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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides
  • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
• • 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
  • C08L77/12—Polyester-amides
• • 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
  • C08G2410/00—Soles

Definitions

• the present invention relates to a thermoplastic impact-resistant composition and its use for the manufacture of various parts.
• Polyamide block copolymers and polyether blocks are particularly advantageous for applications of this type. However, they have a relatively high cost, and their impact resistance is sometimes too low.
• documents EP 0787761 and EP 0787771 describe quaternary compositions based on polyamide, polyamide block and polyether block copolymer, polyolefin copolymer and functionalized polyolefin. These compositions, however, still have an impact resistance which may be too low.
• the document EP 0564338 teaches a composition based on polyamide resin and comprising at least one ethylene polymer having unsaturated epoxide derived units.
• the invention firstly relates to a composition
• a composition comprising:
• At least one polyamide (A) at least one polyamide (A);
• At least one copolymer (B) comprising polyamide blocks and polyether blocks;
• polyolefin a single polyolefin (C), said polyolefin being a polyolefin functionalized with maleic anhydride units or with epoxy units.
• the composition comprises:
• polyamide (A) from 5 to 50%, preferably from 10 to 45%, of polyamide (A);
• copolymer (B) from 35 to 60%, preferably from 45 to 55%, of copolymer (B);
• polyolefin (C) from 5 to 40%, preferably from 10 to 35%, of polyolefin (C);
• the polyamide (A) is chosen from PA 6, PA 1 1, PA 12, PA 10.10, PA 10.12, PA 6.10, PA 6.12 and combinations thereof.
• the polyolefin (C) is chosen from poly (ethylene propylene) grafted with maleic anhydride, poly (styrene ethylene) grafted with maleic anhydride and poly (ethylene acrylate) grafted with maleic anhydride.
• the copolymer (B) is chosen from copolymers comprising PA 6 blocks and polytetramethylene glycol blocks, the copolymers comprising PA BACM.12 blocks and polytetramethylene glycol blocks and the combinations of those -this.
• the polyamide (A) is a PA 6; and / or the copolymer (B) is a block copolymer PA 6 and polytetramethylene glycol.
• the subject of the invention is also a process for producing the composition described above, comprising the provision of the polyamide (A), the copolymer (B) and the sole polyolefin (C) and the mixture thereof, preferably by compounding.
• the invention also relates to an article made from the composition described above.
• the invention also relates to a method of manufacturing this object, comprising providing the composition and shaping the object, preferably by injection.
• the present invention overcomes the disadvantages of the state of the art. It provides more particularly a polymer composition having a high impact resistance, and simple to implement.
• the composition according to the invention is particularly well suited to the injection process.
• A polyamide
• B copolymer
• C polyolefin
• compositions described in US 2013/0172484 which provides a mixture of two different functionalized polyolefins.
• composition according to the invention provides a material having properties close to those of polyurethane thermoplastics or copolymers with polyamide and polyether blocks at a moderate cost (and in any case lower than that of polyamide block copolymers and polyethers taken individually). ).
• composition according to the invention also has a high elongation at break, a low density and a lower sensitivity to water than certain products of the state of the art, a low flexural modulus, and good fatigue properties. bending for example.
• the invention provides a composition comprising:
• At least one polyamide (A) at least one polyamide (A);
• At least one copolymer (B) comprising polyamide blocks and polyether blocks;
• polyolefin a single polyolefin (C), said polyolefin being a polyolefin functionalized with maleic anhydride units or with epoxy units;
• single polyolefin is meant that the composition comprises a polyolefin corresponding to a single formula (it being understood that the individual molecules of this polyolefin in the composition may obey a statistical distribution, especially with an average molecular weight, an average grafting rate, etc.).
• the composition is devoid of unfunctionalized polyolefin; and the composition comprises either a polyolefin functionalized with maleic anhydride units, or a polyolefin functionalized with epoxy units, but not a mixture of the two.
• the polyamide (A) may be a semi-crystalline or amorphous polyamide, prepared in a manner known in the art of polyamides.
• Mixtures of semi-crystalline and / or amorphous polyamides can also be used in the context of the present invention.
• mixtures in which the (or) polyamide (s) (A) are predominantly (to more than 50% by weight) semicrystalline are preferred.
