WO2008074096A1 - Modification par extrusion réactive de polymères fonctionnels - Google Patents

Modification par extrusion réactive de polymères fonctionnels Download PDF

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WO2008074096A1
WO2008074096A1 PCT/AU2007/001996 AU2007001996W WO2008074096A1 WO 2008074096 A1 WO2008074096 A1 WO 2008074096A1 AU 2007001996 W AU2007001996 W AU 2007001996W WO 2008074096 A1 WO2008074096 A1 WO 2008074096A1
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starch
polysaccharide
group
modifying agent
cyclic
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PCT/AU2007/001996
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English (en)
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Kishan C. Khemani
Brendan Morris
Graeme Moad
Guoxin Li
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Plantic Technologies Ltd
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Priority claimed from AU2006907228A external-priority patent/AU2006907228A0/en
Application filed by Plantic Technologies Ltd filed Critical Plantic Technologies Ltd
Publication of WO2008074096A1 publication Critical patent/WO2008074096A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/02—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/08—Ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/08—Ethers
    • C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/16—Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/183—Block or graft polymers containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/06—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/08—Ethers

Definitions

  • This invention relates to a process for one-step modification of functional polymers such as polyvinyl alcohol, or polysaccharides, such as starch, by reactive extrusion. It also relates to modified polymers, particularly starch- and cellulose-based polymers, having improved mechanical and rheological properties.
  • modified graft polymers and especially the modified starches prepared according to the invention may be utilised as biodegradable thermoplastic materials for use particularly as packaging materials such as for example, rigid trays, injection moulded products such as bottles, flexible films and barrier films.
  • a batch process for Lewis Acid catalysed modification of starch with caprolactone in aqueous media was described by Choi et al (Choi, E. J., C. H. Kim, et al (1999), "Synthesis and characterization of starch-g-polycaprolactone copolymer", Macromolecules 32(22): 7402-7408). The process required very long reaction times (16 hours).
  • a process for Lewis Acid catalysed modification of starch with lactide in aqueous media was described by Gong et al (Gong, Q. X., L. Q.
  • Reactive extrusion has been considered impractical in starch modification because it produces a material contaminated with residual reagents and reaction by-products (Kalambur and Rizvi 2006 supra; Xie, Yu et al 2006 supra). Furthermore, the presence of a high level of water in starch leads to difficulties in reactive extrusion modification utilising certain desirable modifying agents which are reactive towards water. Typically these modifications are done in the absence of water to avoid side reactions.
  • a process of reactive extrusion modification of polysaccharides or a functional polymer selected from the group consisting of hydroxyfunctional polymers and amide functional polymers or a combination thereof comprising reacting said polysaccharide or functional polymer, each present in an aqueous state, with a modifying agent optionally in the presence of an acid catalyst.
  • the hydroxyfunctional polymers are selected from polyvinyl alcohol), poly(hydroxyalkyl(meth)acrylates for example poly(hydroxyethyl acrylate) and poly(hydroxyethyl methacrylate) and the amide functional polymers are selected from polyacrylmide and polyalkyl acrylamides.
  • the hydroxyfunctional polymer is polyvinylalcohol.
  • the polysaccharide is cellulose or starch.
  • the modifying agent may be any agent which will graft to the selected functional polymer or polysaccharide under acid catalysis and is preferably a ring opening monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, imidazalones, glycolide, lactide, alkyl substituted glycolides and alkyl substituted cyclic oxetanes.
  • the optional acid catalyst is a Lewis Acid catalyst.
  • the process is carried out as a single step, continuous process. It has been found that in the process of the invention, selectivity of reaction occurs with the result that graft polymerisation of the polymer to the modifying agent occurs in preference to reaction between the water present in the process and the modifying agent. Good grafting efficiency is observed.
  • a biomaterial produced by a process of reactive extrusion modification of functional polymers comprising reacting a functional polymer selected from the group consisting of hydroxyfunctional polymers such as polyvinyl alcohol), poly(hydroxyalkyl(meth)acrylate)s for example poly(hydroxyethyl acrylate) and poly(hydroxyethyl methacrylate) and amide functional polymers such as polyacrylamide and poly(alkyl acrylamide)s and which is present in an aqueous state with a modifying agent which may be any which will graft to said functional polymer under acid catalysis and is preferably one which is a monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, imidazalones, glycolide, lactide, alkyl substituted glycolides and alkyl substituted cyclic oxetanes optionally in the presence of an acid catalyst.
