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
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • 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
• • 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
• • 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
  • 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
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic 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
  • 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
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
• • 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
  • C08G63/78—Preparation processes
  • C08G63/80—Solid-state polycondensation
• • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks

Definitions

• composition based on polyamide and / or polyester matrix and articles produced from this composition
• the present invention relates to a thermoplastic composition
• a thermoplastic composition comprising a polyamide and / or polyester matrix and various additives.
• Said composition has a high fluidity thus making suitable the use of different forming techniques in the molten state such as for example molding, injection molding, extrusion and spinning.
• the composition obtained according to the invention allows in particular the manufacture of molded plastic articles having good mechanical properties and an improved surface appearance.
• Thermoplastic compositions are raw materials capable of being transformed by molding, injection molding, extrusion, or spinning, in particular into articles of multiple shapes, such as plastic parts, threads or fibers.
• thermoplastic compositions there are at least three major properties which it is desired to obtain for these thermoplastic compositions, in particular when they are used in these transformation processes.
• the first of these properties lies in the fact that these thermoplastic compositions used must be characterized, in the molten state, by a fluidity or a rheological behavior compatible with the forming processes mentioned above. Indeed, these thermoplastic compositions must be sufficiently fluid when they are molten, to be able to be transported and handled easily and quickly in certain shaping devices, such as for example injection molding.
• thermoplastic polymer compositions It is also sought to increase the mechanical properties of the thermoplastic polymer compositions. These mechanical properties are in particular impact resistance, the modulus in bending or in traction, the breaking stress in bending or in traction, among others. Reinforcement fillers, such as glass fibers, are generally used for this purpose.
• Reinforcement fillers such as glass fibers
• a clean and uniform surface appearance is sought. This constraint becomes a problem which is difficult to solve, particularly when a thermoplastic composition heavily loaded with glass fibers is used, these glass fibers negatively altering the surface appearance of the molded parts.
• thermoplastic compositions having a high fluidity To obtain an acceptable surface appearance, it is known to use thermoplastic compositions having a high fluidity. However, it results from this increase in fluidity a decrease in the mechanical properties of the articles obtained. As a result, it is difficult to obtain these different properties for the same thermoplastic composition.
• the present invention relates to thermoplastic compositions obtained by mixing a thermoplastic matrix with at least one mono- or multifunctional acid or amino compound and additives, in particular additives of the functionalized branched polyamide type.
• thermoplastic composition according to the invention has a high fluidity in the molten state.
• This composition is thus adapted to the various forming techniques in the molten state, such as for example molding, injection molding, extrusion and spinning.
• This thermoplastic composition has the rheological, molten, and mechanical qualities required in the processing industry for these polymers, without the additivation carried out to improve these properties disturbing the other properties of the polymer.
• the compositions according to the invention allow the manufacture of articles having good mechanical properties.
• the molded articles obtained from the compositions according to the invention also have an improved surface appearance.
• the molded articles obtained from the compositions according to the invention exhibit good resistance to mechanical properties following thermal aging.
• the present invention relates to a thermoplastic composition obtained by mixing a polyamide and or polyester matrix with at least: (i) a first additive of formula RZ u , in which:
• R represents a hydrocarbon radical which may comprise one or more heteroatoms, u is an integer greater than or equal to 1, preferably between 1 and 50, more preferably between 2 and 10, particularly between 2 and 5; Z is an acid, amino or alcohol function, and (ii) a second additive chosen from the group consisting of:
• composition according to the invention can comprise one or more types of additives (i) and (ii).
• the composition according to the invention can be a mixture of the various compounds, for example in the form of granules, powder and or liquid.
• the composition can also result from a melt blend of the various additives with the polyamide and / or polyester matrix.
• the composition may comprise from 0.01 to 5% by weight of the first additive (i) relative to the total weight of the composition, preferably from 0.1 to 2%, more preferably from 0.2 to 1%.
• composition according to the invention can comprise from 0.01 to 20% by weight of the second additive (ii) relative to the total weight of the composition, preferably from 0.3 to 10%, more preferably from 0.5 to 5% .
