EP2247660A2 - Verfahren zur herstellung von thermoplastischen zusammensetzungen auf basis von weichgemachter stärke und resultierende zusammensetzungen - Google Patents

Verfahren zur herstellung von thermoplastischen zusammensetzungen auf basis von weichgemachter stärke und resultierende zusammensetzungen

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Publication number
EP2247660A2
EP2247660A2 EP09705602A EP09705602A EP2247660A2 EP 2247660 A2 EP2247660 A2 EP 2247660A2 EP 09705602 A EP09705602 A EP 09705602A EP 09705602 A EP09705602 A EP 09705602A EP 2247660 A2 EP2247660 A2 EP 2247660A2
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EP
European Patent Office
Prior art keywords
starch
plasticizer
composition
binding agent
thermoplastic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09705602A
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English (en)
French (fr)
Inventor
Léon Mentink
Didier Lagneaux
Jérôme GIMENEZ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roquette Freres SA
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Roquette Freres SA
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Filing date
Publication date
Application filed by Roquette Freres SA filed Critical Roquette Freres SA
Publication of EP2247660A2 publication Critical patent/EP2247660A2/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6484—Polysaccharides and derivatives thereof
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • C08G18/6517—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • 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
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Definitions

  • the present invention relates to a new process for the preparation of starch-based thermoplastic compositions and the compositions thus obtained.
  • thermoplastic composition in the present invention means a composition which reversibly softens under the action of heat and hardens on cooling. It has at least one so-called glass transition temperature (Tg) below which the amorphous fraction of the composition is in the brittle glassy state, and above which the composition can undergo reversible plastic deformations.
  • Tg glass transition temperature
  • the glass transition temperature or at least one of the glass transition temperatures of the starch-based thermoplastic composition of the present invention is preferably from -50 to 150 ° C.
  • This starch-based composition can, of course, be shaped by the processes traditionally used in plastics (extrusion, injection, molding, blowing, calendering, etc.). Its viscosity, measured at a temperature of 100 0 C to 200 0 C, is generally between 10 and 10 6 Pa. S.
  • said composition is "hot melt”, that is to say that it can be shaped without applying significant shear forces, that is to say by simple flow or by simply pressing the melt.
  • Its viscosity measured at a temperature of 100 0 C to 200 0 C, is generally between 10 and 10 3 Pa. S.
  • Starch is a raw material with the advantages of being renewable, biodegradable and available in large quantities at an economically attractive price compared to the oil and gas used as raw materials for today's plastics.
  • the first starch-based compositions developed were about thirty years ago.
  • the starches were then used in the form of mixtures with synthetic polymers such as polyethylene, as filler, in the native granular state.
  • the native starch is then preferably dried to a moisture content of less than 1% by weight, to reduce its hydrophilicity.
  • it can also be coated with fatty substances (fatty acids, silicones, siliconates) or to be modified on the surface of the grains by siloxanes or isocyanates.
  • the materials thus obtained generally contained approximately 10%, at most 20% by weight of granular starch, because beyond this value, the mechanical properties of the composite materials obtained became too imperfect and lowered compared with those of the synthetic polymers forming the matrix.
  • polyethylene-based compositions are only biodegradable and non-biodegradable as expected, so that the expected growth of these compositions has not occurred.
  • PHBV polyhydroxybutyrate-co-hydroxyvalerate
  • PLA poly (lactic acid)
  • the starch was used in a substantially amorphous and thermoplastic state.
  • This state is obtained by plastification of the starch using a suitable plasticizer incorporated into the starch at a level generally between 15 and 25% relative to the granular starch, by supply of energy at a time. mechanical and thermal.
  • U.S. Patent 5,095,054 to Warner Lambert and EP 0 497 706 B1 to Applicants describe in particular this destructured state, with reduced or absent crystallinity, and means for obtaining such thermoplastic starches.
  • thermoplastic starches although they may be to some extent modulated by the choice of starch, plasticizer and the rate of use of the latter, are generally rather poor because the materials and obtained are still very highly viscous at high temperature (120 0 C to 170 0 C) and very brittle, too brittle, and very hard at low temperature, that is to say below the glass transition temperature or the temperature. highest glass transition temperature.
  • thermoplastic starches are very low, still less than about 10%, and this even with a very high plasticizer content of the order of 30%.
  • the elongation at break of low density polyethylenes is generally between 100 and 1000%.
  • thermoplastic starches decreases dramatically as the level of plasticizer increases. It has an acceptable value, of the order of 15 to 60 MPa, for a plasticizer content of 10 to 25%, but decreases unacceptably beyond 30%.
  • thermoplastic starches have been the subject of numerous studies aimed at developing biodegradable and / or water-soluble formulations having better mechanical properties by physical mixing of these thermoplastic starches, or with polymers of petroleum origin such as polyvinyl acetate (PVA), polyvinyl alcohol (PVOH), ethylene / vinyl alcohol copolymers (EVOH), biodegradable polyesters such as polycaprolactones (PCL), poly (butylene adipate terephthalate) (PBAT) and poly (butylene succinate adipate) (PBS), or with polyesters of renewable origin such as poly (lactic acid) (PLA) ) or microbial polyhydroxyalkanoates (PHA, PHB and PHBV), or with natural polymers extracted from plants or animal tissues.