  • a functional polymer selected from the group consisting of hydroxyfunctional polymers such as poly
  • the functional polymer may preferably be polyvinyl alcohol.
  • a modified polysaccharide thermoplastic polymer produced by a process of reactive extrusion modification of polysaccharide comprising reacting optionally in the presence of an acid catalyst a polysaccharide present in an aqueous state with a modifying agent which may be any which will graft to starch under acid catalysis and is preferably one which is a monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, imidazalones, glycolide, lactide, alkyl substituted glycolides and alkyl substituted cyclic oxetanes.
  • the modified polysaccharide polymer is preferably a modified starch polymer.
  • a biomaterial preferably a thermoformed product produced from a modified thermoplastic polymer produced by a process, optionally in the presence of an acid catalyst, of reactive extrusion modification of functional polymer, comprising the reaction of a functional polymer selected from the group consisting of hydroxyfunctional polymers such as polyvinyl alcohol), poly(hydroxyalkyl(meth)acrylate)s for example poly(hydroxyethyl acrylate) and poly(hydroxyethyl methacrylate) and amide functional polymers such as polyacrylamide and poly(alkyl acrylamide)s, said functional polymer being present in an aqueous state with a modifying agent which may be any which will graft to said functional polymer under acid catalysis and is preferably one which is a monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, imidazalones, glycolide, lactide,
  • the product may be a packaging product which is a rigid tray, an injection moulded product such as bottles, a flexible film or barrier film.
  • a biodegradable thermoformed product preferably a packaging product, produced from a modified polysaccharide thermoplastic polymer produced by a process optionally in the presence of an acid catalyst of reactive extrusion modification of polysaccharides comprising the reaction of a polysaccharide present in an aqueous state with a modifying agent which may be any which will graft to starch under acid catalysis and is preferably one which is a monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, imidazalones, glycolide, lactide, alkyl substituted glycolides and alkyl substituted cyclic oxetanes.
  • the packaging product may be an injection moulded product such as a bottle or a rigid tray, a bottle cap, or packaging inserts for consumable products such as chocolates or biscuit
  • a biodegradable, packaging film produced from a modified polysaccharide thermoplastic polymer produced by a process of reactive extrusion modification of polysaccharides comprising the reaction optionally in the presence of an acid catalyst of a polysaccharide present in an aqueous state with a modifying agent which may be any which will graft to starch under acid catalysis and is preferably one which is a monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, and imidazalones.
  • the packaging film may be a barrier film. The film may be used for wrapping or for lining of existing packaging products and in certain grades may also be thermoformed into packaging products or injection moulded in specific shapes.
  • biomaterial formed from a blend of a hydroxy- or amide-functionalised polymer or a polysaccharide based polymer produced according to the process of the invention with other suitable polymers including polylactide and polycaprolactone, and optionally other function- or property- modifying additives such as nanocomposite materials including silica, clays and synthetic materials.
  • suitable polymers including polylactide and polycaprolactone
  • function- or property- modifying additives such as nanocomposite materials including silica, clays and synthetic materials.
  • the blends used for such biomaterials may be modified according to the functional and mechanical properties required for said biomaterials.
  • the ratio of the components of said blended biomaterials and the polymers selected for use in conjunction with the functional polymers or polysaccharide polymers produced according to the process of the invention will be understood by those skilled in the art.
  • the polysaccharide utilised is preferably starch.
  • starch For reactive extrusion processes in which starch is used, it may be a native starch, a modified or unmodified starch or any combination thereof.
  • the starch selected is a high amylose starch.
  • the starch source may be any suitable one including corn (maize), rice, tapioca, potato, cassava, arrowroot and sago including mixtures thereof.
  • a preferred source of starch is corn.
  • preferred catalysts are Lewis Acid or protic (Bronsted) Acid catalysts.