• the first additive (i) has acid, amino or alcohol endings and can react, partially or completely with the polyamide or polyester matrix. We can also find in the thermoplastic composition, the first additive (i) as such, that is to say not covalently bonded to the polyamide and / or polyester matrix.
• R represents a linear or branched, saturated or unsaturated, aliphatic, cyclic and / or aromatic hydrocarbon radical, which may optionally include one or more heteroatoms, the radical R more preferably comprising from 2 to 100, even more preferably from 5 to 20 atoms of carbon. It can include one or more heteroatoms chosen from the group comprising: nitrogen, phosphorus, fluorine, oxygen, silicon and sulfur.
• the radical R does not include an amino, acid or alcohol function capable of forming an amide and / or ester bond.
• a function which does not form an amide and / or ester bond mention may be made of the sulfonate, phosphonate, halogen and tertiary amine functions.
• an additive (i) mention may be made of 2,2,6,6-tetra- ( ⁇ - carboxyethyl) cyclohexanone, diaminopropane - NNN'.N 'tetraacetic acid of the following formula:
• nitrilotrialkylamines in particular nitrilotriethylamine
• dialkylenetriamines in particular diethylenetriamine, trialkylenetetramines and tetraakylenepentamines, the alkylene preferably being ethylene, 4-aminoethyl-1, 8, octanediamine.
• compounds having an aromatic and / or heterocyclic ring for example benzyl, naphthyl, anthracenyl, biphenyl and triphenyl radicals.
• heterocycles such as pyridine, bipyridine, pyrrole, indole, furan, thiophene, purine, quinoline, phenanthrene, porphyrin, phthalocyanine and naphthalocyanine.
• 3,5,3 ', 5'-biphenyltetracarboxylic acid acids derived from phthalocyanine and naphthalocyanine, acid 1, 3,5,7-naphthalene tetracarboxylic acid, acid 2,4, 6-pyridinetricarboxylic acid, 3,5,3 ', 5'- bipyridyltetracarboxylic acid 3,5,3', 5'-benzophenonetetracarboxylic acid 1, 3,6,8-acridinetetracarboxylic acid, more particularly still trimesic acid and 1,2,4,5-benzenetetracarboxylic acid.
• multifunctional compounds whose core is a heterocycle presenting a point of symmetry such as 1, 3,5-triazines, 1, 4-diazines, melamine, compounds derived from 2,3,5,6 -tetraethylpiperazine, 1, 4-piperazines, tetrathiafulvalenes. Mention is more particularly made of 2,4,6-triaminocaproic acid-1,3,5-triazine (TACT).
• TACT 2,4,6-triaminocaproic acid-1,3,5-triazine
• additive (i) comprising one or more alcohol functions. Mention may be made, for example, of glycol, trymethylolpropane, glycerol, pentaerythritol, sorbitol, mannitol, the various oses, such as sucrose, polysaccharides, and / or their mixtures.
• the first additive (i) is preferably chosen from the group comprising: isophthalic acid, terephthalic acid, adipic acid, trimesic acid, 2,2,6,6 - tetrakis ( ⁇ - carboxyethyl) cyclohexanone, diaminopropane - N, N, N ', N' tetraacetic acid, nitrilotrialkylamines, trialkylenetetramines and tetraaikylenepentamines, 4-aminoethyl- 1, 8, octanediamine, acid 3,5,3 ', 5 '-biphenyltetracarboxylic, acids derived from phthalocyanine and naphthalocyanine, acid 1, 3,5,7- naphthalene tetracarboxylic, 2,4,6-pyridinetricarboxylic acid, acid 3, 5,3', 5 '- bipyridyltetracarboxylic acid
• the second additive (ii) is an additive obtained by the reaction between different compounds and monomers comprising the radicals R 1 , R 2 , R 3 and / or R 4 , as mentioned previously.
• the radicals R 1 , R 2 , R 3 and / or R 4 of the second additive (ii) represent, independently of one another, a linear or branched, saturated or unsaturated, aliphatic, cyclic and / or aromatic hydrocarbon radical , possibly comprising one or more heteroatoms. These radicals preferably comprise from 2 to 100, more preferably from 5 to 30 carbon atoms. It can include one or more heteroatoms chosen from the group comprising: nitrogen, phosphorus, fluorine, oxygen, silicon and sulfur. As mentioned previously, the radicals R 1 , R 2 , R 3 and or R 4 do not comprise an amine, acid and / or alcohol function capable of forming an amide and / or ester bond.