  • PVA polyvinyl acetate
  • PVH polyvinyl alcohol
  • EVOH ethylene / vinyl alcohol copolymers
  • PCL polycaprolactones
  • PBAT poly (butylene adipate ter
  • thermoplastic starches are very hydrophilic and are therefore very incompatible with synthetic polymers. It follows that the mechanical properties of such mixtures, even with the addition of compatibilizing agents such as, for example, copolymers comprising hydrophobic units and alternating hydrophilic units such as ethylene / acrylic acid (EAA) copolymers, or even cyclodextrins. or organosilanes, remain quite limited.
  • compatibilizing agents such as, for example, copolymers comprising hydrophobic units and alternating hydrophilic units such as ethylene / acrylic acid (EAA) copolymers, or even cyclodextrins. or organosilanes, remain quite limited.
  • the commercial product MATER-BI grade Y has, according to the information given by its manufacturer, an elongation at break of 27% and a maximum breaking stress of 26 MPa.
  • these composite materials today find limited use, that is to say, limited essentially to the sectors of the overpack, trash bags, crate bags and some rigid, biodegradable mass objects.
  • thermoplastic amorphous starches can be carried out in a medium that is poorly hydrated by the extrusion processes. Obtaining a melted phase from the starch granules requires not only a large supply of mechanical energy and thermal energy but also the presence of a plasticizer at the risk, otherwise, to carbonize the starch.
  • Water is the most natural plasticizer of starch and is therefore commonly used, but other molecules are also very effective, including sugars such as glucose, maltose, fructose or sucrose; polyols such as ethylene glycol, propylene glycol, polyethylene glycols (PEG), glycerol, sorbitol, xylitol, maltitol or hydrogenated glucose syrups; urea, salts of organic acids such as sodium lactate and mixtures of these products.
  • the amount of energy to be applied to plasticize the starch can be advantageously reduced by increasing the amount of plasticizer.
  • a plasticizing agent at a high level relative to the starch induces various technical problems among which may be mentioned the following: a release of the plasticizer of the plasticized matrix at the end of manufacture or over time during storage, so that it is impossible to retain a quantity of plasticizer as high as desired and therefore obtain a sufficiently flexible and film-forming material, o high instability of the mechanical properties of the plasticized starch that hardens or softens depending on the humidity of the air, respectively when its water content decreases or increases, o the whitening or opacification of the surface of the composition by crystallization of the plasticizer used at high dose, as for example in the case of xylitol o a tacky or oily nature of the surface, as in the case of glycerol for example, o a very poor resistance to water, all the more problematic that the plasticizer content is high.
  • the present invention provides an effective solution to the problems stated above.
  • the present invention relates to a process for preparing a thermoplastic composition based on starch comprising the following steps:
  • step (b) preparing a plasticized composition by thermomechanical mixing of this starch and this organic plasticizer, (c) optionally incorporating into the plasticized composition obtained in step (b), at least one functional substance (optional component 4), other than granular starch and carrying active hydrogen functions and / or hydrolysis functions of such active hydrogen functions, and
  • step (d) incorporating, in the plasticized composition obtained, at least one binding agent (component 3) bearing at least two functional groups capable of reacting with molecules carrying active hydrogen functions and capable of allowing fixation, by covalent bonds, at least a portion of the plasticizer on the starch and / or on the functional substance optionally added in step (c), said binding agent having a molar mass of less than 5000, and being chosen from diacids and compounds bearing at least two functions, free or masked, identical or different, chosen from the functions isocyanate, carbamoyl-caprolactam, epoxide, halogeno, acid anhydride, acyl halide, oxychloride, trimetaphosphate and alkoxysilane.
  • at least one binding agent (component 3) bearing at least two functional groups capable of reacting with molecules carrying active hydrogen functions and capable of allowing fixation, by covalent bonds, at least a portion of the plasticizer on the starch and / or on the functional substance optionally added in step
  • the term "granular starch” means a starch that is native or physically modified, chemically or enzymatically, having retained, within the starch granules, a semicrystalline structure similar to that evidenced in FIG. starch grains naturally present in reserve organs and tissues of higher plants, particularly in cereal grains, legume seeds, potato or cassava tubers, roots, bulbs, stems and the fruits.
  • This semi-crystalline state is essentially due to macromolecules of amylopectin, one of the two main constituents of starch.
  • the grains of starch In the native state, the grains of starch have a degree of crystallinity which varies from 15 to 45%, and which depends essentially on the botanical origin of the starch and the possible treatment it has undergone.
  • Granular starch placed under polarized light, has a characteristic black cross, so-called Maltese cross, typical of the granular state.
  • Maltese cross typical of the granular state.
