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
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether 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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/44—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
  • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component

Definitions

• the present invention relates to novel copolymers comprising polyamide blocks (abbreviated PA block) and polyether blocks (abbreviated PE block) having improved optical and / or mechanical properties.
• polyamide blocks abbreviated PA block
• PE block polyether blocks
• Such block copolymers are also called polyether block amides (abbreviation PEBA).
• the PEBA copolymers of the invention belong to the particular class of polyetheresteramides when they result from the copolycondensation of polyamide sequences with reactive carboxyl ends with polyether sequences with reactive ends, which are polyether polyols (polyetherdiols), the bonds between the polyamide blocks. and the polyether blocks being ester bonds or to the class of polyetheramides when the polyether blocks are amine terminated.
• EP1500684 discloses antistatic elastomeric compositions comprising a PEBA copolymer comprising essentially PE PE blocks and PAX blocks.
• Y with X an aliphatic diamine such as hexamethylenediamine and diamines C9 to C25 and Y a diacid aliphatic C9 to C25.
• EP1262527 relates to an antistatic polymer composition
• a PEBA of the PAX type comprising a PEBA of the PAX type.
• the PEG PE blocks imparting the antistatic properties to the copolymer and the composition, can be used with PPG blocks or with PTMG blocks. These copolymers do not enter in the scope of our invention and are, of course, excluded as such.
• WO03 / 050159 discloses PEBAs with a PAX.Y block as a hard segment with X a linear aliphatic diamine containing 4-14 carbon atoms and Y a linear aliphatic diacid containing from 4 to 14 carbon atoms and with PO3G in as a soft segment, the latter may comprise up to 60% by weight of another polyether such as PEG, PPG and PTMG. These copolymers are not within the scope of our invention and are, of course, excluded as such.
• the WO04 / 037898 relates to a block copolymer PA and PE blocks whose PA blocks are copolyamides which may be of the PAXl type. Y1 / X2.Y2 or PAX1.Y1 / Z, X1 and X2 being diamines, Y1 and Y2 being diacids and Z being a lactam or an amino acid. These copolymers are not within the scope of our invention and are, of course, excluded as such.
• the applicant company has surprisingly discovered a new class of PEBA with improved optical properties, in particular a decrease in PEBA opacity and / or improved mechanical properties, in particular a very good resistance to dynamic fatigue.
• PAX.Y / PE copolymer comprising polyamide PA blocks alternating with polyether PE blocks, the PA blocks being constituted by PA XY homopolyamide blocks, obtained by polycondensation. : a linear aliphatic diamine having X carbon atoms; a dicarboxylic acid having Y carbon atoms; said copolymer being characterized in that: said PA blocks are carboxylic ends;
• X is at least 4, preferably at least equal to
• Y is at least 10, preferably at least 12;
• (i) preferably are either hydroxyl end PE blocks, otherwise referred to as PE diol blocks such that the bonds between the carboxyl-end PA blocks and the PE diol blocks are ester bonds; (ii) preferably, are either NH 2 -terminated PE blocks in the case where Y has a number of carbon atoms greater than 14, such that the bonds between the carboxyl-end PA blocks and the PE blocks at NH 2 ends are amide bonds;
• the PAX.Y / PE copolymer has improved transmission optical properties at 460nm, 560nm and 700nm compared to a PA12 / PTMG (iv) copolymer of the same PA block size and the same PE block size. respectively and / or (v) of the same rigidity defined either by a flexural modulus (in MPa), by a tensile modulus (in MPa), or by a shore hardness D.
• the copolymer is characterized in that the 100 to 61% of polyether in (iii) are chosen from PTMG, PPG, their mixtures and their copolymers.
• the copolymer is characterized in that the block PA is chosen from a block PA10.12, PA6.18, PA10.14, PA12.12, PA12.14, PA10.18 and PA12.18.
• the subject of the present invention is therefore, in the context of the improved mechanical properties, a PAX.Y / PE copolymer comprising polyamide PA blocks alternating with polyether PE blocks, the PA blocks being constituted by PA X. Y homopolyamide blocks, obtained by polycondensation
• said PA blocks are at carboxyl ends
• X is at least 4, preferably at least 6;
• Y is at least 10, preferably at least 12;
• (iv) preferably, are either hydroxyl end PE blocks, otherwise called PE diol blocks such that the bonds between the carboxyl-end PA blocks and the PE diol blocks are ester linkages; (v) preferably, are either NH 2 -terminated PE blocks in the case where Y has a number of carbon atoms greater than 14, so that the bonds between the carboxyl-end PA blocks and the PE blocks at NH 2 ends are amide bonds;
• the copolymer is characterized in that the PA block is chosen from a block PA10.14, PA12.12, PA6.18, PA10.12, PA6.14 and PA10.10.
