Classifications

• • 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
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
  • A23G4/00—Chewing gum
  • A23G4/06—Chewing gum characterised by the composition containing organic or inorganic compounds
  • A23G4/08—Chewing gum characterised by the composition containing organic or inorganic compounds of the chewing gum base
• • 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
  • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
  • C08L51/04—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 rubbers
• • 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
  • 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
  • C08L51/08—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
  • C08L51/08—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
  • C08L51/085—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

• the present invention relates to novel elastomeric compositions, based on esters of a starchy material having a high degree of substitution (DS) in esters, plasticizers of these esters and polymers other than starch, of elastomeric nature.
• DS degree of substitution
• the term "elastomeric composition” in the present invention is understood to mean a composition which softens under the action of heat, hardens on cooling and, at low temperature and especially at ambient temperature, exhibits an ability to recover more or less rapidly an original shape. and primitive dimensions after applying strain strain. It has at least one so-called glass transition temperature (Tg) below which all or part of 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 elastomeric composition according to the present invention is preferably between -12O 0 C and + 20 ° C.
• the elastomeric composition according to the invention also has a great capacity of extensibility and elastic recovery like natural or synthetic rubbers.
• the elastomeric behavior of the composition can be obtained or adjusted by crosslinking or vulcanization more or less advanced, after shaping in the plastic state.
• the term "elastomeric composition” also means any "thermoplastic elastomer” type composition having both elastomeric and thermoplastic properties thanks to a structure of the polymer-block type with "soft" segments and "hard” segments.
• the composition contains, in combination with at least one ester of starchy material and a plasticizer of said ester, at least one non-starchy polymer chosen from the group of elastomeric polymers such as, for example, natural or modified rubbers, polystyrene elastomers, polyester elastomers, polypropylene elastomers, silicone elastomers or rubbers and polyurethane elastomers.
• elastomeric polymers such as, for example, natural or modified rubbers, polystyrene elastomers, polyester elastomers, polypropylene elastomers, silicone elastomers or rubbers and polyurethane elastomers.
• the elastomeric composition according to the invention is "heat fusible", that is to say that it can be shaped without the application of large shear forces, that is to say by simple flow or by simply pressing the melted or softened material. Its viscosity, measured at a temperature of 100 ° C. to
• 200 0 C is generally between 10 and 10 3 Pa.s.
• esters at least 5% and at most 70% by weight of an ester of a starchy material with a degree of substitution of esters (DS) of between 1.0 and 3.0, preferably of between 1.2 and 3; , 0.
• DS degree of substitution of esters
• plasticizer of this ester of starchy material, said plasticizer being preferably other than water and,
• composition according to the invention is further characterized in that:
• the ester of starchy material has a degree of biodegradability according to ISO 14851, less than 50%, preferably less than 30%, and / or
• the polymer other than starch has, as such, a degree of biodegradability according to ISO 14851, less than 50%, preferably less than
• the composition according to the invention is characterized in that the ester of starchy material and the polymer other than starch each have a degree of biodegradability according to ISO 14851, less than 50%, preferably less than 30%.
• the composition according to the invention has a biodegradability according to the ISO 14851 standard which is extremely low, less than 20%, in particular less than 15%, or even less than 10% or even more than 5%.
• the composition according to the invention has a degree of biodegradability that can be in higher ranges of values. than those mentioned above, namely a degree of biodegradability according to ISO 14851, at least equal to 50% and less than 100%, in particular between 60 and 100%.
• biodegradability rate means the level of aerobic biodegradation by determining the oxygen demand in a closed respirometer according to the international standard ISO 14851: 1999.
• the biodegradation rate being determined by comparing the biological oxygen demand (BOD) with the theoretical quantity (theoretical oxygen demand, DThO) and expressing it in percentage,
• Starch is already exploited in the manufacture of plastics, in particular because of its property of being also a biodegradable product.
• the first starch-based compositions were developed about thirty years ago.
• the starches were then employed in the form of mechanical blends with synthetic polymers such as polyethylene, as filler, in the native, granular and unmodified state, i.e., in its present state in nature.
• the starch was used in the manufacture of biodegradable objects, but in a state rendered essentially amorphous and thermoplastic. This state, destructured, with reduced crystallinity or absent, is obtained by plastification of the native granular starch by incorporation of a suitable plasticizer at a level generally between 15 and 25% relative to the granular starch, by contribution of mechanical and thermal energy.
• 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 thus obtained are always very highly viscous, even at high temperatures (12O 0 C to 17O 0 C) and very fragile, too brittle, very hard and little forming low temperature, that is to say below the glass transition temperature.
• thermoplastic starches having better mechanical properties by physical mixing of these thermoplastic starches, or with biodegradable petroleum-based polymers (polycaprolactones (PCL), co-polyesters aromatics (PBAT), aliphatic polyesters (PBS) or water-soluble polymers (polyvinyl alcohol) (PVOH), or with polyesters of renewable origin such as polylactates (PLA), microbial polyhydroxyalkanoates
• PCL polycaprolactones
• PBAT co-polyesters aromatics
• PBS aliphatic polyesters
• PVOH water-soluble polymers
• polyesters of renewable origin such as polylactates (PLA), microbial polyhydroxyalkanoates
• the present invention provides an effective solution to the problems stated above by proposing novel compositions based on starch-containing ester, which furthermore have improved properties compared with those of the prior art.
• the elastomeric composition according to the invention advantageously comprises an ester of starchy material having a high or very high DS.
• the DS may especially be between 1.6 and 3.0, preferably between 1.8 and 2.9 and even more preferably between 2.0 and 2.9.
• the ideal may be to retain a DS between 2.2 and 2.8, for example when the composition containing said ester of starch material is intended for the preparation of a gum base chewing gum.
• the elastomeric composition according to the invention may advantageously comprise:
• the elastomeric composition according to the invention may, in particular, advantageously comprise, for example if it is intended for the preparation of a gum base chewing gum:
• the ester of a starchy material is the main or predominant component of the composition according to the invention, which can then be characterized in particular that it comprises from 45 to 70%, preferably from
• the polymer other than starch (or "non-starch polymer”) elastomeric, can then be neither the main component nor the major component of the composition according to the invention, which can then be characterized in particular that it comprises from 25 to 49% by weight, preferably from 25 to 40% by weight and even more preferably from 25 to 35% by weight, of said polymer.
