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WO2015160794A1 - Nanoparticules d'origine biologique et matériaux composites dérivés de celles-ci - Google Patents

Nanoparticules d'origine biologique et matériaux composites dérivés de celles-ci Download PDF

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Publication number
WO2015160794A1
WO2015160794A1 PCT/US2015/025729 US2015025729W WO2015160794A1 WO 2015160794 A1 WO2015160794 A1 WO 2015160794A1 US 2015025729 W US2015025729 W US 2015025729W WO 2015160794 A1 WO2015160794 A1 WO 2015160794A1
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WIPO (PCT)
Prior art keywords
nanoparticle
biopolymer
compound
starch
latex
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PCT/US2015/025729
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English (en)
Inventor
Steven Bloembergen
Jan Van Leeuwen
Niels Mathieu Barbara SMEETS
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Ecosynthetix Ltd
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Ecosynthetix Ltd
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Publication of WO2015160794A1 publication Critical patent/WO2015160794A1/fr
Priority to US15/291,598 priority Critical patent/US20170029549A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/22—Proteins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D21H17/26—Ethers thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D21H17/27—Esters thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape

Definitions

  • This specification relates to bio-based materials, including nanoparticles and reactive intermediates, and to methods of making them, and to latex compositions, as used for example as a binder in coated paper and paperboard manufacturing.
  • US Patent Number 3,839,318, entitled Process for Preparation of Alkyl Glucosides and Alkyl Oligosaccharides describes a process for the preparation of higher alkyl monosaccharides and oligosaccharides which are surface active.
  • Emulsion Copolymers and Methods of Preparing the Same describes a method of preparing a resin-fortified polymer emulsion.
  • the method comprises polymerizing at least one monomer in the presence of a surfactant, an initiator, a resin and sugar-based vinyl monomer under emulsion polymerization reaction conditions effective for initiating polymerization, wherein an emulsion polymerization product is formed that comprises a sugar based vinyl monomer.
  • An ink comprising a pigment and a resin-fortified polymer emulsion is also disclosed.
  • Sugar Monomers in Vinyl Copolymers as Latex Binders and Compositions Thereon describes sugar monomers used to provide comonomers for bio-synthetic hybrid paper binder systems having a controlled hydrophilic-hydrophobic balance.
  • Nanoparticles describes a process for producing biopolymer nanoparticles in which the biopolymer is plasticized using shear forces, a crosslinking agent being added during the processing. After the processing, the biopolymer can be dispersed in an aqueous medium to a concentration between 4 and 40 wt %. This results in starch nanoparticles that are characterized by an average particles size of less than 400 nm.
  • Producing Biopolymer Nanoparticles describes a process for producing biopolymer nanoparticles in which biopolymer feedstock and a plasticizer are fed to a feed zone of an extruder having a screw configuration such that the biopolymer feedstock is processed using shear forces in the extruder, and a crosslinker is added to the extruder downstream of the feed zone.
  • the temperatures in an intermediate section of the extruder are preferably kept above 100 degrees C.
  • the screw configuration may include two or more steam seal sections. Water may be added in a post reaction section located after a point in which the crosslinking reaction has been completed.
  • bio-based nanoparticles includes materials that are partially bio-based.
  • nanoparticles as used herein is not limited to particles having a size of 100 nm or less but also includes larger particles, for example particles up to 1000 nm, and particles that are capable of forming a colloid or latex.
  • the resulting materials may be biodegradable.
  • nanoparticles described herein comprise at least two compounds or a reaction product of at least two compounds.
  • At least the first compound is bio-based.
  • the second compound is a monomer, oligomer, macromer or polymer containing at least one moiety or functional group not present in the first compound.
  • the second compound also contains hydroxyl functional groups.
  • the first and second compounds are crosslinked together.
  • the nanoparticles may be made, for example, by a reactive extrusion process in which the first and second compounds are added to an extruder with water, optionally with a plasticizer and, preferably, with a crosslinker.
  • the nanoparticle becomes functionalized in the sense that the moiety or functional group of the second compound is present.
  • the first compound is not necessarily functionalized itself.
  • Suitable second compounds include for example: bio-based materials; polyols or hydrolizable oligomeric or polymeric compounds having a functional group in addition to hydroxyl groups; compounds with double bond functional groups; acrylic or maleic anhydride comprising monomers, macromers or polymers; telechelic and other multi-functional polymerizable oligomers or polymers and, monomers, oligomers, macromers and polymers that are water soluble or dispersible at a temperature present in the process.
  • nanoparticles are made with a biopolymer such as starch and an oligomer such as alkyl polyglycoside (APG).
  • APG alkyl polyglycoside
  • the nanoparticles may be more readily dispersible than similar nanoparticles made without the oligomer.
  • nanoparticles are made with a biopolymer such as starch and a macromer such as maleated alkyl polyglycoside (alternatively called an alkyl polyglycoside maleic acid ester).
  • nanoparticles contain double bonds and may be used as monomers, macromers, co- monomers or other building blocks themselves. These bio-based nanoparticles,
  • the synthetic component may act for example as a monomer or seed particle, optionally serving as a replacement of a fraction of the petro-based monomer in polymerization process, such as an emulsion polymerization process, suspension polymerization process or precipitation polymerization process, for the production of bio- synthetic hybrid latex particles.
  • the synthetic component may include a polymerizable compound that introduces a biodegradable linkage, such as ester or amide bonds, into the carbon-carbon chains of the main copolymer network structure, such that the latex particles as a whole are rendered biodegradable.
  • comonomers include, but are not limited to, acrylated or maleated APG, acrylated or maleated
  • a dispersion of the nanoparticles may be used, for example, as a binder in the paper industry to completely or partially replace a conventional petroleum based latex binder, including (but not limited to) common synthetic binders such as styrene butadiene latex (XSB), styrene acrylic (SA), poly vinyl acetate (PVAc) and poly vinyl acetate acrylics (PVAc-Acryl).
