EP1560872A1 - Transparente copolymere mit polyamid- und polyätherblöcken - Google Patents

Transparente copolymere mit polyamid- und polyätherblöcken

Info

Publication number
EP1560872A1
EP1560872A1 EP03778448A EP03778448A EP1560872A1 EP 1560872 A1 EP1560872 A1 EP 1560872A1 EP 03778448 A EP03778448 A EP 03778448A EP 03778448 A EP03778448 A EP 03778448A EP 1560872 A1 EP1560872 A1 EP 1560872A1
Authority
EP
European Patent Office
Prior art keywords
blocks
polyamide
polyether
acid
copolymers according
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Withdrawn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
EP03778448A
Other languages
English (en)
French (fr)
Inventor
Frédéric MALET
Annett Linemann
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.)
Arkema France SA
Original Assignee
Arkema France SA
Arkema SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Arkema France SA, Arkema SA filed Critical Arkema France SA
Publication of EP1560872A1 publication Critical patent/EP1560872A1/de
Withdrawn legal-status Critical Current

Links

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
    • C08G69/40—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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • 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
    • 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
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/126—Copolymers block

Definitions

  • the present invention relates to transparent copolymers containing polyamide blocks and polyether blocks. They are also called polyether amide blocks (PEBA), they are thermoplastic elastomers. They are also called elastomeric polyamides. These copolymers are useful for manufacturing many objects and in particular sports shoes. The transparency of the copolymers of the present invention is measured on sheets 2 to 4 mm thick.
  • Patent application JP 05 078477 A published on March 30, 1993 describes copolymers with polyamide blocks and polyether blocks having copolyamide blocks but the polyether blocks are a mixture of PTMG and PEG
  • polyethylene glycol or polyoxyethylene glycol containing between 30 and 99% by weight of PEG.
  • the number-average molar mass Mn of PTMG is between 1000 and 2000.
  • the number-average molar mass Mn of PEG is between 1000 and 2020. They are used to make antistatic resins. It is also written that they have excellent water vapor permeability properties.
  • Patent application WO 99-33659 describes a multilayer structure comprising a material covered by a copolymer with polyamide blocks and hydrophilic blocks, said copolymer having a melting temperature below 135 ° C and preferably between 90 and 135 ° C.
  • the polyamide blocks are of low mass or are copolyamides.
  • the hydrophilic blocks of the copolymer are polyethers having at least 50% by weight of units:
  • the amount of polyether blocks of the copolymer represents 10 to 40% by weight of the copolymer.
  • the material of this multilayer structure is paper, cardboard, a nonwoven of cellulose fibers, a nonwoven based on polyolefin fibers or a fabric chosen from cotton, polyamide or polyester.
  • Patent application EP 1046675 describes copolymers with polyamide blocks and polyether blocks similar to those of the structure described above in the structure according to WO 99-33659. They are useful as additives in thermoplastic polymers to make them antistatic.
  • the present invention relates to copolymers with polyamide blocks and polyether blocks in which: “the polyether blocks consist essentially of PTMG of average molar mass in number Mn of between 200 and 4000 g / mol,
  • the polyamide blocks consist of a majority semi-crystalline linear aliphatic monomer (non-cyclic, unbranched) and of a sufficient amount of at least one comonomer to reduce their crystallinity while remaining immiscible with the amorphous polyether blocks,
  • Transparency is defined as an opacity of less than 12% for a sample at least 2 mm thick.
  • the invention also relates to the objects produced with these copolymers.
  • thermoplastic polymers can be manufactured by injection, molding, extrusion and in general by the techniques of transformation of thermoplastic polymers.
  • sheets of 0.5 to 4 mm thick are useful for making soles for sports shoes.
  • polyamide sequences with dicarboxylic chain ends originate, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid.
  • polyamide sequences with diamine chain ends originate, for example, from the condensation of polyamide precursors in the presence of a chain limiting diamine.
  • polymers containing polyamide blocks and polyether blocks can also comprise units distributed randomly. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.
  • polyetherdiol polyamide precursors and a chain-limiting diacid
  • a polymer is obtained which essentially has polyether blocks, polyamide blocks of very variable length, but also the various reactants which have reacted randomly which are distributed randomly (statistically) along the polymer chain.
  • Polyetherdiamine, polyamide precursors and a chain-limiting diacid can also be reacted.