• a function which does not form an amide and / or ester bond mention may be made of the sulfonate, phosphonate, halogen and tertiary amine functions.
• Only the X and Y functions of the various compounds and monomers forming the additive (ii) are antagonistic reactive functions capable of reacting with one another to form an amide bond.
• Y is an amine function when X represents an acid function
• Y is an acid function when X represents an amine function.
• acid function is meant within the meaning of the invention, any carboxylic acid function or derivative, in particular of the ester or anhydride type.
• the acid and / or amino terminations of said additive (ii) are, completely or in part, linked to R 3 groups not comprising an acid or amine function capable of forming a covalent amide bond.
• at least 50% by number of terminations of the second additive (ii) comprise groups R 3 , which are identical or different.
• the content of terminal groups, acid and amine, of the additive (ii) is between 0 and 300 meq / kg. More preferably, this content is between 0 and 150 meq / kg, particularly between 0 and 100 meq / kg, very particularly between 0 and 50 meq / kg.
• the content of acid and or amine end groups can be determined by potentiometry.
• the molecular weight of the second additive (ii) (A) can be between 500 and 20,000 g / mol.
• the molecular weight of the additive (ii) (A) is between 1000 and 10,000 g / mol, particularly between 1000 and 5000 g / mol.
• the molecular weight of the second additive (ii) (B) can be between 500 and 50,000 g / mol.
• the molecular weight of the additive (ii) (B) is between 1000 and 30,000 g / mol, particularly between 3000 and 15000 g / mol.
• the additives (ii) (A) and or (B) can be obtained by the reaction between compounds comprising bifunctional monomers (II) of formula XR 2 -Y or their corresponding cyclic form.
• the additives (ii) (A) and / or (B) are polyamides. These are branched polyamides insofar as they comprise units derived from multifunctional compounds (I) and / or (IV) of branches. These branched polyamides are functionalized because they comprise monofunctional compounds of formula R 3 -Y.
• the additive (ii) (A) is preferably a functionalized star polyamide obtained by the reaction of at least: a multifunctional compound of formula (I), a bifunctional monomer of formula (II) or the corresponding cyclic form, and a compound monofunctional of formula (III).
• the additive (ii) (B) is preferably a functionalized hyperbranched polyamide obtained by the reaction of at least: optionally a multifunctional compound of formula (I), a bifunctional monomer of formula (II) or the corresponding cyclic form, a compound monofunctional of formula (III), and a branching compound of formula (IV).
• the multifunctional compound of formula (I) may correspond to the additive (i) of formula RZ u , as defined above.
• the multifunctional compound of formula (I) is preferably chosen from the group comprising: 2,2,6,6-tetrakis- ( ⁇ -carboxyethyl) cyclohexanone, diaminopropane - N, N, N ', N' tetraacetic acid, nitrilotrialkylamines, trialkylenetetramines and tetraakylenepentamines, 4-aminoethyl- 1,8, octanediamine, 3,5,3 ', 5'-biphenyltetracarboxylic acid, acids phthalocyanine and naphthalocyanine derivatives, 1, 3,5,7- naphthalenetetracarboxylic acid, 2,4,6-pyridinetricarboxylic acid, 3,5,3 ', 5'- bipyridyltetracarboxylic acid, 3,5,3 ', 5'-benzophenonetetracarboxylic acid, 1,3,6,8-acrid
• the bifunctional monomer of formula (II) is preferably chosen from the group comprising: ⁇ -caprolactam and / or the corresponding amino acid: aminocaproic acid, para or metaaminobenzoic acid, amino-11- undecanoic acid, lauryllactam and / or the corresponding amino acid, amino-12-dodecanoic acid, caprolactone, 6-hydroxy hexanoic acid, their oligomers and their mixtures. These oligomers can have a degree of polymerization of between 2 and 15.