  • starch plasticizer any organic molecule of low molecular weight, i.e. preferably having a molecular weight of less than 5000, in particular less than 1000, which, when incorporated in the starch by thermomechanical treatment at a temperature of between 20 and 200 ° C. results in a decrease in the glass transition temperature and / or a reduction in the crystallinity of a granular starch to a value of less than 15% or even an essentially amorphous state.
  • This definition of the plasticizer does not include water, which, although having a starch plasticizing effect, has the major disadvantage of inactivating most of the functions likely to be present on the surface.
  • crosslinking agent such as epoxide or isocyanate functions.
  • “Functional substance” is understood to mean any molecule, other than granular starch, the binding agent and the plasticizer, carrying active hydrogen functions, that is to say functions having at least one hydrogen atom likely to be displaced if a chemical reaction takes place between the atom carrying this hydrogen atom and another reactive function.
  • Active hydrogen functions are, for example, hydroxyl, protonic acid, urea, urethane, amide, amine or thiol functions.
  • This definition also encompasses in the present invention any molecule, other than granular starch, the binding agent and the plasticizer, carrying functions capable of giving, in particular by hydrolysis, such active hydrogen functions.
  • the functions which can give such functions to active hydrogen are, for example, the alkoxy functions, in particular the alkoxysilanes, or the acyl chloride, acid anhydride, epoxide or ester functions.
  • the functional substance is preferably an oligomer or organic polymer having a weight average molecular weight of between 5,000 and 5,000,000, in particular between 8500 and 3,000,000, in particular between 15,000 and 1,000,000 daltons.
  • binding agent means any molecule carrying at least two functional groups, free or masked, capable of reacting with molecules carrying active hydrogen functions, such as in particular the plasticizer of starch. This binding agent therefore allows the attachment, by covalent bonds, of at least a portion of the plasticizer on the starch and / or on the functional substance.
  • This binding agent is distinguished from adhesion agents, physical compatibilizers or grafting agents in that they either create weak bonds (non-covalent) or carry only a single reactive function .
  • the molecular weight of the binding agent is preferably less than 5000 and most preferably less than 1000. Indeed, the low molecular weight of the binding agent allows its quick and easy incorporation into the plasticized starch composition by the plasticizer.
  • said binding agent has a molecular weight of between 50 and 500, in particular between 90 and 300.
  • the process comprises step (c) of incorporating at least one functional substance into the thermoplastic composition containing the starch and the plasticizer.
  • the binding agent used is preferably chosen so that one of its reactive functional groups is capable of reacting with the reactive functions of this functional group. functional substance. This makes it possible to at least partially fix the plasticizer by covalent bonding to the functional substance.
  • the plasticizer can therefore be fixed at least in part, either on the starch or on the functional substance or on these two components at the same time.
  • the process of the present invention preferably further comprises a step (e) of heating the mixture obtained in step (d) to a temperature sufficient to react the binding agent with, on the one hand, the plasticizer and, secondly, with the starch and / or the functional substance possibly present.
  • Steps (d) and (e) can be implemented simultaneously or one after the other after a very variable time.
  • the incorporation of the binding agent into the thermoplastic composition and the reaction with the starch and / or the functional substance is preferably carried out by hot kneading at a temperature of between 60.degree. and 200 ° C., and better still between 100 and 160 ° C.
  • the binding agent may be chosen for example from compounds carrying at least two functions, free or masked, identical or different, chosen from isocyanate, carbamoylcaprolactam, epoxide, halogeno, acid anhydride, acyl halide functions. , oxychloride, trimetaphosphate and alkoxysilane.
  • the binding agent may also be an organic diacid.
  • diisocyanates and polyisocyanates preferably 4,4'-dicyclohexylmethane diisocyanate (H12MDI), methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), hexamethylene diisocyanate; (HMDI) and lysine diisocyanate (LDI), dicarbamoylcaprolactams, preferably 1,1 'carbonyl-biscaprolactam,
  • diepoxides halohydrins, that is to say compounds having an epoxide function and a halogen function, preferably epichlorohydrin, organic diacids, preferably succinic acid, adipic acid, acid glutaric acid, oxalic acid, malonic acid, maleic acid and the corresponding anhydrides, oxychlorides, preferably phosphorus oxychloride,
  • trimetaphosphates preferably sodium trimetaphoshate
  • alkoxysilanes preferably tetraethoxysilane
  • the binding agent is chosen from the diepoxides, diisocyanates and halohydrins. It is particularly preferred to use a linking agent selected from diisocyanates, methylenediphenyl diisocyanate (MDI) and 4,4'-dicyclohexylmethane diisocyanate (H12MDI) being particularly preferred.
  • a linking agent selected from diisocyanates, methylenediphenyl diisocyanate (MDI) and 4,4'-dicyclohexylmethane diisocyanate (H12MDI) being particularly preferred.
  • the appropriate amount of binding agent depends in particular on the plasticizer content. Surprisingly and surprisingly, the higher the amount of plasticizer introduced, the greater the amount of binding agent can be increased without the end material becoming hard and losing its thermoplastic properties.