  • common synthetic binders such as styrene butadiene latex (XSB), styrene acrylic (SA), poly vinyl acetate (PVAc) and poly vinyl acetate acrylics (PVAc-Acryl).
  • the nanoparticles contain double bond moieties which facilitate copolymerization between the nanoparticles and other monomers such as vinyl monomers including but not limited to styrene, butadiene, (meth)acrylic monomers, acrylonitrile, and vinyl acetate, amongst many other common and specialty vinyl comonomer varieties.
  • Nanoparticles comprising bio-based material and a non-bio-based monomer may be made, for example, by a copolymerization process.
  • the copolymerization process may be a free radical polymerization or copolymerization process.
  • the process may be a dispersed phase polymerization such as emulsion polymerization, suspension polymerization or precipitation polymerization.
  • the process may involve ambient pressure or medium to high pressure systems for handling gaseous comonomers such as butadiene and ethylene and the like, and including those reactors typical for standard ambient pressure acrylic, styrene-acrylic and vinyl acetate emulsion polymerization processes, to medium pressure (typically up to 1000 psi) tanks used, for example, for vinyl acetate ethylene (VAE) copolymer latex emulsions, to ultra-high pressure tubular reactors used for EVA, EAA copolymers.
  • VAE vinyl acetate ethylene copolymer latex emulsions
  • One preferred process is starve-fed emulsion
  • the resulting product may be a latex having some characteristics like a conventional petro- based XSB, SA, PVAc, PVAc-Acryl and other latex polymer products, but with a material amount of bio-based content.
  • the latex may be used as a binder in the coated paper and paperboard industry alone or in a mixture with biopolymer nanoparticles or a conventional latex binder.
  • the latex may also be used in a similar fashion in many other applications where petro-latex products are used, including but not limited to paints and coatings, adhesives, wood products, plywood, OSB (Oriented Strand Board), particle board, MDF (Medium Density Fiberboard), textiles, non-wovens, foam products, carpet, construction & building products, insulation, etc.
  • a biodegradable comonomer such as maleated APG and/or ethylene glycol dimethacrylate may be included in the polymerization process to render the latex biodegradable.
  • Some nanoparticles comprise a biopolymer portion and a synthetic polymer portion. These portions may be arranged in various multiple phase structures such as a core-shell structure, with the biopolymer portion inside of the synthetic polymer portion, or an inverse core-shell structure, a mixed morphology, "current-bun” morphology, or controlled agglomerate morphology.
  • the core and the shell may be hydrophobic, amphiphilic or hydrophilic.
  • the biopolymer portion of a nanoparticle may comprise at least two compounds or a reaction product of at least two compounds as described above.
  • the biopolymer portion may be made without the second compound.
  • the mixed morphology may be produced by a dispersed phase polymerization process, which includes but is not limited to emulsion polymerization (including micro- and mini-emulsion polymerization), suspension polymerization, and precipitation polymerization.
  • the synthetic polymer portion may be made biodegradable through the use of a
  • biodegradable crosslinker such as maleated alkyl polyglycoside or another polymerizable compound that introduces a biodegradable linkage, as mentioned above.
  • a biopolymer is added to the feed zone of an extruder.
  • the extruder may contain a feed zone, a gelatinization zone, an optional reaction (or crosslinking) zone, and a post processing zone.
  • a second compound is preferably added downstream of the feed zone, for example in the gelatinization zone or reaction zone.
  • a latex made with nanoparticles described herein may be used, for example, as a paper coating binder in the paper industry, alone or in a mixture with biopolymer nanoparticles or a conventional latex binder.
  • the latex may also be used in a similar fashion in many other applications where petro-latex products are used, including but not limited to paper and paperboard coating binders, paints, coatings, adhesives, wood products, textiles, non-wovens, foam products, carpet, construction, building products, and insulation.
  • Figure 1 is a schematic representation of the concept of producing bio-synthetic hybrid latex polymer products illustrating the formation of a core/shell morphology.
  • Figure 2 is a TEM image of a core-shell nanoparticle prepared from a biopolymer nanoparticle containing polymerizable double bonds per Example 2.
  • Figure 3 is a TEM image of an inverse core-shell nanoparticle prepared from a biopolymer nanoparticle containing polymerizable double bonds per Example 3.
  • Figure 4 is a TEM image of a mixed morphology nanoparticle prepared from a biopolymer nanoparticle containing polymerizable double bonds per Example 4.
  • Figure 5 is a TEM image of a core-shell nanoparticle prepared from a biopolymer nanoparticle without polymerizable double bonds per Example 6.
  • Figure 6 is a schematic representation of bio-based nanoparticles used in a paperboard coating comprising a base coat and a top coat layer. For the purpose of simplifying this schematic, binder particles in the coating composition are illustrated while pigment particles are not.
  • Figure 7 shows the results for the Aerobic Biodegradation under Composting Conditions (ASTM D-5338) for acrylic copolymers coated on Kraft paper (paper subtracted).
  • APG's are made from renewable resources, namely, sugars such as monosaccharides, oligosaccharides or polysaccharides.
  • sugars such as monosaccharides, oligosaccharides or polysaccharides.
  • the most preferred sugar is dextrose (oD-glucose), which is derived from corn or other starch crops.
  • an aldose sugar such as oD-glucose
  • a primary alcohol or a mixture of primary alcohols R- OH
  • the reaction is preferably conducted in the presence of an acid catalyst, such as concentrated sulfuric acid or para-toluene sulfonic acid or any other suitable acid.
  • the excess alcohol may be removed by vacuum distillation or by other physical separation techniques, such as extraction, optionally after neutralization of the acid.
  • the maleic acid esters of APG's have a polymerizable double bond and they are prepared by the reaction of an APG, maleic anhydride and optionally an alcohol.
