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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
  • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/02—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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
  • C08J2377/06—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
  • 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
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • 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
  • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

Definitions

• TITLE Polyamide compositions comprising reinforcing fibers and exhibiting high modulus stability and their uses [Technical field]
• the present patent application relates to the use of mixtures of semi-crystalline aliphatic and amorphous polyamides for the manufacture of compositions exhibiting a high modulus stability under the effect of temperature and humidity, their manufacturing process as well as said compositions.
• modulus polymer materials for example for televisions, digital cameras, digital games, telephone parts, digital tablets, drones, printers or computer parts.
• the modulus of the material is indeed a crucial factor in allowing a reduction in weight, since it allows a reduction in the thickness of the parts while maintaining great rigidity.
• moduli for example tensile modulus, flexural modulus, etc.
• These modules can be impacted by temperature and by the humidity level contained in the sample.
• the stiffness is little affected by temperature changes or by the water content in the material.
• the stability of the module is also an important factor for subsequent use or for ensuring easy assembly of the parts when this is carried out in places where the temperature and / or humidity may be high.
• the modulus should be stable at a temperature ranging from 10 ° C to 40 ° C, especially in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range from -10 ° C to 40 ° C for compositions having variable water contents (caused by conditioning the compositions in an atmosphere where the humidity can vary from 0 to 100%, or in liquid water)
• polyamide compositions must exhibit moderate molding temperatures and crystallize sufficiently quickly to allow a transformation time, in particular a cycle time, suitable for an industrial process.
• aliphatic polyamides generally exhibit a significant loss in rigidity when the temperature increases, in particular when these polyamides have been packaged in a humid atmosphere beforehand because they contain a certain amount of water.
• copolyamides comprising at least two distinct A / XT units characterized in that said copolyamide has an amine end-of-chain content greater than or equal to 20 peq / g, an end-of-chain content acid less than or equal to 100 peq / g, and a non-reactive chain end content greater than or equal to 20 peq / g.
• the copolyamide can comprise additives, in particular reinforcing fibers, said reinforcing fibers possibly being glass fibers.
• compositions for an electronic mobile device comprising at least 20% of at least one polymer and at least 20% of glass fibers having a non-circular section and an elastic modulus of at least 76 GPa determined. according to ASTM C1557-03.
• the aim of the invention is therefore to provide mixtures of semi-crystalline and amorphous polyamides for the manufacture of compositions exhibiting a high modulus stability under the effect of temperature and humidity. Also, according to a first aspect, the invention relates to the use of a mixture of at least one semi-crystalline aliphatic polyamide and at least one amorphous polyamide in which said semi-crystalline aliphatic polyamide is obtained by polycondensation.
• At least one C 6 to Cis amino acid preferably Cio to Cis, more preferably Cio to C12, or at least one C6 to Cis lactam, preferably Cio to Cis, more preferably Cio to C12 or of at least one aliphatic diamine Ca C4-C36, preferably C 5 -cis, preferably C5 - C12, more preferably C10-C12 with at least one aliphatic dicarboxylic acid Cb C4-C36, preferably C6-C18 , preferably C6-C12, more preferably C10-C12; to prepare a semi-crystalline composition whose modulus does not vary by more than 25% in the temperature range from 10 ° C to 40 ° C, in particular in the temperature range from 0 ° C to 40 ° C , especially in the temperature range from -10 ° C to 40 ° C.
• the Tg of said semi-crystalline composition determined by DMA according to ISO 6721-11: 2019, exhibits an increase greater than or equal to 5 ° C, preferably greater than or equal to 10 ° C, more preferably greater than or equal to 15 ° C. relative to the initial Tg of said semi-crystalline polyamide before mixing.
• the Tg of said semi-crystalline composition above is determined under a dry or humid atmosphere, advantageously under an atmosphere saturated in water at 65 ° C.
• the Tg of said semi-crystalline composition is from 5 ° C to 120 ° C, advantageously from 10 ° C to 120 ° C, more advantageously from 15 ° C to 120 ° C.
• the Tg is determined by dynamic mechanical analysis (DMA) according to ISO 6721-11: 2019.
• DMA dynamic mechanical analysis
• a semi-crystalline polyamide within the meaning of the invention, denotes a polyamide which exhibits a glass transition temperature determined by dynamic mechanical analysis (DMA) according to standard ISO 6721-11: 2019 and a melting point (Tm) determined according to the ISO 11357-3: 2013 standard, and an enthalpy of crystallization during the cooling step at a speed of 20K / min in DSC measured according to the ISO 11357-3 2013 standard greater than 30 J / g, preferably greater at 35 J / g.