  • a polymer is obtained which essentially has polyether blocks, polyamide blocks of very variable length, but also the various reactants which have reacted randomly which are distributed randomly (statistically) along the polymer chain.
  • the semi-crystalline monomer can be a linear aliphatic alpha omega amino carboxylic acid (called amino acid in the remainder of the text), a lactam (corresponding to a linear aliphatic alpha omega amino carboxylic acid), or a diamine associated with a diacid, both being linear aliphatics.
  • alpha omega amino aliphatic carboxylic acid mention may be made of aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids.
  • lactam mention may be made of caprolactam, oenantholactam and lauryllactam.
  • aliphatic diamines mention may be made of hexamethylenediamine and dodecamethylenediamine.
  • aliphatic diacids mention may be made of butane-dioic, adipic, azelaic, suberic, sebacic and dodecanedicarboxylic acids.
  • the semi-crystalline monomer constituted by a diamine associated with a diacid both being linear aliphatics
  • the aliphatic polyamides resulting from the condensation of an aliphatic diamine having from 6 to 12 carbon atoms and an aliphatic diacid having preference are preferred. from 9 to 12 carbon atoms.
  • aliphatic polyamides resulting from the condensation of an aliphatic diamine having from 6 to 12 carbon atoms and from an aliphatic diacid having from 9 to 12 carbon atoms
  • PA 6-12 resulting from the condensation of hexamethylene diamine and of 1,12-dodecanedioic acid
  • PA 9-12 resulting from the condensation of diamine at C9 and of 1,12-dodecanedioic acid
  • PA 10-10 resulting from the condensation of the diamine at C10 and of the 1,10-decanedioic acid
  • the PA 10-12 resulting from the condensation of the diamine at C9 and of the 1,12-dodecanedioic acid.
  • a comonomer is introduced to disorganize the crystal lattice and thus increase the transparency while retaining sufficient crystallinity for there to be phase separation between the polyamide blocks and the PTMG blocks, which makes it possible to keep good mechanical properties.
  • This comonomer can be any, it can be a lactam, it can be an alpha acid omega amino carboxylic, it can be a diamine associated with a diacid. Mention may be made, for example, of cyclic, branched, linear, branched monomers.
  • a lactam, an alpha omega amino carboxylic acid, a cyclic diamine associated with a diacid preferably associated with a linear aliphatic diacid and for example sebacic acid are used.
  • the cyclic diamine can be IPD (isophorone diamine) or PACM 20 (bis_para amino cyclohexyl methane) of the following formulas:
  • the majority crystalline monomer is lactam 12.
  • the Tg of PA 12 is 50 ° C.
  • a comonomer is added to increase the Tg preferably up to 70 ° C. and therefore decrease the crystallinity.
  • the polyamide blocks consist of lactam 12 (majority lens) and IPD.10 (isophorone diamine and sebacic acid) or lactam 12 and PACM.12 (PACM 20 and C12 diacid).
  • the polyamide blocks are consist of lactam 12 (majority lens) and lactam 6 or amino-11-undecanoic acid.
  • the polyamide blocks consist of lactam 12 (majority lens) and lactam 6 and amino-11-undecanoic acid.
  • the crystalline monomer advantageously represents by weight at least 55% and preferably at least 70% of the constituents of the polyamide block.
  • the polyamide blocks are obtained in the presence of a diacid or of a chain-limiting diamine if polyamide blocks with acid or amino ends are desired. If the precursors already comprise a diacid or a diamine, it is sufficient, for example, to use it in excess.
  • the number-average molar mass Mn of the polyamide blocks can be between 500 and 10,000 and preferably between 500 and 4,500.
  • polyamide blocks By way of example of polyamide blocks, mention may also be made of:
  • Blocks 6/11/12 which result from the condensation of caprolactam, amino-11-undecanoic acid and lauryllactam.
  • the proportions by weight can be respectively 10 to 20/20 to 40/50 to 80.
  • the average molar mass in number Mnde of these polyamide blocks can be between 500 and 4200.
  • the proportions by weight can be from 18 to 45% of caprolactam for respectively 55 to 82% of lauryllactam.
  • the number-average molar mass Mn of these polyamide blocks can be between 1000 and 3000.
  • the polyether blocks can represent 5 to 85% by weight of the copolymer with polyamide and polyether blocks.
  • the polyether blocks consist of tetrahydrofuran units which leads to polytetramethylene glycol sequences also called PTMG which can be represented by the formula:
  • the polyether blocks contained small proportions of other alkylene oxides, provided that the properties of the copolymer of the invention are preserved.
  • low proportions is meant a proportion by weight of the order of at most 5%.
  • the copolymer of the invention can contain other polyethers than PTMG, provided that the properties of the copolymer of the invention are preserved.
  • low proportions is meant a proportion by weight of the order of at most 5%.
  • the quantity of polyether blocks in these copolymers with polyamide blocks and polyether blocks is advantageously from 10 to 40% by weight of the copolymer and preferably from 10 to 25%