• the ester of a starchy material is not the majority component and generally not the main component of the composition according to the invention, which can then be characterized in particular that it comprises from 5 to 49 %, preferably from 7 to 49% by weight and more preferably from 10 to 49% by weight, of said ester.
• non-starchy elastomeric polymer can then be the main component, indeed the major component of the composition according to the invention, which can then be characterized in particular by comprising
• the ester of the starchy material of DS between 1.0 and 3 can be present in the composition according to the invention, in any form, in particular in the dispersed state. in the form of fibers, or other particles, micrometric or nanometric, in the elastomeric non-starch polymer or in the phase state, thermoplastic or elastomeric, continuous, discontinuous or co-continuous, more or less well compatibilized with the non-starch elastomeric polymer .
• non-starchy elastomeric polymer may also be present in the composition according to the invention, in any form, in particular in the form of fibers dispersed in the ester of the starchy material or in the phase state, thermoplastic or elastomeric, continuous, discontinuous or co-continuous, more or less well compatibilized with the ester of the starchy material.
• esters of starchy material in particular DS high or very high, has been recommended only for: - the manufacture of so-called biodegradable thermoplastic compositions otherwise containing at least a non-starchy polymer of a generally non-elastomeric nature and known to be biodegradable or water-soluble, such as for example a) modified celluloses b) proteins c) biodegradable polyesters, in particular of the hydroxycarboxylic type as described in US Pat. Nos. 5,462 and 983 , WO 95/04108, EP 1054 599 or EP 1 142 911 or of polyalkylene carbonate type as described in US Pat. Nos. 5,936,014 or WO 98/07782 and d) water-soluble polymers such as those described in the patents and applications EP 638,609, US 5,936,014, US 2002/0032254 or WO 00/73380, or
• elastomeric compositions that can be used as base gums for chewing gums that do not contain a) any non-starchy polymer, in particular elastomeric polymer, and b) any plasticizer for the ester of starchy material, as described, for example, in US Pat. No. 3,666,492 , US 4,035,572 or US 4,041,179,
• starchy material is intended to mean any oligomer or polymer of D-glucose units linked to each other by alpha-linkages.
• This starchy material can come from all types of starch and in particular be chosen from cereal starches such as wheat, corn, barley, triticale, sorghum or rice; starchy tubers such as potato or cassava; leguminous starches such as peas, soybeans or beans; starches rich in amylose, or conversely, rich in amylopectin (“waxy”) from these plants or any mixtures of these starches.
• cereal starches such as wheat, corn, barley, triticale, sorghum or rice
• starchy tubers such as potato or cassava
• leguminous starches such as peas, soybeans or beans
• starches rich in amylose, or conversely, rich in amylopectin (“waxy” from these plants or any mixtures of these starches.
• this starchy material may preferably have a molecular weight of between 10 3 and 10 8 g / mol, better still between 5.10 3 and 10 7 g / mol, and more preferably between 10 4 and 10 6 g / mol.
• this starchy material can result from the esterification to a high degree of a granular starch, optionally hydrolyzed or / and modified.
• granular starch is used herein to mean a starch which is native or physically modified, chemically or enzymatically, and which has retained, within the starch granules, a semicrystalline structure similar to that evidenced in starch grains. naturally occurring in the reserve organs and tissues of higher plants, particularly in cereal or legume seeds, tubers, roots, bulbs, stems and fruits.
• This semi-crystalline state is essentially due to macromolecules of amylopectin, one of the two main constituents of starch.
• the starch grains In the native state, the starch grains 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 that it has undergone.
• Starch in the granular state, placed under polarized light, has a characteristic black cross, called Maltese cross, typical of this state.
• the ester of the starchy material is derived from granular starch hydrolyzed by the acidic, oxidizing or enzymatic route.
• Such starches are commonly referred to as fluidized starches, oxidized starches or white dextrins.
• it can come from the esterification of a starch having essentially preserved the granular structure of the native starch but modified physico-chemically, such as in particular the weakly esterified and / or etherified starches, in particular modified by acetylation, hydroxypropylation, cationization, crosslinking, phosphatation, or succinylation, or starches treated in aqueous medium at low temperature (in English "annealing").
• the ester of the starchy material may in particular result from the esterification of a hydrolyzed, oxidized or modified granular starch, in particular corn, wheat, potato or pea.
• the starchy material selected for the preparation of the composition according to the invention comes from the high level esterification of a non-granular starch, that is to say without starch grains having microscopy. under polarized light, a Maltese cross. It can then be a water-soluble starch or an organomodified starch, which can also come from all botanical origins, including a starch, rich in amylose or conversely, rich in amylopectin (waxy).
• the ester of the DS starch material of from 1 to 3 is a water-soluble non-granular starch ester.
• water-soluble starch means any starchy material having at 20 ° C. and with mechanical stirring for 24 hours, a fraction soluble in deionized water at least equal to 5% by weight.
• the water-soluble starch may advantageously be chosen from pregelatinized starches, extruded starches, atomized starches, dextrins, maltodextrins, functionalized starches or any mixtures of these products, optionally plasticized.
• the pregelatinized, extruded or atomized starches can be obtained by hydrothermal treatment of gelatinization of native starches or modified starches, in particular by steam cooking, jet-cooker cooking, drum cooking, cooking in mixer / extruder systems. then drying, for example in an oven, by hot air on a fluidized bed, on a rotating drum, by spraying, by extrasion, by precipitation by a non-solvent, or by lyophilization, of a suspension or of a starchy solution. Examples include products manufactured and marketed by the Applicant under the brand name PREGEFLO ®.
• Dextrins can be prepared from native or modified starches by dextrinification in acid medium with little hydration. It may be in particular soluble white dextrins or yellow dextrins. By way of example, mention may be made STABILYS ® A 053 or TACKIDEX ® C 072 products manufactured and marketed by the Applicant.
• Maltodextrins can be obtained by acid, oxidative or enzymatic hydrolysis of starches in an aqueous medium. They may in particular have an equivalent dextrose (DE) of between 0.5 and 40, preferably between 0.5 and 20 and better still between 0.5 and 12. Such maltodextrins are for example manufactured and marketed by the Applicant under the trade name GLUCIDEX ®
• the functionalized starches can be obtained in particular by acetylation in aqueous phase of acetic anhydride, mixed anhydrides, hydroxypropylation, cationization, anionization, phosphatation or succinylation. These functionalized starches may have a degree of substitution of between 0.01 and 2.7, and more preferably between 0.05 and 1.
• the water-soluble starch is preferably a water-soluble starch of corn, wheat, potato or pea or a water-soluble derivative thereof.