• DMA dynamic mechanical analysis
• Tm melting point
• An amorphous polyamide within the meaning of the invention denotes a polyamide which exhibits only a glass transition temperature (no melting point (Tm)), or a very poorly crystalline polyamide having a glass transition temperature and a melting point. such that the enthalpy of crystallization during the cooling step at a speed of 20K / min measured according to standard ISO 11357-3: 2013 is less than 30 J / g, in particular less than 20 J / g, preferably less at 15 J / g.
• the semi-crystalline aliphatic polyamide is linear.
• the semi-crystalline aliphatic polyamide is a homopolyamide, in particular a semi-crystalline linear aliphatic homopolyamide.
• the amorphous polyamide used in the invention has a Tg of 100 to 200 ° C, in particular of 120 to 190 ° C.
• said at least one lactam can be chosen from a C 6 to Cis lactam, preferably Cio to Cis, more preferably Cio to C12.
• a C 6 to C12 lactam is in particular caprolactam, decanolactam, undecanolactam, and lauryllactam.
• said at least one semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one lactam, it can therefore comprise a single lactam or several lactams.
• said at least one semi-crystalline aliphatic polyamide is obtained from the polycondensation of a single lactam and said lactam is chosen from lauryllactam and undecanolactam, advantageously lauryllactam.
• said at least one semi-crystalline aliphatic polyamide can be chosen from a C 6 to Cis amino acid, preferably Cio to Cis, more preferably Cio to C12.
• a C 6 to C12 amino acid is in particular 6-aminohexanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 10-aminoundecanoic acid, 12-aminododecanoic acid and 11-aminoundecanoic acid as well as its derivatives, in particular N-heptyl-11-aminoundecanoic acid.
• said at least one semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one amino acid, it can therefore comprise a single amino acid or several amino acids.
• said semi-crystalline aliphatic polyamide is obtained from the polycondensation of a single amino acid and said amino acid is chosen from 11-aminoundecanoic acid and 12-aminododecanoic acid, advantageously 11-aminoundecanoic acid.
• said at least one semi-crystalline aliphatic polyamide is obtained from the polycondensation of at least one C4-C36 diamine Ca, preferably C5-C18, preferably C5-C12, more preferably C10-C12, with at least one diacid Cb to C4-C36, preferentially C6-C18, preferentially C6-C12, more preferentially C10-C12, then said at least one diamine in Ca is an aliphatic diamine and said at least one diacid Cb is an aliphatic diacid.
• the diamine can be linear or branched.
• it is linear.
• Said at least one C4-C36 diamine Ca may in particular be chosen from 1,4-butanediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylèdiamine, 1,10- decamethylèdiamine, 1,11-undecamethylèdiamine, 1,12-dodecamethylèdiamine, 1,13-tridecamethylèdiamine, 1,14-tetradecamethylèdiamine, 1,16-hexadecamethylèdiamine and 1 , 18-octadecamethylediamine, octadecenediamine, eicosanediamine, docosanediamine and diamines obtained from fatty acids.
• said at least one Ca diamine is Cs-Ciget chosen from 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylèdiamine, 1,8-octamethylèdiamine, 1,9-nonamethylenediamine, 1,10-decamethylèdiamine, 1,11- undecamethylèdiamine, 1,12-dodecamethylèdiamine, 1,13-tridecamethylèdiamine, 1,14-tetradecamethylèdiamine, 1,16-hexadecamethylèdiamine and 1,18-octadecamethylèdiamine.
• said at least one C 5 to Cu diamine Ca is in particular chosen from 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9 -nonamethylèdiamine, 1,10-decamethylèdiamine, 1,11- undecamethylèdiamine, 1,12-dodecamethylèdiamine.
• the Ca diamine used is C10 to C12, in particular chosen from 1,10-decamethylèdiamine, 1,11-undécamethylèdiamine, 1,12-dodecamethylèdiamine.
• Said at least one Cb in C 4 to C36 dicarboxylic acid can be chosen from succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid , dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and diacids obtained from fatty acids.
• the diacid can be linear or branched. Advantageously, it is linear.
• said at least one Cb dicarboxylic acid is C 6 to Cis and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid.
• said at least one Cb dicarboxylic acid is C 6 to C12 and is chosen from adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid.
• said at least one Cb dicarboxylic acid is C10 to C12 and is chosen from sebacic acid, undecanedioic acid and dodecanedioic acid.
• said aliphatic semi-crystalline polyamide is obtained from the polycondensation of at least one diamine Ca with at least one dicarboxylic acid Cb, it can therefore comprise a single diamine or several diamines and a single dicarboxylic acid or several dicarboxylic acids.