  • the Lewis Acid is chosen for its stability and/or utility in aqueous media.
  • the Lewis Acid may be any acid which can accept an electron pair to form a covalent bond and may be selected from the group consisting of aluminium based Lewis Acids, for example aluminium triflate, tin based Lewis Acids, for example stannous octoate, dibutyl tin oxide or dibutyl tin dilaurate, titanium based Lewis Acids, for example tetra-2-ethylhexyl titanate, zirconium based Lewis Acids, for example triethanolamine zirconate, rare earth based Lewis Acids, for example ytterbium triflate, phosphorous based Lewis Acids or any other Lewis Acid compatible with water or combination thereof.
  • Lewis Acids such as aluminium chloride, iron (III) chloride, niobium pentachloride which would generate hydrochloric acid or another hydrohalic acid on contact with water are not preferred.
  • Preferred Lewis Acids are stannous octoate and aluminium triflate.
  • the Lewis Acid may be introduced in a solubilised state. Any suitable solvent may be utilised. Preferably the solvent should not react with the Lewis Acid and should be water miscible.
  • solvents may include tri(ethylene glycol) dimethyl ether (triglyme) and di(ethylene glycol) dimethyl ether (diglyme). The amount of solvent is as small as practicable consistent with being sufficient to dissolve the Lewis acid and sufficient to permit accurate addition. If present, a preferred ratio of starch to solvent is 1 to 3%.
  • Preferred protic or Bronsted Acids include organic sulfonic acids, such as p-toluenesulphonic acid, and phosphoric or phosphonic acids. Hydrohalic acids such as hydrochloric acid are not preferred. If used, a preferred ratio of acid to functional polymer or polysaccharide is 0.001 to 1.0% by weight, more preferably 0.01 to 0.5% by weight. It has been observed that higher levels of acid catalyst may promote reaction of the modifying agent with water.
  • Preferred modifying agents are lactones and particularly those which are optionally substituted 4-12 membered ring lactones, for example caprolactone, valerolactone and dodecanolide.
  • Alternate preferred modifying agents are epoxyalkanes and particularly those which are C 2 -C 18 1 ,2-epoxyalkanes including 1 ,2-epoxybutane and 1 ,2- epoxyhexane.
  • the modifying agent may be present in any quantity which achieves, under the process conditions selected, a satisfactory degree of grafting.
  • a preferred ratio of modifying agent to functional polymer or polysaccharide is 0.5 to 25.0% by weight, more preferably 1.0 to 15% by weight.
  • the water present in the material may act as a plasticiser.
  • any other suitable hydrophobic or hydrophilic plasticizer may also be introduced into the process if required.
  • Suitable plasticizers include polyols and may be one or more of polyvinyl alcohol), sorbitol, maltitol, glycerol, mannitol, xylitol, erythritol, ethylene glycol and diethylene glycol.
  • Additional water may be added to act as a hydrophilic plasticizer if desired.
  • Hydroxyfunctional plasticisers such as the various sugars mentioned may preferably be added subsequent to the reactive modification step. Where hydroxy-functional plasticisers. other than water are used it may be preferable to introduce these subsequent to the addition of modifying agents since these may also react with the modifying agents.
  • the process of reactive extrusion is preferably performed at elevated temperatures within the range of 3O 0 C to 200 0 C.
  • the process of reactive extrusion insofar as it is used to modify starch occurs at a temperature greater than 5O 0 C, preferably greater than 70 0 C and more preferably greater than 100 0 C.
  • the reactive extrusion process is preferably carried out at pressures greater than atmospheric pressure. More preferably the reaction is carried out at pressures of 1 to 4 atmospheres.
  • the residence time may be selected so as to be compatible with the required degree of modification or reaction efficiency (that is, the amount of monomer reacted with the functional polymer or polysaccharide) of the polymer. A reaction efficiency of 80% or more is preferred. This correlates to a preferred reaction time of 0.5 to 10 minutes. A more preferred reaction time is 2 to 5 minutes.
  • the order of introduction of the functional polymer or polysaccharide, catalyst and modifying agent to the reaction stream may be varied.
  • One preferred embodiment is to premix the functional polymer, or polysaccharide, and catalyst which are introduced through the feed hopper of the extruder and the modifying agent is added subsequently by injection.
