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WO2010058148A1 - Émulsions stabilisées par des particules organiques rendues hydrophobes - Google Patents

Émulsions stabilisées par des particules organiques rendues hydrophobes Download PDF

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Publication number
WO2010058148A1
WO2010058148A1 PCT/GB2009/002395 GB2009002395W WO2010058148A1 WO 2010058148 A1 WO2010058148 A1 WO 2010058148A1 GB 2009002395 W GB2009002395 W GB 2009002395W WO 2010058148 A1 WO2010058148 A1 WO 2010058148A1
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Prior art keywords
emulsion
particles
phase
cellulose
dispersed phase
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Jonathan James Blaker
Koon-Yong Lee
Alexander Bismarck
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Ip2ipo Innovations Ltd
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Imperial Innovations Ltd
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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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/20—Esterification with maintenance of the fibrous structure of the cellulose
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/028—Foaming by preparing of a high internal phase emulsion
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • 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
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives

Definitions

  • the present invention relates to hydrophobized renewable organic nano-particle stabilized emulsion templates, uses thereof and polymeric foams produced from the said emulsions.
  • An emulsion is a heterogeneous system consisting of two liquids, referred to as phases, which are immiscible or have limited miscibility.
  • one phase (the dispersed phase) is dispersed as droplets within the other phase (the continuous phase).
  • one phase comprises water or an aqueous solution and the other phase comprises an oil, although non-aqueous emulsions comprising two immiscible organic phases can be produced.
  • Emulsions can be classified as oil-in-water emulsions (o/w) in which oil constitutes the dispersed phase or water-in-oil emulsions (w/o) in which water (or an aqueous solution) constitutes the dispersed phase.
  • Emulsions containing multiple phases are also possible.
  • an emulsifier to the emulsion.
  • Conventional emulsifiers such as surfactants, have an amphiphilic molecular structure and stabilise an emulsion by positioning themselves at the phase interface, thereby acting to prevent droplet coalescence. It is also possible to stabilize an emulsion by the addition of a particulate solid.
  • Particle-stabilized emulsions known as Pickering or Ramsden emulsions
  • Pickering or Ramsden emulsions are extremely stable due to the adsorption of particles (which are usually not amphiphilic) at the interface between the continuous and dispersed phases, providing a barrier to prevent droplet coalescence and phase separation.
  • Stability of an emulsion is determined by the extent to which the particles are wetted by the two immiscible phases, particle size, concentration, and mutual interaction between the particles.
  • Emulsions have uses in many fields, including the food, pharmaceutical and cosmetics industries.
  • One application is in the preparation of polymer (and polymer matrix composite) foams.
  • Emulsion templating using high dispersed phase emulsions (HIPEs) is an effective route to prepare polymer foams known as polyHIPEs.
  • polyHIPEs are prepared by a process, which involves providing a w/o HIPE in which the organic continuous phase comprises polymerizable monomers and crosslinkers and initiating polymerization of the continuous monomer phase.
  • the dispersed phase droplets act as a template ahout which polymerization occurs.
  • PoIyHIPEs may also be produced from o/w emulsion or non-aqueous templates.
  • the present application provides renewable (truly green) nanocomposite polymer foams which are synthesized from Pickering-emulsion templates.
  • the first aspect of the invention therefore provides a particle stabilized high or medium dispersed phase emulsion comprising a dispersed phase which constitutes 30% or more of the total volume of the emulsion, a continuous phase and hydrophobized organic particles.
  • the dispersed phase is any phase which is not miscible with the continuous phase (as defined below).
  • the dispersed phase is preferably a hydrophilic dispersed phase, more preferably an aqueous dispersed phase (such as an aqueous solution or water).
  • the dispersed phase constitutes more than 30% of the total volume of the emulsion, such as from 30% to 95%, preferably from 50 to 92%, more preferably 75% to 92%.
