Classifications

• • 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
  • B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
• • 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
  • B29C48/29—Feeding the extrusion material to the extruder in liquid form
• • 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
  • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
  • B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
  • B29C48/82—Cooling
• • 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
  • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/916—Dicarboxylic acids and dihydroxy compounds
• • 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether groups
• • 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
  • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
• • 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
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/04—Particle-shaped
• • 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
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/07—Flat, e.g. panels
• • 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
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
  • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
• • 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
  • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
  • B29C48/2886—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules of fillers or of fibrous materials, e.g. short-fibre reinforcements
• • 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
  • B29C48/50—Details of extruders
  • B29C48/76—Venting, drying means; Degassing means
  • B29C48/762—Vapour stripping
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
  • B29K2105/16—Fillers

Definitions

• the present invention relates to a process for extruding a polymer in the presence of water.
• EP1037941 discloses the extrusion of a composite preparation comprising polyamide and a clay-like solid substance in the presence of water, in order to avoid a preliminary exfoliation step of the clay. This document does not solve the problem, if only because the polyamide is not an elastomer.
• the invention relates first of all to a process for converting a polycondensed elastomeric thermoplastic polymer, comprising a step of extruding the polycondensed elastomeric thermoplastic polymer in the presence of water.
• the extrusion step is carried out in an extruder, the process comprising feeding the polycondensed elastomeric thermoplastic polymer extruder, feeding the extruder with water and steam degassing. of water from the extruder.
• the extrusion step is carried out at a temperature of 20 to 100 ° C higher than the melting point of the polycondensed elastomeric thermoplastic polymer in the presence of water, preferably greater than 30 to 80 ° C. Fusion point.
• the mass proportion of water with respect to the polycondensed thermoplastic elastomer polymer during the extrusion step is from 1 to 50%, preferably from 5 to 30%.
• the polycondensed elastomeric thermoplastic polymer is chosen from copolyether block amides, copolyether or copolyester urethane block, block copolyether block and mixtures thereof, and preferably is a block amide copolyether.
• the polycondensed elastomeric thermoplastic polymer is an amide block copolyether comprising 1 to 80% by weight of polyether blocks and from 20 to 99% by weight of polyamide blocks, preferably from 4 to 80% by weight of polyether blocks. and from 20 to 96% by weight of polyamide blocks.
• the amide block copolyether comprises a flexible block of poly (tetramethylene ether) glycol.
• the polyamide is polyamide 12.
• the polycondensed elastomeric thermoplastic polymer is extruded in the absence of any other compound with the exception of water.
• the polycondensed elastomeric thermoplastic polymer is extruded in the presence of an additional compound capable of forming a composite material with the polycondensed thermoplastic elastomer polymer, the additional compound preferably being a heat-sensitive filler.
• the method comprises obtaining at least one article formed at the end of the extrusion step.
• the process comprises obtaining granules at the end of the extrusion step.
• the method comprises subsequent steps of melting and extrusion of the granules and injection into a mold, to obtain at least one formed article.
• the present invention overcomes the disadvantages of the state of the art. More particularly, it provides a process for converting a polycondensed elastomeric thermoplastic polymer in which the degradation of the polymer during extrusion is reduced compared to the processes of the state of the art.
• thermoplastic polycondensed elastomeric polymers are generally sensitive to hydrolysis (in particular polyamide blocks and aliphatic ester groups).
• hydrolysis in particular polyamide blocks and aliphatic ester groups.
• the inventors believe that the presence of water makes it possible to plasticize and lubricate the material during extrusion, which protects it from thermal degradation.
• the presence of water does not cause significant hydrolysis due to the relatively slow kinetics of hydrolysis and the low contact time of the polymer with water (typically less than about 30 seconds).