  • the polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks with carboxylic ends, or they are aminated to be transformed into polyether diamines and condensed with polyamide blocks with carboxylic ends.
  • the designation PTMG block is retained for the polyether blocks originating from polytetramethyleneglycol (polyetherdiol), the OH ends of which have been replaced by NH 2 functions and then condensed with the polyamide blocks. They can also be mixed with polyamide precursors and a diacid chain limiter to make polymers containing polyamide blocks and polyether blocks having randomly distributed units.
  • the mass Mn of the polyether blocks is advantageously between 300 and 1100 and preferably between 300 and 700. With regard to shore hardness D, it is advantageously between 40 and 70.
  • the hardness increases with the proportion of polyamide relative to the PTMG. The higher the polyamide blocks, the PTMG blocks remaining the same, the higher the hardness.
  • copolymers of the invention can also be characterized by their intrinsic viscosity.
  • These polymers with polyamide blocks and polyether blocks whether they originate from the copolycondensation of polyamide and polyether blocks prepared previously or from a one-step reaction have, for example, an intrinsic viscosity between 0.8 and 2.5 measured in metacresol at 25 ° C. for an initial concentration 0.8 g / 100 ml.
  • the copolymers of the invention can be prepared by any means allowing the polyamide blocks and the polyether blocks to be attached.
  • essentially two methods are used, one said in 2 steps, the other in one step.
  • the polyamide blocks are first manufactured, then in a second step, the polyamide blocks and the polyether blocks are hooked.
  • the polyamide precursors, the chain limiter and the polyether are mixed; a polymer is then obtained which essentially has polyether blocks, polyamide blocks of very variable length, but also the various reactants which have reacted randomly which are distributed randomly (statistically) along the polymer chain. Whether in one or two stages, it is advantageous to operate in the presence of a catalyst.
  • the 2-step process consists first of all in preparing the polyamide blocks with carboxylic ends by condensation of the polyamide precursors in the presence of a chain-limiting dicarboxylic acid, then in a second step in adding the polyether and a catalyst. If the polyamide precursors are only lactams or alpha omega acids aminocarboxylic, a dicarboxylic acid is added. If the precursors already comprise a dicarboxylic acid, it is used in excess relative to the stoichiometry of the diamines. The reaction is usually carried out between 180 and 300 ° C, preferably 200 to 290 ° C the pressure in the reactor is established between 5 and 30 bars, it is maintained approximately 2 to 3 hours. The pressure is slowly reduced by putting the reactor into the atmosphere and then the excess water is distilled, for example an hour or two.
  • the polyether can be added one or more times, as can the catalyst.
  • the polyether is first added, the reaction of the OH ends of the polyether and of the COOH ends of the polyamide begins with ester bond formations and elimination of water; Water is removed as much as possible from the reaction medium by distillation and then the catalyst is introduced to complete the bonding of the polyamide blocks and of the polyether blocks.
  • This second step is carried out with stirring preferably under a vacuum of at least 6 mm Hg (800 Pa) at a temperature such that the reagents and the copolymers obtained are in the molten state.
  • this temperature can be between 100 and 400 ° C.
  • the reaction is followed by measuring the torque exerted by the molten polymer on the agitator or by measuring the electric power consumed by the agitator. The end of the reaction is determined by the value of the target torque or power.
  • the catalyst is defined as being any product making it possible to facilitate the bonding of the polyamide blocks and of the polyether blocks by esterification.
  • the catalyst is advantageously a derivative of a metal (M) chosen from the group formed by titanium, zirconium and hafnium.
  • M represents titanium, zirconium or I 'hafnium and the Rs, identical or different, denote alkyl radicals, linear or branched, having 1 to 24 carbon atoms.
  • C 1 to C 24 alkyl radicals from which are chosen the R radicals of the tetraalkoxides used as catalysts in the process according to the invention are for example such as methyl, ethyl, propyl, isopropyl, butyl, ethylhexyl, decyl, dodecyl, hexadodecyl.
  • the preferred catalysts are the tetraalkoxides for which the radicals R, identical or different, are alkyl radicals Cj to Ce- Examples of such catalysts are in particular Z r (OC 2 H 5 ) 4, Z r (0-isoC 3 H 7 ) 4 , Z r (OC 4 H 9 ) 4, Z r (OC 5 H -1 -1) 4, Z r (OC 6 H 13 ) 4 , Hf (OC 2 H 5 ) 4, Hf (OC 4 Hg) 4, Hf (0-isoC 3 H 7 ) 4.