  • the dispersed phase may be provided as a percentage of the total volume of the emulsion of 75% to 90%, 80 to 90% or 80 to 85%.
  • the dispersed phase may be provided as a percentage of the total volume of the emulsion of 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 92% or 95%. It will be appreciated that emulsion with a dispersed phase volume of greater than 74.4% will consist of deformed spheres as this is the limit of close sphere packing.
  • the continuous phase is preferably one or more of functionalized natural oils, thermoset resins derived from vegetable oils, such as soybean, linseed, cashew, palm, nut, coconut and sunflower, reactive low molecular weight resins based on ftmctionalized poly(cc-hydroxyester) oligomers, (e.g.
  • the continuous phase is an oil- like monomer
  • the continuous phase is hydrophobic and practically immiscible with the dispersed phase.
  • a suitable hydrophobic solvent may be added to improve flow properties during processing. Suitable solvents include toluene, benzene, chloroform, dichloromethane and cyclohexane.
  • the continuous phase may comprise a blend of synthetic monomers such as styrene, di-vinyl benzene and polyethylene glycol (diacrylated or dimethacrylated), the said blend can be tailored to obtain required mechanical properties.
  • the synthetic monomers can be any monomers capable of polymerization or cross-linking.
  • Cross-linkers with renewable credentials such as squalene or keratin may also be incorporated in the continuous phase.
  • the particles are derived from organic (i.e. carbon based material).
  • the particles of the present invention are particularly derived from a renewable source.
  • the particles are therefore derived from an organism such as a plant, animal or a micro-organism such as a bacteria, fungus, amoeba or virus. It will be appreciated that the particles can be derived from an agriculture resource such as a plant.
  • the particles are preferably cellulose derived particles.
  • the particle can be derived from any origin of cellulose for example of plant, bacterial, animal, fungal or amoebic.
  • the particles are preferably derived from nano-cellulose, which can be derived from: bacteria, the banana plant (obtained through steam explosion); parenchymal walls; cotton; animal sources such as Tunicata.
  • the renewable particle may also be derived from chitin, for example, chitosan. It will be appreciated that cellulose derived particles are particularly preferred for the present invention as cellulose is a cheap, renewable source of a particulate/fibrilar/whisker like stabilizer.
  • Cellulose derived from bacteria inherently has aspects in the nano-size range and has high mechanical properties, with stiffness exceeding those of glass fibres and aramid fibres. Furthermore, cellulose particles possess many hydroxyl groups for facile functionalization (hydrophobization), such that the wettability or 3 -phase contact angle between the particles and the continuous and disperse phases can be tuned; thereby enabling cellulose to act as a Pickering emulsion stabilizer.
  • the cellulose (nano)particles can be hydrophobized with bi-functional chlorosilanes, such as chlorodimethylvinylsilane, dimethylchlorosilylpropylmethacrylate or chloromethylphenylvinylsilane.
  • bi-functional chlorosilanes such as chlorodimethylvinylsilane, dimethylchlorosilylpropylmethacrylate or chloromethylphenylvinylsilane.
  • Cellulose can be rendered hydrophobic by organic acid esterification, with organic acids (saturated or ideally unsaturated) of varying carbon chain length, including but not limited to acetic acid (C2), butyric acid (C4), hexanoic acid (C6), lauric acid (C12), oleic acid (Cl 8) and linoleic acid (Cl 8).
  • organic acids saturated or ideally unsaturated
  • the carbon-carbon double bonds can form cross-linkages to crosslink with the polymer matrix and/or to crosslink the particles.
  • the cellulose (nano)particles may also be functionalized by various means known to persons skilled in the art, with other reactive groups, such as dimethacrylates or methacrylates and cross-linked into the polymer matrix.
  • the hydroxyl groups can be functionalized using similar procedures for end-capping polyethylene glycol functionalization, for example by reacting PEG with methacryloyl chloride or acryloyl chloride in the presence of triethylamine.
