Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
  • C08G69/10—Alpha-amino-carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/04—Preparatory processes
• • 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
  • B29C48/25—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
• • 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
  • B29C48/36—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
  • 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
• • 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
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
  • C08G69/14—Lactams
  • C08G69/16—Preparatory processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/28—Preparatory processes
• • 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
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
  • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
  • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
• • 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
  • B29K2105/0002—Condition, form or state of moulded material or of the material to be shaped monomers or prepolymers
• • 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
  • B29K2105/0058—Liquid or visquous
• • 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
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/04—Polyamides derived from alpha-amino carboxylic acids

Definitions

• This patent application relates to a process for the continuous preparation of formulated polyamide prepolymers, by polycondensation, as well as the extruders suitable for implementing such a process.
• Polyamides are conventionally prepared by polycondensation of a diamine with a dicarboxylic acid, or of an amino acid, or even of a lactam, in a reactor by a batch process (discontinuous) in which the monomer or monomers are introduced and heated under pressure until a mixture of sufficient viscosity is obtained.
• the monomers are frequently introduced in aqueous solution and the water present and/or formed during the polycondensation must be eliminated by placing the reactor under reduced pressure.
• the molar mass of polyamide is difficult to control/master due to its “living” character because when emptying the reactor, the product may not have the same molar mass (the same viscosity) at the beginning and at the end. draining the reactor.
• the batch process is a more capital-intensive process (for a quantity of product produced annually) and less ecological (more energy and water consumption, more production of gaseous effluent and waste, etc.).
• patent EP2877516 describes a process for the continuous synthesis of polyamide with a weight-average molecular mass (Mw) greater than or equal to 14,000 g/mol. This process requires at least two water evacuation operations and leads not to prepolymers but to polymers.
• Mw weight-average molecular mass
• Patent US8765902 describes a process for the continuous preparation of 6T/6L copolyamide. This process requires the evaporation of water and leads not to prepolymers but to polymers.
• Patent EP 0410650 describes a process for the continuous preparation of prepolymers by polycondensation of diamines and dicarboxylic acids. This process requires the evaporation of water.
• the formulation of the batch obtained requires an additional step which consists in compounding the product obtained by batch with one or more additives.
• one of the objectives of the present invention is to provide a process for preparing formulated polyamide prepolymers which is simpler, faster, reliable and less expensive than the processes of the prior art and in a single step.
• the present invention therefore relates to a process for the continuous preparation of a formulated polyamide prepolymer whose solution viscosity is between 0.25 dl/g and 0.70 dl/g, as measured according to ISO 307:2007 in the m-cresol at 20°C, characterized in that it comprises a step of polycondensation starting from one or more polyamide precursor monomers, the said polycondensation step being carried out in a single extruder comprising at least two conveying screws rotating in a co-rotating manner, said monomer(s) being introduced beforehand in solid or liquid form without dissolving in a solvent or in water, and said polycondensation stage being carried out without extraction of the by-products formed, in particular of the water formed during said polycondensation, and comprising introducing at least one additive during said polycondensation step into the extruder.
• the inventors have therefore found that a compromise between the residence time of the material in the extruder with the reaction temperature in the extruder could be found without requiring the evacuation of the water, in particular by placing under vacuum. of the extruder, to prepare a prepolymer of the required viscosity and that at the same time, this prepolymer could also be formulated during the polycondensation step in the extruder to lead to the formulated prepolymer.
• the formed product can also be characterized online, which allows feedback to modify the process parameters to guarantee good control of the finished product.
• prepolymer has the same meaning as the term oligomer.
• the term prepolymer denotes a polyamide having a number-average molecular mass Mn of less than 10,000 g/mol, in particular comprised from 1,000 to 9,000, in particular from 1,500 to 7,000, more particularly from 2,000 to 5,000 g/mol.
• the Mn is determined in particular by calculation from the rate of the terminal functions determined by potentiometric titration in solution and the functionality of said prepolymers or by NMR assay (Postma et al. (Polymer, 47, 1899-1911 (2006)).
• each step is a condensation reaction which is carried out with elimination of small molecules, called reaction by-products, such as H2O, depending on the monomers involved.
• the extruder does not have any degassing devices, in particular by introducing an inert gas therein, or any device for removing the polycondensation by-product(s) formed, and in particular the water formed, consisting of an outlet on the outside at atmospheric pressure, or an outlet connected to a device making it possible to create a depression zone in the extruder, such as a vacuum pump during the reaction.