  • a second alternate preferred embodiment is to introduce the functional polymer, or polysaccharide, through the feed hopper and introduce the modifying agent and catalyst subsequently by separate injection.
  • a third alternate preferred embodiment is to premix the functional polymer, or polysaccharide, modifying agent and catalyst and feed this though the main feed hopper.
  • a fourth alternate preferred embodiment is to premix the functional polymer, or polysaccharide, and modifying agent which is introduced through the feed hopper of the extruder and the catalyst is added subsequently by injection. Simultaneous addition of the catalyst and modifying agent to the extruder by injection is not preferred since these conditions promote reaction of the modifying agent with water and the formation of by-products.
  • a twin screw extruder in co-rotating or counter-rotating mode, intermeshing or non-intermeshing may be utilised in the processes of the invention, but equally a single screw extruder or a multi screw extruder may also be suitable providing always that mixing can be achieved.
  • a ten zone extruder may be used, but any other number of zones may be selected depending on the circumstances.
  • the starch and catalyst may be introduced through a feed hopper immediately prior temperature zone 1. Modifying agents and/or catalyst may be injected in temperature zone 5.
  • the point of injection is subsequent to full gelation of the starch. It is advantageous but not essential to use a pre-geiatinised functional polymer or starch.
  • the number of units of modifying agent per graft is low, typically between 1 and 10. More typically between 1 and 2. In many cases the graft will comprise a single unit of modifying agent.
  • the presence, amount and type of incorporated units can be established by spectroscopy, for example by 1 H nuclear magnetic resonance spectroscopy or Fourier transform infrared spectrometry. Extraction techniques such as Soxhlet extraction can also be used to demonstrate the efficiency of incorporation.
  • the process of reactive extrusion modification of a functional polymer may produce a biomaterial prepared by reacting optionally in the presence of an acid catalyst a functional polymer selected from the group consisting of hydroxyfunctional polymers such as polyvinyl alcohol), poly(hydroxyalkyl(meth)acrylate)s for example poly(hydroxyethyl acrylate) and poly(hydroxyethyl methacrylate) and amide functional polymers such as polyacrylamide and poly(alkyl acrylamide)s, said functional polymer being present in an aqueous state, with a modifying agent which may be any which will graft to starch under acid catalysis preferably one which is a monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, imidazalones, glycolide, lactide, alkyl substituted glycolides and alkyl substituted cyclic oxetanes.
  • a modifying agent which may be any which will graft to starch under acid
  • the functional polymer may preferably be polyvinyl alcohol.
  • the modifying agent is preferably selected from the group consisting of ⁇ -caprolactone, dodecanolide, ⁇ -valerolactone, 1 ,2-epoxybutane and 1 ,2-epoxyhexane. Where an acid catalyst is used it is preferably a Lewis Acid, protic or
  • Bronsted acid More preferably a Lewis Acid catalyst is used.
  • the process of reactive extrusion modification of a polysaccharide produces a modified polysaccharide thermoplastic polymer prepared by reacting, optionally in the presence of an acid catalyst, a polysaccharide present as an aqueous gel with a modifying agent which may be any which will graft to starch under acid catalysis and is preferably one which is a monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, imidazalones, glycolide, lactide, alkyl substituted glycolides and alkyl substituted cyclic oxetanes.
  • a modifying agent which may be any which will graft to starch under acid catalysis and is preferably one which is a monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, imidazalones, glycolide, lactide, alkyl substituted glycolides and alkyl substituted cyclic o
  • the modified polysaccharide polymer is preferably a modified starch polymer.
  • the modifying agent is preferably selected from the group consisting of ⁇ -caprolactone, dodecanolide, ⁇ -valerolactone, 1 ,2-epoxybutane and 1 ,2- epoxyhexane.
  • an acid catalyst is used it is preferably a Lewis Acid, protic or Bronsted acid. More preferably a Lewis Acid catalyst is used.
  • the modified thermoplastic polymer resulting from the process of reactive extrusion modification of functional polymer may be thermoformed into a biomaterial product.