  • Other grafting techniques may include reversible addition- fragmentation chain transfer (RAFT) for example of polystyrene to cellulose; or by grafting using plasma treatments.
  • RAFT reversible addition- fragmentation chain transfer
  • the particles have an average diameter of up to 900nm. Preferably, the particles have an average diameter of up to 500 nm.
  • the particles have an average diameter of from 1 Onm to 100 nm, preferably 15 to 50nm, more preferably 20 to 30 nm.
  • the length of the particles is in the region of l ⁇ m to lOO ⁇ m, such as 10 to 90 ⁇ m, preferably 20 to 80 ⁇ m, more preferably 30 to 70 ⁇ m, or 40 to 60 ⁇ m or 40 to 50 ⁇ m.
  • the emulsion may comprise a surfactant.
  • the surfactant is preferably from renewable resources, and includes lecithin or natural fatty alcohols derived from coconut and other triglycerides.
  • Preferred natural surfactants are those having a hydrophilic-lipophilic balance (HLB) value between 4 and 8, that is 4, 5, 6,7 or 8, ideally 7, suitable for stabilizing w/o emulsions.
  • the emulsion may further comprise one or more of additional runctionalized particles, wherein said additional functionalised particles are titania, silica or cellulose, non- stabilizing particles, wherein the non-stabilising particles have a particle size of less than lmm, or biodegradable particles.
  • non-stabilizing particles indicates that the particles do not stabilize at the three phase interface.
  • the non-stablizing particles act to increase the viscosity and therefore the stability of the emulsion, reducing propensity towards coalescence.
  • the non-stabilising particles act as reinforcement or a third phase within in the walls of the resultant foams (such particles may be crosslinked into the polymer matrix).
  • particles provide a means to induce interconnectivity between pores on their degradation.
  • the emulsion may be an o/w emulsion or a w/o emulsion, preferably a w/o emulsion.
  • the second aspect of the invention provides a porous polymer foam produced by polymerization of the continuous phase of a stabilized medium or high dispersed phase emulsion comprising a dispersed phase, a continuous phase comprising at least one type of polymerizable monomer and hydrophobized organic particles.
  • a porous polymer foam comprising bi-modal pores produced by the polymerization of the continuous phase of a stabilised medium or high dispersed phase emulsion comprising a dispersed phase, a continuous phase comprising at least one type of polymerizable monomer and organic hydrophobized particles of at least two differing sizes wherein preferably said organic hydrophobized particles comprise (larger) floes or fibrils of cellulose and hydrolyzed (smaller) fibrils of cellulose, (which may be termed cellulose nano-whiskers).
  • the particles preferably have a section/diameter of from 20 to 200 nm, such as 50 to 150 nm, preferably 75 to 100 nm.
  • the larger particles preferably have a length of from 10 to lOO ⁇ m, such as 10 to 90 ⁇ m, preferably 25 to 75 ⁇ m, more preferably 50 to 60 ⁇ m and the smaller particles preferably have a length of from 200nm to lO ⁇ m, such as 300nm to 5 ⁇ m, preferably 500nm to l ⁇ m, more preferably 700nm to 800nm.
  • the foam can be produced by polymerization of an emulsion according to the first aspect of the invention.
  • all preferred features of the emulsion, in particular as far as they relate to the continuous phase, the dispersed phase and the particles also apply to the foam of the second aspect of the invention.
  • the third aspect of the invention relates to a method of producing a stabilized medium or high dispersed phase emulsion comprising a dispersed phase, a continuous phase and hydrophobized organic particles, wherein the dispersed phase constitutes 30% or more of the total volume of the emulsion, the method comprising suspending hydrophobized organic particles within the continuous phase, within the dispersed phase or within both the continuous phase and the dispersed phase and combining the dispersed phase with the continuous phase to form a stabilized emulsion.
  • the particles can be suspended in either the continuous or the dispersed phase or both.
