EP2652013A1 - Polyamid-polyolefin-copolymer - Google Patents

Polyamid-polyolefin-copolymer

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Publication number
EP2652013A1
EP2652013A1 EP11794787.9A EP11794787A EP2652013A1 EP 2652013 A1 EP2652013 A1 EP 2652013A1 EP 11794787 A EP11794787 A EP 11794787A EP 2652013 A1 EP2652013 A1 EP 2652013A1
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EP
European Patent Office
Prior art keywords
polyamide
polyolefin
function
acid
styrene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11794787.9A
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English (en)
French (fr)
Inventor
Stéphane JEOL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
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Filing date
Publication date
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP2652013A1 publication Critical patent/EP2652013A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08G69/48—Polymers modified by chemical after-treatment
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/028—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyamide sequences

Definitions

  • the present invention relates to a polyamide-polyolefin block copolymer consisting of a polyamide trunk and one or two graft (s) of polyolefin on said trunk; wherein the one or more polyolefin grafts are attached to the trunk by the remains of an X-Y function; resulting from the reaction between a function X located at the end of polyolefin chain and capable of reacting with a Y amine or carboxylic acid function of the polyamide.
  • Immiscible mixtures of polyamide and polyolefin have been known for many, many years.
  • the polyamide constitutes the continuous matrix
  • the polyolefin dispersed in particular in the form of nodules provides a number of properties, such as lightening and impact resistance.
  • the performance of the PA / polyolefin mixtures depends on the morphology of the mixture, that is to say on the organization of the two polyamide and polyolefin phases at different scales.
  • the polypropylene In the case of a simple immiscible PA / polypropylene mixture, for example having a majority of polyamide, the polypropylene roughly disperses in the form of macro-objects, most often nodules, of size up to several tens of micrometers. This negatively impacts certain properties such as mechanical properties or transparency.
  • compatibilizers to promote the dispersion of polyolefins in a polyamide matrix and thus reduce the size of the dispersed phase to a size ranging from several hundred nanometers to a few micrometers.
  • polyolefins bearing maleic anhydride functional groups capable of reacting with the amine functional groups of the polyamide are used most often and thus create more affinity between the two phases. This then makes it possible to improve the mechanical performance of the mixtures, but the main problem is that the morphology of the mixtures obtained is very dependent on the extrusion conditions, such as temperature and shear, and then implementation, so that it is very difficult to guarantee a controlled and constant morphology, and thus constant mechanical properties whatever the extrusion conditions and formatting. In addition, these mixtures retain properties related to the nature of both polymers because of the micrometric nature of the dispersed phase.
  • PA / polyolefin mixtures having very fine morphologies, that is to say having a dispersed phase whose one of its dimensions is less than 100 nm (nanostructuration) and little dependent on mixing conditions. and implementation.
  • an alternative developed by Toray consists in producing nanoalloys which nevertheless requires suitable extrusion means.
  • Another alternative consists in producing copolymers such as those developed by Arkema, for example PA-g-polyolefin copolymers, from a polyolefin trunk carrying randomly distributed maleic anhydride functions and polyamide of molar masses. low.
  • These mixtures are capable of nanostructuring but suffer from an absence of regularity related to the random nature of the distribution of maleic anhydride on the polyolefin chain, leading to an absence of regularity in the structure of the same graft copolymers: the whole nanostructures can not be achieved by this technology, including very regular structures.
  • polyamide-polyolefin block copolymer consisting of a polyamide trunk and one or two graft (s) of polyolefin on said trunk are organized in particular nanoscale structures.
  • the polyolefin blocks group together to form nanostructures, that is to say having at least a dimension of less than 100 nm, such as strips, strips , vesicles, to (worm-like in English) or micelles.
  • Such nanostructuring confers remarkable properties exceeding those of conventional mixtures between two polymers both in terms of mechanical properties, thermal stability, solubility and behavior with respect to water uptake.
  • the Applicant has just also developed a simple way to prepare these polyamide-polyolefin block copolymers capable of nanostructuring by reactive mixing of polyamide and polyolefin particular, little dependent on the conditions of extrusion and implementation; and therefore easily reproducible.
