical properties of various ratios of unmodified Indulin AT-polypropylene blends and a DMDOA- modified Indulin AT-polypropylene blend (NaOH : PhOH : onium ion ratio of 0.25 : 1 : 0.25). The results indicate that the blends comprising the modified lignin had superior tensile modulus as well as flexural strength and modulus and impact strength in comparison to the polypropylene matrix.
  • the source of dehydrogenated tallow)dimethylammonium cations was ArquadTM 2HT-75 which is a dehydrogenated tallow)dimethylammonium chloride (CAS Number 61789-80-8) obtained from Sigma-Aldrich.
  • the lignin was Protobind P1000, a wheat straw lignin extracted by the soda process.
  • the amount of Arquad 2HT-75 was 10, 50 and 100% mol/phenol- mol in lignin corresponding to sample names PB10, PB50 and PB100.
  • the moles of NaOH were equivalent with the moles of Arquad 2HT-75.
  • NaOH was first dissolved in water.
  • the amount of water was about 6 times the volume of the lignin.
  • the Arquad 2HT-75 was also dissolved in water to obtain a 2 wt% solution and this was heated to 60°C.
  • the lignin was then dissolved into the NaOH solution at 50°C for 20 minutes.
  • the lignin suspension/solution was then mixed into the Arquad 2HT-75 solution and maintained at 50°C for 30 minutes.
  • the material obtained was washed several times with water and then dried in air then in an oven.
  • Modified lignins PB10, PB50 and PB100 were soluble in toluene, swelled in hexane and were not soluble in water.
  • Figure 2 shows SEM images comparing a melt compounded blend of unmodified ProtobindTM P1000 lignin and polypropylene (upper left image) and melt compounded blends of modified lignins PB10 (upper right image), PB50 (lower left image) and PB100 (lower right image).
  • an improvement in compatibility with PP was seen with all modified lignins over the unmodified lignin.
  • the fatty acid-based quaternary amine content increased, the finer the lignin dispersion in the PP.
  • Example 3 Antibacterial activity of modified lignin-polypropylene blends
  • Modified lignin 1 (L1 ) and modified lignin 2 (L2) were prepared according to the general procedure described in Example 1 using the parameters summarized in Table 2.
  • Antimicrobial efficacy was evaluated in line with ISO 22196:2007, International Standard for Measurement of Antibacterial Activity on Plastics Surfaces. Test organisms were Escherichia coli ATCC 8739 and Staphylococcus aureus ATCC 6538. Each sample was inoculated with 0.4 ml_ of a 0.2% nutrient broth seeded with a standardized culture of the test organism. The inoculated sample was covered with an inert film and incubated at 36 ⁇ 2°C in a humidity chamber for 24 hours. Microbial counts of the samples were determined and the percent reduction of microorganisms (treated versus untreated sample at timepoint) and antibacterial activity were calculated.
  • Tables 3 and 4 show a summary of the results of the testing for the Gram-negative bacteria E. coli and Gram-positive bacteria S. aureus , respectively. Percent reduction and antibacterial activity were calculated against the untreated control at the corresponding time point. After 24 hours incubation in the ISO 22196 test method, the L1 -PP sample showed a ⁇ 67.03% reduction and an antibacterial activity value of ⁇ 0.48 for E. coli. The L2-PP sample showed a ⁇ 84.49% reduction and an antibacterial activity value of ⁇ 0.81 for E. coli. After 24 hours incubation in the ISO 22196 test method, the L2-PP sample showed no activity against the Gram-positive bacteria S. aureus.
  • the L1 -PP sample showed an 89.23% reduction and an antibacterial activity value of 0.97. While not wishing to be limited by theory, as the characteristics of DMDHTA are very similar to DMODA it is believed that DMDHTA modified lignin-polypropylene blends will behave similar to DMODA modified lignin-polypropylene blends in terms of antibacterial activity.

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Abstract

La présente invention se rapporte à des mélanges antimicrobiens à base de matière plastique comprenant une matière contenant de la lignine modifiée par ammonium quaternaire, les phénols de la lignine étant sous forme anionique, et une matière plastique de dispersion (par exemple du polypropylène), à des procédés pour la préparation de tels mélanges et à des utilisations de tels mélanges, par exemple en tant que surface pour tuer et/ou inhiber la croissance d'un microbe. La présente invention se rapporte également à des compositions à base de matière plastique destinées à être utilisées dans la formation de tels mélanges antimicrobiens à base de matière plastique ainsi qu'à des procédés pour la préparation de telles compositions à base de matière plastique.
PCT/CA2020/050800 2019-06-21 2020-06-11 Mélanges antimicrobiens à base de matière plastique, procédés pour leur préparation et leurs utilisations WO2020252566A1 (fr)

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CN116199848A (zh) * 2022-12-19 2023-06-02 南通新艺材料科技有限公司 一种含有负离子的抗菌型聚氨酯泡沫材料及其制备方法

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CN116199848A (zh) * 2022-12-19 2023-06-02 南通新艺材料科技有限公司 一种含有负离子的抗菌型聚氨酯泡沫材料及其制备方法

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