  • the emulsion can be formed by adding either of the continuous or dispersed phases to each other, in the proportion 0-90% by volume, preferably 30 to 95% by volume of the dispersed phase.
  • the composition can be emulsified using either agitation such as vigorous hand-shaking, homogenization, blending, sonication, pumping through a colloid mill or any other form of emulsifi cation.
  • the fourth aspect of the invention relates to method of producing a porous polymer foam wherein the method comprises providing a medium dispersed phase emulsion as defined in the first aspect of the invention or as produced by the process of the third aspect of the invention wherein the continuous phase comprises a polymerizable monomer and wherein the continuous phase and/or the dispersed phase comprises an initiator, and initiating polymerization of the continuous phase.
  • the initiator can be incorporated in either the continuous, dispersed or both phases.
  • thermal initiators are cumene hyperoxide, azobisisobutyronitrile, potassium persulphate, although many initiators could be used by persons skilled in the art; the principle prerequisite is that the initiator has a thermal decomposition temperature below the boiling point of the lower boiling point of either phase.
  • UV initiators may be used solely or in combination with thermal initiators. In this case, emulsions may be exposed to UV irradiation to trigger polymerization, and once the sample has gelled it may be transferred to an oven for residual thermal curing.
  • Suitable liquid UV initiators may be selected from the classes of oc-hydroxyketones, phenylglyoxylates, oc-aminoketones or iodonium salts, and preferably the oc-hydroxyketone: 2-hydroxy- 2-methyl-l -phenyl- 1-propanone (such as Darocur 1173, from Ciba).
  • the fifth aspect of the invention relates to a method for the hydrophobization of a particle comprising grafting of poly(oc-hydroxyesters), such as polylactide, polyglycolide, p ⁇ lycaprolactone or their co-polymers to the surface of the particle.
  • Ring-opening polymerization of the poly( ⁇ r-hydroxyesters) may be performed in the presence of cellulose, whereby the hydroxyl groups on the cellulose act as initiation sites for the ring-opening polymerization.
  • Grafting can also be performed via redox graft polymerization, whereby an initiator such as cerium ammonium is added and acts as an oxidant for the glucose ring of cellulose, creating a free radical, which can propagate diisomethacrylate linkage of the monomer; for example short chain length polycaprolactone methacrylate.
  • a sixth aspect of the invention relates to the use of hydrophobized organic particles to stabilize an emulsion, which can be destroyed and then reformed. The hydrophobized organic particles therefore provide temporary stabilization of the emulsion for a desired duration.
  • the emulsion can be destroyed and then reformed by varying the dispersed phase volume, the particle concentration and/or the pH of the dispersed phase.
  • the hydrophobized organic particles can be used to stabilise an o/w emulsion which can be destroyed and reformed as a w/o emulsion.
  • the hydrophobized organic particles can be used to stabilise a w/o emulsion which can be destroyed and reformed as an o/w emulsion.
  • the inversion of the emulsion from an o/w to a w/o emulsion and vice- versa can be carried out by varying the dispersed phase volume, the particle concentration and/or the pH of the dispersed phase.
  • the hydrophobized organic particle is a hydrophobically modified bacterial cellulose particle.
  • the reversibility of the emulsion can be tuned by functionalizing the cellulose through different degrees of surface substitution of the hydroxyl groups for hydrophobic groups and by varying the length of those hydrophobic groups.
  • FIG 1 shows polyPickering (MIPE) foam, stabilized by hydrophobized bacterial cellulose. The diameter of the sample was 25 mm;
  • Figure 2 shows polyPickering (MIPE) foam, hydrophobized bacterial cellulose can be seen lining the pores (arrowed);
  • Figure 3 shows a pore wall at high magnification showing hydrophobized bacterial cellulose (arrowed) lining the pore wall in the AESO foam;
  • Figure 4 shows hollow spheres.