  • the present invention thus firstly relates to a process for producing a polyamide-polyolefin block copolymer consisting of a polyamide trunk and one or two graft (s) of polyolefin on said trunk; in which is brought into contact in the molten state:
  • polyamide having a number average molar mass Mn PA of between 1000 and 30000 g / mol; the polyamide has amino terminal groups and / or carboxylic acids per chain;
  • polyolefin having a number average molar mass Mn PO of between 500 and 10000 g / mol; the polyolefin has a single X chain function at the end of the polyolefin chain, this function X is capable of reacting with an amine function and / or carboxylic acid function of the polyamide;
  • n X / n Y is between 0.8 and 1.2
  • n the number of moles of function X of the polyolefin
  • Y represents the number of moles of the amino and / or carboxylic end groups of the polyamide capable of reacting with the X function to form a covalent bond.
  • the present invention also relates to polyamide-polyolefin block copolymers obtainable by the process as described above.
  • copolymers can be obtained in high purity, i.e. at least without being mixed with a significant amount of other polymers. This may in particular enable them to have a nanometric structure and improved properties compared with copolymers of the same type of the prior art.
  • the polyamide-polyolefin block copolymer may be obtained by mixing the various constituents while hot, for example in a single or twin screw extruder, at a temperature sufficient to maintain the polyamide resin and the polyolefin resin in a molten medium: or cold in a mixer mechanics in particular.
  • the mixing is usually done by shearing.
  • the mixture obtained is extruded in the form of rods which are cut into pieces to form granules.
  • Additives may be added at any time during the manufacturing process of the plastic material, in particular by hot or cold mixing with the plastic matrix.
  • the mixture can be obtained by any suitable device such as screw mixers or agitators compatible with the temperature and pressure conditions used for the implementation of polyamides and polyolefins.
  • the molten mixture can be shaped before the cooling step, for example in the form of filaments or rods. This shaping can be advantageously carried out by an extrusion process through a die.
  • the cooling of the molten mixture can be achieved by any means appropriate. Of these, air cooling or dipping in a liquid is preferred.
  • the average residence time of the melt in the extruder can be between 15 seconds and 30 minutes, more particularly between 30 seconds and 5 minutes.
  • the mixtures of the invention can be prepared by melt blending in extruders (single or twin screw), BUSS mixers, BRABENDER mixers and in general the usual mixing devices for thermoplastics and preferably twin-screw extruders. screw.
  • the blends of the invention may also include fluidizing agents such as silica, ethylenebisamide, aluminum stearate, calcium stearate or magnesium stearate. They may also include antioxidants, U.V. inhibitors, mineral fillers and coloring pigments.
  • the mixtures of the invention may be prepared in one or more steps in an extruder.
  • the polyamide may in particular have a number average molar mass Mn PA of between 2000 and 20000 g / mol, more preferably between 5000 and 17000 g / mol.
  • polyamide As polyamide according to the invention, mention may be made of semi-crystalline or amorphous polyamides and copolyamides, such as aliphatic polyamides, semi-aromatic polyamides and, more generally, linear polyamides obtained by polycondensation between an aliphatic or aromatic saturated diacid, and a saturated primary diamine aromatic or aliphatic, polyamides obtained by condensation of a lactam, an amino acid or linear polyamides obtained by condensation of a mixture of these different monomers.
  • semi-crystalline or amorphous polyamides and copolyamides such as aliphatic polyamides, semi-aromatic polyamides and, more generally, linear polyamides obtained by polycondensation between an aliphatic or aromatic saturated diacid, and a saturated primary diamine aromatic or aliphatic, 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 may be, for example, hexamethylene polyadipamide, polyphthalamides obtained from terephthalic and / or isophthalic acid, copolyamides obtained from adipic acid, hexamethylenediamine and caprolactam.
  • the polyamide is preferably chosen from the group comprising polyamides obtained by polycondensation of a linear dicarboxylic acid with a linear or cyclic diamine such as PA 6.6, PA 6.10, PA 6.12, PA 12.12, PA 10.10, PA 10.2, PA 4.6, MXD. Or between an aromatic dicarboxylic acid and a linear or aromatic diamine such as polyterephthalamides, polyisophthalamides, polyaramids, polyamides obtained by polycondensation of an amino acid on itself, the amino acid being able to be generated by the hydrolytic opening of a lactam ring such as, for example, PA 6, PA 7, PA 11, PA 12, PA 13.