• the copolymer is characterized, within the framework of the improved mechanical and / or optical properties:
• dicarboxylic acid having Y carbon atoms is chosen from linear aliphatic diacids
• Y is between 10 and 20 advantageously between 12 and 20, preferably between 10 and 18, even more preferably between 12 and 18 inclusive.
• dicarboxylic acids having Y carbon atoms there may be mentioned sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid;
• X is between 6 and 20 included terminals, preferably between 6 and 14 inclusive.
• linear aliphatic diamines having X carbon atoms mention may be made of tetramethylene diamine, hexamethylenediamine and 1,10-decamethylenediamine.
• the polyamide block PA X. Y is advantageously chosen from polyamide blocks 4.12, polyamide 4.14, polyamide 4.18, polyamide 6.10, polyamide 6.12, polyamide 6.14, polyamide 6.18, polyamide 9.12, polyamide 10.10, polyamide 10.12. , polyamide 10.14 and polyamide 10.18. More preferably, the PA X. Y polyamide block is a PA6.18 or PA10.14 block for improved optical properties and a PA6.12 or PA6.14 block for improved mechanical properties. PA6.12 / PTMG may be excluded from the scope of our invention.
• PAX polyamides. Y result from the condensation of diamine X and diacid Y, such that:
• PA4.12 1,4-tetramethylene diamine and 1,10-decanedicarboxylic acid.
• PA4.14 1,4-tetramethylene diamine and 1,12-dodecanedicarboxylic acid.
• PA4.18 1,4-tetramethylene diamine and 1,16-hexadecanedicarboxylic acid.
• PA6.10 hexamethylene diamine and sebacic acid.
• PA6.12 hexamethylene diamine and 1,10-decanedicarboxylic acid.
• PA6.14 hexamethylene diamine and 1,12-dodecanedicarboxylic acid.
• PA6.18 hexamethylene diamine and 1, 16-hexadecanedicarboxylic acid.
• PA9.12 1, 9-nonanediamine and 1,10-decanedicarboxylic acid.
• PA10.10 1,10-decamethylenediamine and sebacic acid.
• PA10.12 1,10-decamethylenediamine and 1,10-decanedicarboxylic acid.
• PA10.14 1,10-decamethylenediamine and 1,12-dodecane dicarboxylic acid.
• PA10.18 1,10-decamethylenediamine and 1,16-hexadecane dicarboxylic acid.
• the polyether blocks of the PEBA copolymer of the invention are advantageously derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol and more particularly chosen from polypropylene glycol. (PPG), polytetramethylene glycol (PTMG), their blends and copolymers.
• PPG polypropylene glycol
• PTMG polytetramethylene glycol
• the PTMG will be selected.
• the PE blocks may comprise a mixture of PE blocks or be a polyether copolymer. In this case, they comprise 0-39% by weight of PO3G and / or PEG and 100-61%, by weight of polyether (s) different (s) PO3G or PEG, (weight relative to the weight of the blocks PE).
• the PE blocks are never the majority in PEG and never comprise more than 39% by weight of PO3G (weight relative to the weight of PE blocks).
• the polyether blocks of the PEBA copolymer according to the present invention can also be polyoxyalkylene sequences with NH 2 chain ends, such sequences being obtainable by cyanoacetylation of polyoxyalkylene aliphatic alpha-omega dihydroxy sequences known as polyetherdiols. More particularly, it is possible to use Jeffamines (for example Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products from Huntsman, see also JP 2004346274, JP 2004352794 and EP1482011).
• Jeffamines for example Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products from Huntsman, see also JP 2004346274, JP 2004352794 and EP1482011.
• the number-average molecular weight of a copolymer according to the present invention is advantageously between 5000 and 50000, preferably between 10000 and 30000.
• the number-average molecular mass of the PA blocks is advantageously between 500 and 10,000, preferably between 600 and 7,000, more advantageously between 1,500 and 6,000.
• the number-average molecular mass of the PE blocks is advantageously between 250 and 5000, preferably between 250 and 2000, and even more advantageously between 350 and 1000.
