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
  • C08L77/06—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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/02—Applications for biomedical use
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • 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
  • 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

Definitions

• the present invention relates to a composition based on amorphous transparent polyamide or very low crystallinity, and copolyamide with ether units and amide units.
• Transparent amorphous polyamides or those which are very slightly crystalline, that is to say whose enthalpy of fusion during the second heating of an ISO DSC (delta Hm (2)) is at most equal to 30 J / g, even 10J / g (in the case of the "Trogamid CX7323" cited below), are materials which have the following advantages: high transparency, very good thermomechanical behavior (high deflection temperature under load (HDT) due to the glass transition temperature (Tg) high and above 90 ° C), held fairly good shock, chemical resistance and stress cracking resistance "stress cracking" good and superior to other common amorphous transparent polymers, such as polycarbonate, polystyrene, polymethylmethacrylate.
• HDT high deflection temperature under load
• Tg glass transition temperature
• amPA TR amorphous or very slightly crystalline transparent polyamides
• amPA TR amorphous or very slightly crystalline transparent polyamides
• IPD isophoronediamine
• amorphous or very slightly crystalline transparent polyamides have the following drawbacks: rather difficult injectability because of their high viscosity (if they are chosen as fluids, then their mechanical properties, in particular in impact, are reduced, as well as their holding properties chemical); medium impact strength, especially in comparison with polycarbonate or non-transparent semi-crystalline polyamides, especially if these are modified shock; rigidity often too high; - alternating fatigue strength ("ross-flex" ASTM1052); chemical behavior significantly lower than that of semi-crystalline polyamides; and medium UV resistance, especially in the absence of stabilizer (the addition of compounding stabilizer resulting in yellowing of the polymer or the formation of black spots, which is often too detrimental to its use in applications where aesthetics is important as for example glasses frames).
• a well-known improvement route is to mix the amorphous transparent polyamide with a minor amount of semi-crystalline polyamide (typically non-transparent).
• the European patents EP 550 308 and EP 725 101 describe alloys of transparent amorphous polyamide combined with a non-transparent semicrystalline polyamide, all giving a transparent and amorphous or substantially amorphous material, that is to say of which the enthalpy of fusion is less than 30 J / g, even 10J / g, and no real mechanical strength above its Tg and before its Tm (melting temperature).
• this type of material are the "Cristamid MS1100" marketed by ARKEMA.
• This composition has the advantage of a remarkably improved chemical resistance.
• This composition also has the advantage of being less rigid and less difficult to inject.
• the problem that the invention intends to solve is the following: improvement of the injectability of the composition, namely the ability of it to be easily implemented by injection, short cycle times, longer flow lengths , lower pressures, no deformation during the ejection of the part, no shrinkage or shrinkage bubble, not too many stored stresses, no breakage; Improved impact resistance reduction of rigidity; improved resistance to chemicals and stress cracking; optionally, improvement of alternating fatigue strength and / or improvement of the UV resistance.
• the Applicant has discovered that by adding to a transparent or very slightly crystalline amorphous polyamide (A), a flexible copolyamide (B) based on amide units and ether units, in particular based on polyamide units or blocks and on patterns or polyether blocks, one can then solve the problem in an effective way.
• A transparent or very slightly crystalline amorphous polyamide
• B flexible copolyamide
• the composition according to the invention consists of a mixture of: 60 to 99% by weight of a polymer component (A) formed from at least one of (i) transparent homopolyamides and copolyamides: a) amorphous or having a crystallinity such that the heat of fusion during the second heating of an ISO DSC (delta Hm (2)) is at most equal to 30 J / g, the mass being related to the quantity of amide units contained or of polyamide content, this fusion corresponding to that of the amide units; b) having a glass transition temperature (Tg) greater than 90 ° C; and c) consisting at least partly of cycloaliphatic and / or aromatic units, and / or (ii) alloys based on at least one homopolyamide or copolyamide, said alloys being amorphous or having a crystallinity corresponding to the same definition as ci -above ; and
• the polymer component (A) represents 80 to 97% by weight of the composition.
• the polymer component (B) represents from 20 to 3% by weight of the composition.