• the starchy material esterified with a DS of from 1 to 3 is an ester of an organomodified starch, preferably organosoluble, which may also come from all botanical origins.
• organomodified starch means any starchy component other than a granular starch or a water-soluble starch according to the definitions given above.
• this organomodified starch is almost amorphous, that is to say has a starch crystallinity level of less than 5%, generally less than 1% and especially zero.
• organo that is to say to present 2O 0 C, a soluble fraction in a solvent selected from ethanol, ethyl acetate, propyl acetate, of butyl, diethyl carbonate, propylene carbonate, dimethyl glutarate, triethyl citrate, dibasic esters, dimethyl sulfoxide (DMSO), dimethyl isosorbide, glycerol triacetate, isosorbide diacetate, dioleate isosorbide and methyl esters of vegetable oils, at least equal to 5% by weight.
• a solvent selected from ethanol, ethyl acetate, propyl acetate, of butyl, diethyl carbonate, propylene carbonate, dimethyl glutarate, triethyl citrate, dibasic esters, dimethyl sulfoxide (DMSO), dimethyl isosorbide, glycerol triacetate, isosorbide diacetate, dioleate isosorbide and methyl est
• the organomodified starch can be prepared from native or modified starches such as those presented above, by esterification or etherification at a sufficiently high level to confer on it an insolubility in water and preferably a solubility in one. organic solvents above.
• the organomodified starch can be obtained in particular by grafting oligomers of caprolactones or lactides, by hydroxypropylation and crosslinking, by cationization and crosslinking, by anionization, phosphatation or succinylation and crosslinking, by silylation, by butadiene telomerization.
• These organomodified starches, which are preferably organosoluble can have a degree of substitution (DS) of between 0.01 and 2.7, preferably of between 0.05 and 2.0 and in particular of between 0.1 and 1.5.
• the organomodified starch is preferably an organomodified starch of corn, wheat, potato or pea or an organomodified derivative thereof.
• the esterifying agent used for the preparation of the ester of the starchy material may be an organic acid anhydride, an organic acid, a mixed anhydride, an organic acid chloride or any mixture of these products.
• This esterification agent may be chosen from acids having from 2 to 24 carbons, saturated or unsaturated, and more specifically from acetic acid, propionic acid, butyric acid, valeric acid and hexanoic acid.
• heptanoic acid pelargonic acid
• octanoic acid decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid the anhydrides of these acids, the mixed anhydrides of these acids, and any mixtures of these products.
• the ester of the starchy material having a degree of substitution (DS) of between 1.0 and 3.0, preferably between 1.2 and 3.0, in particular between 1.6 and 3.0, and especially between 1 and , 8 and 2.9 is preferably an ester of a water-soluble starch or an organomodified starch, preferably an ester of a pregelatinized starch, an extruded starch, an atomized starch, a dextrin, a maltodextrin, a functionalized starch, an organosoluble starch, or any mixture of these optionally plasticized products.
• said ester of the starchy material carries chains of 2 to 22 carbons and is an acetate, a propionate, a butyrate, a valerate, a hexanoate, an octanoate, a decanoate, a laurate, a palmitate, an oleate or starch, dextrin or maltodextrin stearate, pure or in admixture.
• it is an acetate of starchy material.
• composition according to the invention comprises, in particular, as ester of starchy material, an ester of DS included in any one of the abovementioned ranges, preferably of acetate type, of water-soluble or organomodified starch, in particular of pregelatinized starch extruded, atomized, dextrin, maltodextrin, functionalized starch or organosoluble starch.
• the ester of the starchy material is a water-soluble or organomodified starch acetate, a dextrin acetate or a maltodextrin acetate.
• the ester of the starch material may be mixed in all proportions with a granular starch, optionally hydrolyzed or modified, with a water-soluble starch or an organomodified starch, as defined above.
• esterification conditions a person skilled in the art will easily be able to refer, with regard to the esterifying agent employed, to the techniques and conditions described in the literature, in particular in the applications and patents
• the esterification can be obtained in particular by acetylation in solvent phase in organic acid medium, in the presence of the anhydride or a mixed anhydride of this organic acid and an acid catalyst.
• the esterified starchy material may carry other groups, introduced by grafting, for example, oligomers of caprolactones or lactides, or introduced by hydroxypropylation, crosslinking, cationization, anionization, succinylation, silylation or telomerization.
• the elastomeric composition according to the invention comprises, from 5 to 40% by weight, a plasticizer of the ester of the starchy material.
• plasticizer of the ester of the starchy material or “plasticizer of the ester of the amylaceous material” is meant any molecule of low mass which, when it is incorporated in the ester of the starchy material or in the composition according to the invention, in particular by a thermomechanical treatment with a molecular weight, that is to say preferably having a molecular weight of less than 5000.
• a thermomechanical treatment with a molecular weight that is to say preferably having a molecular weight of less than 5000.
• the ester of the starchy material when used in the present invention in relation to "the ester of the starchy material”, this necessarily implies the presence of a plasticizer.
• the esterified starchy material may contain an amount of one or more compounds on the list of plasticizers below.
• the plasticizer may be chosen from water, esters and ethers of the diols, triols and polyols glycerol, polyglycerols, isosorbide, sorbitans, sorbitol, mannitol, and hydrogenated glucose syrups. organic acid esters, urea and any mixtures of these products.
• the plasticizing agent may in particular be chosen from methyl, ethyl or fatty esters of organic or inorganic acids such as lactic, citric, succinic, adipic, sebacic, phthalic, glutaric or phosphoric acids or the acetic or fatty esters of mono alcohols, diols, triols or polyols such as ethanol, diethylene glycol, glycerol or sorbitol.
• glycerol diacetate diacetin
• glycerol triacetate triacetin
• isosorbide diacetate isosorbide dioctanoate
• isosorbide dioleate isosorbide dilaurate
• esters of dicarboxylic acids or dibasic esters dibasic esters
• the plasticizer may also be an epoxidized vegetable oil, a glycol or derivative such as an ethylene glycol polyester.
• the plasticizer may also be chosen from the abovementioned products coupled together by coupling agents such as epichlorohydrin or an isocyanate.
• the plasticizing agent is characterized by its solubility parameter (known as HILDEBRAND), which in fact translates the force of attraction existing between the molecules of said plasticizer and of any polymer (of amylaceous nature or not) present in the composition according to the invention, and more particularly the cohesion energy density variation of the plasticizer, ie the energy necessary to vaporize it.