• the polyamides are generally manufactured by polycondensation of starting monomers, which can be either an amino acid, a lactam, or a mixture of a diacid and a diamine.
• aliphatic diacids such as adipic (6), azelaic (9), sebacic (10) and dodecanoic (12) diacids; or aromatic diacids such as terephthalic (T), isophthalic (I) ... diacids;
• aliphatic diamines such as butylenediamine (4), hexamethylenediamine (6 or HMDA), isomers of trimethylhexamethylenediamine (TMHMDA), octamethylenediamine (8), decamethylenediamine (10), dodecamethylenediamine (12), etc.
• aromatic diamines such as metaxlylenediamine (MXD); or cycloaliphatic diamines such as isomers of bis- (4-aminocyclohexyl) -methane (BACM), bis- (3-methyl-4-aminocyclohexyl) methane (BMACM), 2-2-bis- (3-methyl-4) - aminocyclohexyl) propane (BMACP) ...; or other diamines such as isophoronediamine (IPDA), 2,6-bis (aminomethyl) norbornane (BAMN) ...;
• NDA isophoronediamine
• BAMN 2,6-bis (aminomethyl) norbornane
• lactams such as caprolactam (L6), lauryllactam (L12) ...; amino acids such as 1-amino-1-undecanoic acid (1 1), N-heptylamino-1 1 -undecanoic acid (NHAU) ...
• the polyamides of the invention may be aliphatic or semi-aromatic polyamides.
• PA 6 polycaprolactam
• PA 1 polyundecanamide
• PA 12 me polylauryllactam
• PA 4.6 polybutylene adipamide
• PA 6.6 polyhexamethylene azelamide
• PA 6.9 polyhexamethylene sebacamide
• PA 6.10 polyhexamethylene dodecanamide
• PA 10.12 polydecamethylene dodecanamide
• PA 10.10 polydecamethylene sebacanamide
• PA 12.12 polyamides and copolyamides PA 11 / NHAU
• PA BACM.6, PA BACM.10, PA BACM.12 PA 6 / 6.6, PA 6/12 and mixtures thereof.
• PA 6 / 6.T PA 6.6 / 6.T
• PA 6.T / 6.I PA 6.6 / 6.T / 6 I
• PA 1 1 / 6.T PA 12 / 6.T
• PA MXD.6, PA MXD.10 PA MXD.10 and mixtures thereof.
• amorphous polyamides mention may be made, without limitation, of the following polyamides and copolyamides: polyhexamethylene isophthalamide (PA 6.I), polytrimethylhexamethylene terephthalamide (PA TMHMDA.T), PA BACM.12, copolyamides PA 6 / BMACP .I, PA 6 / BAMN.T, PA 1 1 / BMACM.I, PA 1 1 / BMACM.T / BMACM.I,
• the polyamide (A) is a semi-crystalline polyamide.
• semicrystalline polyamides in the meaning of the invention is generally meant linear aliphatic polyamides.
• those selected from PA 6, PA 11, PA 12, PA 10.10, PA 10.12, PA 6.10, PA 6.12 and combinations thereof are preferred.
• PA 6 is preferred.
• the copolymer (B) comprising polyamide blocks and polyether blocks is a copolymer resulting from the copolycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, such as, inter alia:
• polyamide sequences with diamine chain ends with polyoxyalkylene sequences with dicarboxylic chain ends polyamide sequences having dicarboxylic chain ends with polyoxyalkylene sequences having diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic dihydroxy aliphatic polyoxyalkylene aliphatic sequences known as polyetherdiols;
• polyamide sequences having dicarboxylic chain ends with polyetherdiols the products obtained being, in this particular case, polyetheresteramides.
• polyamide sequences with dicarboxylic chain ends result, for example, from the condensation of alpha-omega-aminocarboxylic acids of lactams or of dicarboxylic and dicarboxylic acids in the presence of a dicarboxylic acid chain-limiting agent.
• the polyamide blocks are made of polyamide 12 or a polyamide 6.
• the molar mass in number of the polyamide blocks is advantageously between 300 and 15,000; preferably between 600 and 5000.
• the number-average molecular weight of the polyether blocks is between 100 and 6000 and preferably between 200 and 3000.