  • the amount of binding agent used is preferably between 0.01 and 15 parts, in particular between 0.1 and 12 parts and better still between 0.1 and 9 parts per 100 parts of plasticized composition of the step ( b), optionally containing the functional substance.
  • this amount of binding agent can be between 0.5 and 5 parts, especially between 0.5 and 3 parts, per 100 parts by weight of plasticized composition of step (b), containing possibly the functional substance.
  • triethylcitrate acts as a plasticizing agent only for the PLA phase but not for the amylaceous phase which remains in the form of pelletized granules. starch dispersed in a PLA matrix plasticized with triethyl citrate.
  • thermoplastic starch / linear low-density polyethylene blends The article entitled "The influence of citric acid on the properties of thermoplastic starch / linear low-density polyethylene blends" by Ning et al. Carbohydrate Polymers, 67, (2007), 446-453, investigates the effect of the presence of citric acid on thermoplastic starch / polyethylene blends. This document does not envisage at any time the fixing of the plasticizer used (glycerol) on the starch via a bi- or polyfunctional compound. The spectroscopy results show no covalent bond between citric acid and starch or polyethylene. It is simply observed that the physical bonds (hydrogen bonds) between starch and glycerol are reinforced by the presence of citric acid.
  • the granular starch can come from any botanical origin. It may be starch native to cereals such as wheat, maize, barley, triticale, sorghum or rice, tubers such as potato or cassava, or legumes such as peas and soybeans, and mixtures of such starches.
  • the granular starch is an acid hydrolyzed starch, oxidizing or enzymatic, or an oxidized starch. It can be a starch commonly called fluidized starch or a white dextrin.
  • starch modified physico-chemically but having essentially retained the structure of the native starch starting such as starches esterified and / or etherified, in particular modified by acetylation, hydroxypropylation, cationization, crosslinking, phosphatation, or succinylation, or starches treated in aqueous medium at low temperature ("annealing"), treatment which is known to increase the crystallinity of starch.
  • the granular starch is a native, hydrolyzed, oxidized or modified starch of wheat or pea.
  • the granular starch generally has a degree of solubles at 20 ° C. in demineralized water, less than 5% by weight. It is preferably almost insoluble in cold water.
  • the plasticizer of the starch is preferably chosen from diols, triols and polyols such as glycerol, polyglycerol, isosorbide, sorbitans, sorbitol, mannitol, and hydrogenated glucose syrups. organic acids such as sodium lactate, urea and mixtures of these products.
  • the plasticizer advantageously has a molar mass of less than 5000, preferably less than 1000, and in particular less than 400.
  • the organic plasticizer naturally has a molar mass greater than 18, ie it does not encompass the water.
  • the amount of plasticizer used in the present invention may advantageously be relatively high relative to the amount of plasticizer used in the plasticized starches of the prior art.
  • the plasticizer is incorporated into the granular starch preferably in the proportion of 10 to 150 parts by weight, preferably in the proportion of 25 to 120 parts by weight and in particular in the proportion of 40 to 120 parts by weight per 100 parts by weight. starch weight.
  • the functional substance carrying active hydrogen functional groups and / or functions which, in particular by hydrolysis of such active hydrogen functions may be a polymer of natural origin, or a synthetic polymer obtained from monomers of fossil origin and / or monomers from renewable natural resources.
  • Polymers of natural origin can be obtained by extraction from plants or animal tissues. They are preferably modified or functionalized, and are in particular of the protein type, cellulosic, lignocellulosic, chitosan and natural rubbers.
  • PHAs polyhydroxyalkanoates
  • Such a polymer of natural origin may be chosen from flours, modified or unmodified proteins, unmodified or modified celluloses, for example by carboxymethylation, ethoxylation, hydroxypropylation, cationization, acetylation, alkylation, hemicelluloses, lignins, guars. modified or unmodified chitins and chitosans, gums and natural resins such as natural rubbers, rosins, shellacs and terpene resins, polysaccharides extracted from algae such as alginates and carrageenans, polysaccharides bacterial origin such as xanthans or PHAs, lignocellulosic fibers such as flax fibers.
  • the synthetic polymer obtained from monomers of fossil origin, preferably comprising active hydrogen functions may be chosen from synthetic polymers of polyester, polyacrylic type, polyacetal, polycarbonate, polyamide, polyimide, polyurethane, polyolefin, functionalized polyolefin, styrenic, functionalized styrene, vinyl, functionalized vinylic, functionalized fluorinated, functionalized polysulfone, functionalized polyphenyl ether, functionalized polyphenylsulfide, functionalized silicone and functionalized polyether.