  • the modified thermoplastic polymer may be prepared by the reaction, optionally in the presence of an acid catalyst, of a functional polymer selected from the group consisting of hydroxyfunctional polymers such as polyvinyl alcohol), poly(hydroxyalky!(meth)acrylate)s for example poly(hydroxyethyl acrylate) and poly(hydroxyethyl methacrylate) and amide functional polymers such as polyacrylamide and poly(alkyl acry!amide)s, said functional polymer being present in an aqueous state, with a modifying agent which may be any which will graft to said functional polymer under acid catalysis and is preferably one which is a monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, imidazalones, glycolide, lactide, alkyl substituted glycolides and alkyl substituted
  • the modifying agent is preferably selected from the group consisting of ⁇ - caprolactone, dodecanolide, ⁇ -valerolactone, 1 ,2-epoxybutane and 1 ,2- epoxyhexane.
  • an acid catalyst is used it is preferably a Lewis Acid, protic or Bronsted acid. More preferably a Lewis Acid catalyst is used.
  • the modified polysaccharide thermoplastic polymer may be thermoformed into a product, preferably a packaging product.
  • the modified polysaccharide thermoplastic polymer may be produced by a process, optionally in the presence of an acid catalyst, of reactive extrusion modification of polysaccharides prepared by the reaction of a polysaccharide present in an aqueous state with a modifying agent which may be any which will graft to starch under acid catalysis and is preferably one which is a monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, imidazalones, glycolide, lactide, alkyl substituted glycolides and alkyl substituted cyclic oxetanes.
  • the packaging product may be an injection moulded product such as a bottle or a rigid tray, a bottle cap, or packaging inserts for consumable products such as chocolates or biscuits or other foodstuffs.
  • the modifying agent is preferably selected from the group consisting of ⁇ - caprolactone, dodecanolide, ⁇ -valerolactone, 1 ,2-epoxybutane and 1 ,2- epoxyhexane.
  • an acid catalyst is used it is preferably a Lewis Acid, protic or Bronsted acid. More preferably a Lewis Acid catalyst is used.
  • the modified polysaccharide thermoplastic polymer may be formed into a biodegradable, packaging film.
  • the modified polysaccharide thermoplastic polymer may be produced by a process of reactive extrusion modification of polysaccharides prepared by the reaction, optionally in the presence of an acid catalyst, of a polysaccharide, present in an aqueous state, with a modifying agent which may be any which will graft to starch under acid catalysis and is preferably one which is a monomer selected from the group consisting of cyclic esters, cyclic carbonates, epoxides, and imidazalones.
  • the packaging film may be a barrier film. The film may be used for wrapping or for lining of existing packaging products and in certain grades may also be thermoformed into packaging products or injection moulded in specific shapes.
  • biomaterial formed from a blend of an amide or functionalised polymer or a polysaccharide based polymer produced according to the process of the invention with other suitable polymers including polylactide and polycaprolactone and optionally other function- or property-modifying additives such as nanocomposite materials including silica, clays and synthetic materials.
  • suitable polymers including polylactide and polycaprolactone and optionally other function- or property-modifying additives such as nanocomposite materials including silica, clays and synthetic materials.
  • the blends used for such biomaterials may be modified according to the functional and mechanical properties required by said blends.
  • the ratio of the components of said blended biomaterials and the polymers selected for use in conjunction with the functional polymers or polysaccharide polymers produced according to the process of the invention will be understood by those skilled in the art.
  • Starch was modified with 1 ,2-epoxyhexane, 1 ,2-epoxybutane, ⁇ - caprolactone, dodecanolide ( ⁇ -heptyl- ⁇ -valerolactone) and ⁇ -valerolactone by reactive extrusion, using a Lewis Acid as catalyst.
  • Reactive extrusion was performed with a twin screw extruder comprising ten temperature controlled barrel zones each with length/diameter (L/D) of 3.5, three unheated zones with L/D 1.167, and a cooled feed block with L/D 3.
  • the temperatures of the ten zones were as shown in Table 1.
  • Solid materials starch, starch mixtures
  • Water was introduced at zone 4.