  • the polyamide matrix comprises at least one polyamide chosen from the group comprising polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polymetaxylylene adipamide (MXD6 ), blends and copolymers based on these polyamides.
  • the composition of the invention may also comprise copolyamides derived in particular from the above polyamides, or mixtures of these polyamides or copolyamides.
  • polyamides suitable for injection molding processes are generally used, although polyamides with lower viscosities can also be used.
  • the polyamide may especially be a polymer comprising star or H macromolecular chains, and optionally linear macromolecular chains.
  • the polymers comprising such star or H macromolecular chains are for example described in the documents FR2743077, FR2779730, US5959069, EP0632703, EP0682057 and EP0832149.
  • the polyamide may also be a random tree type polymer, preferably a copolyamide having a random tree structure. These copolyamides of random tree structure and their method of production are described in particular in document WO99 / 03909.
  • the polyamide may also comprise a hyperbranched copolyamide of the type of those described in WO 00/68298. Any combination of linear thermoplastic polymer, star, H, shaft, hyperbranched copolyamide as described above may be used.
  • the polyamide has end groups amino groups and / or carboxylic acids per chain, and may optionally comprise end groups blocked by the action of polyamide chain blocking agents, in particular by alkylamide functions. Mention may be made, as chain blocking agents, of those chosen from monoacids such as acetic acid, benzoic acid, propionic acid, hexanoic acid, sodium 3-sulphobenzoic acid or monoamines such as hexylamine or laurylamine.
  • monoacids such as acetic acid, benzoic acid, propionic acid, hexanoic acid, sodium 3-sulphobenzoic acid or monoamines such as hexylamine or laurylamine.
  • the polyolefin preferably has a number average molar mass Mn PO of 2000 and 8000 g / mol.
  • the polyolefin used in the process of the invention has a single chain X chain located at the end of polyolefin chain, this function X is capable of reacting with an amine function and / or carboxylic acid polyamide.
  • the polyolefin is defined as a homopolymer or copolymer of alpha olefins or diolefins, such as, for example, ethylene, propylene, butene-1, octene-1, butadiene.
  • LDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • metallocene polyethylene homopolymers or copolymers of propylene
  • ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (abbreviation of ethylene-propylene-rubber) and ethylene / propylene / diene (EPDM).
  • EBS ethylene-propylene-rubber
  • EPDM ethylene / propylene / diene
  • SEBS styrene-ethylene-butene / styrene block copolymers
  • SBS styrene-butadiene-styrene
  • SIS styrene-isoprene-styrene
  • SEPS styrene-ethylene-propylene-styrene
  • unsaturated carboxylic acid salts or esters such as alkyl (meth) acrylate (for example methyl acrylate), or vinyl esters of saturated carboxylic acids such as vinyl acetate.
  • the polyolefin has a single functional group X located at the end of the polyolefin chain, this function X is capable of reacting with an amine and / or carboxylic acid function of the polyamide.
  • diacids in position 1, 2 (hydrolysed form of an acid anhydride) capable of binding covalently with the amine end groups of the polyamide, forming imide and / or amic acid functional groups;
  • carboxylic acids capable of binding covalently with the amine end groups of the polyamide, forming an amide bond
  • epoxies capable of binding covalently with the amino and / or acid end groups of the polyamide.
  • the X functions forming imide, amic acid and amide bonds are preferred for their high stability.
  • X functions of acid anhydride type are particularly preferred.
  • the functions X allow the formation of imide bonds.
  • These functions X can thus be chosen from cyclic acid anhydrides, in particular comprising a 5- or 6-membered cyclic anhydride unit, and dicarboxylic acids 1, 2.
  • the imide bonds may make it possible to obtain copolymers having improved properties, especially in terms of thermal stability.
  • This function X can be attached at the end of the polyolefin chain by grafting or copolymerization of an unsaturated monomer bearing the X function.