• composition according to the invention may further comprise one or more conventional additives for thermoplastic polymers or copolymers, in a proportion of up to 15% by weight, advantageously up to 10% by weight, of the total composition. comprising then the polymeric components (A) + (B) + the one or more additives, which can be introduced directly.
• At least one of the polymer components of (A) and (B) may also contain at least one usual additive for thermoplastic polymers and copolymers, without the content of the additive (s) in each of the polymeric components (A) and (B) is no more than 30%, preferably 20%, by weight of said polymeric component.
• copolyamide based on ether units and amide units is itself additive by anti-UV stabilizers, antioxidants, release agents, lubricating agents and / or adjuvants or processing aids or processing aids.
• a particularly favorable way of solving the problem is to mix the melt and amide-patterned copolyamide with the additives in question in a first step.
• This first step can take place in an extruder, the composition then being recovered in the form of granules.
• This composition constitutes what is called a masterbatch.
• the composition based on copolyamide with ether units and with amide units is mixed with amorphous or very slightly crystalline transparent polyamide granules, this mixture being able to be the solid state, the amorphous or very slightly crystalline transparent polyamide not being remelted in the presence of air, which does not cause any risk of detrimental yellowing of it.
• This latter mixture constitutes the final composition according to the invention and meets the technical problem defined above.
• Table 2 summarizes the different properties of the two known families of polyamide, which has just been described, with which the family according to the present invention is compared.
• PEBA polyetheramides and, in particular, polyether-block-amides
• composition according to the invention makes it possible to obtain materials which are both transparent and have good mechanical properties, such as
• the polymeric constituents (A) and (B) are preferably chosen in nature and in such proportions that the composition is transparent with a light transmission at 560 nm on a 2 mm plate which is greater than 65%, in particular greater than 75%, knowing that it is not excluded that the presence of additives such as
• Dark dye especially black dye
• delta Hm (2) we mean the enthalpy of fusion during the second heating of a DSC according to the ISO standard, the DSC (“Differential Scanning Calorimetry”) being differential scanning calorimetry.
• the homopolyamides and copolyamides forming part of the constitution of (A) have a crystallinity such that the heat of fusion during the second heating of a DSC ISO (delta Hm (2)) is at most equal to 10 J / g, the mass being related to the amount of amide units contained or polyamide content, this fusion
• the homopolyamides and the copolyamides forming the polymer component (A) can in particular be chosen from those containing both cycloaliphatic units and linear aliphatic units.
• cycloaliphatic and linear aliphatic units advantageously consist of an equimolar association of at least one diamine and at least one dicarboxylic acid, the diamine (s) being predominantly cycloaliphatic and the dicarboxylic acid (s) being predominantly linear aliphatic.
• amide units that may optionally include, but not be limited to, at least one other polyamide comonomer.
• predominantly means "more than 50% by weight (>50%)".”
• Minority means "less than 50% by weight ( ⁇ 50%)”.
• the cycloaliphatic diamine (s) are advantageously chosen from bis (3-methyl-4-aminocyclohexyl) -methane (BMACM), para-aminodicyclohexyl methane (PACM), isophoronediamine (IPD) and bis (4-aminocyclohexyl). ) -methane (BACM), 2,2-bis- (3-methyl-4-aminocyclohexyl) propane (BMACP), 2,6-bis (amino methyl) norbornane (BAMN).
• BMACM bis (3-methyl-4-aminocyclohexyl) -methane
• PAM para-aminodicyclohexyl methane
• IPD isophoronediamine
• BAMN 2,6-bis (amino methyl) norbornane
• the cycloaliphatic diamine (s) are chosen from BMACM, PACM and I 1 IPD.
• At least one non-cycloaliphatic diamine may be used in the composition of the monomers of the amide units of component (A) in a proportion of at most 30 mol% relative to the diamines of said composition.
• Non-cycloaliphatic diamines that may be mentioned include linear aliphatic diamines, such as 1,4-tetramethylene diamine, 1,6-hexamethylenediamine, 1,9-nonamethylenediamine and 1,10-decamethylenediamine.
• the aliphatic dicarboxylic acid or diacids may be chosen from aliphatic dicarboxylic acids having from 6 to 36 carbon atoms, preferably from 9 to 18 carbon atoms, in particular 1,10-decanedicarboxylic acid (sebacic acid), 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid and 1,18-octadecanedicarboxylic acid.