  • a maleated APG is available commercially from EcoSynthetix Inc. under the trademark EcoMer. Parts of the description of methods for making APGs and maleated APGs in US Patent Number 5,872, 199 will be repeated below for convenience.
  • R" is selected from the group consisting of a hydrogen and C1 to C30 alkyl groups or mixtures thereof, and all other symbols are as previously defined.
  • APG's for use in making maleated APGs may be those containing lower alkyl groups of four to six carbons (butyl to hexyl) or mixtures thereof, because such APG's are viscous liquids which can be readily reacted with maleic acid anhydride in the absence of a solvent.
  • APG's for use in making maleated APGs may be those containing higher alkyl groups of eight to sixteen carbons or higher, or mixtures thereof, because such alcohols are more readily available from bio-based sources such as from the saponification of coconut oil and other natural oils.
  • the APG is a viscous liquid or solid which is soluble in the organic phase to facilitate reaction with maleic acid anhydride.
  • maleic acid anhydride is a liquid that is miscible with the APG. This avoids the use of a solvent that would contribute to VOC's.
  • other anhydrides such as succinic anhydride, itaconic anhydride, and different alkenyl succinic anhydrides can be used.
  • itaconic anhydride is expected to have residual polymerizable double bonds after being reacted with APG. It is therefore expected that a reaction product of itaconic anhydride and APG could function as an alternative to maleated APG in the processes and compositions described in this specification.
  • disaccharides, oligosaccharides and polysaccharides generally contain appreciable levels of water (typically 8 to 12 weight %).
  • the APG's which are prepared by the method described above, have a very low moisture content (typically less than 1 weight %). This is important because maleic acid anhydride is readily hydrolyzed by water to produce maleic acid as an undesired byproduct.
  • an APG can be reacted with maleic anhydride at temperatures from about 55 degrees C up to 120 degrees C under anhydrous and homogeneous reaction conditions.
  • APG's having higher alkyl groups also can be used, in combination with a primary alcohol or a mixture of primary alcohols, having an alkyl group of preferably a C4 to C18 or a mixture thereof, or a dialkyl maleic ester, as a solvent for the APG during the maleation step.
  • a primary alcohol or a mixture of primary alcohols having an alkyl group of preferably a C3 to C8 or a mixture thereof, can be added during this step as a solvent for the APG.
  • Other suitable solvents may also be used.
  • R'-OH alcohol is a reactive solvent which, upon reaction with maleic acid anhydride, provides an alkyl maleic acid monomer.
  • this alcohol acts as a solvent during the maleation step, but is itself reacted quantitatively with maleic anhydride to provide a copolymerizable solvent/monomer in which the maleated APG is soluble.
  • a dialkyl maleic ester can be used as a copolymerizable solvent, having alkyl groups of preferably a C1 to C18 alkyl or a mixture thereof, more preferably a C1 to C8 alkyl or a mixture thereof, and most preferably a C4 alkyl.
  • a primary alcohol (R"OH) or a mixture of primary alcohols having an alkyl group of preferably C1 to C18 or a mixture thereof, more preferably C8 to C18 alkyl or a mixture thereof, and most preferably a C12 to C14 alkyl or a mixture thereof, can optionally be added to esterify any residual unreacted maleic anhydride, a portion or all of the free acid groups of the alkyl polyglycoside maleic acid and of the alkyl maleic acid, if present.
  • the alcohols for use in the above process are those hydroxyl-functional organic compounds capable of alkylating a saccharide at the "C1 " position.
  • the alcohols can be naturally occurring, synthetic or derived from natural sources.
  • the molar stoichiometry of maleic anhydride to APG is controlled to be more than one to afford incorporation of the sugar molecules into the main polymeric network structure.
  • the maleic acid esters of the APG's which are prepared by reacting an APG with maleic anhydride contain a polymerizable double bond. These sugar macromers are Generally Recognized As Safe (GRAS) and contain no Volatile Organic Compounds (VOCs).
  • GRAS Generally Recognized As Safe
  • VOCs Volatile Organic Compounds
  • biopolymer nanoparticle is sometimes used to refer to particles that are 100 nm and smaller. However, the term “nanoparticle” is also sometimes used to refer to larger particles, up to for example 1000 nm.
  • biopolymer nanoparticle is used to refer to polymeric particles that (i) have an average particle size of about 1000 nm or less or (ii) form a polymer colloid or colloidal (latex) dispersion in water.
  • biopolymer nanoparticles are regenerated particles, meaning that some structure of the native biopolymer (for example the crystalline structure of a native starch granule) is removed or changed in the manufacturing process.
  • Biopolymers for example polysaccharides and proteins, and in principle any other biopolymer, and mixtures thereof, may be the biopolymer used in these processes.
  • Any starch for example waxy or dent corn starch, potato starch, tapioca starch, dextrin, dextran, starch ester, starch ether, carboxymethyl starch (CMS), and in principle any other starch or starch derivative, including cationic or anionic starch, and mixtures thereof, may be the biopolymer used in these processes.
  • Any starch for example waxy or dent corn starch, potato starch, tapioca starch, dextrin, dextran, starch ester, starch ether, carboxymethyl starch (CMS), and in principle any other starch or starch derivative, including cationic or anionic starch, and mixtures thereof, may be the biopolymer used in these processes.
  • CMS carboxymethyl starch
  • Any polysaccharide, cellulosic polymer or cellulose derivative for example microcrystalline cellulose, carboxymethyl cellulose (CMC), any nanofibrillar cellulose (CNF), nanocrystalline cellulose (CNC), or cellulose ester, cellulose ether, chitin, chitosan, and in principle any other polysaccharide, cellulose or cellulose derivative, and mixtures thereof, may be the biopolymer used in these processes.