  • PLA polyamides
  • PA polyamides
  • EVA polyvinyl alcohol
  • EMA ethylene-methyl acrylate copolymers
  • EMA ethylene-vinyl alcohol copolymers
  • ASA polyoxymethylenes
  • TPU thermoplastic polyurethanes
  • SBS acrylic or maleic anhydride units
  • SEBS styrene-ethylene-butylene-styrenes
  • the polymer used as a functional substance may also be a polymer synthesized from monomers derived from natural resources which are renewable in the short term such as plants, microorganisms or gases, in particular from sugars, glycerin, oils or their derivatives such as alcohols or acids, mono-, di- or polyfunctional, and in particular from molecules such as bio-ethanol, bio-ethylene glycol, bio-propanediol, 1,3-propanediol biosourced, bio-butane-diol, lactic acid, succinic acid biosourced, glycerol, isosorbide, sorbitol, sucrose, diols derived from vegetable or animal oils and resin acids extracted from pine.
  • monomers derived from natural resources which are renewable in the short term such as plants, microorganisms or gases, in particular from sugars, glycerin, oils or their derivatives such as alcohols or acids, mono-, di- or polyfunctional, and in particular from molecules such as bio-ethanol, bio-ethylene
  • It may be in particular polyethylene obtained from bioethanol, polypropylene derived from bio-propanediol, polyesters of PLA or PBS type based on lactic acid or succinic acid biosourced, polyesters of PBAT type based on butane- diol or biosourced succinic acid, SORONA®-type polyesters based on 1,3-propanediol biosourced, polycarbonates containing isosorbide, polyethylene glycols based on bio-ethylene glycol, polyamides based on castor oil or plant polyols, and polyurethanes based for example on plant diols, glycerol, isosorbide, sorbitol or sucrose.
  • the non-starchy polymer is chosen from ethylene-vinyl acetate copolymers (EVA), polyethylenes (PE) and polypropylenes (PP) which are not functionalized or functionalized, in particular by silane units, acrylic units or maleic anhydride units.
  • EVA ethylene-vinyl acetate copolymers
  • PE polyethylenes
  • PP polypropylenes
  • thermoplastic polyurethanes TPU
  • PBS poly (butylene succinate)
  • PBSA poly (butylene succinate-co-adipate)
  • PBAT poly (butylene adipate terephthalate)
  • SEBS styrene-ethylene-butylene-styrene
  • PETG amorphous poly (ethylene terephthalate)
  • synthetic polymers obtained from bio-sourced monomers, polymers extracted from plants, animal tissues and microorganisms, optionally functionalized, and mixtures thereof.
  • non-starch polymers are polyethylenes (PE) and polypropylenes (PP), preferably functionalized, styrene-ethylene-butylene-styrene copolymers (SEBS), preferably functionalized, amorphous poly (ethylene terephthalate) (PETG) and thermoplastic polyurethanes.
  • PE polyethylenes
  • PP polypropylenes
  • SEBS styrene-ethylene-butylene-styrene copolymers
  • PETG amorphous poly (ethylene terephthalate)
  • thermoplastic polyurethanes thermoplastic polyurethanes
  • the non-starchy polymer has a weight average molecular weight of between 8500 and 10,000,000 daltons, in particular between 15,000 and 1,000,000 daltons.
  • non-starchy polymer preferably consists of carbon of renewable origin according to ASTM D6852 and is advantageously non-biodegradable or non-compostable in the sense of the standards EN 13432, ASTM D6400 and ASTM 6868.
  • the plasticized composition of step (b), optionally containing a functional substance (optional component 4), is dried or dehydrated, before the incorporation of the binding agent. (component 3) in step (d), to a residual moisture content of less than 5%, preferably less than 1%, and in particular less than 0.1%.
  • this drying or dehydration step can be carried out batchwise or continuously during the process.
  • the thermomechanical mixture of the native starch and the plasticizer is carried out by hot kneading at a temperature of preferably between 60 and 200 ° C., more preferably between 100 and 160 ° C., in a discontinuous manner, for example by kneading. mixing, or continuously, for example by extrusion.
  • the duration of this mixture can be from a few seconds to a few hours, depending on the mixing mode selected.
  • the incorporation, during step (d), of the binding agent into the plasticized composition can be carried out by thermomechanical mixing, discontinuously or continuously and in particular online, by reactive extrusion. . In this case, the mixing time can be short, from a few seconds to a few minutes.
  • the present invention also relates to a thermoplastic composition based on starch obtainable by the method of the invention.
  • composition in accordance with the invention is thermoplastic in the meaning defined above and therefore advantageously has a complex viscosity, measured on a PHYSICA MCR 501 or equivalent type rheometer, of between 10 and 10 6 Pa.s, for a temperature of between 100 and 200 ° C. For injection uses for example, its viscosity at these temperatures may be rather low and the composition is then preferentially heat-fusible in the sense specified above.
  • This composition is either a simple mixture of the three or four components (starch, plasticizer, binding agent, optional functional substance), or a mixture comprising macromolecular products resulting from the reaction of the binding agent with each of two or three other components.
  • the subject of the present invention is not only the composition obtained at the end of step (e), but also that obtained at the end of step (d), that is to say before reaction. in step (e), the binding agent with the other components.
  • thermoplastic compositions of the present invention those of the compositions resulting from step (e) having undergone the reaction step of the binding agent.
  • compositions of the present invention contain a functional substance, they preferably have a "solid dispersion" type structure.