• thermoplastic polymer refers to a polymer which constitutes a multiphase material having at least two transitions, namely a first transition at a temperature T1 (generally this is the glass transition temperature) and a second transition at a temperature of T2 temperature greater than T1 (usually this is the melting point). At a temperature below T1, the material is rigid, between T1 and T2 it has an elastic behavior, and above T2 it is melted. Such a polymer combines the elastic behavior of rubber-like materials with the processability of thermoplastics.
• polycondensed polymer denotes a polymer that can be obtained by a set of condensation steps, a small molecule (such as a water molecule for example) being removed at each stage.
• the polymers used in the context of the invention may be selected from the group consisting of copolyether block amides, copolyether or block copolyesters urethanes and copolyether block esters and combinations thereof.
• the implementation of the invention assumes the use of polymers having good miscibility with water, which excludes relatively hydrophobic polymers.
• Copolyether block amides also called polyether block copolymers and polyamide blocks, abbreviated as "PEBA"
• PEBA polyether block copolymers and polyamide blocks
• polyamide blocks with reactive ends such as, inter alia: 1) polyamide blocks with diamine chain ends with polyoxyalkylene blocks with dicarboxylic chain ends;
• polyamide blocks with dicarboxylic chain ends with polyoxyalkylene blocks with diamine chain ends obtained by cyanoethylation and hydrogenation of polyoxyalkylene aliphatic alpha-omega dihydroxylated blocks called polyetherdiols;
• the polyamide blocks with dicarboxylic chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid.
• the polyamide blocks with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-limiting diamine.
• the molar mass in number Mn of the polyamide blocks is between 400 and 20000 g / mol and preferably between 500 and 10000 g / mol.
• Polymers with polyamide blocks and polyether blocks may also comprise randomly distributed units.
• Three types of polyamide blocks can advantageously be used.
• the polyamide blocks come from the condensation of a dicarboxylic acid, in particular those having from 4 to 20 carbon atoms, preferably those having from 6 to 18 carbon atoms and an aliphatic or aromatic diamine, in particular those having 2 to 20 carbon atoms, preferably those having 6 to 14 carbon atoms.
• dicarboxylic acids examples include 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, octadecanedicarboxylic acids and terephthalic and isophthalic acids, but also dimerized fatty acids. .
• diamines examples include tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, the isomers of bis (4-aminocyclohexyl) methane (BACM), bis - (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2-2-bis- (3-methyl-4-aminocyclohexyl) -propane (BMACP), and para-amino-di-cyclohexyl-methane (PACM), and isophoronediamine (IPDA), 2,6-bis- (aminomethyl) -norbornane (BAMN) and piperazine (Pip).
• PA4.12, PA4.14, PA4.18, PA6.10, PA6.12, PA6.14, PA6.18, PA9.12, PA10.10, PA10.12, and PA10.14 blocks are used.
• the polyamide blocks result from the condensation of one or more alpha omega-aminocarboxylic acids and / or one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having from 4 to 12 carbon atoms or a diamine.
• lactams include caprolactam, oenantholactam and lauryllactam.
• alpha omega amino carboxylic acid there may be mentioned aminocaproic acid, amino-7-heptanoic acid, amino-1 1-undecanoic acid and amino-12-dodecanoic acid.
• the polyamide blocks of the second type are made of polyamide 11, polyamide 12 or polyamide 6.
• the polyamide blocks result from the condensation of at least one alpha omega aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
• polyamide PA blocks are prepared by polycondensation:
• comonomer (s) ⁇ Z ⁇ chosen from lactams and alpha-omega aminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having X 1 carbon atoms and at least one dicarboxylic acid having Y 1 carbon atoms, (X1, Y1) being different from (X, Y);
• said one or more comonomers ⁇ Z ⁇ being introduced in a proportion by weight of up to 50%, preferably up to 20%, even more advantageously up to 10% relative to all the polyamide precursor monomers;
• the dicarboxylic acid having Y carbon atoms which is introduced in excess with respect to the stoichiometry of the diamine or diamines, is used as chain limiter.