• the extruder is nevertheless equipped with a device for restoring atmospheric pressure after completion of the reaction and therefore after the screws.
• the extruder used includes two feed screws
• the method for preparing a polyamide according to the invention comprises the following successive steps, all carried out within the extruder: a step of mixing the selected monomer(s), and a step of polycondensation carried out by carrying out shearing operations on the material conveyed by the conveying screws.
• a step is also carried out for forming a plug or seal of material that is renewed continuously by conveying the material on the conveying screws, between the mixing and polycondensation stages.
• the stopper or gasket consisting of the advancing material fills the entire volume available for the passage of the material and constitutes a zone which is hermetic to vapours, and in particular to monomer vapors which may be generated.
• each conveying screw is made up of different elements which follow one another according to the conveying direction. These different elements are placed next to each other on a rotating shaft.
• the polyamide precursor monomers are introduced beforehand in solid or liquid form depending on their natural appearance but are in no case dissolved in any solvent or in water.
• the monomers are introduced, without prior reaction and without prior preparation of the corresponding salt.
• the polyamide can be any polyamide, whether it is an aliphatic, cyclo-aliphatic, aromatic or semi-aromatic polyamide.
• It can be homopolyamide or copolyamide.
• said polyamide is a homopolyamide.
• Said aromatic polyamide is in particular obtained from the polycondensation of an arylamine which can be chosen from meta-xylylene diamine (MXD, CAS No.: 1477-55-0) or para-xylylene diamine (PXD, CAS No. : 539-48-0), with an aromatic dicarboxylic acid, in particular chosen from a terephthalic acid, an isophthalic acid and a naphthalenic acid.
• MXD meta-xylylene diamine
• PXD para-xylylene diamine
• Said semi-aromatic polyamide, optionally modified with urea units may in particular be a semi-aromatic polyamide of formula X/YAr, as described in EP1505099, in particular a semi-aromatic polyamide of formula A/XT in which A is chosen from a unit obtained from a monomeric amino acid), a unit obtained from a lactam (monomer) and a unit corresponding to the formula (Ca diamine).
• (Cb diacid) all deus representing the monomers, with a representing the number of carbon atoms of the diamine and b representing the number of carbon atoms of the diacid, a and b each being between 4 and 36, advantageously between 9 and 18, the unit (diamine in Ca) being chosen from aliphatic diamines, linear or branched, cycloaliphatic diamines and alkylaromatic diamines and the unit (diacid in Cb) being chosen from aliphatic diacids, linear or branched, the cycloaliphatic diacids and aromatic diacids;
• XT denotes a unit obtained from the polycondensation of a Cx diamine and terephthalic acid, with x representing the number of carbon atoms of the Cx diamine, x being between 6 and 36, advantageously between 9 and 18, in particular a polyamide of formula A/6T, A/9T, A/10T or A/11T, A being as defined above,
• T stands for terephthalic acid
• MXD stands for m-xylylene diamine
• MPMD stands for methylpentamethylene diamine
• BAC stands for bis(aminomethyl)cyclohexane.
• Said cycloaliphatic polyamide is in particular obtained by polycondensation of the following monomers: a cycloaliphatic diamine with an aliphatic dicarboxylic acid or an aliphatic diamine with a cycloaliphatic dicarboxylic acid or a cycloaliphatic diamine with a cycloaliphatic dicarboxylic acid.
• the cycloaliphatic diamine can be chosen, for example, from bis(3,5-dialkyl-4-aminocyclohexyl)-methane, bis(3,5-dialkyl-4-aminocyclohexyl)ethane, bis(3,5-dialkyl-4 -aminocyclohexyl)-propane, bis(3,5-dialkyl-4-aminocyclo-hexyl)-butane, bis-(3-methyl-4-aminocyclohexyl)-methane or 3'-dimethyl-4,4'-diamino -dicyclohexyl-methane commonly referred to as "BMACM” or "MACM” (and denoted B below), p-bis(aminocyclohexyl)-methane commonly referred to as "PACM” (and denoted P below), isopropylidenedi(cyclohexylamine ) commonly called "PACP", iso
• the cycloaliphatic dicarboxylic acid may comprise the following carbon skeletons: norbornyl methane, cyclohexane, cyclohexylmethane, dicyclohexylmethane, dicyclohexylpropane, di(methylcyclohexyl) or di(methylcyclo-hexyl)propane.