  • Proteins for example zein (corn protein) or soy protein, and in principle any other protein or modified protein, and mixtures thereof, may be the biopolymer used in these processes.
  • the first compound may comprise one or more compounds selected from the group consisting of polyols, biopolymers, and bio-based materials.
  • the first compound may be starch, or a mixture containing starch, for example 50% by weight of starch, with one or more other biopolymers, polysaccharides, proteins, polyols or bio- based materials.
  • the second compound may comprise one or more compounds selected from the group of monomers, oligomers, macromers or polymers that are water soluble or dispersible at a temperature present in the process, bio-based materials, polyols or hydrolizable compounds having a functional group in addition to hydroxyl groups, compounds with double bond functional groups, and maleic anhydride comprising polymers.
  • the second compound is APG or maleated APG.
  • the resulting material is a dispersion of nanoparticles.
  • the addition of the second compound changes the properties of the first compound or functionalizes the first compound.
  • nanoparticles preferably contain at least 50% by weight of bio-based materials, or at least 75% by weight of bio-based materials, or at least 90% by weight of bio-based materials.
  • the first compound and the second compound are co-extruded with water and a crosslinker.
  • the extruder is preferably a co-rotating twin screw extruder.
  • the first compound is preferably provided at a concentration of at least 10 wt% or more preferably at a concentration of at least 40 wt% in an aqueous solvent, for example water or a mixture of water and alcohol or another hydroxylic liquid, to a feed zone of an extruder, or most preferably it is fed in neat or as-received form and then mixed in the extruder with an aqueous solvent, for example water or a mixture of water and alcohol or another hydroxylic liquid.
  • a plasticizer for example a polyol such as glycerol, may be added at a level of up to about 40% by weight of the first compound. Water also acts as a plasticizer and the total amount of water and other plasticizers may be 15-50%.
  • the temperature is maintained between 60 and 200 degrees C, or between 100 and 140 degrees C. At least 100 J/g, or at least 250 J/g, of specific mechanical energy per gram of the first compound, is applied in the intermediate zone.
  • the pressure in the intermediate zone may be between 5 and 150 bar.
  • the first component is substantially gelatinized in the intermediate zone.
  • the second compound is optionally added to the intermediate zone, or downstream of a barrel in which the first compound is substantially gelatinized.
  • a crosslinker if any, may be added in a reaction zone that follows, or overlaps with the end of the intermediate zone. The crosslinker may be added with or downstream of the second compound.
  • the crosslinker may be, for example, selected from the group consisting of dialdehydes, polyaldehydes, acid anhydrides, mixed anhydrides, glutaraldehyde, glyoxal, oxidized carbohydrates, periodate-oxidized carbohydrates, epichlorohydrin, epoxides, triphosphates, petroleum-based monomeric, oligomeric and polymeric crosslinkers, biopolymer crosslinkers, and divinyl sulphone.
  • the crosslinking is preferably reversible, i.e. the crosslinks are partly or wholly cleaved during continued mechanical treatment.
  • Suitable reversible crosslinkers include those which form chemical bonds at low water concentrations, which dissociate or hydrolyze in the presence of higher water concentrations.
  • Examples of reversible crosslinkers are dialdehydes and polyaldehydes, which reversibly form
  • hemiacetals acid anhydrides and mixed anhydrides (e.g. succinic and acetic anhydride) and the like.
  • Suitable dialdehydes and polyaldehydes are glutaraldehyde, glyoxal, periodate- or Tempo- or peroxide- or otherwise oxidized carbohydrates, and the like.
  • Such crosslinkers may be used alone or as a mixture of reversible crosslinkers, or as a mixture of reversible and non-reversible crosslinkers.
  • crosslinkers such as epichlorohydrin and other epoxides, triphosphates, divinyl sulphone, can be used as non-reversible crosslinkers for polysaccharide biopolymers, while dialdehydes, thiol reagents and the like may be used for proteinaceous biopolymers.
  • the crosslinking may be done with a combination of reversible and non-reversible crosslinkers.
  • the crosslinking reaction may be acid- or base-catalyzed.
  • the level of crosslinking agent can conveniently be between 0.1 and 10 weight % with respect to the biopolymer or other first compound.
  • the crosslinking agent may be present at the start of the mechanical treatment, but in case of a non-pre- gelatinized biopolymer such as a starch with native starch granules, the crosslinking agent may be added later on, i.e. during the mechanical treatment in or after the intermediate zone.
  • starch is co-extruded with a sugar based compound such as maleated APG and water, and preferably with a crosslinker.
  • a sugar based compound such as maleated APG and water
  • a crosslinker there may also be a plasticizer in addition to the water.
  • the sugar based compound is preferably added downstream of where the starch has been converted into a thermoplastic melt phase.
  • the crosslinker if any, is preferably added downstream of where the sugar based compound is added.
  • the inventors have co-extruded starch with APG and maleated APG. Based on visual observation and viscosity data, starch-based nanoparticles made by co-extrusion with either APG or maleated APG disperse more readily than starch-based nanoparticles made according to the same formulation but without APG or maleated APG.
  • the inventors have also observed that APG and maleated APG are stable in a reactive extrusion process for making starch based nanoparticles as described above.
  • maleated APG does not homopolymerize in the extruder. Accordingly, the double bonds of maleated APG are still available for use in further reactions with the nanoparticles. The presence of double bonds in the nanoparticles post-extrusion was verified by proton NMR spectroscopy.
  • the maleated APG may be added in a range between about 0.1 to 10 parts per hundred parts of starch.
  • the maleated APG is a viscous liquid but may be added to the extruder by heating it to above about 55 degrees C and then conveying it with a pump designed to handle high viscosity materials, such as a standard hot-melt pump.
  • the maleated APG could be first dissolved in water and added to the extruder as an aqueous solution.
  • water optionally with glycerol or another plasticizer
  • starch are added first to the extruder.