• Polymers with polyamide blocks and polyether blocks may also comprise randomly distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.
• polyetherdiol, a lactam (or an alpha-omega amino acid) and a chain-limiting diacid can be reacted in the presence of a little water.
• a polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted randomly are obtained which are distributed statistically along the polymer chain.
• polymers with polyamide blocks and polyether blocks whether they come from the copolycondensation of previously prepared polyamide and polyether blocks or from a one-step reaction, have, for example, Shore D durations which can be between 20 and 75 and advantageously between 30 and 75. and 70 and intrinsic viscosity between 0.8 and 2.5 measured in metacresol at 25 ° C.
• polyether blocks are derived from polyethylene glycol, polyoxypropylene glycol or polyoxytetramethylene glycol, they are either used as such and copolycondensed with polyamide blocks having carboxylic ends, or they are aminated to be converted into polyether diamines and condensed with polyamide blocks having extremities carboxylic. They can also be mixed with polyamide precursors and a chain limiter to form the polyamide block and polyether block polymers having statistically distributed patterns.
• the polyether may be for example a polyethylene glycol (PEG), a polypropylene glycol (PPG) or a polytetramethylene glycol (PTMG) - the latter is also called polytetrahydrofuran (PTHF).
• PEG polyethylene glycol
• PPG polypropylene glycol
• PTMG polytetramethylene glycol
• polyether blocks are introduced into the polyamide block and polyether block polymer chain in the form of diols or diamines, they are referred to simply as PEG blocks or PPG blocks or PTMG blocks.
• polyether blocks contained different units such as units derived from ethylene glycol (-OC 2 H 4 -), propylene glycol (-O-CH 2 -CH (CH 3 ) -), or tetramethylene glycol (-O- (CH 2 ) 4 -).
• the polyamide blocks comprise the same units as the polyamide (A).
• the polyamide block and polyether block polymer comprises a single type of polyamide block and a single type of polyether block.
• PA 6 block polymers and PTMG blocks are advantageously used.
• the polyamide block and polyether block polymer is such that the polyamide is the major constituent by weight, that is to say the amount of polyamide which is in the form of blocks and that which is optionally distributed statistically in the chain represents 50% by weight or more of the polyamide block polymer and polyether blocks.
• the amount of polyamide and the amount of polyether are in the ratio (polyamide / polyether) 50/50 to 80/20.
• the polyamide blocks and the polyether blocks of the same polymer (B) have number-average molecular masses of 1000/1000, 1300/650, 2000/1000, 2600/650 and 4000/1000, respectively.
• the functionalized polyolefin (C) is an olefin polymer having reactive units: functionalities. Such reactive units are the maleic anhydride or epoxy functions.
• homopolymers or copolymers of alpha olefins or of diolefins such as, for example, ethylene, propylene, butene-1, octene-1, butadiene, and more may be mentioned as polyolefins. especially:
• LDPE low density polyethylene
• HDPE high density polyethylene
• LLDPE linear low density polyethylene
• ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (ethylene-propylene rubber) and EPDM (terpolymer based on ethylene / propylene / diene),
• SEBS styrene / ethylene-butylene / styrene block copolymers
• SBS styrene / butylene / styrene
• SIS styrene / isoprene / styrene
• SEPS styrene / ethylene-propylene / styrene
• unsaturated carboxylic acid salts or esters such as alkyl (meth) acrylate (for example methyl, ethyl or butyl acrylate, for example those of Arkema's Lotader® range), or vinyl esters of saturated carboxylic acids such as vinyl acetate (EVA), the comonomer content up to 40% by weight.
• polyolefins described above may be grafted, copolymerized or terpolymerized by reactive units (functionalities), namely maleic or epoxy anhydride functional groups.
• these polyolefins may be grafted or copolymerized with unsaturated epoxides such as glycidyl (meth) acrylate, or with maleic anhydride.
• unsaturated epoxides such as glycidyl (meth) acrylate, or with maleic anhydride.