  • the catalyst used in this process according to the invention can consist solely of one or more of the tetraalkoxides of formula M (OR) 4 defined above. It can also be formed by the association of one or more of these tetraalkoxides with one or more alkali or alkaline earth alcoholates of formula (R-tO) pY in which R-
  • Y represents an alkali or alkaline earth metal and p is the valence of Y.
  • the amounts of alkali or alkaline earth alcoholate and of zirconium or hafnium tetraalkoxides which are combined to constitute the mixed catalyst can vary within wide limits. However, it is preferred to use amounts of alcoholate and tetraalkoxides such that the molar proportion of alcoholate is substantially equal to the molar proportion of tetraalkoxide.
  • the proportion by weight of catalyst that is to say of the tetraalkoxide (s) when the catalyst does not contain alkali or alkaline earth alcoholate or else of all of the tetraalkoxide (s) and of alkali or alkaline alcoholates earthy when the catalyst is formed by the association of these two types of compounds, advantageously varies from 0.01 to 5% of the weight of the mixture of the polyamide dicarboxylic with the polyoxyalkylene glycol, and is preferably between 0.05 and 2% of this weight.
  • salts of the metal (M) in particular the salts of (M) and of an organic acid and the complex salts between the oxide of (M) and / or (M) hydroxide and an organic acid.
  • the organic acid can be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, acid caprylic, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, cyclohexane carboxylic acid, phenylacetic acid, benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid and crotonic acid.
  • Acetic and propionic acids are particularly preferred.
  • M is zirconium.
  • zirconyl salts These salts can be called zirconyl salts.
  • the Applicant without being bound by this explanation, believes that these zirconium and organic acid salts or the complex salts mentioned above release ZrO ++ during the process.
  • the product sold under the name of zirconyl acetate is used.
  • the quantity to be used is the same as for the derivatives M (OR) 4.
  • all the reagents used in the two-step process are mixed, that is to say the polyamide precursors, the chain-limiting dicarboxylic acid, the polyether and the catalyst. These are the same reagents and the same catalyst as in the two-step process described above. If the polyamide precursors are only lactams, it is advantageous to add a little water.
  • the copolymer has essentially the same polyether blocks, the same polyamide blocks, but also a small part of the various reactants which have reacted randomly which are distributed statistically along the polymer chain.
  • the reactor is closed and heated with stirring as in the first step of the two-step process described above.
  • the pressure is between 5 and 30 bars.
  • the reactor is placed under reduced pressure while maintaining vigorous stirring of the molten reactants.
  • the reaction is followed as above for the two-step process.
  • the catalyst used in the one-step process is preferably a salt of the metal (M) and an organic acid or a complex salt between the oxide of (M) and / or the hydroxide of (M) and an organic acid.
  • Dyes, pigments, fillers, anti UV, antioxidants can be added to the copolymers of the invention.
  • the final product has an inherent viscosity of 1.5 dl / g and an MFI (235 ° C / 2.16 kg) of 6.15 g / 10 min.
  • the injection molding of 100 * 100 * 2 mm plates confirms the transparency of the product with a transmission at 460 nm of 68%, at 560 nm of 78% and at 700 nm of 85%, as well as an opacity of around 13%.
  • Example 2 Synthesis of a 6/12 - PTMG where the PA sequence is 1300 g.mol "1 and of composition 6/12: 20/80 and where the polyether is the PTMG of Mn 650.
  • the following monomers are introduced into an autoclave equipped with a stirrer: 3.60 kg of Lactam 6, 14.40 kg of Lactam 12 and 2.32 kg of adipic acid.
  • the mixture thus formed is placed under an inert atmosphere and heated until the temperature reaches 280 ° C. and 22 bar of pressure. After holding for 3 hours, a 2 hour expansion operation is then carried out to return to atmospheric pressure.
  • the polytetramethylene glycol with a mass of 650 g.mol “ 1 (9.8 kg) and Zr (OBu) 4 (60 g) are then added to the reactor to complete the polymerization at 240 ° C under absolute pressure of 13 mbar (1300 Pa).
  • the final product has an inherent viscosity of 1.5 dl / g and an MFI (235 ° C / 1 kg) of 10.5 g / 10 min.
  • the injection molding of 100 * 100 * 2 mm plates confirms the transparency of the product with a transmission to 460 nm of 66%, 560 nm of 77% and 700 nm of 84%, as well as an opacity of around 12%.
  • IPD.10 designates the condensation of isophorone diamine with sebacic acid
  • PTMG 65 o designates the PTMG of average molar mass in number 650, the proportion of PTMG is expressed in the form of the association with C10 acid,
  • PTMG-iooo- designates the PTMG of average molar mass in number 1000, the proportion of PTMG is expressed in the form of the association with the acid in
  • PACM 12 denotes the condensation of PACM 20 with the C12 acid, the proportion of PTMG is expressed in the form of the association with the acid in