  • the starch has been plasticized by heat and shear forces in the extruder (i.e. downstream of where the starch is substantially plasticized in the extruder)
  • the maleated APG is added to the extruder and mixed into the thermoplastic starch melt.
  • one or more crosslinkers are then added to the extruder (i.e. the one or more crosslinkers are added downstream of the maleated APG) and allowed to react.
  • the second compound is a monomer, oligomer, macromer or polymer, preferably carrying double bonds, that is inherently stable or stabilized so that it does not homopolymerize during its reaction with the first compound
  • the resulting nanoparticles are themselves polymerizable compounds, which may be referred to as a monomer or macromers.
  • monomer and macromer as used herein do not necessarily mean a compound with only one reactive site.
  • the bio-based nanoparticles may act as monomer or seed particles in a free radical or other copolymenzation process, including for example as a replacement of a fraction of the petro-based monomer in a conventional polymerization process.
  • the free radical copolymenzation process may be any free radical polymerization or copolymenzation process including, but not limited to emulsion polymerization, suspension polymerization, precipitation polymerization, and may include ambient pressure or medium to high pressure systems for handling gaseous comonomers such as butadiene and ethylene and the like, and including those reactors typical for standard ambient pressure acrylic, styrene-acrylic and vinyl acetate emulsion polymerization processes, to medium pressure (typically up to 1000 psi) tanks used, for example, for vinyl acetate ethylene (VAE) copolymer latex emulsions, to ultra-high pressure tubular reactors used for EVA, EAA copolymers.
  • One preferred process is starve-fed emulsion
  • FIG. 1 is a schematic drawing and is not intended to show all steps in the reaction or structural characteristics of the seed particle or hybrid particle, or to be to scale.
  • the seed particle may be made up of multiple sub-particles and so may have polymerizable double bonds also in its interior.
  • the seed particle may be much smaller than the hybrid particle, and the core of the hybrid particle may contain multiple seed particles.
  • the core of the hybrid particle may have some of the vinyl monomer in it.
  • an intermediate stage appears to exist in the intermediate stage.
  • bio-based material which might or might not be small particles (relative to the final hybrid particle) or perhaps even individual molecules either of which might have previously formed one or more larger dispersed particles, surround or extend beyond a small synthetic particle .
  • intermediate stage might be analogous to a Pickering stabilization in which the bio-based material helps to stabilize the synthetic particle.
  • the particle grows in size and develops a layer of synthetic material extending beyond the bio- based material.
  • bio-based particles or molecules in the shell of the intermediate stage they appear to aggregated to form a core as synthetic monomer is added, thereby forming a hybrid particle with biopolymer-based (or at least biopolymer-containing) core and synthetic shell.
  • the intermediate stage may optionally be preserved as the final morphology by stopping the addition of synthetic monomer such that a hybrid particle is produced with a synthetic (or bio-synthetic hybrid) core and a biopolymer-based shell.
  • a bio- based core with synthetic shell is preferred for use in making a paper coating binder.
  • copolymers may be prepared by reacting the nanoparticles with other monomers, for example vinyl monomers, to produce further novel nanoparticles.
  • the novel nanoparticles can comprise copolymers of alkyl polyglycoside maleic acid esters and vinyl monomers as represented by the followin formula:
  • Glu is a saccharide moiety which is derived from oD-glucose (dextrose), fructose, mannose, galactose, talose, gulose, allose, altrose, idose, arabinose, xylose, lyxose, ribose, or mixtures thereof, or which can be derived by hydrolysis from the group consisting of starch, corn syrups or maltodextrins, maltose, sucrose, lactose, maltotriose, xylobiose, mellibiose, cellobiose, raffinose, stachiose, levoglucosan, and 1 , 6-anhydroglucofuranose.
  • oD-glucose oD-glucose
  • fructose mannose
  • galactose talose
  • gulose allose
  • altrose idose
  • arabinose arabinose
  • Ri and R 2 are substituent groups of a vinyl monomer or mixture of vinyl monomers, wherein said vinyl monomer or mixture of vinyl monomers is selected from the group consisting of vinyl acetate, ethyl hexyl acrylate, butyl acrylate, ethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, lauryl acrylate, methyl methacrylate, methacryclic acid, acrylic acid, and other acrylates or mixtures of different acrylate monomers, ethylene, 1 ,3-butadiene, styrene, vinyl chloride, vinylpyrrolidinone, and other vinyl monomers, or mixtures thereof, R is selected from the group consisting of a C1 to C30 alkyl or a mixture thereof, more preferably a C3 to C8 alkyl or a mixture thereof, R'" is selected from the group consisting of a C1 to C30 alkyl or a mixture thereof, or
  • Glu may be physically or chemically attached to a nanoparticle.
  • a nanoparticle For example,
  • Glu may be all or part of the second compound in the manufacture of nanoparticles as described above.
  • Glu may be attached to a pre-existing biopolymer nanoparticle by a crosslinker.
  • the vinyl monomers may be conventional petroleum-based vinyl monomers and may include but are not limited to styrene and styrene based monomers, butadiene, (meth)acrylic monomers, acrylonitrile, and vinyl acetate, amongst many other common and specialty vinyl comonomer varieties.
  • the vinyl monomers may be ethyl hexyl acrylate, butyl acrylate, ethyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, lauryl acrylate, methyl methacrylate, methacrylic acid, acrylic acid, itaconic acid, and other acrylates or mixtures of different acrylate monomers, ethylene, 1 ,3-butadiene, styrene, vinyl chloride, vinylpyrrolidinone, and other vinyl monomers or mixtures thereof.
  • Other suitable vinyl monomers include-those disclosed in Table 11/1-1 1 in Polymer Handbook, J. Bandrup, 3rd Ed. John Wiley & Sons Inc., (1989).