  • the compositions of the present invention contain the plasticized starch in the form of domains dispersed in a matrix of continuous functional substance.
  • This dispersion-type structure must be distinguished in particular from a structure where the plasticized starch and the functional substance constitute only one and the same phase, or else compositions containing two co-continuous networks of plasticized starch and substance. functional.
  • the object of the present invention is indeed not to prepare materials that are above all biodegradable, but plastics with a high starch content having excellent rheological and mechanical properties.
  • the functional substance is preferably chosen from non-biodegradable synthetic polymers in accordance with the standards EN 13432, ASTM D6400 and ASTM 6868.
  • thermoplastic compositions according to the invention have the advantage of being sparingly soluble or even totally insoluble in water, of being difficult to hydrate and of maintaining good physical integrity after immersion in water.
  • Their level of insolubles in water, at 20 ° C. is preferably greater than 72%, in particular greater than 80%, more preferably greater than 90%. Very advantageously, it may be greater than 92%, especially greater than 95%. Ideally, this insoluble content may be at least 98% and in particular be close to 100%.
  • the degree of swelling of the thermoplastic compositions according to the invention, after immersion in water at 20 ° C. for a period of 24 hours is preferably less than 20%, in particular less than 12%, more preferably less than at 6%. Very advantageously, it may be less than 5%, especially less than 3%. Ideally, this swelling rate is at most equal to 2% and may especially be close to 0%.
  • the composition according to the invention advantageously has characteristic stress / strain curves of a ductile material, and not of a fragile type material.
  • the elongation at break, measured for the compositions of the present invention is greater than 40%, preferably greater than 80%, more preferably greater than 90%.
  • This elongation at break can advantageously be at least 95%, especially at least equal to 120%. It can even reach or exceed 180% or even 250%. It is generally reasonably less than 500%.
  • the maximum breaking stress of the compositions of the present invention is generally greater than 4 MPa, preferably greater than 6 MPa, more preferably greater than 8 MPa. It can even reach or exceed 10 MPa, or even 20 MPa. It is generally reasonably less than 80 MPa.
  • the thermoplastic composition of the present invention contains a functional substance as described above.
  • This functional substance is preferably a polymer chosen from functionalized polyethylenes (PE) and polypropylenes (PP), styrene-ethylene copolymers Functionalized butylene-styrene (SEBS), amorphous poly (ethylene terephthalate) and thermoplastic polyurethanes (PTU).
  • composition according to the invention may also comprise various other additional products. It may be products intended to improve its physico-chemical properties, in particular its implementation behavior and its durability or its mechanical, thermal, conductive, adhesive or organoleptic properties.
  • the additional product may be an improving or adjusting agent for the mechanical or thermal properties chosen from minerals, salts and organic substances, in particular from nucleating agents such as talc, compatibilizing agents such as surfactants, impact or scratch-resistant improvers such as calcium silicate, shrinkage control agents such as magnesium silicate, scavengers or deactivators of water, acids, catalysts, metals, oxygen , infra-red rays, UV rays, hydrophobing agents such as oils and greases, hygroscopic agents such as pentaerythritol, flame retardants and fireproofing agents such as halogenated derivatives, anti-smoke agents, reinforcing fillers, mineral or organic, such as clays, carbon black, talc, vegetable fibers, glass fibers or Kevlar.
  • nucleating agents such as talc
  • compatibilizing agents such as surfactants, impact or scratch-resistant improvers such as calcium silicate
  • shrinkage control agents such as magnesium silicate, sca
  • the additional product may also be an improving agent or an adjustment of the conductive or insulating properties with respect to electricity or heat, for example sealing against air, water or gases.
  • solvents, fats, essences, aromas, perfumes chosen among the minerals, salts and organic substances, in particular among nucleating agents such as talc, compatibilizers such as surfactants, scavengers or deactivators of water, acids, catalysts, metals, oxygen or infrared radiation, hydrophobing agents such as oils and fats, pearling agents, hygroscopic agents such as pentaerythritol, heat conduction or dissipation agents such as metal powders, graphites and salts, and micrometric reinforcement like clays and carbon black.
  • nucleating agents such as talc
  • compatibilizers such as surfactants, scavengers or deactivators of water, acids, catalysts, metals, oxygen or infrared radiation
  • hydrophobing agents such as oils and fats, pearling agents, h
  • the additional product may be an agent that improves the organoleptic properties, in particular:
  • odorant properties perfumes or odor masking agents
  • optical properties glossing agents, whitening agents such as titanium dioxide, dyes, pigments, dye enhancers, opacifiers, matting agents such as carbonate calcium, thermochromic agents, phosphorescence and fluorescence agents, metallizing or marbling agents and anti-fogging agents), sound properties (barium sulphate and barytes), and
  • the additional product may also be an enhancing or adjusting agent for adhesive properties, including adhesion to cellulosic materials such as paper or wood, metal materials such as aluminum and steel, glass or ceramic materials, textiles and mineral materials, such as pine resins, rosin, ethylene / vinyl alcohol copolymers, fatty amines, lubricating agents, mold release agents, antistatic agents and anti-blocking agents.