• At least one non-aliphatic dicarboxylic acid can be used in the composition of the monomers of the amide units of component (A) in a proportion of at most 15 mol% relative to the dicarboxylic acids of said composition.
• the non-aliphatic dicarboxylic acid is chosen from aromatic diacids, in particular isophthalic acid (I), terephthalic acid (T) and mixtures thereof.
• the monomer or monomers entering in a minority way in the composition of the monomers of the amide units are in particular chosen from lactams and alpha-omega aminocarboxylic acids.
• the lactam or lactams are, for example, chosen from lactams having at least
• the at least one alpha-omega aminocarboxylic acid is for example chosen from those having at least 6 carbons, in particular aminocaproic acid, 7-amino-heptanoic acid, 11-amino-undecanoic acid or amino-6-amino acid. 12-aminododecanoic.
• the polymer component (A) may in particular have amide units whose average number of carbons per amide is at least 9. W
• the polymer component (B) is advantageously chosen from PEBA copolymers consisting of amide unit blocks and ether unit blocks.
• PEBA copolymers belong to the particular class of polyetheresteramides when they result from the copolycondensation of polyamide sequences with reactive carboxyl ends with polyether blocks with reactive ends, which are polyether polyols (polyetherdiols), the bonds between the polyamide blocks and the blocks. polyether being ester bonds, or to the class of polyether amide or polyether-block-amide when the polyether blocks are amine ends.
• polyether polyols polyetherdiols
• polyether being ester bonds, or to the class of polyether amide or polyether-block-amide when the polyether blocks are amine ends.
• the two families above fall within the definition of the polymeric component (B) according to the invention.
• the PEBAs that can be used according to the present invention include the family in which the monomers at the origin of the amide units are not solely aliphatic monomers (such as Arkema's Pebax series 33, 13, 31 and 11, the Vestamid and the Ubesta) but also, at least partially, cycloaliphatic or even aromatic monomers, examples of which are BMACM.14 / PTMG.14 where the BMACM.14 pattern has a mass of 2000g / mole and the PTMG pattern has a mass of 650g /mole.
• BMACM.14 / PTMG.14 where the BMACM.14 pattern has a mass of 2000g / mole and the PTMG pattern has a mass of 650g /mole.
• the units or ether blocks of the polymer component (B) are, for example, derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol, preferably chosen from polyethylene glycol (PEG) and polypropylene glycol (PPG). , polytrimethylene glycol (PO3G), polytetramethylene glycol (PTMG) and mixtures or copolymers thereof.
• PEG polyethylene glycol
• PPG polypropylene glycol
• PO3G polytrimethylene glycol
• PTMG polytetramethylene glycol
• the polyether blocks may also comprise, as indicated above, polyoxyalkylene sequences with NH 2 chain ends, such sequences being obtainable by cyanoacetylation of aliphatic dihydroxy aliphatic polyoxyalkylene aliphatic sequences known as polyetherdiols. More particularly, Jeffamines (for example Jeffamine® D400, D2000, ED 2003, XTJ 542, Huntsman's commercial products, see JP 2004346274, JP 2004352794 and EP1482011).
• Jeffamines for example Jeffamine® D400, D2000, ED 2003, XTJ 542, Huntsman's commercial products, see JP 2004346274, JP 2004352794 and EP1482011.
• the units or amide blocks of the copolymer component (B) can in particular be residues of linear aliphatic monomers such as: linear aliphatic diamines such as 1,4-tetramethylene diamine, 1,6-hexamethylenediamine, 1,9-nonamethylenediamine and 1,10-decamethylenediamine; Aliphatic dicarboxylic acids, which may be chosen from aliphatic dicarboxylic acids having from 6 to 36 carbon atoms, preferably from 9 to 18 carbon atoms, in particular 1,10-decanedicarboxylic acid (sebacic acid), 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid and 1,18-octadecanedicarboxylic acid ; lactams such as caprolactam, poenantholactam and lauryllactam; and alpha-omega aminocarboxylic acids such as aminocaproic acid, 7-amino-h
• PEBA copolymers for the polymer component (B) of the composition according to the present invention include those consisting of amide units which are residues of linear aliphatic monomers and polyether sequences of PTMG, PPG or PEG type, the residues of linear aliphatic monomers may in particular be residues of a diamine and a diacid.