  • the use of nanoparticles made with alkyl polyglycoside maleic acid ester monomers produces random copolymers when reacted with conventional vinyl monomers.
  • Various degrees of randomness in the copolymers can be attained by using a monomer pre-emulsion which is slowly added to the polymerizing mixture according to the so-called starve-fed copolymerization process.
  • a nanoparticle made from starch and maleated APG may form a bio- based monomer or seed particle with polymerizable double bonds.
  • the seed particle may be used in the manner of a petro-based seed particle or otherwise serve as a replacement of a fraction of one or more petro-based monomers.
  • the inventors believe that the partially hydrophobic nature of the maleated APG causes the maleated APG to be concentrated near the surface of the nanoparticle when the nanoparticle is dispersed. However, this is not necessarily an essential characteristic of the nanoparticle.
  • the nanoparticles may be used as monomer or seed particles in a dispersed phase polymerization such as free radical emulsion polymerization.
  • the nanoparticles considering their reactive double bonds, may be reacted with any vinyl monomer according the any of the examples described in US Patent Number 5,872,199 and International Publication Number WO 2012/045159.
  • the resulting nanoparticle is a unique and novel hybrid or composite made up of the bio-based monomer or seed particle and the bio-synthetic copolymer.
  • a dispersion of the nanoparticles may be used, for example, as a coating binder in the paper industry to completely or partially replace a conventional petroleum based latex binder, including (but not limited to) common synthetic binders such as XSB, SA, PVAc and PVAc-Acryl.
  • XSB latex is typically prepared by the emulsion copolymerization of styrene and butadiene monomers along with other minor comonomers including for example acrylic acid, methacrylic acid, itaconic acid and/or acrylonitrile.
  • the X in XSB represents these other minor comonomers.
  • SA's are prepared from styrene and acrylic comonomers
  • PVAc's are prepared by the polymerization of vinyl acetate monomer and may also include acrylate comonomers (PVAc-Acryl).
  • PVAc-Acryl acrylate comonomers
  • Carboxylation and other functionalities including acrylonitrile generally provide enhanced stability and binding power to synthetic latex binders.
  • the nanoparticles may be used in the manner of a petro-based monomer or seed particle normally used in dispersed phase polymerization, such as free radical emulsion polymerization, to make these conventional materials.
  • the nanoparticles thereby replace a fraction of the petro-based monomers normally used in creating a latex polymer.
  • the functional nanoparticle provides a polymerizable bio-based chemical intermediate that may be used to introduce bio-content into petro-based latex polymers. This may be desirable simply to provide an alternative product, to mitigate the effects of increasing oil prices or oil price volatility, or from Nature's Carbon Cycle perspective (see Narayan, R.
  • the synthetic component may include a polymerizable compound that introduces a biodegradable linkage, such as ester or amide bonds, into the carbon-carbon chains of the main copolymer network structure.
  • a biodegradable linkage such as ester or amide bonds
  • the inventors believe that introduction of a heteroatom such as oxygen and nitrogen into the carbon-carbon backbone polymer chains of the main copolymer network structure produces linkages that can be biodegradable.
  • the bio-synthetic hybrid latex particles as a whole may become fully biodegradable.
  • the process of biodegradation either in nature, in a composting facility or in a sewage sludge operation, for example, will cleave those biodegradable linkages to produce low molecular weight carbon-carbon oligomers that in turn are biodegradable provided the molecular weight of these oligomers is sufficiently low so that these molecules can be assimilated by the microorganisms.
  • the inventors have demonstrated this for acrylic copolymers in which up to 40 wt% EcoMer ® (maleated APG or
  • “Sugar Macromer” was incorporated (see Figure 7).
  • examples of such comonomers include, but are not limited to, acrylated, itaconic or maleated APG, acrylated or maleated biodegradable oligomers, macromers of polymers, telechelic and other multi-functional polymerizable oligomers, macromers or polymers, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, N,N-methylenebisacrylamide and other amide- containing multifunctional monomers.
  • the bio- synthetic copolymer in one embodiment of the invention, can form a shell around a bio- based core (referred to as a "core-shell" structure).
  • a hybrid latex forming particle may exist in other configurations.
  • different latex particle morphologies can be prepared. These morphologies might include either core-shell or inverse core-shell structures, or "current-bun” or other highly organized, or mixed, or random hybrid particle morphologies.
  • Such specific conditions may include, but are not limited to, the selection and concentration of the surfactant, the alkyl tail length of the APG, the type of maleated APG, the overall vinyl comonomer composition, the ratio between the bio-based nanoparticle and vinyl monomer content, and the monomer feed strategy.
  • TEM Transmission Electron Microscopy
  • ruthenium tetroxide Ru0 4 was used to provide contrast to the biopolymer component.
  • Ru0 4 was synthesized by reacting Ruthenium (IV) oxide hydrate (0.075 g) with sodium periodate (0.5 g) in distilled deionized water (12.5 ml.) in an ice bath for 3-4 hours with continuous stirring. This 1 % Ru0 4 solution was used directly to stain the dried polymer latex samples approximately 15 min prior to imaging (see John S. Trent and co-workers, Macromolecules 1983, 16, 589-598, and the book: Linda C. Sawyer and co-workers, Polymer Microscopy 3rd Ed. 2008, Springer, for more information on Ru0 4 staining in electron microscopy). This staining method was used with biopolymer nanoparticles made with starch and maleated APG and the biopolymer portion appears darker in the images.
  • Suitable polymers for this technique include but are not limited to vinyl monomers such as N-isopropylacrylamide (NIPAAm), N-isopropylmethacrylamide (NIPMAAm), N-diethylacrylamide (NDEAAm), diethylene glycol methacrylate (M(EO) 2 MA), combinations of M(EO) 2 MA and oligoethylene glycol methacrylates with average molecular weight 300, 500, 1 100 and 2200 (OEGMA) and vinylcaprolactam (VCL).