  • cellulosic materials such as paper or wood, metal materials such as aluminum and steel, glass or ceramic materials, textiles and mineral materials, such as pine resins, rosin, ethylene / vinyl alcohol copolymers, fatty amines, lubricating agents, mold release agents, antistatic agents and anti-blocking agents.
  • the additional product may be an agent improving the durability of the material or an agent for controlling its (bio) degradability, especially chosen from hydrophobing agents such as oils and greases, anti-corrosion agents, antimicrobial agents such as Ag, Cu and Zn, degradation catalysts such as oxo-catalysts and enzymes such as amylases.
  • hydrophobing agents such as oils and greases
  • anti-corrosion agents such as Ag, Cu and Zn
  • antimicrobial agents such as Ag, Cu and Zn
  • degradation catalysts such as oxo-catalysts and enzymes such as amylases.
  • thermoplastic composition of the present invention also has the advantage of being essentially renewable raw materials and can be presented, after adjustment of the formulation, the following properties, useful in multiple applications in plastics or other fields : suitable thermoplasticity, melt viscosity and glass transition temperature, in the usual known value ranges of the current polymers (Tg from -50 ° to 150 ° C.), allowing implementation using existing industrial installations and used conventionally for the usual synthetic polymers,
  • thermoplastic starch compositions of the prior art flexibleibility, elongation at break, maximum breaking stress
  • starch-based thermoplastic composition according to the invention can, in particular, present simultaneously:
  • thermoplastic composition according to the invention can be used as such or in admixture with synthetic, artificial or naturally occurring polymers. It can be biodegradable or compostable according to EN 13432, ASTM D6400 and ASTM 6868, and then include polymers or materials that meet these standards, such as PLA, PCL, PBSA, PBAT and PHA.
  • the barrier effects to water and insufficient water vapor, insufficient heat resistance for the manufacture of bottles and resistance to heat very insufficient for use as textile fibers, and
  • composition according to the invention is however preferably non-biodegradable or non-compostable in the sense of the above standards, and then comprises, for example, known synthetic polymers or starches or extraction polymers highly functionalized, crosslinked or etherified.
  • known synthetic polymers or starches or extraction polymers highly functionalized, crosslinked or etherified The best performances in terms of rheological properties, mechanical properties and insensitivity to water have indeed been obtained with such non-biodegradable and non-compostable compositions.
  • composition according to the invention advantageously contains at least 33%, preferably at least 50%, in particular at least 60%, more preferably at least 70%, or more than 80% of renewable carbon in the sense of the standard. ASTM D6852.
  • This carbon of renewable origin is essentially that constitutive of the starch necessarily present in the composition according to the invention but can also be advantageously, by a judicious choice of the constituents of the composition, that present in the plasticizer of the starch as in the case for example glycerol or sorbitol, but also that present in the functional substance, any other functional product or any additional polymer when they come from renewable natural resources such as those defined preferentially above.
  • thermoplastic compositions based on starch according to the invention as barrier films with water, with water vapor, with oxygen, with carbon dioxide, with aromas, to fuels for automotive fluids, organic solvents and / or fats, alone or in multi-layer or multi-ply structures obtained by coextrusion, lamination or other techniques, for the field of packaging of carriers printing, insulation, or textile in particular.
  • compositions of the present invention may also be used to increase hydrophilicity, electrical conduction ability or microwaves, printability, dyeability, bulk coloring or paintability. anti-static or anti-dust effect, scratch resistance, fire resistance, adhesive power, heat sealability, sensory properties, in particular touch and acoustic properties, permeability to water and / or water vapor, or the resistance to organic solvents and / or fuels, of synthetic polymers in the context for example of the manufacture of membranes, films, printable electronic labels, textile fibers, containers or reservoirs, synthetic hot melt films, parts obtained by injection or extrusion such as automobile parts.
  • thermoplastic composition according to the invention considerably reduces the risks of accumulation in adipose tissue of living organisms and thus also in the food chain.
  • composition according to the invention may be in pulverulent, granular or bead form and form the matrix of a dilutable masterbatch in a bio-sourced matrix or not.
  • the invention also relates to a plastic or elastomeric material comprising the thermoplastic composition of the present invention or a finished or semi-finished product obtained therefrom.
  • a native wheat starch marketed by the Applicant under the name "SP wheat starch” having a water content of about 12% (component 1),
  • a concentrated aqueous composition of polyols based on glycerol and sorbitol marketed by the Applicant under the name POLYSORB G84 / 41/00 having a water content of about 16% (component 2) of methylene diphenyl diisocyanate ( MDI) marketed under the name Suprasec 1400 by the company Hunstman (component 3).
  • thermoplastic compositions A thermoplastic composition according to the prior art is prepared.
  • a TSA brand twin-screw extruder with a diameter (D) of 26 mm and a length of 56 D is fed with the starch and the plasticizer, so as to obtain a total material flow rate of 15 kg / h, varying the ratio of plasticizer mixture (POLYSORB) / wheat starch as follows:
  • composition AP5050 -100 parts / 100 parts
  • composition AP6040 - 67 parts / 100 parts
  • composition AP6535 Composition AP6535
  • composition AP7030 Composition AP7030.
