Classifications

• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
  • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
  • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
  • B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
  • B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/285—Feeding the extrusion material to the extruder
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
  • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
  • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
  • B29C48/405—Intermeshing co-rotating screws
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/04—Anhydrides, e.g. cyclic anhydrides
  • C08F222/06—Maleic anhydride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
  • C08G63/08—Lactones or lactides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/91—Polymers modified by chemical after-treatment
  • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
• • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
  • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/03—3 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/716—Degradable
  • B32B2307/7163—Biodegradable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/726—Permeability to liquids, absorption
  • B32B2307/7265—Non-permeable
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2439/00—Containers; Receptacles

Definitions

• the invention relates to a polylactic acid-based polymer composition, more specifically to polylactic acid having a particular cografting intended to confer properties of particularly interesting uses without degrading its physical properties.
• the invention also relates to a binder that can be used in coextrusion, comprising said composition, having good adhesion properties, useful in multilayer structures.
• polymer composition is intended to mean compositions of polymers, copolymers, terpolymers and so on.
• Biorenewable polymers make it possible to limit the consumption of fossil fuels and to resort to resources derived from the cultivation of plants.
• Biodegradable polymers are rapidly transformed into products that can, in part or totally, be absorbed by the plants present in the environment.
• polylactic acid-based polymer compositions are for example described in the article entitled “Maleation of Polylactide (PLA) by reactive extrusion” published in 1998 by D. Carlson, L. Nie, Narayan R., P. Dubois (in particular "Journal of Applied Polymer Science,” 72, 477-485 (1999)).
• the addition of the maleic anhydride grafts results in a very significant increase in the MFI ("Melt Flow Index") of the PLA so that this composition becomes extremely fluid.
• MFI Melt Flow Index
• the MFI of the polymer composition should ideally be between 1 and 6 g / 10 minutes (gram per ten minutes) at 190 ° C under 2.16 kilograms.
• composition present in the yellow index test (ASTM E313-96) be less than 65, preferably less than 35, more preferably less than 20.
• PLA-based polymers have a particular chemical structure which distinguishes them in the broad family of biopolymers comprising in particular poly (hydroxyalkanoate) homo or copolymers or PHA, succinates of poly (alkylene) or PAS, succinate poly (butene) adipate or PBSA, poly (butylene) terephthalate adipate or PBAT, poly (caprolactone) or PCL, poly (trimethylene terephthalate) or PTT, thermoplastic starch or TPS, polyethylene succinate or PES, polybutylene succinate or PBS poly (hydroxybutyrate) or PHB, hydroxybutyrate-valerate or PHBV copolymers such as poly (3-hydroxybutyrate) -poly (3-hydroxyvalerate), copolymers of hydroxy butyratehexanoate or PHBHx and copolymers hydroxybutyratehexanoate or PHBO.
• JP 313401 1 discloses an exemplary composition comprising polycaprolactone (PCL), specifically polycaprolactone-styrene-maleic anhydride copolymers, which is excluded from the PLA family.
• PCL polycaprolactone
• this document provides, for these compositions, the use of a solvent at about 70 ° C for nearly ten hours while the manufacturing method of the present invention is fundamentally different.
• this document does not intend to solve the specific technical problems raised here and solved by the present invention.
• PLA-based polymer compositions comprising maleic anhydride grafts are thermoplastic materials that are very interesting with regard in particular to their functionality, but so far there are no such compositions in the prior art. able to meet the disadvantages listed above.
• the present invention relates to a polymer composition, said polymer having a main chain consisting of a polylactic acid, the main chain comprising a plurality of unsaturated acid anhydride grafts, characterized in that said main chain comprises in addition to activating comonomer grafts.
• the invention particularly has the following advantages: a rheology satisfying the industrial transformation requirements, a more conventional and acceptable transparency for the various applications of the product, that is to say having no coloration or a very weak coloration,
• the unsaturated acid anhydride grafts preferably consist of maleic anhydride
• the activating comonomer grafts consist of styrenic monomers
• the styrenic monomers consist of styrene
• the amount of activating comonomers in the composition is between 0.01 1 and 2.1% by weight, so that said activating comonomers represent in the composition between 0.01 and 2 molar equivalents of saturated acid anhydride;
• the amount of activating comonomers in the composition is between 1.2 and 1.9% by weight, so that the activating comonomers represent in the composition between 1, 1 and 1.8 molar equivalents of the anhydride. unsaturated acid;
• the composition may further comprise additives present between 10 and 50,000 ppm and in that the additives comprise antioxidants, UV protection agents, processing agents such as amides fatty acids, stearic acid and its salts, fluoropolymers, anti-fogging agents, anti-blocking agents such as silica or talc, antistatic agents, nucleating agents, dyes.