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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)
  • Polyamides (AREA)
EP03778448A 2002-10-23 2003-10-23 Transparente copolymere mit polyamid- und polyätherblöcken Withdrawn EP1560872A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0213218 2002-10-23
FR0213218A FR2846332B1 (fr) 2002-10-23 2002-10-23 Copolymeres transparents a blocs polyamides et blocs polyethers
PCT/FR2003/003148 WO2004037898A1 (fr) 2002-10-23 2003-10-23 Copolymères transparents à blocs polyamides et blocs polyéthers

Publications (1)

Publication Number Publication Date
EP1560872A1 true EP1560872A1 (de) 2005-08-10

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP03778448A Withdrawn EP1560872A1 (de) 2002-10-23 2003-10-23 Transparente copolymere mit polyamid- und polyätherblöcken

Country Status (9)

Country Link
US (1) US20050165210A1 (de)
EP (1) EP1560872A1 (de)
JP (1) JP2006503951A (de)
KR (1) KR100648878B1 (de)
CN (1) CN1329431C (de)
AU (1) AU2003285447A1 (de)
CA (1) CA2503074A1 (de)
FR (1) FR2846332B1 (de)
WO (1) WO2004037898A1 (de)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
EP1783156A1 (de) 2005-11-03 2007-05-09 Arkema France Verfahren zur Herstellung von Copolymeren mit Polyamid-und Polyetherblöcken

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US20050165210A1 (en) 2005-07-28
FR2846332A1 (fr) 2004-04-30
FR2846332B1 (fr) 2004-12-03
WO2004037898A1 (fr) 2004-05-06
KR20050067198A (ko) 2005-06-30
AU2003285447A1 (en) 2004-05-13
KR100648878B1 (ko) 2006-11-24
CN1708538A (zh) 2005-12-14
CA2503074A1 (fr) 2004-05-06
CN1329431C (zh) 2007-08-01

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