• the plasticizer optionally used may in particular have a solubility parameter of between 15 and 28 (J.cm 3 ) 0 ' 5 , preferably between
• the HILDEBRAND parameter calculated from its latent heat of vaporization (85.74 kJ / mol) or its boiling point (259 ° C. ), is 21 (J.cm "3 ) 0 ' 5 .
• the plasticizer of the ester of the starchy material used advantageously has a molar mass of less than 1500, and in particular less than 500.
• the plasticizer preferably has a molar mass greater than 18, in other words it preferably does not include water.
• the plasticizer has a molecular weight of between 150 and 450.
• the plasticizer may in particular present simultaneously, for example, triacetin (molar mass of 218):
• Said plasticizer is preferably 5 to 30%, more preferably 5 to 20%
• composition according to the invention % of the composition according to the invention. This, for example, when said composition is intended for the preparation of a gum base chewing gum.
• this plasticizer is present in a proportion of from 1 to 150 parts by dry weight, preferably from 10 to 120 parts by dry weight and in particular from 25 to 120 parts by dry weight, for 100 parts by weight. by dry weight of ester of the starchy material.
• the incorporation of the plasticizer can be carried out cold, for example by mixing at room temperature with the ester of the starchy material or directly during the preparation of the elastomeric composition according to the invention, that is to say at a temperature preferably between 60 and 200 0 C, more preferably between 100 and 180 0 C, discontinuously, for example by kneading / kneading, or continuously, for example by extrusion.
• the duration of this mixture can range from a few seconds to a few hours, depending on the mixing mode selected.
• the composition according to the invention is characterized in that the ester of the starchy material contained in the composition has a degree of crystallinity of less than 15%, preferably less than 5% and more preferably less than 1%. .
• This degree of crystallinity can in particular be measured by X-ray diffraction technique as described in US Pat. No. 5,362,777 (column 9, lines 8 to 24).
• the elastomeric composition according to the invention further comprises at least one polymer other than starch (also called “non-starchy polymer”) chosen from elastomeric polymers (also called “elastomers").
• elastomeric polymer (or “elastomer”) is understood to mean any polymer that softens under the action of heat, hardens on cooling and, at a low temperature and especially at ambient temperature, exhibits an ability to take up a more or less rapid reaction. original shape and primitive dimensions after applying strain strain. It has a so-called vitreous transition temperature (Tg) below which all or part of its amorphous fraction is in the brittle glassy state, and above which it can undergo reversible plastic deformations.
• Tg vitreous transition temperature
• elastomeric polymer is also meant any polymer of the “thermoplastic elastomer” type, having both elastomeric and thermoplastic properties through a structure of polymer type sequence with "soft" segments and "hard” segments.
• the non-starchy elastomeric polymer may be of any chemical nature other than starchy. It may advantageously be a thermoplastic elastomer.
• It may be a polymer of natural origin, or a synthetic polymer obtained from monomers of fossil origin and / or monomers from renewable natural resources.
• NR natural rubbers
• SR synthetic rubbers
• ACM ethylene-vinyl acetate elastomers
• EVA ethylene-vinyl acetate elastomers
• NBR nitrile rubbers
• BR polybutadienes
• CR polychloroprenes
• IR Neoprene ® and polyisoprenes
• the non-starchy elastomeric polymer has a glass transition temperature (Tg) of between -5 and -1200 ° C., preferably between -10 and -105 ° C. and more preferably between -20 and -80 ° C. vs.
• non-starch elastomeric polymer in particular natural rubbers and their derivatives, polyisobutylenes (PIB or IRR), polyisoprenes, butadiene-styrene copolymers
• SBR butadiene-acrylonitrile copolymers, optionally hydrogenated
• NBR and H-NBR acrylonitrile-styrene-acrylate copolymers
• ASA acrylonitrile-styrene-acrylate copolymers
• TPU thermoplastic polyurethanes of the ether or ester-ether type, polyethylenes or polypropylenes functionalized for example with silane, halogen, acrylic or maleic anhydride units, elastomers based on ethylene (ethylene acrylates or EAM) or polypropylene (ethylene-propylene-diene monomer or EPDM) or ethylene and propylene (EPM), thermoplastic elastomers derived from polyolefins (TPO), styrene-based copolymers butylene-styrenes (SBS) and styrene-ethylene-butylene-styrene (SEBS) functionalized for example with maleic anhydride units and any mixtures
• all or part of the non-starchy elastomeric polymer is synthesized from monomers derived from renewable natural resources in the short term, such as plants, microorganisms or gases, in particular from sugars, glycerine, oils or of their derivatives such as alcohols or acids, mono-, di- or polyfunctional.
• the elastomeric polymer may in particular be synthesized from bio-sourced monomers such as bioethanol, bio-ethylene glycol, bio-propanediol, 1,3-propanediol biosourced, bio-butanediol, lactic acid, succinic acid biosourced, glycerol, isosorbide, sorbitol, sucrose, diols derived from vegetable or animal oils and resin acids extracted from pine, as well as their derivatives.
• the non-starchy elastomeric polymer is a synthetic polymer obtained from monomers of fossil origin and / or monomers derived from renewable natural resources and which has, as such, a degree of biodegradability of less than 50%. preferably less than 30%.
• the non-starchy polymer has a low solubility in water, namely less than 10% (less than 10% of matter soluble in water at 20 ° C.) and in particular less than 5%. It is preferably insoluble in water (less than 0.1% of matter soluble in water at 20 ° C.).
• 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.
• the 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 incorporation of the polymer non-starchy, elastomeric, to the ester of the starchy material in the composition according to the invention may be preferably by hot kneading at a temperature between 35 and 300 0 C, especially between 60 and 200 0 C, and better still from 100 to 180 ° C.
• This incorporation can be carried out by thermomechanical mixing, discontinuously or continuously and in particular in line. In this case, the mixing time can be short, from a few seconds to a few minutes.
• the elastomeric composition according to the invention may consist exclusively or almost exclusively of the three components that are the ester of starchy material, the plasticizer of said ester and the non-starchy, elastomeric polymer.
• the elastomeric composition according to the invention can be characterized in that it comprises, in total, from 35 to 100% by weight of ester of starch material, plasticizer of said ester and elastomeric non-starchy polymer.
• this total percentage of these three components is between 50 and 100%.
• composition may especially be between 70 and 100%, for example when said composition is intended for the preparation of a gum base chewing gum.