  • the diameter of the sample shown in the background image was 25 mm;
  • Figure 5 shows organic acid hydrophobized bacterial celh ⁇ lose/photopolymerized acrylated epoxidized soybean oil nano-composite foam (23 mm in diameter);
  • Figure 6 shows organic acid hydrophobized bacterial cellulose shown to line the pore wall of the photopolymerized acrylated epoxidized soybean oil nano-composite foam (shown in Fig. 5.);
  • Figure 7 shows low magnification SEM image of the foam morphology of a polyPickering MIPE based on AEOS stabilised by titania particles
  • Figure 8 shows a high magnification SEM image showing the titania particles at the pore wall surfaces
  • Figure 9 shows (A) a picture of a 50 vol.-% emulsion solely stabilised by 0.5 wt.-% hydrophobized bacterial cellulose particles. A w/o emulsion was formed. (B) a picture of a fractured section of the resultant polymerized foam;
  • Figure 10 shows SEM images at low (A) and high (B) magnification of a polyMIPE synthesised from a 50 vol.-% MIPE stabilised solely by 0.5 wt.-% hydrophobized bacterial cellulose particles;
  • Figure 11 shows a low magnification SEM image showing the interconnected pore structure resulting from the fosed sphere (polymerized AEOS) network
  • Figure 12 shows a high magnification SEM image showing the fused sphere (polymerized AEOS) network that was stabilised by lecithin and hydrophobized bacterial cellulose.
  • Bacterial cellulose was extracted from nata-de-coco, a commercially available product, CHAOKOHR coconut gel in syrup (Thep. Padung Porn coconut Co. Ltd,
  • Bacterial cellulose was extracted from nata-de-coco, by first rinsing the food product three times with deionized water (dH2O), the product was then sieved, homogenized and blended using a variable speed laboratory blender operated at maximum speed (Waring Laboratory, Essex, UK). The bacterial cellulose was then purified by boiling a mixture having a concentration of 0.6 w/v% in 0.1 M NaOH at 80 0 C for 2 h to remove any remaining microorganisms and soluble polysaccharides. Bacterial cellulose was successively centrifuged, homogenized and rinsed to neutral pH. The cellulose was hydrophobized by adapting a protocol described in a) L. Ladouce et al.
  • the CDMIPS reacts with the hydroxyl groups of the cellulose resulting in hydrophobization of its surface.
  • the reaction mixture was agitated using an orbital shaker (600 rpm) for 16 h prior to centrifugation (15 000 g) and decantation.
  • a mix of methanol and THF (20:80, v/v) was added to dissolve the imidizolium chloride byproduct and any disilylethers that may have formed, followed by centrifugation and decantation to obtain a modified cellulose plug.
  • Dispersions of hydrophobized bacterial cellulose in AESO were obtained after rinsing twice with THF and successive centrifugation and re-dispersion operations to exchange the THF with toluene, and exchange of toluene with AESO.
  • emulsion stability index which is the time dependent emulsion volume relative to the total volume of the water and oil phases, was assessed over a 3 -day period.
  • Emulsions containing aqueous phase levels > 70 vol.% underwent catastrophic phase inversion from w/o to o/w emulsions, this type of inversion has been reported to occur for other Pickering emulsions at this volume fraction (0.7) as this is near the limit of sphere close packing.
  • Samples F and G (Table 1), creamed into an o/w phase at the top, with a water phase at the bottom; increasing the cellulose loading increased the creamed volume and stability.
  • Emulsions that undergo catastrophic phase inversion can be multiple emulsions (w/o/w for example).
  • Bacterial cellulose was extracted as previously described in Example 1 and solvent exchanged from water through methanol into pyridine at a concentration of 0.3% w/v. After each solvent exchange the mixture was homogenised at 20 000 rpm for 1 min to disperse the nano-fibrils, then centrifuged at 15 000 g prior to redispersion in the required solvent. Three solvent exchanges were performed for each solvent during the exchange. The cellulose was adjusted to a concentration of 0.5% w/v with respect to pyridine in a 3 -neck round bottom flask and p-toluenesulfonyl chloride added at a ratio of 1 ;4 by weight with respect to the pyridine.