• said semi-crystalline aliphatic polyamide is obtained from the polycondensation of a single diamine Ca with a single dicarboxylic acid Cb.
• XY is a repeating unit obtained by polycondensation of at least one cycloaliphatic diamine (X) and of at least one aliphatic dicarboxylic acid (Y) at C 4 - C36, preferably C6-C18, preferably C6-C12, more preferably C10-C12OU of at least one aromatic dicarboxylic acid (Y) and
• A is a repeating unit obtained by polycondensation of at least one amino acid C 6 to Cis, preferably Cio to Cis, more preferably Cio to C12, or of at least one C 6 to Cis lactam, preferably Cio to Cis, more preferably Cio to C12, or at least one C4-C36 diamine Ca, preferably C5-C18, preferably C5-C12, more preferably C10-C12, with at least one Cb
• the cycloaliphatic diamine (X) can be chosen from bis (3,5-dialkyl-4-aminocyclohexyl) - methane, bis (3,5-dialkyl-4-aminocyclohexyl) ethane, bis (3,5-dialkyl- 4-aminocyclohexyl) - propane, bis (3,5-dialkyl-4-aminocyclo-hexyl) -butane, bis- (3-methyl-4-aminocyclohexyl) - methane or 3,3'-dimethyl-4,4 '-diamino-dicyclohexyl-methane commonly referred to as (BMACM) or (MACM) (and noted B below), bis (p-aminocyclohexyl) -methane commonly referred to as (PACM)
• Dicykan ® isopropylidenedi (cyclohexylamine) commonly known as (PACP), isophorone-diamine (noted IPD below) and 2,6-bis (amino methyl) commonly referred to as norbornane (BAMN) and bis (aminomethyl) cyclohexane (BAC), in particular 1,3-BAC or Ia, in particular 1,4-BAC.
• PCP isopropylidenedi
• IPD isophorone-diamine
• BAMN 2,6-bis (amino methyl) commonly referred to as norbornane
• BAC bis (aminomethyl) cyclohexane
• BMACM bis- (3-methyl-4-aminocyclohexyl) -methane or 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane commonly called (BMACM) or (MACM) (and noted B below), bis (p-aminocyclohexyl) -methane commonly referred to as (PACM) (and noted P below) and bis (aminomethyl) cyclohexane (BAC), in particular 1,3-BAC or la, in particular 1,4-BAC.
• BMACM bis- (3-methyl-4-aminocyclohexyl) -methane or 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-methane
• PAM bis (p-aminocyclohexyl) -methane
• BAC bis (aminomethyl) cyclohexane
• A, Ca and Cb are as defined above.
• (Y) is at least one C4-C36 aliphatic dicarboxylic acid, preferably C6-C18, preferably C6-C12, more preferably C10-C12, it is as defined for Cb.
• (Y) is at least one aromatic dicarboxylic acid (Y)
• Y aromatic dicarboxylic acid
• Y it is advantageously chosen from terephthalic acid (denoted T), isophthalic acid (denoted I) and 2,6 naphthalene dicarboxylic acid (denoted N) or their mixtures, in particular it is chosen from terephthalic acid (denoted T), isophthalic acid (denoted I) or their mixtures.
• the modulus of a composition changes as a function of the temperature and in general, the modulus decreases with the increase in temperature.
• the modulus does not vary by more than 25% in the temperature range from 10 ° C to 40 ° C, in particular in the temperature range from 0 ° C to 40 ° C, in particular in the temperature range going from - 10 ° C to 40 ° C "means that in these different ranges from 10 ° C to 40 ° C, from 0 ° C to 40 ° C and from -10 ° C to 40 ° C, the modulus of the same composition, whether it is the flexural modulus or the tensile modulus measured after identical conditioning (dry or humid atmosphere), does not change by more than 25%.
• the modulus of said composition does not vary by more than 35% in the temperature range going from -10 ° C to 50 ° C.
• the modulus does not vary by more than 35% in the temperature range from - 10 ° C to 50 ° C
• the modulus d the same composition, whether it is the flexural modulus or the tensile modulus measured after identical conditioning (dry or humid atmosphere), does not change by more than 35%.
• the modulus of said composition does not vary by more than 40% in the temperature range going from -10 ° C to 60 ° C.
• the modulus does not vary by more than 40% in the temperature range from - 10 ° C to 60 ° C
• the modulus d the same composition, whether it is the flexural modulus or the tensile modulus measured after identical conditioning (dry or humid atmosphere), does not change by more than 40%.
• conditioning in a humid atmosphere means after saturation in liquid water at 65 ° C.