• composition according to the invention may however comprise other components than the aforementioned three and in particular comprise a binding agent.
• binding agent in the present invention, any organic molecule carrying at least two functional groups, free or masked, capable of reacting with molecules carrying active hydrogen functions such as for example those of the ester starchy material or plasticizer.
• This binding agent may be added to the composition to allow the attachment, by covalent bonds, of at least a portion of the plasticizer to the ester of the starchy material and / or on the added non-starchy polymer. It may optionally also be added as a crosslinking or vulcanizing agent
• This binding agent can then be chosen for example from compounds carrying at least two functions, free or masked, identical or different, chosen from isocyanate functions, carbamoylcaprolactam, aldehydes, epoxide, halogen, protonic acid, acid anhydride acyl halide, oxychloride, trimetaphosphate, alkoxysilane and combinations thereof.
• diisocyanates preferably methylenediphenyl diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), hexamethylene diisocyanate
• MDI methylenediphenyl diisocyanate
• TDI toluene diisocyanate
• NDI naphthalene diisocyanate
• HMDI lysine diisocyanate
• dicarbamoylcaprolactams preferably 1-1'-carbonyl-caprolactam
• diepoxides compounds comprising an epoxide function and a halogen function, preferably epichlorohydrin,
• organic diacids preferably succinic acid, adipic acid, glutaric acid, oxalic acid, malonic acid, maleic acid and the corresponding anhydrides; oxychlorides, preferably oxychloride; phosphorus,
• trimetaphosphates preferably sodium trimetaphoshate
• alkoxysilanes preferably tetraethoxysilane
• the linking agent is a diisocyanate, in particular methylenediphenyl diisocyanate (MDI).
• MDI methylenediphenyl diisocyanate
• composition contains a binding agent
• said binding agent is preferably present in an amount of from 0.1 to 15 parts by dry weight, preferably from 0.2 to 9 parts by dry weight and in particular at from 0.5 to 5 parts by dry weight, per 100 parts by dry weight of ester of the starchy material.
• the composition according to the invention may also comprise a compatibilizing agent between the ester of the starchy material and the non-starchy polymer. he This may be for example other polymers or even low molecular or polymeric surfactants, having within them at least a relatively hydrophilic portion and at least a relatively hydrophobic portion.
• composition according to the invention may comprise in particular one or more polymers other than the ester of starchy material and the non-starchy, elastomeric polymer.
• This or these polymers represent (s), in total, at most 65% of the total weight of the composition according to the invention.
• This total percentage of additional polymer (s) is, preferably at most 55%, and more preferably still, at most 40%, expressed with respect to the total weight of the composition according to the invention. This is the case, for example, when said composition is intended for the preparation of a gum base chewing gum.
• this percentage is advantageously between 2 and 40%, in particular between 5 and 35%, expressed relative to the total weight of the composition according to the invention.
• Any additional polymer may be a polymer of natural origin, or a synthetic polymer obtained from monomers of fossil origin and / or monomers from renewable natural resources.
• the additional polymers of natural origin can in particular be obtained directly by extraction from plants or animal tissues. They are preferably modified or functionalized, and in particular chosen from polymers of protein, cellulosic or lignocellulosic nature and chitosan. It may also be polymers obtained by extraction from microorganism cells, such as polyhydroxyalkanoates (PHA).
• PHA polyhydroxyalkanoates
• Such additional polymer of natural origin may also be chosen from flour, proteins, preferably modified; celluloses unmodified or modified in particular by carboxymethylation, ethoxylation, hydroxypropylation, cationization, acetylation, alkylation; hemicelluloses; lignins; modified or unmodified guars; chitin and chitosan; gums and natural resins such as rosins, shellacs, terpene resins and bitumens; polysaccharides extracted from algae such as alginates and carrageenans; polysaccharides of bacterial origin such as xanthans or gellans; lignocellulosic fibers such as flax, hemp, coconut or other natural fibers; any mixtures of the aforementioned polymers.
• the additional polymer may be synthetic and obtained in particular by polymerization, polycondensation or polyaddition.
• the additional polymer has, as such, a degree of biodegradability of at least 50% and is preferably chosen from biodegradable polyesters such as polyhydroxy acids (such as PLA, PGA, PHA, PHB, PHV, PHBV). or PCL), polyesteramides (such as BAKs) or aromatic or aliphatic copolyesters (such as PBS and PBAT), among polyalkylene carbonates (such as PEC and PPC) and from water-soluble polymers such as polyvinylalcohols, ethylenevinylalcohols proteins, celluloses and their derivatives; any mixtures of the aforementioned polymers. .
• biodegradable polyesters such as polyhydroxy acids (such as PLA, PGA, PHA, PHB, PHV, PHBV). or PCL), polyesteramides (such as BAKs) or aromatic or aliphatic copolyesters (such as PBS and PBAT), among polyalkylene carbonates (such as PEC and PPC) and from water-soluble
• the additional polymer has, as such, a degree of biodegradability of less than 50%, preferably less than 30% and preferably be chosen from non-starch and non-elastomeric polymers such as polyolefins, especially polyethylene, polypropylene and their non-elastomeric copolymers, non-elastomeric vinyl polymers or copolymers, non-elastomeric styrenic polymers or copolymers, non-elastomeric acrylic or methacrylic polymers and copolymers, polyoxyphenylenes, polyacetals, non-elastomeric polyamides, biodegradability rate polycarbonates less than 50%, biodegradability polyesters lower than 50% such as poly (ethylene terephthalate) (PET), including amorphous (PETG), non-elastomeric fluoropolymers, polysulfones, phenylene polysulfides ( or polyphenylsulfides), non-elastomeric polyurethanes,
• Additional polymers which may be used especially according to the invention include poly (ethylene terephthalates) (PET), including amorphous poly (ethylene terephthalate) (PETG), polyethylenes (PE) and polypropylenes (PP). functionalized or non-functionalized, polyacrylonitriles (PAN), polyethersulfones, polymethylmethacrylates (PMMA), polyamides, in particular polyamides 6, 6-6, 6-10 and 6-12, polyacrylates, polyvinyl acetate , non-elastomeric polyurethanes, polyoxymethylenes (POMs) and any mixtures of these polymers.
• PET poly (ethylene terephthalates)
• PET amorphous poly (ethylene terephthalate)
• PE polyethylenes
• PP polypropylenes
• PAN polyacrylonitriles
• PMMA polymethylmethacrylates
• polyamides in particular polyamides 6, 6-6, 6-10 and 6-12, polyacrylates, polyvinyl acetate ,
• composition according to the invention may also comprise other additional products.
