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
  • C08L77/12—Polyester-amides
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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

Definitions

• Polyamide blocks and polyether blocks copolymers are also called polyether block amides (PEBA), they are thermoplastic elastomers. They are also called elastomeric polyamides.
• the invention relates to mixtures of copolymers with polyamide blocks and polyether blocks which have polyamide blocks consisting mainly of lauryllactam residues with a polyamide other than a polyamide 12 or another polyamide block and polyether block copolymer having polyamide blocks which do not do not consist mainly of leftover lauryl lactam.
• the “rest” is the structure of the monomer after polycondensation.
• These copolymers do not include ionic functions. They are useful for making many objects and especially sports shoes.
• No. 4,820,796 describes copolymers with polyamide blocks and polyether blocks whose polyamide blocks are made of PA 6 (polyamide 6 or polycaprolactam) and polyether blocks with PTMG (polytetramethylene glycol or polyoxytetramethylene glycol or polytetrahydrofuran) with a number-average molar mass Mn between 680 and 4040. They have insufficient transparency.
• PA 6 polyamide 6 or polycaprolactam
• PTMG polytetramethylene glycol or polyoxytetramethylene glycol or polytetrahydrofuran
• Patent Application JP 05 078477 A published on March 30, 1993 discloses 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% PEG weight.
• the average molar mass in number Mn of PTMG is between 1000 and 2000
• the average molar mass in number Mn PEG is between 1000 and 2020. They are used to make antistatic resins. It is also written that they have excellent properties of permeability to water vapor.
• the polyether blocks consist essentially of PTMG with a number-average molar mass Mn of between 200 and 4000 g / mol
• the polyamide blocks consist of a linear aliphatic (non-cyclic, unbranched) semi-crystalline majority monomer and a sufficient quantity of at least one comonomer to decrease their crystallinity while remaining immiscible with the amorphous polyether blocks
• polyamide block and polyether block copolymers which have polyamide blocks consisting mainly of residues of lauryllactam by mixing them with a polyamide other than a polyamide 12 or another polyamide block copolymer and polyether blocks having polyamide blocks which do not consist mainly of remains of lauryllactam.
• the optical properties are improved.
• the present invention relates to a mixture comprising by weight, the total being 100%:
• copolyamides which do not consist mainly of residues of lauryllactam, "
• (B) is transparent.
• (B) is PA 11.
• (B) is chosen from copolyamides consisting mainly of residues of 11-amino-undecanoic acid.
• (B) is chosen from polyamide block and polyether block copolymers whose polyamide blocks are PA 11 or copolyamides consisting mainly of amino-11-undecanoic acid. According to one embodiment of the mixture, the proportion of (B) is from 5 to 40% for respectively 95 to 60% of (A).
• the proportion of (B) is from 10 to 35% for respectively 90 to 65% of (A).
• the invention also relates to objects made with this mixture. These are, for example, films, sheets, plates, rushes, tubes.
• the copolymers (A) with polyamide blocks and polyether blocks result from the copolycondensation of polyamide sequences with reactive ends with polyether sequences with reactive ends, such as, inter alia: 1) Polyamide sequences with diamine chain ends with polyoxyalkylene sequences with ends dicarboxylic chains. 2) Polyamide sequences with dicarboxylic chain ends with polyoxyalkylene sequences with diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic dihydroxylated aliphatic polyoxyalkylene aliphatic sequences called polyether diols. 3) Polyamide sequences with dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides.
• the copolymers of the invention are advantageously of this type.
• the polyamide sequences with dicarboxylic chain ends come for example from the condensation of polyamide precursors in the presence of a dicarboxylic acid chain limiter.
• the polyamide blocks with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-limiting diamine.
• 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. For example, polyetherdiol, polyamide precursors and a chain-limiting diacid can be reacted. A polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted randomly which are distributed randomly (statistically) along the polymer chain. It is also possible to react polyetherdiamine, polyamide precursors and a chain-limiting diacid. A polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted randomly which are distributed randomly (statistically) along the polymer chain.
• the polyamide blocks of (A) consist mainly of residues of lauryllactam. That is, they comprise at least 50.5% by weight of residues of lauryllactam, preferably at least 55% and preferably 60%. They may also consist only of leftover lauryl lactam. This proportion is expressed relative to the monomer residues constituting the polyamide blocks but does not include the chain limiter.
• the other possible constituents of the polyamide block may be another lactam such as caprolactam or oenantholactam or an alpha omega acid. _
• aliphatic amino carboxylic acid such as 7-amino-heptanoic acid and 11-amino-undecanoic acid.
• the other constituents of the polyamide block may also be an equimolar mixture of a diacid and a diamine.
• the other possible constituents of the polyamide block may also be another lactam or an aliphatic alpha omega amino carboxylic acid having not 12 carbon atoms and an equimolar mixture of a diacid and a diamine.
• aliphatic diamines mention may be made of hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine.
• cycloaliphatic diacids mention may be made of 1,4-cyclohexyldicarboxylic acid.