  • polyolefin bearing a function X according to the invention, mention may notably be made of the following compounds: polyethylenes and terminated monoacid carboxylic acid copolymers, monoamine, monoanhydride, dicarboxylic acid in position 1, 2, polypropylenes and copolymers terminated monoacid carboxylic, monoamine, monoanhydride, dicarboxylic acid in position 1, 2, elastomers ethylene-propylene rubber (EPR) terminated monoacid carboxylic acid , monoamine, monoanhydride, dicarboxylic acid in position 1, 2, the ethylene-propylene-diene elastomers (EPDM) terminated monoacidic carboxylic acid, monoamine, monoanhydride, dicarboxylic acid in position 1, 2, the copolymers of ethylene with at least one product selected from unsaturated carb
  • n X / n Y is between 0.8 and 1, 2, more preferably between 0.9 and 1.1.
  • the method uses a polymer mixture in which the content of polyamide constituting the trunk and polyolefin constituting the graft (s) is greater than or equal to 80% by weight, in particular greater than or equal to 90% by weight, especially greater than or equal to 95% by weight, or even greater than or equal to 99% by weight relative to the total weight of the polymers.
  • the polymer mixture used is constituted by at least one, in particular a polyamide constituting the trunk and at least one, in particular a polyolefin constituting the graft (s).
  • the present invention also relates to a polyamide-polyolefin block copolymer consisting of a polyamide trunk and one or two graft (s) of polyolefin on said trunk; wherein: the copolymer has a number average molar mass Mn CP of between 5000 and 40,000 g / mol;
  • the polyamide trunk has an average molar mass in number Mn PA of between 1000 and 30000 g / mol;
  • polyolefin graft or grafts have an average molecular weight Mn PO of between 500 and 10,000 g / mol;
  • Mn PA greater than or equal to Mn PO
  • the polyolefin graft or grafts are attached to the trunk by the remains of an XY function; resulting from the reaction between a function X capable of reacting with an amino function Y or carboxylic acid of the polyamide.
  • the XY functions are preferably amide or imide functions, and in particular imides.
  • the average molecular weight in Mn CP number can be measured by GPC.
  • an NMR can be carried out, in particular so as to determine:
  • the number of bonds between the polyamide and the polyolefin for example to determine the number of imide functions
  • the copolymer has an amino terminal group content, GTA, ranging from 20 to 500 meq / kg.
  • the invention also relates to a composition comprising at least one polyamide-polyolefin block copolymer according to the invention.
  • this composition comprises in particular the polyamide-polyolefin block copolymer according to the invention as a thermoplastic polymer matrix, and does not include other thermoplastic polymeric compounds.
  • the invention also relates to a composition comprising at least one thermoplastic matrix, which consists solely of a blend of polyamide and polyamide-polyolefin block copolymer of the invention.
  • the composition may comprise a copolymer content according to the invention greater than or equal to 90% by weight relative to the total weight of the composition.
  • the composition may comprise a copolymer content according to the invention and in its precursors greater than or equal to 90% by weight, in particular greater than or equal to 95% by weight, more particularly greater than or equal to 99% by weight relative to the weight. total of polyamide and polyolefin, or is made of copolymer according to the invention.
  • composition may comprise a content of polymer (s) other (s) that the copolymer according to the invention and its precursors less than or equal to 20% by weight, in particular less than or equal to 10%, in particular less than or equal to to 5% by weight, and most preferably less than or equal to 1% by weight relative to the total weight of polymers.
  • the composition comprises a content of polyolefin, in particular devoid of function X, less than 20% by weight, especially less than 10% by weight, more particularly less than 5% by weight relative to the total weight. of the composition.
  • Such a composition may contain one or more additives or compounds selected from the group comprising mattifying agents, heat stabilizers, light stabilizers, pigments, dyes, reinforcing fillers, such as glass fibers or mineral fibers, glass beads and carbon fibers, nucleants, and shock reinforcing agents such as elastomers, various metals and anti-foaming agents or molding aids.
  • additives or compounds selected from the group comprising mattifying agents, heat stabilizers, light stabilizers, pigments, dyes, reinforcing fillers, such as glass fibers or mineral fibers, glass beads and carbon fibers, nucleants, and shock reinforcing agents such as elastomers, various metals and anti-foaming agents or molding aids.
  • the copolymer of the invention can be used as raw material for feeding various processes for the manufacture of articles known to the plastic industry, such as the injection, extrusion and extrusion-blow molding processes. .