• fillers, fibers or additives which can be incorporated in the elastomeric composition of the present invention. It may be products intended to further 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. It may be nucleating agents such as talc, impact or scratch-resistant agents such as calcium silicate, withdrawal control agents such as magnesium silicate, scavengers or deactivators of water, acids, catalysts, metals, oxygen, infrared rays, UV rays, hydrophobing agents such as oils and greases, flame retardants and fire retardants such as halogenated derivatives, anti-smoke agents, reinforcing fillers, mineral or organic, such as calcium carbonate, talc, plant fibers including coconut, sisal, cotton, hemp and flax, fibers glass or Kevlar.
• nucleating agents such as talc, impact or scratch-resistant agents such as calcium silicate
• withdrawal control agents such as magnesium silicate, scavengers or deactivators of water, acids, catalysts, metals, oxygen, infrared rays, UV rays
• 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. , to solvents, to fatty substances, to essences, to aromas, to perfumes, chosen in particular from minerals, salts and organic substances, in particular from heat-conduction or dissipation agents such as metal powders and graphites .
• the additional product may be an agent that improves the organoleptic properties, in particular:
• optical properties whiteners such as titanium dioxide, dyes, pigments, dye enhancers, opacifiers, matting agents such as calcium carbonate, thermochromic agents, phosporescence and fluorescence agents, agents metallizers or marbles and anti-fogging agents
• whiteners such as titanium dioxide, dyes, pigments, dye enhancers, opacifiers, matting agents such as calcium carbonate, thermochromic agents, phosporescence and fluorescence agents, agents metallizers or marbles and anti-fogging agents
• 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, rosins, 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, rosins, 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, in particular chosen from hydrophobic or pearling agents such as oils and greases, anticorrosive agents, preservatives as in particular organic acids, in particular acetic acid or lactic acid, antimicrobial agents such as Ag, Cu and Zn, degradation catalysts such as oxo-catalysts and enzymes such as amylases.
• the additional product can be a nanometric product that significantly reduces the water and water vapor sensitivity of the final elastomeric composition obtained, compared with the prior art comprising starch.
• the nanometric product may also be added to improve the behavior in the implementation and the shaping of the composition according to the invention but also its mechanical, thermal, conductive, adhesive or organoleptic properties.
• the product The nanoscale particle consists of particles of which at least one dimension is between 0.5 and 200 nanometers, preferably between 0.5 and 100 nanometers, and more preferably between 1 and 50 nanometers. This dimension can in particular be between 5 and 50 nanometers.
• the nanometric product can be of any chemical nature and possibly be deposited or fixed on a support.
• It can be chosen from natural or synthetic lamellar clays, organic, mineral or mixed nanotubes, organic, mineral or mixed nanocrystals and nanocrystallites, organic, mineral or mixed nanospheres and nanospheres, individualized, in clusters or agglomerates, and blends. any of these nanoscale products.
• lamellar clays also called silicates / phyllosilicates of calcium and / or sodium
• montmorillonite bentonite, saponite, sepiolite, hydrotalcite, hectorite, fluorohectorite, attapulgite, beidellite, nontronite, vermiculite, hallysite, stevensite, manasseite, pyr
• Such lamellar clays are already commonly marketed, for example by ROCKWOOD under the trade names NANOSIL and CLOISITE. Hydrotalcites may also be mentioned, such as SASOL's PURAL products.
• the nanotubes that can be used in the context of the invention have a tubular structure with a diameter of the order of a few tenths to several tens of nanometers. Some of these products are already commercially available, such as carbon nanotubes, for example by the company Arkema under the brand names GRAPHISTRENGTH and NANOSTRENGTH and NANOCYL under the brand names NANOCYL, PLASTICYL, EPOCYL, AQUACYL, and THERMOCYL.
• Such nanotubes may also be cellulose nanofibrils, with a diameter of around 30 nanometers for a length of a few microns, which are constitutive of the natural fibers of wood cellulose and can be obtained by separation and purification from them.
• the nanocrystals or nanocrystals can in particular be obtained by crystallization, within or without the elastomeric composition, of very diluted solvent medium, said solvent being constitutive of the composition according to the invention.
• nanometals such as iron or silver nanoparticles useful as reducing or antimicrobial agents and the nanocrystals of oxides known as agents for improving the resistance to scratching.
• nanoscale synthetic talcs which can be obtained for example by crystallization from an aqueous solution.
• amylose / lipid complexes of structures of Vh (stearic), Vbutanol, Vglycerol, Visopropanol, Vnaphthol type from 1 to 10 microns in width or in length, for a thickness of about ten nanometers. It may also be complexes with cyclodextrins, similar characteristics.
• it may be polyolefin nucleating agents able to crystallize in the form of nanometric particles such as sorbitol derivatives such as dibenzylidene sorbitol (DBS) and its own alkyl derivatives.
• sorbitol derivatives such as dibenzylidene sorbitol (DBS) and its own alkyl derivatives.
• the usable nanometric product may be in elementary nanobead or nanosphere type particles, that is to say in the form of pseudospheres with a radius of 1 to 500 nanometers, in individualized form, in a cluster or in agglomerates.
• carbon blacks commonly used as a filler for elastomers and rubbers may be mentioned. These carbon blacks comprise primary particles ranging in size from about 8 nanometers (oven blacks) to about 300 nanometers (thermal blacks) and generally have oil absorption capacities of typically between 40 and 180 cc. per 100 grams for STSA specific surfaces of between 5 and 160 m2 per gram.
• Such carbon blacks are in particular marketed by CABOT, EVONIK, SID RICHARDSON, COLUMBIAN and CONTINENTAL CARBON.
• Hydrophilic or hydrophobic silicas, precipitation or combustion (pyrogenic), such as those used as flow agents for powders or fillers in tires called “green” may also be mentioned.
• Such silicas are sold especially in the form of powder or dispersions in water, in ethylene glycol or in acrylate or epoxy resins, by the companies GRACE, RHODIA, EVONIK, PPG and NANORESINS AG.
• nanoprecipitated calcium carbonates or metal oxides (titanium dioxide, zinc oxide, cerium oxide, silver oxide, iron oxide, magnesium oxide, aluminum oxide, etc.) rendered nanometric for example by combustion such as the products marketed by the company EVONIK under the names AEOROXIDE or AEORODISP, or by acid attack such as the products sold by SASOL under the names DISPERAL or DISPAL.