• the number-average molecular mass of the polyamide blocks is advantageously between 500 and 12000 g / mol, preferably between 2000 and 6000 g / mol; and the number-average molecular weight of the ether unit blocks is advantageously between 200 and 4000 g / mol, preferably between 300 and 1100 g / mol.
• the polymer component (B) may advantageously have amide units whose average number of carbons per amide is at least 9.
• the amide units of the polymer component (B) may represent 50 to 95% by weight of said polymer component (B).
• Flexible PEBA copolyamides that can be used particularly are the
• PEBAs marketed by the DEGUSSA Company and the PEBA Ubesta XPA 9063X1, 9055X1, 9055X2 and 9044X2 sold by the UBE Company, which are based on polyethers (and their mixtures) at the end of the NH 2 chain, of the Jeffamines type. .
• the additive or additives, introduced into the composition or into the polymer component (A) and / or the polymer component (B), are chosen from " catalysts, especially those based on phosphorus, UV stabilizers, colorants, nucleating agents, plasticizers, shock-improving agents, antioxidants, release agents, adjuvants or processing aids or implementation, said additives preferably having a refractive index close to that of said polymer component (B) of said composition.
• the release agents and the adjuvants or auxiliaries of treatment or implementation are chosen in particular from stearates, such as calcium stearate, zinc stearate and magnesium stearate, fatty acids, fatty alcohols, esters of the same type. montanic ester, sebacic acid esters, dodecanedioic acid esters, polyolefin waxes, amide waxes, stearamides such as ethylene bis stearamide (EBS), erucamides, fluorinated additives, especially of the Dyneon type Dynamer FX 5914 or FX 5911.
• the polymeric components (A) and (B) are advantageously selected in their nature and proportions such that the resulting composition has a glass transition temperature of at least 75 ° C.
• the polymeric constituents (A) and (B) are advantageously chosen in their nature and their proportions so that the composition has a high transparency such that the transmittance at 560 nm on a 2 mm thick plate is greater than 75%, knowing that it is not excluded that the presence of additives such as a dark dye (especially black dye) may reduce the transparency of the final composition.
• the constituents (A) and (B) are chosen such that: n is the number of carbons per amide group of the transparent amorphous polymer component (A); and where m is the number of carbons per amide group of the moiety of units derived from polyamide monomer residues of the polymeric component (B), then n>m> n / 2; and / or the refractive index of the polymer component (A) and that of the polymer component (B) are chosen as close as possible to each other, that is to say that the difference between the two values refractive index is less than 0.004 and preferentially less than 0.002; and / or the density of the polymeric component (A) and that of the polymeric component (B) are chosen as close as possible to each other, i.e.
• a particular form of the present invention consists in choosing a composition characterized in that its flexible ether units are chosen to be very hydrophilic in nature, preferably of a PEG, PPG or PO3G type polyether block nature, which gives an advantageous increase in properties. antistatic and impervious to the composition (ie allowing the passage of water vapor, but not liquid water).
• This composition may, in addition, be additivated by third-party antistatic additives in order to reinforce the overall antistatic effect, and also by additives making it possible to increase the compatibility of the mixture with other polymers, the copolymer, alone or with added additives, which can then be used as an additive of another polymer or material in order to give the latter additional antistatic or waterproof properties, that is to say, allowing the passage of water vapor, but no liquid water.
• compositions according to the invention In order to prepare the compositions according to the invention, the following procedure is generally carried out as follows: The constituents (A) and (B), which are in the form of granules, are mixed together. This mixture is then injected at a temperature generally between 23O 0 C and 33O 0 C, in particular at a temperature of about 270 0 C, on an injection press to obtain the desired objects and test pieces. Working at a temperature above 330 0 C can improve transparency, but this has the disadvantage of giving greater yellowing and degrade the product. A compromise is therefore desirable.
• the constituents (A) and (B) can also be mixed in the molten state, in particular in an extruder such as a twin-screw extruder at a temperature of between 230 ° C. and 330 ° C., in particular at a temperature of approximately 270 ° C and recovered in the form of granules, granules which will subsequently be injected at a temperature between 23O 0 C and 330 0 C on an injection molding machine, to obtain the desired objects and test pieces.