• the polyamide blocks result from the condensation of at least two alpha omega aminocarboxylic acids or at least two lactams having from 6 to 12 carbon atoms or a lactam and an aminocarboxylic acid. not having the same number of carbon atoms in the possible presence of a chain limiter.
• alpha omega amino carboxylic acid mention may be made of aminocaproic acid, amino-7-heptanoic acid, amino-1 1 -undecanoic acid and amino-12-dodecanoic acid.
• lactam mention may be made of caprolactam, oenantholactam and lauryllactam.
• aliphatic diamines there may be mentioned hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine.
• cycloaliphatic diacids mention may be made of 1,4-cyclohexyldicarboxylic acid.
• aliphatic diacids By way of example of aliphatic diacids, mention may be made of butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid or dimerized fatty acid (these dimerized fatty acids preferably have a dimer content of at least 98% preferably they are hydrogenated, they are marketed under the trade name Pripol® by the company Unichema, or under the brand name Empol® by Henkel) and the polyoxyalkylenes- ⁇ , ⁇ diacids.
• aromatic diacids mention may be made of terephthalic (T) and isophthalic (I) acids.
• cycloaliphatic diamines By way of example of cycloaliphatic diamines, mention may be made of the isomers of bis (4-aminocyclohexyl) methane (BACM), bis (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2- (2-bis) - (3-methyl-4-aminocyclohexyl) propane (BMACP), and para-amino-di-cyclohexyl methane (PACM).
• BMACP bis (4-aminocyclohexyl) methane
• BMACP 2- (2-bis) - (3-methyl-4-aminocyclohexyl) propane
• PAM para-amino-di-cyclohexyl methane
• IPDA isophoronediamine
• BAMN 2,6-bis (aminomethyl) norbornane
• polyamide blocks of the third type As examples of polyamide blocks of the third type, the following can be cited:
• 6.6 denotes hexamethylenediamine condensed with adipic acid.
• 6.10 denotes hexamethylenediamine condensed with sebacic acid.
• 1 1 denotes patterns resulting from the condensation of aminoundecanoic acid.
• 12 denotes patterns resulting from the condensation of lauryllactam.
• the mass Mn of the polyether blocks is between 100 and 6000 g / mol and preferably between 200 and 3000 g / mol.
• the polymer comprises from 1 to 80% by weight of polyether blocks and from 20 to 99% by weight of polyamide blocks, preferably from 4 to 80% by weight of polyether blocks and 20 to 96% by weight of polyamide blocks.
• the polyether blocks consist of alkylene oxide units. These units may be, for example, ethylene oxide units, propylene oxide or tetrahydrofuran units (which leads to polytetramethylene glycol linkages).
• PEG blocks polyethylene glycol
• PPG blocks propylene glycol
• PO3G blocks polytrimethylene glycol
• PTMG blocks ie those consisting of tetramethylene glycol units also called polytetrahydrofuran.
• the PEBA copolymers may comprise in their chain several types of polyethers, the copolyethers may be block or statistical.
• the polyether blocks may also consist of ethoxylated primary amines.
• ethoxylated primary amines mention may be made of the products of formula:
• m and n are between 1 and 20 and x between 8 and 18.
• These products are commercially available under the trademark Noramox® from the company CECA and under the brand Genamin® from the company Clariant.
• the flexible polyether blocks may comprise polyoxyalkylene blocks with NH 2 chain ends, such blocks being obtainable by cyanoacetylation of aliphatic polyoxyalkylene aliphatic alpha-omega dihydroxy blocks known as polyether diols. More particularly, Jeffamines (for example Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products of Huntsman, also described in JP2004346274, JP2004352794 and EP148201 1) can be used.
• the polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks having carboxylic ends, or they are aminated to be converted into polyether diamines and condensed with polyamide blocks having carboxylic ends.
• the general two-step preparation method for PEBA copolymers having ester bonds between PA blocks and PE blocks is known and is described, for example, in French patent FR2846332.