• proteins precipitated or coagulated in the form of nanoscale beads may be mentioned.
• polysaccharides can be mentioned, such as starches in nanospheric form, such as, for example, crosslinked starch nanoparticles with a size of between 50 and 150 nanometers, sold under the name ECOSPHERE by the company ECOS YNTHETIX or else acetate nanoparticles.
• any additional product can be done by physical mixing cold or low temperature but preferably by hot mixing at a temperature above the glass transition temperature of the composition.
• This mixing temperature is advantageously between 60 and 20O 0 C and better still 100 to 18O 0 C.
• This incorporation can be carried out by thermomechanical mixing, discontinuously or continuously and in particular online. In this case, the mixing time can be short, from a few seconds to a few minutes.
• the composition according to the invention preferably has a complex viscosity, measured on a rheometer of the PHYSICA MCR 501 or equivalent type, of between 10 and 10 6 Pa ⁇ s, for a temperature of between 100 and 200 ° C.
• a complex viscosity measured on a rheometer of the PHYSICA MCR 501 or equivalent type, of between 10 and 10 6 Pa ⁇ s, for a temperature of between 100 and 200 ° C.
• its viscosity at these temperatures is preferably located in the lower part of the range given above and the composition is then preferentially heat fusible in the sense specified above.
• the elastomeric compositions according to the invention also have the advantage of being able to be practically or completely insoluble in water, to hydrate with difficulty and to maintain a good physical integrity after immersion in water, saline, oxidizing and acidic solutions. or alkaline or the media More complex aqueous media such as biological media such as saliva, sweat and digestive juices.
• the composition according to the invention advantageously has characteristic stress / strain curves of a ductile material, and not of a fragile type material.
• the tensile mechanical characteristics of the various compositions are determined according to Standard NF T51-034 (Determination of tensile properties) using a Lloyd Instrument LR5K test bench, a tensile speed: 50 mm or 300 mm / min and specimens. normalized type H2.
• the elongation at break measured for the compositions of the present invention for a stretch rate of 50 mm / min, is generally between
• this elongation at break is at least 70% and less than 500% and in particular between 80% and. 480%.
• the maximum tensile strength of the compositions of the present invention, also measured at a stretching speed of 50 mm / min, is generally between 4 and 50 MPa. It is generally greater than 4 MPa, preferably greater than 5 MPa, more preferably greater than 6 MPa. Remarkably, it can even reach or exceed 7 MPa, or even 10 MPa, or even much more (15 to 50 MPa). According to an advantageous variant, this constraint maximum at break is at least 7 MPa and less than 50 MPa, especially between 10 MPa and 45 MPa ..
• composition according to the present invention may furthermore have the advantage of being essentially renewable raw materials and of being able to present, after adjustment of the formulation, the following properties, useful in multiple applications in the plastics industry, in the elastomer industry and rubbers, in the adhesive industry, in pharmacy, in cosmetics, in confectionery or in many other fields:
• thermoplasticity suitable thermoplasticity, melt viscosity and glass transition temperature, within the usual known ranges of current polymers, which can be implemented using existing industrial installations and conventionally used for the usual natural, artificial or synthetic polymers,
• thermoplastic starch compositions of the prior art Flexibility, elongation at break, maximum breaking stress
• the present invention also relates to a method for preparing an elastomeric composition as described above in all its variants, said method comprising the following steps:
• the elastomeric composition according to the invention can be used as such or in admixture with synthetic, artificial or naturally occurring polymers. It may also include polymers known to be biodegradable or compostable within the meaning of EN 13432, ASTM D6400 and ASTM 6868, or materials meeting these standards, such as PLA, PCL, PBS, PBAT and PHA.
• composition according to the invention may in particular be non-biodegradable (degree of biodegradability less than 5%, and better close to 0%) and / or preferably non-compostable within the meaning of the EN or ASTM standards mentioned above. It is possible to modulate the lifetime and the stability of the composition according to the invention by adjusting in particular its affinity for water, so as to suit the expected uses as a material and the recovery methods envisaged in the end. of life.
• the elastomeric composition according to the present invention advantageously contains at least 15%, preferably at least 30%, in particular at least 50%, more preferably at least 70% or even more than 80% of carbon of renewable origin in the sense of ASTM D6852, relative to all the carbon present in the composition.
• This carbon of renewable origin is essentially that constitutive of the ester of the starch material 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 possible or any other constituent of the composition, when they come from renewable natural resources such as those defined preferentially above.
• compositions according to the invention as gaskets or barrier products to oxygen, carbon dioxide, flavorings, fuels and / or fats, alone or in multi structures. coextruded layers for the field of food packaging in particular.
• They can also be used to increase the hydrophilicity, electrical conductivity, permeability to water and / or water vapor, or resistance to organic solvents and / or fuels, of synthetic polymers in the framework for example of the manufacture of membranes, films or printable electronic labels, textile materials, containers or tanks, or to improve the adhesive properties of heat-sealing films or sticky films on hydrophilic supports such as the wood, glass or skin.
• thermoplastic or elastomeric composition according to the invention considerably reduces the risk of bioaccumulation in the adipose tissue of living organisms and therefore also in the food chain.
• Said composition may be in pulverulent, granulated or bead form. It can constitute as such a masterbatch or the matrix of a masterbatch, intended to be diluted in a bio-sourced matrix or not. It can also constitute a plastic raw material or a compound that can be used directly by an equipment manufacturer or a fabricator for the preparation of plastic or elastomeric objects.
• an adhesive in particular of the hot-melt type, or a matrix for the formulation of an adhesive, in particular of the hot-melt type. It may constitute part or all of a base gum or the matrix of a base gum, in particular chewing gum or a resin, co-resin or nano-filler, in particular biosourced, which can be used in industry, including rubber and elastomers including tires, road bitumen or other, inks, varnishes, paints, paper and paperboard, woven and non-woven products. It may be for example treads or carcasses of tires, belts, cables, pipes, seals and molded parts, pacifiers, gloves, soles of shoes, coated fabrics.
• the present invention particularly relates to the use of an elastomeric composition according to the invention, for the preparation of a gum base chewing gum.
• a gum base for chewing gum containing a composition according to the invention, preferably in an amount of between 5 and 50%, preferably between 10 to 45% and in particular between 10 and 40%.
• the present invention also relates to the use of an elastomeric composition according to the invention, for the preparation of a workpiece, tire or equipment for the transport industry, in particular for the industry. automotive, aeronautical, railway or naval, for the electrical, electronic or household appliance industry, for the sports and leisure industry or for the pharmacy or cosmetics industries.