• the functionalized polyolefin (C) may be chosen from the following (co) polymers, grafted with maleic anhydride or glycidyl methacrylate, in which the degree of grafting is, for example, from 0.01 to 5% by weight:
• PE polyethylene
• PP polypropylene
• ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR and EPDM
• ethylene and alkyl (meth) acrylate copolymers containing up to 40% by weight of alkyl (meth) acrylate (for example those of the Arkema Lotader® range),
• the functionalized polyolefin may be, for example, a PE / EPR mixture, the weight ratio of which may vary widely, for example between 40/60 and 90/10, said mixture being co-grafted with maleic anhydride, according to a rate grafting, for example 0.01 to 5% by weight.
• the functionalized polyolefin (C) may also be chosen from ethylene / propylene predominantly propylene copolymers grafted with maleic anhydride and then condensed with monoamino polyamide (or a polyamide oligomer) (products described in EP-A-0342066). .
• the functionalized polyolefin (C) may also be a co- or terpolymer of at least the following units:
• alkyl (meth) acrylate refers to methacrylates and C 1 -C 6 alkyl acrylates, and may be selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, and the like. , iso-butyl acrylate, acrylate 2-ethylhexyl, cyclohexyl acrylate, methyl methacrylate and ethyl methacrylate.
• polyolefins (C) may also be crosslinked by any suitable method or agent (diepoxy, diacid, peroxide, etc.).
• the polyolefins mentioned above (C) can be copolymerized randomly or sequentially and have a linear or branched structure.
• the molecular weight, the melt flow index (MFI), the density of these polyolefins may also vary to a large extent, which one skilled in the art will appreciate.
• MFI index is measured according to ASTM 1238.
• the functionalized polyolefins (C) are chosen from any polymer comprising alpha olefinic units and units carrying polar reactive functional groups which are the epoxy or maleic anhydride functional groups.
• examples of such polymers include terpolymers of ethylene, alkyl acrylate and maleic anhydride or glycidyl methacrylate such as compounds of the LOTADER® range marketed by Arkema, or polyolefins grafted with maleic anhydride, such as compounds from the OREVAC® range marketed by Arkema. Mention may also be made of homopolymers or copolymers of polypropylene grafted with a maleic anhydride and then condensed with polyamides or monoamino oligomers of polyamide, as described in application EP 0342066.
• the functionalized polyolefins (C) may be:
• copolymers of ethylene and octene grafted with maleic anhydride are copolymers of ethylene and octene grafted with maleic anhydride.
• the additives (D), when present, can comprise, in particular, fillers, adjuvants which aid in the transformation ("Processing aids"), stabilizers, colorants, release agents, flame retardants, surfactants, optical brighteners and mixtures thereof.
• fillers mention may be made of silica, graphite, expanded graphite, carbon black, glass beads, kaolin, magnesia, slag, talc, nanofillers (carbon nanotubes), pigments, metal oxides (titanium oxide), metals, fibers (aramids, glass, carbon).
• the amount of these can represent up to 35% by weight, advantageously up to 30% by weight, of the total weight of the composition, and for example from 5 to 30% by weight. 20 to 30% by weight.
• Expenses such as expanded graphite may make it possible to increase the thermal conductivity of the material (for example in order to promote a heat exchange between a light of a tube comprising a composition layer of the invention and the outside, or between two lumens of a tube comprising a composition layer of the invention).
• the fibers may for example have a length of 0.05 to 1 mm, and especially 0.1 to 0.5 mm. Their average diameter may be from 5 to 20 ⁇ , preferably from 6 to 14 ⁇ .
• the adjuvants assisting the transformation include stearates, such as calcium or zinc stearates, natural waxes, polymers comprising tetrafluoroethylene (TFE).
• stearates such as calcium or zinc stearates, natural waxes, polymers comprising tetrafluoroethylene (TFE).
• TFE tetrafluoroethylene
• processing aids is conventionally between 0.01 and 0.3% by weight, advantageously between 0.02 and 0.1% by weight, relative to the total weight of the composition.
• the dyes mention may in particular be made of carbon black.
• the dyes or pigments may be present for example at a level of from 0.1 to 0.2% by weight.
• a thermal stabilizer may be present in an amount of 0 to 4%, especially 0.01 to 2% or 0.1 to 0.3% by weight relative to the total weight of the composition.
• It may be a copper thermal stabilizer.
• it may be a copper salt or a copper salt derivative, for example copper iodide, copper bromide, copper halides, derivatives or mixtures thereof. -this.