• the monofunctional compound of general formula (III) can be chosen from the group comprising: an aliphatic mono-acid or mono-amine compound, an aromatic mono-amine or mono compound -acid, a mono-amino or mono-carboxylic organophosphorus compound, a mono-amino or mono-carboxylic organosulfonated compound, a mono-amino or mono-carboxylic acid quaternary ammonium compound and / or mixtures thereof.
• the monofunctional compound of general formula (III) is an aliphatic linear chain of alkyl type comprising an amine function or an acid function.
• the monofunctional compound of general formula (III) is chosen from the group comprising: n-hexadecylamine, n-octadecylamine, n-dodecylamine, benzylamine, amino methyl phosphonic acid, sulfanilic acid , sulfobenzoic acid, betaine, and / or mixtures thereof.
• the branching compound of formula (IV) is chosen from the group comprising: 5-amino-isophthalic acid, 6-amino-undecandioic acid, 3-aminopimelic diacid, aspartic acid, acid 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, lysine, and / or mixtures thereof.
• the additives (ii) can for example bring the different compounds of the additives (ii) into contact and carry out a polycondensation.
• the various compounds can be added in a single step or in several steps during the polycondensation.
• one or more compounds of formula (I), (II), (III) and / or (IV) of different types can be mixed during the reaction.
• the additive (ii) (A) can be obtained by the reaction between a multifunctional compound of formula (I) in proportions of between 1 and 30% by weight, a monofunctional compound of formula (III) in proportions of between 5 at 60% by weight, and optionally a bifunctional monomer of formula (II) in proportions of between 0 and 95% by weight.
• the additive (A) is obtained by the reaction between a multifunctional compound of formula (I) in proportions of between 2 and 20% by weight, a bifunctional monomer of formula (II) in proportions of between 30 and 90 % by weight, and a monofunctional compound of formula (III) in proportions of between 10 to 50% by weight.
• the additive (B) can be obtained by the reaction between a monofunctional compound of formula (III) in proportions of between 20 to 70% by weight, a branching compound of formula (IV) in proportions of between 10 to 50 % by weight, optionally a multifunctional compound of formula (I) in proportions of between 0 to 10% by weight and optionally a bifunctional monomer of formula (II) in proportions of between 0 to 50% by weight.
• the additive (B) can be obtained by the reaction between a monofunctional compound of formula (III) in proportions of between 30 to 60% by weight, a branching compound of formula (IV) in proportions of between 20 at 40% by weight, a multifunctional compound of formula (I) in proportions of between 1 to 5% by by weight and a bifunctional monomer of formula (II) in proportions of between 10 to 30% by weight
• the percentage sum of the various compounds must be equal to 100%.
• the addition of additives (ii) mixed with the polymer matrix results in a reduction in the molar mass of less than 15% of said matrix, compared with the same matrix not comprising additives (ii); the molar mass measurement being carried out according to a determined P protocol.
• the details of the protocol P for measuring the molar mass are given below.
• the additive (ii) therefore advantageously has the characteristic of being able to modify the rheological behavior of the polymer matrix, without affecting its structural integrity, and in particular without significantly reducing its molar mass.
• the molar mass is defined as the maximum of the distribution of the molar masses of the polymer matrix added with the branched polyamide, in Polystyrene equivalent, by chromatography by
• the molar mass measurement is carried out on the composition to be analyzed and on the control composition (not comprising any additive (ii)), extruded, solidified and then optionally put in the form of granules.
• the abovementioned protocol P for measuring the molar mass of the polymer matrix, in a composition to be analyzed and in a control composition involves an extrusion, which leads to the production of rods, which are then cut into granules.
• the actual molar mass determination can be carried out, for example, on the granules or on a final molded part.
• the polyamide matrix and the additive (ii) are in crushed or crushed form in powder, flakes or granules, and are then premixed.
• the mixture is melted in a twin-screw extruder, LEISTRITZ model (screw diameter 30 mm - L / D ratio: 4), under the following conditions: Flow rate: 10 kg / h;
• Screw speed 250 rpm
• temperature profile 250-280 ° C for a polyamide 66, 220-250 ° C for a polyamide 6.
• Rods are collected at the extruder outlet, then put in the form of granules.
• the actual molar mass measurement is carried out on the granules by gel permeation chromatography (GPC) in dichloromethane after derivatization of the polyamide by trifluoroacetic anhydride, compared to polystyrene standards.