• the aliphatic diamine and the aliphatic dicarboxylic acid are as for the aliphatic polyamide described below.
• Said aliphatic polyamide may be derived from the polycondensation of one or more monomer(s) which is (are) at least one C6 to C18 amino carboxylic acid, in particular C6 to C12, more particularly CIO to C12, in particular 11-aminoundecanoic acid.
• Said aliphatic polyamide may result from the polycondensation of one or more monomer(s) which is (are) at least one C6 to C18 lactam, in particular C6 to C12, more particularly C10 to C12, in particular laurylactam.
• Said aliphatic polyamide may result from the polycondensation of one or more monomer(s) which is (are) at least one C6 to C18 aliphatic diamine, in particular C6 to C12, more particularly CIO to C12, and at least an aliphatic dicarboxylic acid C6 to C18, in particular C6 to C12, more particularly C10 to C12.
• the aliphatic diamine used is an aliphatic diamine which has a linear main chain comprising at least 6 carbon atoms.
• This linear main chain may, where appropriate, comprise one or more methyl and/or ethyl substituents; in this last configuration, one speaks of "branched aliphatic diamine". In the case where the main chain has no substituent, the aliphatic diamine is called “linear aliphatic diamine”.
• this diamine is a linear aliphatic diamine, it then corresponds to the formula H2N- (CH2)x-NH2 and can be chosen for example from hexanediamine, heptanediamine, octanediamine, nonane-diamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, hexadecanediamine and octadecanediamine.
• the linear aliphatic diamines which have just been mentioned can all be bioresourced within the meaning of standard ASTM D6866.
• this diamine is a branched aliphatic diamine, it may in particular be 2-methylpentanediamine, 2-methyl-1,8-octanediamine or trimethylene (2,2,4 or 2,4,4) hexanediamine.
• the dicarboxylic acid can be chosen from aliphatic, linear or branched dicarboxylic acids.
• the diamine is a linear aliphatic diamine
• the dicarboxylic acid is aliphatic and linear, it can be chosen from adipic acid (6), heptanedioic acid (7), octanedioic acid (8), azelaic acid (9), sebacic acid (10), undecanedioic acid (11), dodecanedioic acid (12), brassylic acid (13), tetradecanedioic acid (14), hexadecanedioic acid (16), octadecanedioic acid ( 18), octadecenedioic acid (18).
• adipic acid (6) heptanedioic acid (7), octanedioic acid (8), azelaic acid (9), sebacic acid (10), undecanedioic acid (11), dodecanedioic acid (12), brassylic acid (13), tetradecanedioic acid (14), hexade
• the polyamide is a semi-aromatic, cyclo-aliphatic or semi-aromatic polyamide. More advantageously, said polyamide is semi-aromatic or aliphatic, in particular said polyamide is aliphatic.
• the polyamide is aliphatic and obtained from a single aminocarboxylic acid or a single lactam, in particular it is obtained from 11-aminoundecanoic acid or lauryllactam, in particular it is obtained from the acid 11-aminoundecanoic.
• Said at least one additive is chosen from catalysts, fillers, colorants, stabilizers, in particular light stabilizers, in particular UV and/or heat stabilizers, plasticizers, surfactants, nucleating agents, pigments, brighteners, antioxidants, lubricants, flame retardants, natural waxes and mixtures thereof.
• the pigment can in principle be freely chosen from the pigments used in the conventional manner. It can in particular be chosen from mineral pigments such as titanium dioxide, carbon black, cobalt oxide, nickel titanate, molybdenum disulphide, aluminum flakes, iron oxides, zinc, zinc phosphate, and organic pigments, such as phthalocyanine and anthraquinone derivatives.
• mineral pigments such as titanium dioxide, carbon black, cobalt oxide, nickel titanate, molybdenum disulphide, aluminum flakes, iron oxides, zinc, zinc phosphate, and organic pigments, such as phthalocyanine and anthraquinone derivatives.
• the dye can also be of any type known to those skilled in the art. Mention may be made in particular of azo dyes, anthraquinone dyes, dyes derived from indigo, triarylmethane dyes, chlorine dyes and polymethine dyes.
• the anti-crater and/or spreading agent can be of any type known to those skilled in the art.
• the anticrater and/or spreading agent is selected from the group consisting of polyacrylate derivatives.