• the copper salts I are preferred. Examples are copper iodide, copper bromide, copper chloride, copper fluoride, copper thiocyanate, copper nitrate, copper acetate, copper naphthenate, copper caprate, copper laurate, copper stearate, copper acetylacetonate, copper oxide. Copper iodide, copper bromide, copper chloride, copper fluoride are preferred.
• thermal stabilizer a metal halide salt in combination with Lil, NaI, Kl, Mgl 2 , KBr or Ca. K1 and KBr are preferred.
• the copper thermal stabilizer is a mixture of potassium iodide and copper iodide (KI / CaI).
• the mixture of potassium iodide and copper iodide useful according to the present invention is in a ratio of 90/10 to 70/30.
• the composition of the invention comprises from 0.10 to 0.25% by weight of copper thermal stabilizer.
• composition of the invention is devoid of such hindered phenolic antioxidants.
• HALS sterically hindered amine UV stabilizers
• this additional supply of polyolefin is preferably less than 1%, more particularly less than 0.5% or 0.2% or 0.1% relative to the total mass of the composition.
• composition of the invention may be prepared by any method which makes it possible to obtain a homogeneous mixture such as extrusion in the molten state, compacting or roller milling.
• composition of the invention may be prepared by melt blending of the compounds (A), (B) and (C). Any additives may, in turn, be introduced at the same time or possibly in a subsequent step.
• composition according to the invention comprises, or consists essentially of, or consists of:
• composition according to the invention comprises, or consists essentially of, or consists of:
• the composition can be obtained in the form of granules by compounding, in particular by means of a twin-screw extruder, a co-kneader or an internal mixer.
• granules of the composition of the invention obtained by the method of preparation described above, can then be transformed using tools known to those skilled in the art (such as an injection molding machine or an injection molding machine). extruder), especially in the form of tubes, films and / or molded articles. It is also possible to use a twin-screw extruder feeding, without intermediate granulation, an injection molding machine or an extruder, in particular for producing tubes, films and / or molded articles.
• the objects that can be manufactured with the composition according to the invention are in particular shoes, medical devices, sporting goods, automobile parts, mechanical tools, electronic products, or elements or parts of the preceding products.
• the articles or articles according to the invention can be obtained from the above composition by a known transformation process such as injection, extrusion, extrusion blow molding, coextrusion or multi-injection. .
• injection or multi-injection is used.
• compositions are formulated by compounding on a twin-screw extruder (EVOLUM 32, 35 kg / h at 300 rpm).
• the starting products that are used are:
• PEBAX 5513 Block copolymer of PA 6 and PTMG, sold by Arkema (reference MP 1878).
• LOTADER AX8900 poly (methyl ethylene acrylate) grafted with glycidyl methacrylate, marketed by Arkema.
• LOTADER 4700 poly (ethylene ethyl acrylate) grafted with maleic anhydride, marketed by Arkema.
• LUCALENE 31 10M poly (butyl acrylate) grafted with carboxylic acid, marketed by Lyondellbassell.
• EPR VA 1801 poly (ethylene propylene) grafted with maleic anhydride, sold by Exxon.
• EVA 2403 poly (ethylene vinyl acetate), marketed by Arkema.
• SEBS FG 1924X poly (styrene ethylene butylene styrene), marketed by Univar (Kraton);
• LOTRYL 24MA005 poly (ethylene acrylate) marketed by Arkema;
• LOTADER 3410 poly (ethylene butyl acrylate) grafted with maleic anhydride, marketed by Arkema.
• ULTRAMID B27E polyamide 6 marketed by BASF.
• compositions C1 to C4 represent comparative examples comprising both a non-functionalized polyolefin and a polyolefin functionalized (C1 to C3) or only representing the block copolymer (C4).
• the compositions E1 to E5 are examples according to the invention.
• Dv particle size in ⁇ . The observation is carried out by scanning electron microscopy on rods facies after cryogenic fracture with extraction of the chloroform dispersed phase at 50 ° C. for 30 min. The Dv corresponds
• Charpy shock at -40 ° C. (Charpy -40 ° C.) in kJ / m 2 , measured according to the ISO 179-1 eA standard.

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