• GPC gel permeation chromatography
• the detection technique used is refractometry (RI ERMA model refractometer, sensitivity 16).
• the GPC columns have the following characteristics: 3 mixed-C columns, 5 ⁇ m, diameter 3/8, length 60cm + precolumn 5 ⁇ m.
• the polyamide matrix is generally composed of at least one (co) polyamide chosen from the group comprising: polyamide 6, polyamide 6.6, polyamide 4, polyamide 11, polyamide 12, polyamides 4-6, 6-10 , 6-12, 6- 36, 12-12, their copolymers and mixtures.
• semi-crystalline or amorphous polyamides such as aliphatic polyamides, semi-aromatic polyamides and more generally, linear polyamides obtained by polycondensation between a saturated aliphatic or aromatic diacid, and a primary saturated aromatic or aliphatic diamine, polyamides obtained by condensation of a lactam, an amino acid or linear polyamides obtained by condensation of a mixture of these different monomers.
• these copolyamides can be, for example, the polyadipamide of hexamethylene, the polyphthalamides obtained from terephthalic and / or isophthalic acid, the copolyamides obtained from adipic acid, hexamethylene diamine and caprolactam.
• the polyamide matrix of the composition consists of a mixture and / or alloy of a polyamide with one or more other polymers, preferably polyamides or copolyamides.
• a mixture and / or alloy of (co) polyamide with at least one polymer of the propylene polyoxide (PPO), polyvinyl chloride (PVC), polyacrylobutadiene-styrene (ABS) type is also conceivable.
• the polyester matrix is generally composed of at least one polyester chosen from the group comprising: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT).
• PET polyethylene terephthalate
• PBT polybutylene terephthalate
• PPT polypropylene terephthalate
• the composition according to the invention can be obtained by mixing at least: a polyamide matrix, optionally in the molten state; a first additive (i) chosen from the group comprising: trimesic acid, isophthalic acid, terephthalic acid, adipic acid and 2,2,6,6-tetrakis- ( ⁇ -carboxyethyl) cyclohexanone; and a second additive (ii) of hyperbaric polyamide type comprising alkyl functional endings.
• a first additive chosen from the group comprising: trimesic acid, isophthalic acid, terephthalic acid, adipic acid and
• thermoplastic composition obtained according to the present invention there are different methods for determining the matrix and the types of additives used.
• IR infrared spectrometry
• thermoplastic composition of the invention can be hydrolyzed, and the hydrolyzate can be analyzed by liquid chromatography (HPLC) or gas (CPG), optionally coupled to a mass spectrometer, so as to determine and measure the proportions of the monomers and constituent compounds of the additives used and of the polyamide and / or polyester matrix.
• HPLC liquid chromatography
• CPG gas
• mass spectrometer a mass spectrometer
• compositions obtained and to measure by nuclear magnetic resonance (NMR) techniques and / or UV and / or IR spectrometry, the types of additives used as well as their proportions.
• NMR nuclear magnetic resonance
• UV and / or IR spectrometry the types of additives used as well as their proportions.
• the solubilization of the composition can be carried out using an appropriate solvent, such as hexa-fluoro-iso-propanol (HSIP) or formic acid.
• HSIP hexa-fluoro-iso-propanol
• composition according to the invention it is also possible to extract the various additives from the composition according to the invention with an appropriate solvent.
• solvent can be determined by liquid chromatography (HPLC) or gas (CPG).
• reinforcing and / or filling fillers to it, chosen from the group comprising fibrous fillers such as glass fibers, mineral fillers such as clays, kaolin, or reinforcing nanoparticles or in thermosetting material, and powdered fillers such as talc.
• the incorporation rate of these fillers complies with standards in the field of composite materials. It may, for example, be a loading rate of 1 to 70% by weight, preferably 10 and 60% by weight, more specifically 30 to 50% by weight, relative to the total weight of the composition.
• Resilience modifiers can also be added, such as optionally grafted elastomers.
• composition according to the invention may also contain any other suitable additives or adjuvants, for example flame retardants, UV stabilizers, heat stabilizers, matifiers (TiO 2 ), lubricants, plasticizers, compounds useful for the catalysis of synthesis of the polymer matrix, antioxidants, antistatics, pigments, dyes, molding aid additives or surfactants.