• composition according to the invention may optionally be used to prepare thermoset resins (duroplasts) by irreversibly extensive crosslinking, said resins thus definitely losing any elastomeric character.
• thermoset resins duroplasts
• the invention also relates to a plastic material, an elastomeric material or an adhesive material comprising the composition of the present invention or a finished or semi-finished product obtained therefrom.
• ester of starchy material a potato starch acetate having an ester DS of 2.7 and hereinafter referred to as "ACET 1", as a plasticizer of this starch ester, a liquid composition of glycerol triacetate (triacetin), - as non-starchy polymer elastomer, a polyether TPU polymer type marketed under the name Estane ® 58887 by Noveon,
• MDI methylene diphenyl diisocyanate
• control composition containing, by weight:
• ACET 1 ester 60 parts of ACET 1 ester and 40 parts of triacetin are mixed in a Hobart mixer for 5 minutes. After crumbling the resulting mixture, it is introduced, through the main feed chute, into a single-screw extruder type HAAKE, diameter (D) of 19 mm and length 25 D according to the following temperature profile, respectively for the 4 sleeves: 40 0 C,
• the plasticized ACET 1 starch ester rod is then granulated.
• the plastic ACET 1 ester granules (“ACET 1 ⁇ l") are then mixed with the PLA in a 50/50 weight ratio in a Hobart mixer for 5 minutes.
• the resulting extruded composition (hereinafter "COMP 1") is in the form of a cream-colored ring which is continuous, stretchable under its weight and which appears visually homogeneous. To the touch, it has good flexibility but a rather slow elastic response of non-crosslinked rubber type. It has the following tensile mechanical characteristics, measured in accordance with the protocol described previously in the section "Measurement of mechanical properties” and for a stretching speed of 50 mm / min: elongation at break: 23%, - maximum stress at rupture: 16 MPa.
• COMP 1 composition described above was then implemented within extruded compositions ("COMP 2" and "COMP 4"), also not in accordance with the present invention, and in a extruded composition ("COMP 3"), according to the invention, these compositions respectively containing, by weight:
• COMP 3 50 parts of COMP 1 + 50 parts of ESTANE ® 58887 polyether TPU + 2% of MDI,
• COMP 4 50 parts of COMP 1 + 45 parts of low density polyethylene (LDPE) + 5% of PE grafted maleic anhydride BONDYRAM ® 4001.
• LDPE low density polyethylene
• composition COMP has, under the same measurement conditions as those used for the composition COMP 1, the mechanical characteristics listed in the table below, with, for other control compositions, a composition consisting solely of low density polyethylene (“LDPE”) or only acrylonitrile butadiene styrene copolymer (“ABS").
• LDPE low density polyethylene
• ABS acrylonitrile butadiene styrene copolymer
• composition COMP 3 according to the invention which nevertheless contains a very high proportion of COMP 1, possesses thermal and mechanical characteristics which could be comparable to those of thermoplastic elastomers.
• so-called "technical” market such as TPU or ABS and in any case, this COMP 3 had an excellent compromise between elongation at break (value exceeding 200%) and maximum stress at break (significantly higher value at 10 MPa).
• biodegradability rate values generally greater than 50%.
• compositions according to the invention to replace at least partially a gum base based on synthetic polymer used for the preparation of chewing gums.
• esters of starchy material respectively: an acetate of a maltodextrin obtained from waxy corn starch (maltodextrin)
• Potato starch acetate having an ester DS of about 2.6, said acetate being further hydroxypropylated with a MS (Molecular Substitution Degree) of about 0.4 (hereinafter referred to as "ACET"); 5 ").
• PLAST 1 triacetin
• an elastomeric composition comprising, in total, about 52% by weight of a mixture of non-starch polymers consisting of polyvinyl acetate (PVAc), rosin esters, copolymers butadiene / styrene and polyisobutylene, the 100% complement consisting mainly of calcium carbonate, paraffin wax and emulsifier.
• PVAc polyvinyl acetate
• rosin esters polyvinyl acetate
• copolymers butadiene / styrene and polyisobutylene the 100% complement consisting mainly of calcium carbonate, paraffin wax and emulsifier.
• the butadiene / styrene and polyisobutylene elastomers represent about one third of the polymers of this composition, ie 14% of the 52% of polymers.
• each of the ACET 2 starch ester esters is mixed with ACET 5 with the PLAST plasticizer.
• Chewing gum compositions are prepared according to the formula below. 2.4.1: formula
• GUM 2 70% by weight of gum base + 30% by weight of ACET plasticized starchy acetate 2 ',
• the hardness expressed in Newtons of the prepared sticks is measured. This, either after their preparation (OJ) and at different temperatures (45, 35 or 200 ° C.) or after, respectively, 1, 8 and 15 days of storage inside an aluminum packaging itself placed in an air-conditioned chamber (temperature: 20 ° C, relative humidity RH): 50%).
• Those with the INSTRON texture closest to the control are those prepared with GUM 2 gum base containing 30% of ACET plasticized starch material, namely 30% of a plasticized GLUCIDEX® 2 acetate. triacetin.
• ester of plasticized starchy material maltodextrin acetate ACET 2 as described in Example 2, as a plasticizer, benzyl alkyl in weight per 100 parts by weight said ester, - as non-starchy polymer elastomer, TPU type polymeric ester sold under the name Estane ® 58447 by Noveon,
• Example 1 a composition according to the invention (hereinafter "COMP 5") containing:
• composition COMP 5 has the following tensile mechanical characteristics, measured according to the protocol described above in the section "Measurement of mechanical properties" and for a stretching speed of 50 mm / min: elongation at break: 80%, - maximum stress at break: 14 MPa.
• the COMP 5 composition although containing a high proportion of ester of starchy material, has a behavior close to certain performances of "shock polystyrene” type polymer or "EVA for agricultural film” type.

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  • 2009-10-13 CN CN2009801413367A patent/CN102186916A/zh active Pending
  • 2009-10-13 CA CA2739051A patent/CA2739051A1/fr not_active Abandoned
  • 2009-10-13 MX MX2011003901A patent/MX2011003901A/es not_active Application Discontinuation
  • 2009-10-13 US US13/123,600 patent/US20110196071A1/en not_active Abandoned
  • 2009-10-13 WO PCT/FR2009/051952 patent/WO2010043814A1/fr active Application Filing

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