• additives present between 10 and 50,000 ppm and in that the additives comprise antioxidants, UV protection agents, processing agents such as amides fatty acids, stearic acid and its salts, fluoropolymers, anti-fogging agents, anti-blocking agents such as silica or talc, antistatic agents, nucleating agents, dyes.
• the polymer also comprises at least one secondary chain constituted by a polylactic acid.
• the final polymer has a main chain on which is fixed, during the preparation / manufacturing process, one or more polylactic acid chains; the latter may possibly comprise the same grafts as the main chain, namely unsaturated acid anhydride grafts and activators of comonomer grafts.
• chain breaks can take place at the same time as branching phenomena (giving rise to this secondary chain); these two phenomena concomitant (cuts and branching) giving rise to a final rheology as presented hereinafter in the tests carried out.
• the secondary chain comprises at least one unsaturated acid anhydride graft, preferably maleic anhydride, and / or at least one graft of activating comonomers, preferably styrenic monomers and more preferably styrene.
• the invention also relates to a method for producing the polymer composition according to any one of the preceding claims, characterized in that it comprises a step of extrusion, via an extruder, of the polylactic acid polymer (PLA) in the presence of radical generators, unsaturated acid anhydride, preferentially maleic anhydride, and activating monomers, preferably styrene monomers and more preferably styrene; the temperature during this extrusion step being chosen so that the polylactic acid polymer is present in the molten state and the radical generator decomposes completely during said step.
• PVA polylactic acid polymer
• the polylactic acid polymer (PLA), the radical generator, the unsaturated acid anhydride and the activating monomers are introduced into the extruder at the same time, that is to say that all or part of these elements has been previously mixed to form a uniform assembly or that all or part of these elements are introduced simultaneously into the extruder.
• the manufacturing method according to the invention comprises a final degassing step.
• the present invention also relates to a multilayer structure, such as a film or a sheet, comprising at least three polymer layers. adjacent, or a binder core layer whose primary function is to provide a link between the two peripheral layers, characterized in that the core layer comprises the composition as described above.
• the structure will comprise two binder layers located at level 2 and 4 so as to bond the two peripheral layers (layers 1 and 5) to the central layer (layer 3) .
• binder layer comprising the composition according to the invention may include other components intended to confer other mechanical / physical / chemical properties on said layer.
• the two adjacent layers are arranged in association with the layer comprising the composition according to the invention, and described above, according to techniques well known to those skilled in the art, in particular by coextrusion.
• layers which may constitute one or the other (or both) of these two adjacent layers, mention may be made of the layer or coating compositions disclosed in the following documents: EP 1 136536, EP 802207, WO 97/27259, EP 1022310, EP 742236, EP 1400566, FR 2850975, WO 01/34389, EP 2029672, EP 629678, EP 1375594, FR 2915203 and FR 2916203.
• polylactide polymers for example, polymers or copolymers of lactic acid (PLA) or polymers or copolymers of glycolic acid (PGA).
• the PLA polymer is cografted with unsaturated acid anhydride and at least one activating comonomer.
• the degree of grafting has a significant influence on the properties of the polymer composition.
• the amount of grafted monomer may, for example, be easily determined by those skilled in the art through the technique of infrared spectroscopy or acid-base assay followed by potentiometry for unsaturated acid anhydrides and by infrared spectroscopy technique. or NMR (Nuclear Magnetic Resonance) spectroscopy for activating comonomers.
• activating comonomers is meant any monomer having an unsaturation and characterized by a parameter "e" lower than the value of the parameter "e” of maleic anhydride, in this case 2.25.
• styrenic monomers By way of examples of these activating monomers, without this list being exhaustive, we mean the styrenic monomers.
• styrene monomer is to be understood in the present description any monomer or combination of monomers having the chemical structure of styrene.
• styrenic monomers examples include styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, ethylstyrene, isopropenyltoluene, vinylnaphthalene, isopropenylnaphthalene, vinylbiphenyl, dimethylstyrene, tert-butylstyrene, hydroxystyrene, alkoxystyrenes, acetoxystyrenes, bromostyrene, chlorostyrene, vinylbenzoic acid, cinnamic acid or alkyl cinnamates.