  • Acetic acid chosen as the organic acid (although other organic acids can be applied here, such hexanoic, lauric, oleic and linoleic acids as examples), was added equimolar with respect to the p- toluenesulfonyl chloride. Batches of 2 g equivalent dry weight of bacterial cellulose were modified using this route. The mixture was magnetically stirred and the reaction allowed to progress at 50 0 C for 2 h under nitrogen. The reaction was subsequently quenched using 1.5 1 of ethanol and the mixture then solvent exchanged from pyridine/ethanol through ethanol to water as previously described using successive centrifugation and homogenization steps. This was performed until the colour of the supernatant did not change.
  • Water-in-AESO emulsions were prepared via an organic phase exchange method, described below. This method was used because the AESO phase was initially too viscous to prepare the emulsions. 20 ml water containing 0.5 wt.% acetic acid esterified bacterial cellulose were added into a 50 ml capacity FalconTM tube and an equal volume of soybean oil (with a density of 0.9 g cm "3 ) was added. The mixture was homogenized at 20 000 rpm for 1 min to disperse the cellulose nano-fibrils throughout the system. The mixture was then left overnight in the capped tube to allow the modified nano-fibrils to swell and migrate to the water-oil interface.
  • the sample was shaken by hand for a period of 30 s, resulting in the formation of a water-in-oil emulsion.
  • the emulsion was allowed to sediment to a stable volume; water droplets were observed to sediment to the bottom of the FalconTM tube, reaching a stable level at circa 30 ml after several hours.
  • the ejected oil phase was then removed using pipette from the top of the tube and an equal mass of soybean oil replaced by AESO, which was added at 80 0 C to allow the otherwise viscous monomer to flow.
  • the sample was then re-shaken by hand to reform the stable emulsion.
  • the sample was then exposed to UV radiation using a 100 W mercury lamp (SB-IOOP flood lamp, Spectronics, NY, USA) with a wavelength > 280 nm to photopolymerize the AESO phase; the FalconTM tube containing the sample was rotated on a stage in front of the lamp at 20 rpm to enable more homogeneous polymerization.
  • the polymerized sample was then removed from the tubes and dried in vacuo at 80 0 C for 24 h.
  • the resultant foam is shown (sectioned) in Fig. 3a; the heterogeneously esterified bacterial cellulose nano-fibrils can be seen lining the pore walls in the SEM (Fig.
  • Example 6 akin to the silylated nano-fibril example (Example 1 and shown in Fig. 3).
  • the porosity of the sample shown in Fig. 5 was 69 ⁇ 1%, consistent with the dispersed aqueous phase volume present prior to polymerization.
  • Example 3
  • Poly-Pickering foams made from water-in-functionalized soybean oil emulsions stabilised solely by hydrophobized titania nano particles.
  • Functionalized titania particles rendered hydrophobic by treatment in oleic acid are sufficiently hydrophobic to adsorb at the interface of w/o emulsions (International patent application number PCT/GB2008/002537).
  • water-in- acrylated epoxidized soybean oil emulsions have also been stabilized by addition of 1 wt.% of titania particles with respect to the organic phase.
  • the mixture of 15 ml AEOS oil and particles were homogenized at 20 000 rpm for 1 min to disperse the particles.
  • the aqueous phase containing 0.3M CaCl 2 . 2H 2 O was added drop-wise under further homogenization.
  • the tube containing the emulsion was placed in an ice bath during homogenization to prevent premature polymerization.
  • Samples were then capped and placed in a vacuum oven at 80 °C for 24 h; samples were then removed from the tubes, dried in vacuo for 12 h and post-cnred at 90 0 C for 12 h.