• aliphatic diacids mention may be made of butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid or dimerized fatty acid (these dimerized fatty acids preferably have a dimer content of at least 98%; preferably they are hydrogenated, they are marketed under the trademark "PRIPOL” by the company "UNICHEMA”, or under the brand name EMPOL by the company HENKEL) and the polyoxyalkylenes - ⁇ , ⁇ diacids.
• aromatic diacids By way of example of aromatic diacids, mention may be made of terephthalic (T) and isophthalic (I) acids.
• the cycloaliphatic diamines may be the isomers of bis- (4-aminocyclohexyl) -methane (BACM), bis- (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2-2-bis- (3-methyl-4) aminocyclohexyl) propane (BMACP), and para-amino-di-cyclohexyl methane (PACM).
• BMACP bis- (4-aminocyclohexyl) -methane
• BMACP bis- (3-methyl-4-aminocyclohexyl) methane
• PAM para-amino-di-cyclohexyl methane
• IPDA isophoronediamine
• BAMN 2,6-bis (aminomethyl) norbornane
• the polyether blocks represent from 5 to 49.5%, advantageously from 10 to 30%, and even more advantageously from 10 to 25% by weight of the polyamide and polyether block copolymer.
• the polyether blocks consist of alkylene oxide units. These units may be, for example, ethylene oxide units, propylene oxide units, trimethylene ether units or tetrahydrofuran units (which leads to polytetramethylene glycol units). "
• PEG blocks are thus used, that is to say those consisting of ethylene oxide units, PPG blocks, ie those consisting of propylene oxide units and PTMG blocks, ie those consisting of tetramethylene glycol units. also called polytetrahydrofuran.
• PPG blocks ie those consisting of propylene oxide units
• PTMG blocks ie those consisting of tetramethylene glycol units. also called polytetrahydrofuran.
• block copolyethers or statistics The amount of polyether blocks in these polyamide block and polyether block copolymers is advantageously from 10 to 70% by weight of the copolymer and preferably from 35 to 60%.
• the polyetherdiol blocks 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 carboxylic ends. They can also be mixed with polyamide precursors and a diacid chain limiter to make the polyamide block and polyether block polymers having statistically distributed patterns.
• the number-average molar mass Mn of the polyamide sequences may be between 500 and 10,000 and preferably between 500 and 4000.
• the mass Mn of the polyether blocks may be between 100 and 6000 and preferably between 200 and 3000.
• polymers with polyamide blocks and polyether blocks whether from the copolycondensation of previously prepared polyamide and polyether blocks or from a one-step reaction, have, for example, an intrinsic viscosity of between 0.8 and 2.5 measured in metacresol. at 25 ° C for an initial concentration of 0.8 g / 100 ml.
• Such copolymers with polytrimethylene ether blocks are described in US Pat. No. 6,590,665. The preparation of the copolymers (A) is described in the prior art.
• the rigid polyamide blocks are predominant in percentage by weight of the polyamide block copolymer and polyether blocks.
• the polyether blocks, flexible, are minor in percentage by weight of the polyamide block copolymer and polyether blocks.
• polymer (B) it is chosen from: polyamides other than polyamides 12, "
• copolyamides which do not consist mainly of residues of lauryllactam
• PA 6 PA 6.6, PA 6.9, PA 6.10, PA 6.12, PA 6.18 and PA 11.
• copolymers with polyamide blocks and polyether blocks having polyamide blocks which do not mainly consist of residues of lauryllactam they are, for example, copolymers such as (A) but the polyamide blocks are polyamides other than polyamides 12 or copolyamides which do not consist mainly of remains of lauryllactam.
• polyamide or copolyamide blocks of the copolymer (B) containing polyamide blocks and polyether blocks mention may be made of polyamides other than polyamides 12 and copolyamides which do not consist predominantly of lauryl lactam residues which have been cited. upper.
• the polyether blocks represent from 5 to 49.5%, advantageously from 10 to 30%, and even more advantageously from 10 to 25% by weight of the polyamide and polyether block copolymer.
• the proportion of (B) is advantageously from 5 to 40% for respectively 95 to 60% of (A). Of preferably the proportion of (B) is from 10 to 35% for respectively 90 to 65% of (A).
• the mixture of (A) and (B) can be made in the molten state in the usual apparatus used for thermoplastics.
• the mixture of the invention may comprise the usual additives of polyamides.
• a Mn 5000 PA 12 block copolymer and Mn 650 PTMG blocks were used as product (A).
• the inherent viscosity of this copolymer is between
• the shore hardness D is 70.
• a Mn 5000 PA 11 block copolymer and Mn 650 PTMG blocks were used as the product (B).
• the inherent viscosity of this copolymer is between
• the shore hardness D is 70.
• the opacity (expressed in%) is the reflectance ratio of the material placed on a black support on the reflectance of the material placed on a white support. The results are summarized in Table 1 below.
• the transparency of the copolymers of the present invention was measured on plates 2 to 4 mm thick.
• the transmission and opacity are shown in the following figures 1 and 2.

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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)
• Compositions Of Macromolecular Compounds (AREA)
• Polyamides (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

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• 2006
  • 2006-04-12 EP EP06743679A patent/EP1869125A1/de not_active Withdrawn
  • 2006-04-12 JP JP2008505926A patent/JP5528698B2/ja not_active Expired - Fee Related
  • 2006-04-12 KR KR1020077026299A patent/KR101313515B1/ko not_active IP Right Cessation
  • 2006-04-12 WO PCT/FR2006/000803 patent/WO2006108959A1/fr active Application Filing
  • 2006-04-12 US US11/911,219 patent/US7718740B2/en not_active Expired - Fee Related
  • 2006-04-13 TW TW095113219A patent/TWI326698B/zh not_active IP Right Cessation

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