• suitable additives or adjuvants for example flame retardants, UV stabilizers, heat stabilizers, matifiers (TiO 2 ), lubricants, plasticizers, compounds useful for the catalysis of synthesis of the polymer matrix, antioxidants, antistatics, pigments, dyes, molding aid additives or surfactants.
• the present invention also relates to a process for manufacturing a composition as described above obtained by mixing at least the first additive (i) and the second additive (ii) with the polyamide and / or polyester matrix. There are different methods for making the composition as described above.
• This mixture can also be produced in the molten state. It is thus possible to mix the additives (i) and (ii), simultaneously or delayed in time, in the molten matrix, and optionally subject the mixture to shearing, for example in a twin-screw extrusion device, in order to to achieve good dispersion.
• the extrusion device is generally arranged upstream of devices for shaping the molten plastic material, such as for example suitable molding, extrusion, injection or spinning devices. It is also possible to extrude this mixture in the form of rods which are then cut into granules. The molded parts are then produced by melting the granules produced above and feeding the composition in the molten state in suitable molding, extrusion, injection or spinning devices.
• the composition obtained at the extruder outlet optionally directly feeds a spinning installation.
• the present invention also relates to a method of manufacturing an article by shaping a composition according to the invention by a method chosen from the group comprising an extrusion device, molding such as compression molding, injection, such as injection molding, and spinning.
• the invention also relates to articles obtained by shaping the composition of the invention, by all thermoplastic transformation techniques, such as those mentioned above.
• the articles of the invention are articles obtained by a device chosen from the group comprising an extrusion device, molding device such as compression molding, and injection device, such as injection molding.
• the articles of the invention can be, for example, any type of part obtained by injection molding in which good mechanical properties and a suitable surface appearance are required, such as boxes, handles, plastic parts of household elements, automotive parts such as, for example, parts for a car cooling system, trim or coating parts.
• PA 66 Viscosity index, measured at 25 ° C in 90% formic acid, 137 ml / g (ISO 307). Amine terminal group content of 53 meq / kg and acid terminal group content of 72 meq / kg (dosage by potentiometry).
• T2 Isophthalic acid
• T3 Trimesic acid
• EXAMPLE 1 Synthesis of a Functionalized Hyperbranched Copolyamide
• the respective overall composition is 1/6/6/9 in BTC / AIPA / CL / Ci6.
• the monomers are fully loaded at the start of the test into the reactor preheated to 70 ° C. 49.8 kg of hexadecylamine melted at 90% purity (0.19 mol), 14.0 kg of ⁇ -caprolactam (0.12 mol), 22.4 kg of acid are successively introduced into the reactor.
• -aminoisophthalic (0.12 mol)
• 4.3 kg of acid 1 3.5- benzene tricarboxylic (0.02 mol)
• 163 g of a 50% aqueous solution (w / w) of hypophosphorous acid The reactor is purged using dry nitrogen.
• the reaction mass is heated from 70 ° C to 260 ° C, in about 200 min. About 6 kg of distillate is recovered.
• a Sandwick pelletiser is connected to the reactor outlet.
• compositions are prepared from polyamide PA 66, glass fibers, acids T2, T3, and / or T4 (corresponding to the additive (i)) and a hyperbranched copolyamide of Example 1 (corresponding to l 'additive (ii)), at various incorporation rates.
• compositions are produced by mixing granules of polyamide 66, additives (i) and (ii) and carbon black and calcium stearate in a twin-screw extruder, WERNER ZSK 40 model (diameter of the screw 40 mm - L / D ratio: 3.2), under the following conditions: Flow rates: 40 Kg / h; Screw speed: 260 rpm, Temperature profile (° C) 250-280 ° C.
• Table 2 Table 2
• compositions all comprise 1% by weight of carbon black and 0.3% by weight of calcium stearate. The percentages are expressed by weight relative to the total weight of the composition.
• composition PA 66 + 50% of glass fibers +/- additive (i) +/- additive (ii) are melted and then injected into a plate mold 100 * 100 * 1.6 mm thick, with a DEMAG H200-80 press at a barrel temperature of 300 ° C and a mold temperature of 80 ° C.