• the general method for preparing the PEBA copolymers of the invention having amide linkages between PA blocks and PE blocks is known and described, for example in European Patent EP148201 1.
• the polyether blocks can also be mixed with polyamide precursors and a diacid chain limiter to make the polyamide block and polyether block polymers having statistically distributed units (one-step process).
• PEBA designation in the present description of the invention relates as well to Pebax® marketed by Arkema, Vestamid® marketed by Evonik®, Grilamid® marketed by EMS, Kellaflex® marketed by DSM or to any other PEBA from other suppliers.
• the PEBA copolymers have PA blocks in PA 6, PA 1 1, PA 12, PA 6.12, PA 6.6 / 6, PA 10.10 and / or PA 6.14, preferably PA 11 blocks and / or or PA 12; and PE blocks made of PTMG, PPG and / or PO3G.
• PEBAs based on PE blocks consisting mainly of PEG are to be included in the range of PEBA hydrophilic.
• PEBAs based on PE blocks consisting mainly of PTMG are to be included in the range of hydrophobic PEBA.
• said PEBA used in the composition according to the invention is obtained at least partially from bio-resourced raw materials.
• Raw materials of renewable origin or bio-resourced raw materials are materials that include biofouled carbon or carbon of renewable origin. In fact, unlike materials made from fossil materials, materials made from renewable raw materials contain 14 C.
• the "carbon content of renewable origin” or “bio-resourced carbon content” is determined according to the standards ASTM D 6866 (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).
• PEBAs based on polyamide 1 1 come at least partly from bioprocessed raw materials and have a bio-resourced carbon content of at least 1%, which corresponds to an isotopic ratio of 12 C / 14 C of at least 1.2 ⁇ 10 -14 .
• the PEBAs according to the invention comprise at least 50% by mass of bio-resourced carbon on the total mass of carbon, which corresponds to a 12 C / 14 C isotope ratio of at least 0.6 ⁇ 10 -12 .
• This content is advantageously higher, especially up to 100%, which corresponds to a 12 C / 14 C isotopic ratio of 1.2 ⁇ 10 -12 , in the case of PEBA with PA 1 1 blocks and PE blocks comprising PO 3 G , PTMG and / or PPG from renewable raw materials.
• urethane block copolyether comprising a flexible block of poly (oxyalkylene) and a polyurethane block.
• the polyurethane blocks can be obtained by reaction between a diisocyanate and a diol.
• the polyether soft blocks may be as described above in connection with the PEBAs.
• ester block copolyether comprising a flexible block of poly (oxyalkylene) and a polyester block can also be used.
• the polyester block can be obtained by polycondensation by esterification of a carboxylic acid, such as isophthalic acid or terephthalic acid or a bio-sourced carboxylic acid (such as furan dicarboxylic acid), with a glycol, such as ethylene glycol, trimethylene glycol, propylene glycol or tetramethylene glycol.
• a carboxylic acid such as isophthalic acid or terephthalic acid or a bio-sourced carboxylic acid (such as furan dicarboxylic acid)
• a glycol such as ethylene glycol, trimethylene glycol, propylene glycol or tetramethylene glycol.
• the polyether soft blocks may be as described above in connection with the PEBAs.
• the process according to the invention comprises feeding an extruder (for example a twin-screw extruder) with the above polymer in the solid state, and supplying the extruder with water.
• the polymer is melted and mixed with the water, and the water is then removed by degassing water vapor before the polymer is extruded from the extruder (by means of a degassing opening), or possibly simultaneously with the output of the polymer from the extruder.
• the water is preferably introduced in a mass proportion of 1 to 50%, and for example from 5 to 30% relative to the amount of polymer.
• the presence of water in the extruder makes it possible to reduce the extrusion temperature, for example from about 10 ° to 60 ° C. in the case of polymers of the copolyether ester amide block type.
• the temperature during the extrusion may be from 20 to 100 ° C higher than the melting point of the material (polymer and water), preferably greater than 30 to 80 ° C with respect to this melting point.