  • the invention also relates to articles obtained by shaping the composition of the invention by any plastic transformation technique, for example by extrusion, such as, for example, extrusion of sheets and films or extrusion blow molding; by molding such as compression molding, thermoforming molding or rotational molding; by injection such as for example by injection molding or injection blow molding.
  • another subject of the invention is the use of a copolymer according to the invention as a viscosifying agent for the solution, in particular the aqueous solution, of acid.
  • These acids can be inorganic or organic.
  • Said inorganic acids may be chosen from hydrochloric, hydrofluoric and sulfuric acid.
  • Said organic acids may be chosen from formic and acetic acid.
  • the acid concentration may be at least 3%, especially at least 5% by weight relative to the total weight of the solution.
  • the acid concentration can range from 3 to 28% by weight, and even more particularly from 5 to 25% by weight relative to the total weight of the solution.
  • the present invention also relates to an acid solution, especially as described above, comprising a copolymer as defined in the present description.
  • Said solution may comprise the copolymer in a content ranging from 0.01 to 5% by weight, especially from 0.1 to 3% by weight relative to the total weight of the solution.
  • the subject of the invention is also the use of a solution as defined above in a petroleum extraction process, in particular for the purpose of enlarging the pore size and improving the permeability of a rock matrix. in formations comprising hydrocarbons.
  • the polyamides used for the preparation of the PA-b-PP block copolymers are the following:
  • the content of acid (GTC) and amine (GTA) end groups is determined by a potentiometric assay and is expressed in meq / kg.
  • GTAh acid content x1000 / (2XM K OH) with MKOH, the molar mass of potassium hydroxide KOH taken equal to 56.1 g / mol.
  • the melting temperature (T f ) and the associated enthalpy ( ⁇ ) is determined by Differential Scanning Calorimetry (DSC), using a Perkin Elmer Pyris 1 device, at a speed of 10 ° C / min.
  • the thermal stability is evaluated by ThermoGravimetric Analysis (TGA) using a Perkin Elmer TGA7 operating apparatus, by measuring the loss of mass of a few mg sample heated to 10 ° C / min under inert gas (nitrogen).
  • the PA6-b-PP block copolymers are produced by introducing PA 6 or PA 66 polyamide and monofunctional polypropylene into a DSM MIDI 2000 micro-compounder ("micro-compounder”) ( 15 cm 3 ) heated at a temperature of 250 ° C for PA 6 or 280 ° C for PA 66.
  • the rotational speed tested bi-screws is 100 or 250 revolutions per minute.
  • This micro-extruder contains a loop of recirculation of the melt which makes it possible to regulate the residence time. Three residence times were chosen: 2, 6 and 10 min.
  • Mass quantities of polyamide and PP introduced into the micro-extruder are determined so as to have the same molar amount of amine carried by the PA and anhydride carried by the PP. Whatever the mixture, the extruded rods have a transparency similar to that of the original polyamide or even in some cases more transparent than the polyamide. For comparison, a PA / PP / PP-g-MA maleic anhydride grafted PP-g-MA compatibilizer mixture of reference Orevac is itself opaque.
  • Examples Ex1, Ex2, Ex3, Ex4, Ex5 and Ex6 were made with a screw speed of 100 rpm.
  • Examples Exi bis, Ex2bis and Ex3bis were made with a screw speed of 250 rpm.
  • PA 6 is soluble in formic acid while PP X-10088 is not.
  • the copolymers of Examples 1, 1 bis, 2, 2bis, 3 and 3bis are themselves totally soluble in formic acid, which shows the existence of the copolymers formed during the melt mixing. Moreover, a viscosification of formic acid by the addition of the block copolymer of Examples 1, 1a, 2, 2a, 3 and 3a is observed, even at a very low concentration, of the order of 1%. This is also the case of the copolymer of Example 4 which is perfectly soluble in formic acid whereas PP X-10065 is absolutely not soluble in formic acid.
  • the perfect solubility of the copolymers is necessary for certain methods of manufacturing articles requiring a first solution step, such as coating, coating or electrostatic spinning.
  • the nanostructuration is stable for at least 10 minutes of melt time, which corresponds to a time equivalent to several cycles of molding or extrusion in the molten state.