  • the pore structure of the resulting foam is shown at low magnification (Fig. 7) and at high magnification (Fig. 8); the hydrophobized titania particles are visible at the pore wall surfaces.
  • a macroporous polymer made via Pickering emulsion templating made from water-in-styrene emulsions, stabilized by hydrophobized bacterial cellulose
  • Hydrophobized bacterial cellulose dispersed in suspension of toluene was centrifuged and then re-dispersed in purified styrene by homogenization at 20 000 rpm and subsequent ultrasonication for 5-10 min using an ultrasound bath. This step was repeated twice.
  • the cellulose plug was finally re-dispersed at a concentration of 0.5 wt.-% (dry equivalent of hydrophobized bacterial cellulose) into a styrene/divinyl benzene mixture (50:50 by vol.).
  • the initiator (2 mol% with respect to the monomers) abisisobutyronitrile (AIBN) was dissolved in the oil phase.
  • the microstructure of the resultant poly-Pickering foam is shown in Fig. 10. There was negligible shrinkage of the foam, as noted during extraction from the polypropylene tube.
  • the pore size was determined from image analysis of scanning electron micrograph images to be between 200-550 ⁇ m with a median pore size of 350 ⁇ 90 ⁇ m; smaller pores were evident in the walls of the matrix of sizes ⁇ 20 ⁇ m.
  • Example 5 A macroporous polymer made via Pickering emulsion templating made from functionalized soybean oil resin/water emulsion templates, stabilized using a combination of hydrophobized bacterial cellulose, hydrophobic silica nanoparticles and a natural surfactant, lecithin.
  • Water-in-acrylated epoxidized soybean oil emulsions (with 50 vol.% aqueous phase) have also been stabilized by addition, relative to the organic phase, of 20 wt.% lecithin, a natural surfactant; 1 wt.% hydrophobized bacterial cellulose and 1 wt.% hydrophobized silica nano-particles (R202, of particle size ⁇ 10 nm, Degussa, Germany).
  • a mixture of ⁇ 2 ml AEOS, lecithin and particles together was homogenized at 20 000 rpm for 1 min.
  • the initiator, cumene hyperoxide (3 wt.% relative to the organic phase) was added immediately prior to the aqueous phase addition.
  • the aqueous phase containing 0.3M CaG 2 .2H 2 O was added drop-wise under further homogenization.
  • the curing methodology described in Example 1 was applied to polymerize the AEOS phase.
  • the resultant foam (from the emulsion stabilized using lecithin and particles) has a pore structure formed of a network of fused spheres shown at low magnification (Fig. 11) and high magnification (Fig. 12), indicating that the emulsions were oil-in-water; the spheres fused together during curing to produce the interconnected foam structure.
  • Example 6 Cellulose nano-particles hydrophobized with organic acids act as emulsifiers which permit emulsions to be rapidly destroyed but reformed (reversible emulsions) and display a pH dependency; changing pH allows the emulsions to be phase inverted from w/o to o/w
  • Cellulose was hydrophobized by organic acids of different chain length, nominally, acetic acid (C2), hexanoic acid (C6) and lauric acid (C12) as described in Example 2.
  • Water-in-toluene emulsions were initially formed by adding a 50:50 by volume mixture of these phases to 50ml Falcon TM tubes containing 1 wt.% of hydrophobized cellulose (relative to the organic phase). Emulsions were shaken by hand at 4Hz for a period of 1 minute and the emulsion stability subsequently recorded after a period of 3 h, provided the emulsion was stable, after some sedimentation and ejection of the oil phase, some of the toluene was removed from the emulsions.
  • the removal of toluene acted to increase .the effective dispersed phase (aqueous) volumes.
  • the samples were subsequently re-shaken after altering the dispersed phase volume and the point (dispersed phase volume) at which the emulsions were destroyed was recorded.