• the PA blocks advantageously represent between 5 and 95, preferably between 10 and 95% by weight of the sum of the PA blocks and the PE blocks of the copolymer of the present invention.
• the subject of the invention is also a process for the preparation of a copolymer as defined above, in several stages, characterized in that:
• the polyamide PA blocks are prepared by polycondensation of the linear aliphatic diamine having X carbon atoms; o dicarboxylic acid having Y carbon atoms; and o in the presence of a chain limiter selected from dicarboxylic acids; then
• the polyamide PA blocks obtained are reacted with polyether PE blocks in the presence of a catalyst.
• the general method for the two-step preparation of the PEBA copolymers of the invention having ester bonds between the PA blocks and the PE blocks is known and is described, for example, in the French patent FR 2 846 332.
• the general method of preparation PEBA copolymers of the invention having amide linkages between PA blocks and PE blocks is known and described, for example in European Patent EP 1 482 011.
• the formation reaction of the PA block is usually between 180 and 300 ° C., preferably between 200 and 60 ° C., the pressure in the reactor is between 5 and 30 bar and is maintained for about 2 to 3 hours. The pressure is slowly reduced by putting the reactor at atmospheric pressure, then the excess water is distilled for example for one hour or two.
• the carboxylic acid terminated polyamide having been prepared, the polyether and a catalyst are then added.
• the polyether can be added in one or more times, as can the catalyst.
• the polyether is first added, the reaction of the OH ends of the polyether and the COOH ends of the polyamide begins with the formation of ester bonds and elimination of water. We removes as much water as possible from the reaction medium by distillation, and then the catalyst is introduced to complete the bonding of the polyamide blocks and the polyether blocks.
• This second step is carried out with stirring, preferably under a vacuum of at least 6 mmHg (800 Pa) at a temperature such that the reagents and copolymers obtained are in the molten state.
• this temperature can be between 100 and 400 ° C. and most often 200 and 300 ° C.
• the reaction is followed by measuring the torsion torque exerted by the molten polymer on the stirrer or by the measuring the electrical power consumed by the agitator. The end of the reaction is determined by the value of the target torque or power.
• the invention also relates to a process for the preparation of a copolymer as defined above, characterized in that a polycondensation is carried out in a single step:
• chain limiter chosen from dicarboxylic acids
• the process is characterized in that the dicarboxylic acid having Y carbon atoms, which is introduced in excess with respect to the stoichiometry of the diamine, can be used as a chain limiter;
• the process is characterized in that a derivative of a metal selected from the group formed by titanium can be used as a catalyst, zirconium and hafnium or a strong acid such as phosphoric acid or boric acid;
• the process is characterized in that one can conduct the polycondensation at a temperature of 180 to 300 0 C;
• the catalyst is defined as being any product making it possible to facilitate the bonding of the polyamide blocks and the polyether blocks by esterification or by amidation.
• the esterification catalyst is advantageously a derivative of a metal selected from the group consisting of titanium, zirconium and hafnium or a strong acid such as phosphoric acid or boric acid.
• catalysts are those described in US Pat. Nos. 4,331,786, 4,115,415, 4,195,155, 4,839,441, 4,884,014, 4,230,838 and 4,332,920.
• One or more molecules used as an antioxidant may also be added during the synthesis at the time deemed most appropriate.
• the present invention also relates to a shaped article, which can be advantageously transparent or translucent, such as for example fiber, fabric, film, sheet, ring, tube, any injected part (shoe sole parts, etc.) including the copolymers as defined above.
• the invention further relates to the use of a PAX.Y / PE copolymer mentioned above for producing an object whose optical properties are improved with respect to the same object manufactured with a PA12 PA12 / PTMG block PA12 copolymer. and PE blocks in PTMG, knowing that: the size of the PA blocks of the said PAX.Y / PE and PA12 / PTMG copolymers is the same or substantially the same and the size of the PE blocks of the said PAX.Y / PE and PA12 / PTMG copolymers is the same or substantially the same; and / or the rigidity of said PAX.Y / PE and PA12 / PTMG copolymers is the same or substantially the same, said stiffness being defined either by a flexural modulus (in MPa) or by a tensile modulus (in MPa), or by a hardness shore D.
• “Substantially” means that the value of either the flexural modulus (in MPa), the tensile modulus (in MPa), or the Shore D hardness of the PAX.Y / PE copolymer, according to the invention, is greater or less of at most 20%, preferably at most 10%, advantageously at most 5% to the value respectively of either the flexural modulus (in MPa), the tensile modulus (in MPa), or the Shore D hardness of the PA12 / PTMG copolymer.