• the parts are injected as a sheet over the entire width of the plate and the thickness of the injection threshold is equal to 2/3 of the thickness of the part.
• the parts are classified with respect to the surface appearance obtained on a control composition (standard commercial formulation PA 66 + 50% glass fibers): 0 means that the surface appearance obtained is similar to that of the control; + means that the surface appearance obtained is better than that of the control; ++ means that the surface appearance obtained is clearly better than that of the control; means that the surface appearance obtained is degraded compared to that of the control; and means that the surface appearance obtained is greatly degraded compared to that of the control.
• 0 means that the surface appearance obtained is similar to that of the control
• + means that the surface appearance obtained is better than that of the control
• ++ means that the surface appearance obtained is clearly better than that of the control
• compositions evaluated in this test all have a moisture content before molding equivalent to 0.1% with respect to the control composition.
• compositions without glass fibers Compositions (Table 3), not containing glass fibers, based on polyamide 66 additivated with variable amounts of additive (i) and (ii) are produced by mixing with the molten state in a twin-screw extruder, LEISTRITZ model (screw diameter 30 mm - L / D ratio 4), under the following conditions: Flow rates: 10 Kg / h; Screw speed: 250 rpm, Temperature profile (° C) 250-280 ° C. Table 3
• compositions all comprise 1% by weight of carbon black and 0.3% by weight of calcium stearate. The percentages are expressed by weight relative to the total weight of the composition.
• CL spacer of type XR 2 -Y
• the reaction is carried out at atmospheric pressure in a 7.5 liter autoclave, commonly used for the melt synthesis of polyamides.
• the monomers are fully loaded at the start of the test into the reactor preheated to 70 ° C.
• 84 g of 1,3,5-benzene tricarboxylic acid are successively introduced into the 1811 reactor.
• the stirring is then adjusted to 50 rpm and the reaction mass is heated from 70 to 260 ° C, in about 200 min.
• the nonfunctionalized hyperbranched copolyamide obtained is called
• This branched polyamide has a content of amine end groups of 0 meq / kg and a content of acid end groups of
• Example 6 Preparation of compositions based on polyamide 6 + non-functionalized PAHB from Example 5
• compositions are prepared from polyamide PA 6, glass fibers, and a hyperbranched copolyamide from Example 5, at various incorporation rates. These compositions are produced by adding non-functionalized PAHB from Example 5 in a polyamide 6 matrix in the molten state and of 50% by weight of glass fibers, in a twin-screw extruder, WERNER ZSK 40 model (diameter of the 40 mm screw - L / D ratio: 3.2), under the following conditions: Flow rates: 40 Kg / h; Screw speed: 260 rpm, Temperature profile (° C) 220-250 ° C. A control composition is also prepared without adding non-functionalized PAHB.
• compositions based on polyamide 66 + alkylated functionalized PAHB of Example 1
• Compositions are prepared from polyamide PA 66, glass fibers, and a hyperbranched copolyamide of Example 1 (corresponding to additive (ii)), at various incorporation rates.
• compositions are produced by adding functionalized PAHB from Example 1 in a polyamide 66 matrix in the molten state and of 50% by weight of glass fibers, in a twin-screw extruder, WERNER ZSK 40 model (diameter of the screw
• the molar mass of the polyamide matrices of the compositions of Examples 6 and 1 is measured, according to the protocol P defined above.
• the actual molar mass measurement is carried out on the granules by gel permeation chromatography (GPC) in dichloromethane after derivatization of the polyamide by trifluoroacetic anhydride, compared to polystyrene standards.
• the detection technique used is refractometry (RI ERMA model refractometer, sensitivity 16).
• the GPC columns have the following characteristics: 3 mixed-C columns, 5 ⁇ m, diameter 3/8, length 60cm + precolumn 5 ⁇ m.
• PA6 75,000 PA6 + 2% PAHB / COOH 70,000 6.6 PA6 + 5% PAHB / COOH 60,000 20 PA6 + 10% PAHB / COOH 57,000 24
• compositions comprise 50% by weight of glass fibers relative to the total weight of the composition. The percentages are expressed by weight relative to the total weight of the composition.

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