  • NIPAAm N-isopropylacrylamide
  • NIPMAAm N-isopropylmethacrylamide
  • NDEAAm N-diethylacrylamide
  • M(EO) 2 MA diethylene glycol methacrylate
  • combinations of M(EO) 2 MA and oligoethylene glycol methacrylates with average molecular weight 300, 500, 1 100 and 2200 (OEGMA) and vinylcaprolactam (VCL).
  • the synthetic polymer portion was stained to appear darker by reacting
  • the monomers described above can be copolymerized with any other vinyl monomer in a precipitation polymerization as long as the monomer is to some extent soluble in water.
  • Emulsion polymerizations can be performed in standard polymerization equipment, including a temperature controlled reactor vessel, mechanical agitation, and syringe or fluid metering pumps.
  • automated reactor equipment is used to provide superior control over the reactor temperature and addition rate of reactive ingredients.
  • Mass-based addition of nanoparticles, monomers, initiator, and surfactant is preferred.
  • Dispersion of the nanoparticles and subsequent polymerization may be performed using standard pitched blade or anchor impellers, depending on the final latex viscosity.
  • high shear agitation devices such as an Ultra-Turrax or Silverson laboratory mixer or production scale Kady type or similar high shear dispersion equipment is used. Examples
  • Nanoparticles were made with 100 parts waxy corn starch, 3 parts APG, 12.5 parts water, 10 parts glycerol and 2 parts glyoxal (see sample no. 1 , Table 1 ).
  • the starch, water and glycerol were added to the feed zone of an intermeshing self-wiping co-rotating twin screw extruder.
  • the APG was added to an intermediate zone of the extruder where the starch was already fully gelatinized.
  • the APG was added to the extruder as a 10% aqueous solution.
  • the glyoxal was added in the intermediate zone after the APG.
  • the extrudate was produced as foam through a die in the end zone of the extruder and ground into a fine powder product.
  • nanoparticles were made with 100 parts waxy corn starch, 3 parts maleated APG, 12.5 parts water, 0 parts glycerol and 3 parts glyoxal (see sample no. 2, Table 1 ).
  • the starch and water were added to the feed zone of an intermeshing self-wiping co-rotating twin screw extruder.
  • the maleated APG was added to an intermediate zone of the extruder where the starch was already fully gelatinized.
  • the maleated APG is a viscous liquid and was added to the extruder by heating it to about 105 degrees C and then conveying it using a hot-melt pump.
  • the glyoxal was added in the intermediate zone after the maleated APG.
  • the extrudate was produced as foam through a die in the end zone of the extruder.
  • nanoparticles were made with 100 parts waxy corn starch, 6 parts maleated APG, 12.5 parts water, 10 parts glycerol and 2 parts glyoxal (see sample no. 3, Table 1 ).
  • the starch, water and glycerol were added to the feed zone of an intermeshing self-wiping co-rotating twin screw extruder.
  • the maleated APG was added to an intermediate zone of the extruder where it is believed that the starch was already gelatinized.
  • the maleated APG is a viscous liquid and was added to the extruder by heating it to about 1 10 degrees C and then conveying it using a hot-melt pump.
  • the glyoxal was added in the intermediate zone after the maleated APG.
  • the extrudate was produced as foam through a die in an end zone of the extruder.
  • the nanoparticles functionalized with maleated APG which serve as a polymerizable biobased chemical intermediate in some examples below, take the form of an agglomerate powder in dry form with an average particle size of approximately 300 ⁇ .
  • These dry powder agglomerates can be readily dispersed in warm water (at 40 to 50 degrees C) under continuous mechanical agitation. It is preferred to maintain a slightly basic pH of about 8.0 via the addition of a weak base such as 0.1 M sodium carbonate solution or its neat powder. Proper dispersion will result in a transparent light yellow to brown homogeneous suspension or dispersion (color depending on solids content and pH).
  • the functionalized nanoparticles are dispersed under mechanical agitation up to a final solids content of about 40 w/w% in water at 50 degrees C within 20 min.
  • Example 2 Sample Copolymerization Recipe - Bio-based Core-Shell Latex particles
  • Functionalized nanoparticles were further polymerized to produce inverse core-shell latex particles by emulsion polymerisation under the following conditions:
  • the functionalized nanoparticles Prior to polymerization, the functionalized nanoparticles are dispersed under mechanical agitation at 50 degrees C as described above to prepare the seed dispersion. For example, 87.5 g of powder was dispersed in 325 ml. water and the pH pre-adjusted using 0.1 M sodium bicarbonate solution. An aqueous solution (25.0 ml.) of sodium bicarbonate (0.35 g) and the surfactant AerosolTM EF-800 (0.25 g) was added to the dispersion. The reactor contents were purged with nitrogen for 30 min and heated to 80 degrees C.
  • Example 4 Sample Copolymerization Recipe - Mixed Morphology Latex Particles
  • the functionalized nanoparticles are dispersed under mechanical agitation at 50 degrees C as described above to prepare the seed dispersion.
  • 50 g of powder was dispersed in 325 ml. water and the pH pre-adjusted using 0.1 M sodium bicarbonate solution.
  • the reactor contents were purged with nitrogen for 30 min and heated to 80 degrees C.
  • Example 5 Sample Copolymerization Recipe - Pressure Sensitive Adhesive (PSA) Formulation
  • the 30 g of functionalized nanoparticles are dispersed as described above to prepare the seed dispersion, and sodium bicarbonate (0.30 g) were added to 236 g water.
  • a pre-emulsion was prepared by emulsifying butyl acrylate (BA, 194 g) and MMA (10 g) in 36 g water containing either sodium dodecyl sulphate (SDS) surfactant
  • EF-800 surfactant 4.0 g
  • a 1/3 aliquot of the aqueous solution of potassium persulfate 1.7 g in 30 g water
  • the pre-emulsion and initiator were fed continuously over 3.5 and 4.0 hours, respectively.