• the UV stabilizer may be of any type known to those skilled in the art.
• the UV stabilizer is selected from the group consisting of resorcinol derivatives, benzotriazoles, phenyltriazines and salicylates.
• the antioxidants can be of any type known to those skilled in the art.
• the antioxidants are selected from the group consisting of copper iodide combined with potassium iodide, phenol derivatives and hindered amines.
• the fluidizing agent may be of any type known to those skilled in the art.
• the fluidizing agent is selected from the group consisting of aluminas and silicas.
• the corrosion inhibitors can be of any type known to those skilled in the art.
• the corrosion inhibitors are selected from the group consisting of phosphosilicates and borosilicates.
• catalyst denotes a polycondensation catalyst such as an inorganic or organic acid.
• the catalyst is chosen from phosphoric acid (H3PO4), phosphorous acid (H3PO3), hypophosphorous acid (H3PO2), or one of its salts such as sodium hypophosphite, which is marketed under its monohydrate form or another of its salts such as the calcium, lithium, magnesium, potassium, vanadium, zinc, manganese, tin, titanium, zirconium, antimony, germanium, aluminum and ammonium salts, or a mixture thereof.
• H3PO4 phosphoric acid
• H3PO3PO3 phosphorous acid
• hypophosphorous acid H3PO2
• one of its salts such as sodium hypophosphite, which is marketed under its monohydrate form or another of its salts such as the calcium, lithium, magnesium, potassium, vanadium, zinc, manganese, tin, titanium, zirconium, antimony, germanium, aluminum and ammonium salts, or a mixture thereof.
• At least one additive is introduced into the extruder and its proportion introduced depends on the type of additives.
• the additives are preferably present in a mass quantity, relative to the total sum of the weights of the monomers and the additives introduced, of 1 to 30%, more preferably of 2 to 10%, even more preferably of 3 to 5%, per example from 0 to 5%, or from 5 to 10%, or from 10 to 15%, or from 15 to 20%, or from 20 to 25%, or from 25 to 30%.
• the proportion by weight of catalyst is between about 50 ppm to about 20,000 ppm, in particular from about 100 to about 10,000 ppm, more particularly from 1,000 to 10,000 ppm with respect to the total sum the weights of the monomers and of the additives introduced.
• the proportion by weight of catalyst is between about 50 ppm to about 20,000 ppm, in particular from about 100 to about 10,000 ppm, more particularly from 1,000 to 10,000 ppm with respect to the total sum the weights of the monomers and of the additives introduced.
• the average degree of polymerization (DPn) of the polyamide obtained according to the process of the invention is less than 50, in particular less than or equal to 45, in particular comprised from 5 to 45.
• the average degree of polymerization (DPn) of the polyamide obtained according to the process of the invention is comprised from 8 to 40, in particular from 12 to 30.
• average degree of polymerization is meant the average number of structural units present in a polymer chain.
• the average degree of polymerization (DPn) is typically evaluated from the number-average molar mass (Mn) of the polyamide according to the following formula:
• the weight-average molecular mass (Mn) of the polyamide obtained according to the process of the invention is less than 10000 g/mol, in particular comprised from 1000 to 9000, in particular from 1500 to 7000, more particularly from 2000 to 5000 g /mol.
• the weight average molecular weight can be determined by size exclusion chromatography.
• said extruder includes two to twelve co-rotating feed screws.
• said extruder is a twin-screw extruder comprising two conveying screws rotating in a co-rotating manner.
• said process is carried out at a temperature of 220 to 340°C, preferably of 260 to 300°C.
• the residence time of the material in the extruder at the temperature between 220 and 340° C. makes it possible to carry out the polycondensation reaction to achieve the desired average degree of polymerization.
• the desired degree of polymerization is comprised from 8 to 40, in particular from 12 to 30.
• the residence time of the material in the extruder at the temperature comprised from 220 to 340 ° C allows the polycondensation reaction to be carried out to achieve the desired viscosity between 0.25 and 0.7 dl/g.
• said extruder is an extruder comprising annular multi-screw comprising at least 6 conveying screws, in particular 12 conveying screws, rotating in a co-rotating manner.
• the residence time of the material in the extruder at the temperature between 220 and 340° C. makes it possible to carry out the polycondensation reaction to achieve the desired average degree of polymerization.
• the desired degree of polymerization is comprised from 8 to 40, in particular from 12 to 30.