• an extruder such as a twin-screw extruder
• a temperature of between 230 ° C. and 330 ° C. in particular at a temperature of approximately 270 ° C
• recovered in the form of granules granules which will subsequently be injected at a temperature between 23O 0 C and 330 0 C on an injection molding machine, to obtain the desired objects and test pieces.
• component (B) in a first step, component (B) is mixed in the molten state with said additives, in particular in an extruder, the composition then being recovered in the form of granules; in a second step, the composition obtained in the first step is mixed with granules of the polymer component (A).
• the present invention also relates to a shaped article, such as fiber, fabric, film, sheet, ring, tube, injected part, in particular transparent or translucent comprising the composition as defined above.
• composition according to the present invention is advantageous for the easy manufacture of articles, in particular articles or elements of sports articles, having in particular having both good transparency, good impact resistance and good endurance. mechanical, chemical, UV, thermal attack.
• sports articles include elements of sports shoes, sports implements such as ice skates or other articles of winter sports and mountaineering, bindings of skis, snowshoes, bats of sports, boards, horseshoes, fins, golf balls, recreational vehicles, especially those intended for cold weather activities.
• protective items such as visors helmets, glasses, and branch of glasses.
• Non-limiting examples include car components, such as headlamps, mirrors, small parts of all-terrain vehicles, tanks, in particular, mopeds, motorcycles, scooters, subject to mechanical aggression. and chemical, hardware, cosmetic items subject to mechanical and chemical aggression, lipstick sticks, manometers, aesthetic protection elements such as gas cylinders.
• PT / 12 transparent amorphous polyamide whose molar composition is 1 mol of P, 1 mol of T and 1.2 mol of 12.
• P is the diamine PACM
• T is the terephthalic diacid
• 12 is the lactam 12.
• the PACM is 4,4 'diamino dicyclo hexyl methane.
• B.14 transparent amorphous polyamide whose molar composition is 1 mol of
• B 1 mol of 14.
• B is diamine BMACM
• 14 is linear diacid C14, tetra decanedioic.
• PEBA1 copolyamide block copolymer 12 having a mass of 2000 g / mol and a PTMG polyether block with a mass of 1000 g / mol.
• PEBA2 copolyamide block copolymer 12 having a mass of 4000 g / mol and a polyether PTMG block with a mass of 1000 g / mol.
• PEBA3 copolyamide block copolymer 12 with a mass of 5000 g / mol and with a PTMG polyether block with a mass of 650 g / mol.
• PEBA-H composition based on PEBA2 to which are added 8.4% of anti-UV additive Tinuvin 350, (Ciba company), 8.4% of Tinuvin 770 (Ciba Company), 9.75% antioxidant Irganox 1010 (Company Ciba) and 11.2% dioctadecyl bis (phosphite) pentaerythritol
• PEBA-L PEBA2-based composition to which 14.3% calcium stearate is added.
• PEBA-E composition based on PEBA2 to which 14.3% of EBS (ethylene bis-steramide) is added.
• PA11 polyamide 11 with a molecular mass of between 45,000 and 55,000 g.
• compositions are injected at 260 ° C. in a spiral mold with a thickness of 2 mm at a given pressure (600 bar or 1200 bar). The length is then measured that the melt has been able to fill
• Shock test or crease test The test is performed as follows. Bars 80 x 10 x 4 mm are injection molded in an ISO mold. The bar is folded rapidly 180 ° at the injection threshold, between the bar and the cluster, where the thickness is reduced to 1 mm. The number of breakages is then measured on a series of 20 bars, and expressed as a percentage of breakage.
• Notched Charpy impact test The test is carried out according to the ISO179 standard, on notched test piece, the notch being in V and wide of 0.25 mm.
• UV resistance It is evaluated using a QUV test. The yellowing compared to the sample is compared to the initial state.
• Transparency It is described by a test of light transmission of a light of 560nm through a polished plate of 2mm. It is expressed as a percentage of transmission. Beyond 65% transparency is good. Above 80% she is very good. Beyond 88% it is excellent. The most transparent polymer is about 92%.
• Table 4 shows Charpy shock test values at -30 ° C. with a wide U-shaped cut of 1 mm. It represents the shock test by folding.

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