• Activating comonomers also include 1,1-diphenyl ethylene, stilbene, phenyl acetylene, vinyl pyridine, 2-isopropenyl naphthalene, butadiene, isoprene, dimethyl butadiene, cyclopentene, alkyl vinyl ethers, alkyl vinyl sulfides, phenyl vinyl ethers, alkyl phenylvinyl ethers, vinyl acetate, methyl methacrylate, naphthyl methacrylate, furan, indole, indole vinyl, N vinyl pyrrolidone, N vinyl carbazole and vinyl chloride.
• the styrenic monomers represent the preferred activating comonomers and even more preferably styrene.
• the grafting monomer relative to the unsaturated acid anhydride grafts, it may be chosen from unsaturated carboxylic acids or their functional derivatives.
• unsaturated carboxylic acids are those having 2 to 20 carbon atoms such as acrylic, methacrylic, maleic, fumaric and itaconic acids.
• Functional derivatives of these unsaturated carboxylic acids include anhydrides, ester derivatives, amide derivatives, imide derivatives and metal salts (such as alkali metal salts) of these unsaturated carboxylic acids.
• grafting monomers include, for example, the acids and their functional derivatives maleic, fumaric, itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic, 4-methyl-cyclohex-4-ene-1, 2 dicarboxylic acid, bicyclo (2,2,1) -hept-5-ene-2,3-dicarboxylic acid, x-methylbicyclo (2,2,1) -hept-5-ene-2,3-dicarboxylic acid, maleic anhydrides itaconic, citraconic, allylsuccinic, cyclohex-4-ene-1,2-dicarboxylic, 4-methylenecyclohex-4-ene-1,2-dicarboxylic, bicyclo (2,2,1) hept-5-ene-2,3 -dicarboxylic, and x-methylbicyclo (2,2,1) hept-5-ene-2,2-dicarboxylic acid.
• MAH Maleic anhydride
• additives usually used during the implementation of the polymers for example at contents of between 10 ppm and 50,000 ppm, such as antioxidants, UV protective agents, delivery agents and the like.
• additives usually used during the implementation of the polymers for example at contents of between 10 ppm and 50,000 ppm, such as antioxidants, UV protective agents, delivery agents and the like.
• fatty amides, stearic acid and its salts such as fatty amides, stearic acid and its salts, fluoropolymers known as agents to avoid extrusion defects, anti-fogging agents, anti-blocking agents such as silica or talc.
• Additives of other types may also be included to provide the desired specific properties. For example, antistatic agents, nucleating agents, dyes. Preparation of the composition according to the invention
• maleic anhydride-grafted PLA-based composition various known processes (reactive extrusion method, in solution, by irradiation or in the solid state) can be used to graft a functional monomer such as anhydride. maleic on the PLA polymer.
• the grafting of maleic anhydride onto the PLA polymer can be carried out in the molten state in an extruder in the presence of a radical generator.
• Suitable radical generators that can be used include t-butyl hydroperoxide, cumene hydroperoxide, di-iso-propyl benzene hydroperoxide, di-t-butyl peroxide, di-t-amyl peroxide, t-butyl cumylperoxide, dicumylperoxide, 1,3-bis- (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperoxybenzoate, t-butyl -peroxy-2-ethylhexanoate, O-t-butyl-O- (2-ethyl-hexyl) -monoperoxycarbonate, O-t-amyl-O- (2-ethyl-hexyl) -monoperoxycarbonate, acetyl peroxide, dibenzoyl-peroxide
• the process for producing the composition according to the invention is more particularly concerned with the cografting of a styrene monomer and of maleic anhydride on PLA.
• the manufacturing process consists of extruding the PLA polymer in a co-rotating twin-screw extruder in the presence of a radical generator, maleic anhydride and a styrenic monomer.
• the temperature is chosen so that the reaction takes place in the molten state of the polymer and the radical generator decomposes completely in the time given to the extrusion. It should be noted that degassing is carried out at the end of the extruder in order to remove from the PLA polymer the decomposition products of the radical generator and the unreacted monomers.
• compositions based on maleic anhydride grafted PLA and styrenic monomer were made in a Haake PTW 16/25 co-rotating twin-screw extruder.
• the PLA used is NatureWorks Ingeo® 2003D
• the styrene monomer used is styrene supplied by Aldrich®
• maleic anhydride is supplied by CristalMan®
• the radical generator is Luperox® 101 of the company. Arkema.
• the feeding of the extruder was ensured by a weight feeder. To ensure a homogeneous feed composition, the various constituents of the formulation were mixed with the bag before filling the doser.