• the invention also relates to the use of a PAX.Y / PE copolymer mentioned above to manufacture an object whose mechanical properties are improved with respect to the same object manufactured with PA block copolymer PA12 and PE blocks.
• PTMG PTMG
• Y is> at the crystallinity of a PA12 block of the same size and / or the PA / PE phase separation of said PAX.
• Y / PE copolymer> is that of a PA12 / PTMG copolymer consisting of PA12 blocks of the same size the PA X.
• the following examples illustrate the present invention without, however, limiting its scope.
• a PEBA was prepared from PA 6.18 blocks of molar mass 2000 g / mol and PTMG blocks of molar mass 1000 g / mol according to the following procedure:
• PA blocks 6.18 5 kg of hexamethylenediamine, 16.9 kg of octadecanedioic acid.
• the mixture thus formed is put under an inert atmosphere and heated until the temperature reaches 250 ° C. and 32 bar pressure. After maintaining Ih, then performs a relaxation operation of Ih to return to atmospheric pressure.
• the polytetramethylene glycol of mass 1000 g / mol (10.22 kg) and Zr (OBu) 4 (30 g) are then added to the reactor to complete the polymerization at 240 ° C. under an absolute pressure of 8 mbar (800 Pa).
• the final product PA 6.18-PTMG has an inherent viscosity of 1.4 dl / g.
• a PEBA was prepared from PA blocks 10.14 of molar mass 5000 g / mol and PTMG blocks of molecular weight 650 g / mol according to the preceding procedure with however, as 1,1,10-decamethylenediamine diamine (11.95 kg), 1,12-dodecane dicarboxylic acid (19.4 kg) and polytetramethylene glycol (3.7 kg) diacid.
• the final product PA 10.14-PTMG has an inherent viscosity of 1.28 dl / g.
• Injection molding of 100 * 100 * 2 mm plates confirms the improved optical properties of the product with transmission at 460 nm of 49.5%, 560 nm of 62.9% and 700 nm of 71.7% (measurements made according to ASTM D 1003), an opacity of approximately 20% (measured according to ASTM D 1003) and a haze of 11 (measured according to ISO 2814), which can be compared to the values obtained for a copolymer of the same size of PA blocks and of the same PE block size respectively but based on PA 12 and PTMG, said values being respectively 14, 23, 35, unmeasured and 25.
• the thermal properties in particular the melting point of the PA phase, may be higher than in the case of a PA 12 / PTMG copolymer and this, for the same molar mass of the PA block and the PE block.
• a PEBA 6.14 / PTMG copolymer with a PA 6.14 block having a mass of 5000 g / mol and a PTMG block of 650 g / mol has a melting point of 196-206 ° C.
• a PEBA copolymer of PA12 type / PTMG of the same block size has a melting point of 172 ° C.
• a PEBA was prepared from PA 6.14 blocks of 5000 g / mol molar mass and PTMG blocks of molar mass. 650 g / mol according to the preceding procedure with 1,6-hexamethylenediamine diamine (13.2 kg), for example 1,12-dodecane dicarboxylic acid (31.6 kg) and polytetramethylene glycol (5, 3 kg).
• the final product PA 6.14-PTMG has an inherent viscosity of 1.44 dl / g. The bending modulus of the product thus obtained (after conditioning for 14 days at 23 ° C.
• a PEBA was prepared from PA 6.12 blocks with a molar mass of 4000 g / mol and with PTMG blocks with a molecular weight of 650 g / mol according to the preceding procedure with, however, as diamine 1,6-hexamethylenediamine (13.9 kg). as diacid dodecanedioic acid (29.8 kg) and polytetramethylene glycol (6.4 kg).
• the final product PA 6.12-PTMG has an inherent viscosity of 1.38 dl / g.
• the bending modulus of the product thus obtained (after conditioning for 14 days at 23 ° C. and 50% relative humidity) was measured at 730 MPa, which can be compared with the flexural modulus of 380 MPa for a copolymer of block size PA greater than and equal to the size of PE blocks respectively but based on PA 12 and PTMG.
• the PA 6.12-PTMG product is significantly more rigid and does not break after 150,000 cycles during a flexural fatigue test at -10 ° C. ( Ross Flex test).

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  • 2007-02-16 WO PCT/FR2007/050814 patent/WO2007093751A2/fr active Application Filing
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