  • the extrusion conditions are as follows:
  • compositions AP5050 and AP6040 are too sticky at high levels of plasticizer (compositions AP5050 and AP6040) to be granulated on a material commonly used with synthetic polymers. It is also noted that the compositions are still too sensitive to water to be cooled in a cold water tank. For these reasons, the plasticized starch rods are cooled in air on a conveyor belt and then dried at 80 ° C. in a vacuum oven for 24 hours and then granulated.
  • thermoplastic composition thus obtained in the form of granules, during a second passage in the extruder, 0, 1, 2, 4, 6, 8 and 12 parts of MPI per 100 parts of thermoplastic composition ( pcr). Due to an excessive increase in the viscosity, or even a crosslinking of the material in the extruder, and an irreversible loss of the thermoplastic character of the composition, it was impossible to incorporate:
  • composition AP6535 more than 4 phr of MDI in the composition AP6535 and more than 2 phr of MDI in the composition AP7030.
  • the water and moisture sensitivity of the compositions prepared and the ability of the plasticizer to migrate to water and thereby to induce degradation of the structure of the material are evaluated.
  • the level of insoluble in water of the compositions obtained is determined according to the following protocol:
  • the rate of moisture uptake is determined by measuring the mass of a plasticized starch sample after one month of storage, before drying (M h ) and after drying under vacuum at 80 ° C. for 24 hours (M s ).
  • the moisture recovery rate corresponds to the difference (1-M s / M h ) expressed in percent.
  • Table 1 shows that the incorporation of MDI according to the invention results in both a clear decrease in the rate of moisture uptake, a very significant decrease in the solubilization kinetics and a significant increase in the level of insolubles in the water.
  • thermoplastic compositions thus prepared in accordance with the invention contain specific entities of glucose-MDI-glycerol and glucose type. -MDI-sorbitol, attesting the fixing of the plasticizer on the starch via the binding agent.
  • compositions according to the invention prepared by reaction of a binding agent (MDI) with the starch-based thermoplastic compositions of the state of the art are more stable to moisture and water than the compositions. of the prior art without MDI.
  • MDI binding agent
  • thermoplastic base starch mixture AP6040 obtained according to Example 1 MDI and a polyethylene grafted with 2% vinyltrimethoxysilane (PEgSi) are mixed with this composition, thus forming a dry blend.
  • the PEgSi used was obtained beforehand by grafting vinyltrimethoxysilane on a low density PE by extrusion.
  • An example of such a PEgSi available on the market is the product BorPEX ME 2510 or BorPEX HE2515 both marketed by Borealis.
  • the twin-screw extruder previously described is fed by this dry blend.
  • the extrusion conditions are as follows:
  • Temperature profile (ten heating zones Z1 to Z10): 150 ° C.
  • compositions are prepared by introducing different levels of MDI: 0; 2 and 4 parts per 100 parts of thermoplastic composition AP6040 (phr).
  • compositions prepared are shown in the table below.
  • the mechanical tensile characteristics of the various samples are determined according to standard NF T51-034 (Determination of tensile properties) using a Lloyd Instrument LR5K test bench, a tensile speed of 50 mm / min and standard test specimens. H2.
  • the 07641 mixture containing 30% silane-grafted PE, produced without MDI, is very hydrophilic and therefore can not be cooled in the water leaving the die because it dislocates very quickly by hydration in the cooling bath.
  • the alloys made with MDI are very hydrophobic.
  • compositions prepared with MDI are also good to very good in terms of elongation and tensile strength.
  • the MDI by binding the plasticizer to the macromolecules of starch and PEgSi, greatly improves the properties of water resistance and mechanical strength, thus opening the compositions according to the invention, multiple new uses possible compared to those of the prior art.
  • compositions thus prepared according to the invention are in the form of starch dispersions in a continuous polymer matrix of PegSi.
  • All these alloys have in particular a good scratch resistance and a "leather" feel. They can thus find for example an application as a coating of fabrics, wood panels, paper or cardboard.

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EP09705602A 2008-02-01 2009-01-29 Verfahren zur herstellung von thermoplastischen zusammensetzungen auf basis von weichgemachter stärke und resultierende zusammensetzungen Withdrawn EP2247660A2 (de)

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AU2009208826B2 (en) 2014-06-19
MX2010008454A (es) 2010-12-06
FR2927084B1 (fr) 2011-02-25
BRPI0906981A2 (pt) 2015-07-21
AU2009208826A1 (en) 2009-08-06
FR2927084A1 (fr) 2009-08-07
JP2011511120A (ja) 2011-04-07
RU2010136737A (ru) 2012-03-10
RU2524382C2 (ru) 2014-07-27
US20100311905A1 (en) 2010-12-09
KR20100113612A (ko) 2010-10-21
WO2009095618A3 (fr) 2009-09-24
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