  • Thermogravimetric analysis of PA 1, PP-X10088 and the copolymer of Example 3 is carried out up to 1000 ° C. It is observed that the copolymer of Example 3 has the same thermal stability of a polyamide 6 (loss of mass from a temperature of 380 ° C., whereas PP X-10088 has a limited thermal stability (loss of mass from a temperature of 220 ° C.) It has thus been possible, thanks to the copolymerization of the present invention, to improve the thermal stability of the polyolefin.
  • the analysis of the melting temperature of PA (Tf1 PA) and PP (Tf1 PP) is performed on the first temperature rise (Tf1) up to 300 ° C. A step of 5 min at 300 ° C is used and a temperature descent to 40 ° C is performed. A second temperature rise is performed up to 300 ° C and the melting temperature of the PA (Tf2 PA) and the PP (Tf2 PP) is recorded. The stability of the thermal properties of the copolymers is thus evaluated after reflow. Table 2
  • the analysis of the water uptake of the extruded rods is performed by dipping 1 g of extruded rod into a beaker filled with water at room temperature.
  • the recovery in water weight expressed in% is determined by the following formula:
  • PA6-b-PP block copolymers water uptake of the PA6-b-PP block copolymers is slowed down. It is thus shown that the particular organization of PA-b-PP block copolymers results in a different water uptake of a single polyamide and polyolefin.
  • the granules of block copolymers thus prepared are analyzed by different techniques. They are perfectly soluble in formic acid, sign of the reaction of the PP block with the PA block. The rheological analysis is carried out at 250 ° C. using a Gottfert capillary rheometer 2002. It appears that the block copolymer has a molten viscosity profile (Table 3) as a function of the shear rate which is very different from that of the PA1 from which it comes:
  • the copolymer does not have a Newtonian plateau at low shear rates (ie no constant viscosity irrespective of the shear rate) whereas the PA1 has a Newtonian plateau.
  • the result is all the more surprising in that the copolymer has a melt viscosity that is much greater than that of a polyamide which would have an average molar mass in equivalent number (MnPA1 + MnPPX10088). It is therefore the particular structuring of block copolymers that explains this behavior. This behavior is sought to perform, for example, extrusion blow molding (high viscosity at low shear rate) and injection (low viscosity at high shear rate, similar to that of PA1).
  • the block copolymer granules are injected onto an Arburg press in a 75 ° C controlled mold in the form of 4 mm thick specimens.
  • the temperature at the injection nozzle head is set at 254 ° C. It appears that the injection is stable and makes it very easy to obtain test pieces with a good surface appearance.
  • the mechanical dynamic temperature analysis of -100 ° C. to 200 ° C. is carried out on a Rheometrics Solids Analyzer (RSA II) rheometer at a frequency of 1 Hz and a strain of 0.01%.
  • the PP thus brings a relaxation to the PA block.
  • Tensile measurements (ISO527 / 1A) are carried out at 23 ° C on the block copolymer. A tensile modulus of 2600 MPa (against 2900 MPa for PA 1) and a breaking stress of 65 MPa are obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
EP11794787.9A 2010-12-16 2011-12-15 Polyamid-polyolefin-copolymer Withdrawn EP2652013A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1060618A FR2969160B1 (fr) 2010-12-16 2010-12-16 Copolymere polyamide-polyolefine
PCT/EP2011/072927 WO2012080404A1 (fr) 2010-12-16 2011-12-15 Copolymere polyamide-polyolefine

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US (1) US20130267664A1 (de)
EP (1) EP2652013A1 (de)
CN (1) CN103261282A (de)
FR (1) FR2969160B1 (de)
WO (1) WO2012080404A1 (de)

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EP4244264A1 (de) * 2020-11-13 2023-09-20 Braskem, S.A. Verarbeitung von polypropylen und daraus hergestellte produkte
CN112341716A (zh) * 2020-11-24 2021-02-09 江苏金发科技新材料有限公司 一种激光焊接用聚丙烯复合材料及其制备方法
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FR2969160B1 (fr) 2014-04-18
CN103261282A (zh) 2013-08-21
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US20130267664A1 (en) 2013-10-10
FR2969160A1 (fr) 2012-06-22

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