  • the starch, Gelose 80 (Penfords Australia) was mixed with Tin (II) 2- ethylhexanoate (Sn(Oct) 2 ) (Aldrich) in Tri(ethyleneglycol)dimethylether (triglyme) (Aldrich) or di(ethyleneglycol)dimethylether (diglyme) (Aldrich) in a rotating mixer.
  • the catalyst solution was added to the starch through a syringe pump at a flow rate of 2.000 ml/min. After addition, the mixture was stored in container for at least two days prior to use. Ratios of starch, catalyst and solvent used are shown in Tables 2-5.
  • Liquid reagents (1 ,2-epoxyhexane, 1 ,2-epoxybutane, ⁇ -caprolactone, dodecanolide ( ⁇ -heptyl- ⁇ -valerolactone) and ⁇ -valerolactone were added via a Teledyne lsco Model 500D syringe pump connected to zone 5. Amounts of reagent used are shown in Tables 2-5.
  • the extrudate was obtained as a strand which was dried and pelletised. After extrusion the level of grafting was determined by extracting the starch using the following procedure. The pellets were ground to a powder using a Glen Mills Inc. S, 500 Disc Mill. The resultant starch powder was extracted in a Soxhlet extractor. The epoxyhexane modified starch was extracted using acetone. The caprolactone and dodecanolactone modified starch were extracted using toluene for 48 hours. After extraction, the residual solid was washed with acetone, filtered and dried in vacuum oven at 8O 0 C for 24 hours before analysis by 1 H NMR. In selected cases the filtrate was examined and showed the presence of negligible caprolactone or polycaprolactone.
  • ⁇ -Hydroxycaproic acid was distinguished from polycaprolactone which has a similar spectrum by addition of base (NaHCO 3 ) which causes a shift in the spectrum of ⁇ - Hydroxycaproic acid but not of polycaprolactone.
  • caprolactone and polycaprolactone are completely soluble in toluene and so unreacted reagents are expected to be removed from the modified starch by Soxhlet extraction.
  • Caprolactone and polycaprolactone are also quite distinct from ⁇ -hydroxycaproic acid (as would be formed by reaction with water). Products obtained after extrusion generally contained very low or undetectable amounts of ⁇ -hydroxycaproic acid unless high catalyst levels were used (see Examples 32-34). Low yields of incorporated caprolactone after dissolution in DMSO and precipitation show that the incorporated caprolactone is largely removed by this process.
  • Caprolactone alone or mixed with gelose 80 show a sharp strong carbonyl absorption at 1731 cm "1 .
  • the modified starch before and after Soxhlet extraction shows a complex pattern of absorption bands with a maxima in the range 1700-1728 cm “1 . This demonstrates that the caprolactone is modified from the caprolactone precursor.
  • Reactive extrusion conditions were as follows:
  • feed rate 3.5 kg/hr; re-hydrated pellets were fed from F1 ;
  • Caprolactone was added through C5; screw speed: 149 rpm; motor output: 15; liquid pump: output 15/35 g/min.
  • feed rate 3.5kg/hr; mixed Gelose 80/cat was fed from F1 ; water was added through C4; all reagents were added through C5; screw speed: 149 rpm; motor output: 15; liquid pump: output 15/35g/min.
  • the temperature profile of the process is as set out in Table 3.
  • First number is amount of incorporated caprolactone.
  • Value in parentheses is amount of ⁇ -hydroxycaproic acid.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

La présente invention porte sur un procédé pour la modification par extrusion réactive d'un polymère ou polysaccharide fonctionnel comprenant la réaction, facultativement en présence d'un catalyseur acide, dudit polymère ou polysaccharide fonctionnel dans un état aqueux avec un agent de modification. L'invention concerne en outre des biomatériaux obtenus par le procédé d'extrusion réactive de la présente invention. Les biomatériaux trouvent des utilisations dans le thermoformage, la production de films et dans la préparation de mélanges de polymères.
PCT/AU2007/001996 2006-12-21 2007-12-21 Modification par extrusion réactive de polymères fonctionnels WO2008074096A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AU2006907227 2006-12-21
AU2006907228 2006-12-21
AU2006907228A AU2006907228A0 (en) 2006-12-21 Reactive Extrusion Modification of Functional Polymers
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