• PLA was used in powder form and the liquid constituents (styrene and Luperox® 101) were impregnated on PLA powder.
• the PLA polymer grafted maleic anhydride and styrene leaving the extruder is cooled in contact with air on a conveyor belt and then granulated using a rod granulator.
• the quantity of maleic anhydride introduced is 1% by mass relative to the total mass of the various constituents.
• the amount of Luperox® 101 introduced is 0.4% by mass.
• the amount of styrene introduced is between 0 and 1.8% by weight, so that the amount of styrene introduced represents between 0 and 1.7 molar equivalents of the maleic anhydride introduced.
• compositions tested are the following:
• composition No. 1 composition based on PLA grafted with maleic anhydride
• composition No. 2 composition based on PLA cografted maleic anhydride and styrene monomers with 0.5 equivalents
• composition No. 3 composition based on PLA cografted maleic anhydride and styrene monomer with 1 equivalent
• composition No. 4 composition based on PLA cografted maleic anhydride and styrene monomer with 1, 2 equivalents
• composition 5 composition based on PLA cografted maleic anhydride and styrene monomers with 1, 5 equivalents
• composition no. 6 composition based on PLA cografted with maleic anhydride and styrene monomers containing 1, 7 equivalents
• composition PLA 2003D lngeo® 2003D polylactic acid composition from NatureWorks (without maleic anhydride graft or styrenic graft)
• maleic anhydride cograft and X-equivalent styrenic monomers is understood to mean that, in the PLA under consideration, for one (1) molecule of maleic anhydride, there is present X molecule (s) of monomer (s) styrenic (s) during the grafting reaction.
• graft is meant maleic anhydride or styrenic monomers, any sequence of maleic anhydride or styrene monomer grafted directly or indirectly on the PLA chain. So, a graft may consist of an independent unit grafted on said PLA chain, in which case said graft is counted as a unit of maleic anhydride or styrenic monomer.
• graft may also consist of a branch, grafted on the PLA chain, said branch comprising one or more units of maleic anhydride and / or of styrenic monomers, in this case must be counted as “graft” (s) "of maleic anhydride the number of maleic anhydride units present on the branching considered and as” graft (s) "of styrene monomer the number of units of styrene monomer present (s) on the branch considered.
• the first test carried out on the compositions is a measurement of the MFI ("Melt Flow Index") at 190 ° C. (Celsius) under 2.16 kg (kg), according to the ISO 1,133 standard:
• the second test performed on the compositions is a measurement of the yellow index according to the ASTM E313-96 standard:
• the third and final test carried out on the compositions is a thermal stability measurement at 180 ° C. under a stream of nitrogen (PHYSICA MCR301 rheometer, parallel planes 25 mm in diameter, 10 minutes at 1 rad.s -1 ). Thermal stability is expressed in% viscosity variation at 180 ° C and 1 rad.s -1 as a function of time.

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• Manufacturing & Machinery (AREA)
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• Materials Engineering (AREA)
• Graft Or Block Polymers (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Biological Depolymerization Polymers (AREA)
• Laminated Bodies (AREA)
• Compositions Of Macromolecular Compounds (AREA)
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• 2012
  • 2012-08-09 FR FR1257724A patent/FR2994435B1/fr not_active Expired - Fee Related
• 2013
  • 2013-07-11 MX MX2015001791A patent/MX2015001791A/es unknown
  • 2013-07-11 EP EP13745150.6A patent/EP2882787A1/fr not_active Withdrawn
  • 2013-07-11 SG SG11201501795TA patent/SG11201501795TA/en unknown
  • 2013-07-11 CA CA2880144A patent/CA2880144A1/fr not_active Abandoned
  • 2013-07-11 IN IN1118DEN2015 patent/IN2015DN01118A/en unknown
  • 2013-07-11 KR KR20157005978A patent/KR20150041096A/ko not_active Withdrawn
  • 2013-07-11 WO PCT/FR2013/051666 patent/WO2014023884A1/fr active Application Filing
  • 2013-07-11 AU AU2013301437A patent/AU2013301437A1/en not_active Abandoned
  • 2013-07-11 JP JP2015525917A patent/JP2015529722A/ja active Pending
  • 2013-07-11 US US14/420,524 patent/US20150307686A1/en not_active Abandoned
  • 2013-07-11 BR BR112015002705-9A patent/BR112015002705A2/pt not_active IP Right Cessation
  • 2013-07-11 CN CN201380042310.3A patent/CN104520343A/zh active Pending

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