• the residence time of the material in the extruder at the temperature comprised from 220 to 340 ° C allows the polycondensation reaction to be carried out to achieve the desired viscosity between 0.25 and 0.7 dl/g.
• the residence time of the material in the extruder of the first or second variant is greater than or equal to 1 minute, and in particular comprised from 1 to 10 minutes, in particular comprised from 2 to 6 minutes.
• the throughput of the extruder is greater than or equal to 10 kg/h, in particular greater than or equal to 15 kg/h, in particular greater than or equal to 30 kg/h. h, more particularly greater than or equal to 50 kg/h.
• the extruder used with a flow rate greater than or equal to 10 kg/h, in particular greater than or equal to 15 kg/h, in particular greater than or equal to 30 kg/h, more particularly greater than or equal to 50 kg/h is an extruder comprising six twelve co-rotating conveying screws, in particular twelve co-rotating conveying screws.
• the length of the extruder comprising six to twelve co-rotating conveying screws, in particular twelve co-rotating conveying screws with the flow rate described above is greater than or equal to 30L/ D, in particular from 30 to 100L/D.
• At least one additive is added during the polycondensation in the extruder.
• the introduction of said at least one additive can be done in the zone for introducing the monomer(s), or in a subsequent working zone, or even in two places, for example, in the zone for introducing the monomer(s), then in a later work area.
• each additive introduced can be introduced according to the methods defined above.
• an online analysis is carried out during said method.
• the online analysis characterizes a product obtained that does not have the required characteristics and in particular the desired degree of polymerization
• the operating parameters of the process in particular the pair of residence time and temperature of the extruder, are modified to make it possible to obtain a product having the required characteristics and in particular the desired degree of polymerization.
• said at least one additive is added to said single extruder in the main hopper.
• said at least one additive is chosen from catalysts, fillers, colorants, stabilizers.
• said at least one additive is added in said single extruder after the main hopper.
• said at least one additive is chosen from phosphoric acid and phosphorous acid.
• At least one additive is added to said single extruder in the main hopper and at least one additive is added to said single extruder after the main hopper.
• said at least one additive added in the main hopper is chosen from catalysts, fillers, dyes, stabilizers and said additive added after the main hopper is chosen from phosphoric acid and phosphorous acid.
• the present invention relates to the formulated product capable of being obtained by the process as defined above.
• the formulated product therefore corresponds to the formulated polyamide prepolymer obtained by the process defined above.
• the present invention relates to an extruder suitable for implementing the method as defined above.
• a PAU prepolymer formulated with H3PO2 was prepared in two stages: a first stage by batch process for the preparation of the prepolymer: In a 14-litre autoclave reactor, 5 kg of the following raw materials are introduced: 500 g of water, the diamine and the dicarboxylic acid and/or the amino acid, 0.1 g of a WACKER AK1000 defoamer (from Wacker Silicones).
• the closed reactor is purged of its residual oxygen then heated to a material temperature of 230° C. After 30 minutes of stirring under these conditions, the steam under pressure which has formed in the reactor is gradually expanded over 60 minutes, while gradually adjusting the material temperature so that it settles at Tf + 10 °C at atmospheric pressure.
• the oligomer (prepolymer) is then drained through the bottom valve then cooled in a tank of water then ground.
• aqueous solution 5300 ppm in H3PO4
• Examples 2 and 3 show that a formulated PAU can be obtained in a single step by the process of the invention continuously with the required viscosity characteristics.
• the formulated products obtained by the process of the invention are comparable to those obtained by the batch process as regards several points such as the viscosity in solution, the grindability, the shaping and the mechanical properties of the product. obtained.

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• Mechanical Engineering (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyamides (AREA)

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• 2020
  • 2020-11-12 FR FR2011600A patent/FR3116058B1/fr active Active
• 2021
  • 2021-11-10 EP EP21820662.1A patent/EP4244289A1/de active Pending
  • 2021-11-10 CN CN202180076149.6A patent/CN116547126A/zh active Pending
  • 2021-11-10 JP JP2023527661A patent/JP2023548885A/ja active Pending
  • 2021-11-10 WO PCT/FR2021/051987 patent/WO2022101580A1/fr active Application Filing
  • 2021-11-10 US US18/251,790 patent/US20230407006A1/en active Pending
  • 2021-11-10 KR KR1020237019299A patent/KR20230104924A/ko unknown

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