  • These emulsions could be reformed by mere addition of some of the organic phase (toluene in this example).
  • the pH of the aqueous phase was reduced or increased by addition of hydrochloric acid or sodium hydroxide and the effect of pH on emulsion type and stability assessed. Changing the pH to increasingly lower values resulted in the emulsions phase inverting from w/o to o/w emulsions; this effect could be reversed on raising the pH.
  • the cellulose particles provide the ability to destroy and recreate emulsions, as well as reversibly phase inverting the emulsions.
  • the maximum dispersed phase that could be achieved for water-in-toluene emulsions for acetic acid modified bacterial cellulose (BC), hexanoic acid modified BC and lauric acid modified BC was 71 vol.%, 82% and 77% by volume, respectively, relative to the total volume.
  • the viscosity of w/o emulsions stabilized by hexanoic acid modified BC increases as the pH was reduced to 1; on changing the pH to 14 the emulsion is destroyed.
  • Films of unmodified bacterial cellulose were formed by taking some centrifuged sample (circa 1 g equivalent dry weight), rolling and pressing this in between release film to remove the water. The films were near fully dried in a hot press (George E. Moore and Sons, Birmingham, UK) and then pressed at 100 °C and 50 kN for 5 min, then further dried in a vacuum oven over night. Films of the modified bacterial cellulose (silylated, as in Example 1, and modified by organic acids (acetic acid, hexanoic and lauric acid) as in Example 2) were made by dispersing the nano-fibrils in chloroform and then filtering this through PTFE membranes; the resultant films that formed on top of the membrane were then pressed.
  • a hot press George E. Moore and Sons, Birmingham, UK
  • the degree of hydrophobization was assessed by advancing and receding sessile drop contact angle measurement.
  • the wettability of cellulose films was determined by contact angle analysis using a Drop Shape Analyser (DSA 10 MK2, Kr ⁇ ss, Germany). Advancing and receding contact angles were measured by increasing the volume of water droplets placed on the cellulose films in the range 2 ml-20 ml at a rate of 6.32 ml min-1 and then decreasing the drop volume at the same rate, using a motorized syringe. At least six independent determinations at different sites for each sample were made.
  • AESO resin-in water contact angles were obtained by the sessile drop method (at 8O 0 C, which was the curing temperature applied in the presence of the initiator) to better represent the real three-phase contact angle in the emulsion.
  • AESO resin-in water contact angles were 134° ⁇ 10 and 40° ⁇ 9, on hydrophobized and unmodified bacterial cellulose films, respectively.
  • Table 1 Composition of the emulsion templates stabilized by silylated bacterial cellulose and their stability as a function of time.
  • AESO organic phase
  • b wt.% of hydrophobized bacterial cellulose relative to the organic phase volume.
  • volume of emulsified phase relative to the total volumes of monomer and aqueous phases.

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
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Abstract

La présente invention concerne une émulsion à teneur moyenne ou élevée en phase dispersée, stabilisée par des particules, ladite émulsion comprenant une phase dispersée qui constitue 30 % ou plus du volume total de l'émulsion, une phase continue, et des particules organiques rendues hydrophobes. L'invention concerne également des procédés de production de ladite émulsion et des mousses polymères poreuses produites à partir de celle-ci.
PCT/GB2009/002395 2008-10-08 2009-10-08 Émulsions stabilisées par des particules organiques rendues hydrophobes Ceased WO2010058148A1 (fr)

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FR2974312A1 (fr) * 2011-04-20 2012-10-26 Agronomique Inst Nat Rech Procede d'obtention d'emulsions a haute phase interne
WO2014011112A1 (fr) * 2012-07-10 2014-01-16 Cellutech Ab Mousse nfc stabilisée
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FR2996848A1 (fr) * 2012-10-16 2014-04-18 Agronomique Inst Nat Rech Composition comprenant une phase interne dispersee dans une phase continue hydrophile
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