  • the reactor was agitated for an additional 60 min to ensure complete polymerization.
  • the monomer conversion to polymer was followed via a standard gravimetric analysis and plotted against time, showing close to 100% conversion was attained in 250 mins.
  • the Intensity average particle diameter was measured via dynamic light scattering analysis, showing for the EF-800 surfactant an increase from -160 nm at -8% conversion, followed by a close to linear increase to -260 nm at close to 100% conversion.
  • the monomer conversion to polymer was followed via a standard gravimetric analysis and plotted against time, showing close to 100% conversion was attained in 240 minutes.
  • the Intensity average particle diameter was measured via dynamic light scattering analysis, showing for the SDS surfactant an increase from -160 nm at -15% conversion, followed by a close to linear increase to -225 nm at close to 100% conversion.
  • the resulting latex had good film forming properties and formed homogeneous films with a translucent appearance.
  • blends of the seed particles and poly(butyl acrylate-co-methyl methacrylate) latex particles resulted in macroscopic phase separation and poor optical properties.
  • the composite films swell in both water and organic solvents such as tetrahydrofuran, however, do not lose structural integrity.
  • surfactant peel strength 17 N/m after 75 hours and tack of 250 N/m after 100 hours was measured at 25-30 degrees C and 50-60% relative humidity.
  • Example 6 Sample Copolymerization Recipe - Bio-based Core-Hydrophilic Shell latex particles
  • FIG. 5 shows a TEM micrograph of the latex for the final product after uranyl acetate staining and illustrates the core/shell particle morphology. Note that in Figure 5, which shows the particle morphology, the biopolymer nanoparticle core is light and the acrylamide copolymer shell is dark. The particles were stained with uranyl acetate to provide the contrast between acrylic & biopolymer components.
  • Example 7 Exemplary Use of Functional Bio-Based Nanoparticles and their Bio-Synthetic Hybrid Latex Products
  • bio-based nanoparticles per the prior art, of for example International Publication Number WO 00/69916, are used to replace a portion of conventional XSB or SA latex binders in the pigmented pre-coat and top coat in a fine paper or paperboard coating process.
  • the pre-coat may have contained a minor portion of a conventional cooked coating starch cobinder, while the top coat typically only contained conventional petro-based XSB or SA latex.
  • bio-synthetic hybrid latex products described above may be used to replace some or all of the XSB or SA or petro-based other latex binder.
  • the resulting coated paper and paperboard products have a pre-coat 20 comprising a pigmented coating that contains a mixture of conventional bio-based latex nanoparticles 14 and bio-synthetic hybrid
  • bio- synthetic hybrid latex compositions can replace petroleum-based latex products used in applications related to any other latex polymer application, including but not limited to paints, coatings, adhesives, wood products (plywood, OSB, particle board, MDF, etc.), textiles, non- wovens, foam products, carpet, construction, building products, and insulation.
  • Example 8 Rendering the synthetic copolymer component biodegradable

Landscapes

  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne des nanopraticules dont certaines comprennent au moins deux composés, ou un produit de réaction de ceux-ci. Au moins le premier composé est en partie ou entièrement d'origine biologique. Le second composé est un monomère, un oligomère, un macromère ou un polymère contenant au moins une fraction ou un groupe fonctionnel qui n'est pas présent dans le premier composé. Les nanoparticules peuvent être préparées, par exemple, en faisant appel à un procédé d'extrusion réactive. Dans un exemple, les nanoparticules sont composées d'amidon et de polyglycoside d'alkyle (APG), un oligomère tensioactif d'origine biologique. Dans un autre exemple, les nanoparticules sont composées d'amidon et de polyglycoside d'alkyle maléaté, un macromère d'origine biologique. Ces nanoparticules peuvent être copolymérisées avec d'autres monomères, pour produire par exemple un liant latex, dans un procédé de copolymérisation radicalaire.
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WO2021214764A1 (fr) 2020-04-21 2021-10-28 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. Particules et dispersions solides ainsi que procédés pour la libération contrôlée d'actifs liposolubles ou lipodispersibles
CN115050963A (zh) * 2022-06-29 2022-09-13 上海道赢实业有限公司 一种用于锂离子电池负极的粘结剂及其制备方法和用途
WO2022218539A1 (fr) 2021-04-16 2022-10-20 Wacker Chemie Ag Copolymères hybrides d'amidon
CN116575260A (zh) * 2023-06-27 2023-08-11 湖北达雅生物科技股份有限公司 造纸涂布用改性羧甲基纤维素及其制备方法和应用
WO2024183924A1 (fr) 2023-03-09 2024-09-12 Wacker Chemie Ag Copolymères hybrides d'amidon
CN119241867A (zh) * 2024-12-06 2025-01-03 浙江大学 一种微热诱导界面链响应的微纳淀粉颗粒基Pickering乳液制备方法

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CN115050963A (zh) * 2022-06-29 2022-09-13 上海道赢实业有限公司 一种用于锂离子电池负极的粘结剂及其制备方法和用途
CN115050963B (zh) * 2022-06-29 2024-05-10 上海道赢实业有限公司 一种用于锂离子电池负极的粘结剂及其制备方法和用途
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CN116575260A (zh) * 2023-06-27 2023-08-11 湖北达雅生物科技股份有限公司 造纸涂布用改性羧甲基纤维素及其制备方法和应用
CN119241867A (zh) * 2024-12-06 2025-01-03 浙江大学 一种微热诱导界面链响应的微纳淀粉颗粒基Pickering乳液制备方法
CN119241867B (zh) * 2024-12-06 2025-04-22 浙江大学 一种微热诱导界面链响应的微纳淀粉颗粒基Pickering乳液制备方法

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