• the polymer may be extruded alone (apart from the presence of water) or in the presence of an additional compound capable of forming a composite material with the polymer.
• a heat-sensitive filler there may be mentioned starch, and in particular native starch.
• these granules can in turn be used to manufacture formed articles, by means of a subsequent step of extruding the granules and injecting into a mold.
• the molded material is pressurized and cooled to provide the formed articles.
• the temperature during extrusion can be 20 to 100 ° C higher than the melting point of the material, preferably 30 to 80 ° C higher than this melting point.
• the product can be selected from automotive parts, textiles, woven or non-woven fabrics, clothing, footwear, sporting goods, leisure items, electronic objects, computer equipment, health equipment, industrial additives, packaging and household products.
• the inventors have surprisingly found that the low degradation effect of the polymer obtained according to the invention is preserved even when the initial extrusion is followed by a second extrusion and injection, even though the second extrusion is not carried out in presence of water.
• Example 1 miscibility of an amide block copolymer (PEBA) with water
• a PEBA based on polyamide 12 marketed by Arkema France under the trade name Pebax®, is used. Its molar composition is 24.8% polytetramethylene ether glycol, 73% polyamide 12 and 2.2% adipic acid as a connecting element.
• a low pressure differential scanning calorimeter (Mettler Toledo HPDSC 827 e , 100 bar maximum pressure) is used to study the phase separation or miscibility of PEBA and water at elevated pressure and high temperature.
• the measuring chamber is connected to a pressure control valve (Brooks PC 5866) controlled by a Brooks valve controller (ReadOut & Control Electronics 0152).
• the temperature and the pressure are independently set in the calorimeter furnace and constant pressure heating or cooling curves can be obtained, which makes it possible to simulate the extrusion conditions.
• Water and PEBA powder are mixed with a mass ratio of 70:30, the total sample weighing about 10 mg.
• the PEBA granules are cryocrushed in a mill (Pulverisette 14, Fritsch) at 14,000 rpm.
• the first (main) peak is just above 100 ° C and corresponds to the evaporation of water.
• the second is located at 171 ° C and corresponds to the melting of the polymer.
• the melting temperature is identical to that of pure PEBA since the water has evaporated before.
• the cooling curve is similar, with a single crystallization peak of the polymer at 146 ° C.
• Example 1 The PEBA of Example 1 is introduced into a co-rotating twin-screw extruder (Coperion Megacompounder, 1 m in length, L / D ratio of 40, screw diameter 25 mm) equipped with an injection pump. water and two degassing openings. The melting pressure imposed by the screws (70 to 100 bar) at the water injection point is higher than the water vapor pressure curve.
• a co-rotating twin-screw extruder Coperion Megacompounder, 1 m in length, L / D ratio of 40, screw diameter 25 mm
• the melting pressure imposed by the screws (70 to 100 bar) at the water injection point is higher than the water vapor pressure curve.
• the temperature is set at 190 ° C throughout the screw (with an actual temperature of 20 ° C below the water injection point) and the rotational speed is 200 rpm.
• the polymer is introduced at a flow rate of 7 kg / h and the water at a flow rate of 3 L / h.
• dumbbells ISO 527-2 (type 1A) was performed on Kraus Maffei 80-160 e .
• the injection temperatures were set from 190 ° C (feed zone) to 230 ° C (nozzle), with a mold temperature of 20 ° C, a back pressure of 75 bar, a rotational speed of screw of 80 mm / s and a holding pressure of 400 bar for 29 s.
• the molecular weight of the materials is evaluated by exclusion-diffusion chromatography (GPC, Waters Alliance 2695) using hexafluoroisopropanol as a solvent at 40 ° C. Samples are dissolved for 24 hours at a concentration of 1 g / L. A UV refractometer detector set at 228 nm is used and a calibration is carried out with polymethyl methacrylate references. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are thus given in "PMMA equivalents".

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