• M-io be the modulus measured at -10 ° C and M T be the modulus measured at a temperature T for a composition conditioned under the same dry or humid atmosphere conditions, then:
• the modulus is measured as defined above according to the ISO 178: 2010 standard and corresponds to the flexural modulus.
• the modulus is measured as defined above according to the ISO 527-1 and 2: 2012 standard and corresponds to the tensile modulus.
• the modulus corresponds to both the flexural modulus and the tensile modulus, both being measured as defined above.
• the variation in flexural modulus, measured at 20 ° C on a sample saturated in water at 65 ° C, and measured at 20 ° C on a dry sample is less than or equal to 15%, in particular less than or equal at 7%, both measurements being carried out according to ISO 178: 2010.
• said at least one amorphous polyamide is a homopolyamide of formula XY or a copolyamide of formula A / XY, XY being a repeating unit obtained by polycondensation of at least one cycloaliphatic diamine (X) and at least a C 4 -C 36 aliphatic (Y) dicarboxylic acid, preferably C 6 -C 18 , preferably C 6 -C 12 , more preferably C 10 -C 12 or at least one aromatic dicarboxylic acid (Y) and A is a pattern repetitive obtained by polycondensation of at least one amino acid C 6 Cis, preferably Ci to Cio to 8, more preferably a Cio to C12, or at least one lactam C 6 Cis, preferably in the Cio to Cis, more preferably C10 to C12, or at least one diamine Ca in C4-C36, preferentially C 5 -Cis, preferentially C5-C12, more preferentially C10
• said at least one amorphous polyamide is a copolyamide of formula A / XY, A being obtained by polycondensation of at least one amino acid or obtained by polycondensation of at least one lactam, X being chosen from B or P or BAC and Y being terepthalic and / or isophthalic acid.
• a / XY is chosen from the patterns 11 / BI / BT, 12 / BI / BT, 11 / BACI / BACT, 12 / BACI / BACT, 11 / BACI, 12 / BACI, 11 / PI / PT, 12 / PI / PT and a mixture thereof.
• said at least one amorphous polyamide is a copolyamide of formula A / XY, A being obtained by polycondensation of at least one amino acid or obtained by polycondensation of at least one lactam, X being chosen from B or P and Y being sebacic acid or dodecanedioic acid.
• a / XY is chosen from the units 11 / B10, 11 / B12, 11 / P10, 11 / P12, 12 / B10, 12 / B12, 12 / P10, 12 / P12, and the one of their mixtures.
• said at least one amorphous polyamide is a copolyamide of formula A / XY, A being obtained by polycondensation of at least one diamine Ca with at least one dicarboxylic acid Cb, X being chosen from B or P and Y being sebacic acid or dodecanedioic acid.
• a / XY is chosen from the units 1010 / B10, 1010 / B12, 1010 / P10, 1010 / P12, 1012 / B10, 1012 / B12, 1012 / P10, 1012 / P12, 1210 / B10, 1210 / B12, 1210 / P10, 1210 / P12, 1212 / B10, 1212 / P10, 1210 / P12, 1212 / B10, 1212 / B12, 1212 / P10, 1212 / P12, and a mixture thereof.
• said at least one amorphous polyamide is a homopolyamide of formula XY, X being chosen from B or P and Y being sebacic acid or dodecanedioic acid.
• XY is chosen from the units B10, B12, P10, P12, and one of their mixtures.
• the proportion by weight of said amorphous polyamide is from 10 to 45%, preferably from 15 to 35% by weight, more preferably from 20 to 30% by weight per relative to the sum by weight of said at least one semi-crystalline polyamide and of said at least one amorphous polyamide.
• the present invention relates to the use of a mixture of at least one semi-crystalline aliphatic polyamide and at least one amorphous polyamide for preparing a semi-crystalline composition as defined above, said composition comprising from 35 to 75% by weight of reinforcing fibers, in particular from 35 to 65% by weight of reinforcing fibers.
• composition according to the invention may comprise short reinforcing fibers or short fibrous reinforcement.
• the fibers are short and of length between 2 and 13 mm, preferably from 3 to 8 mm before use of the compositions.
• These short reinforcing fibers can be chosen from:
• carbon fibers which includes fibers of carbon nanotubes or nanotubes (CNTs), carbon nanofibers or graphenes; silica fibers such as glass fibers, in particular of type D, E, R, S2 or T; boron fibers; ceramic fibers, in particular silicon carbide fibers, boron carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers or basalt-based fibers; fibers or filaments based on metals and / or their alloys; fibers of metal oxides, in particular of alumina (Al2O3); metallized fibers such as metallized glass fibers and metallized carbon fibers or mixtures of the aforementioned fibers.
• CNTs carbon nanotubes or nanotubes
• silica fibers such as glass fibers, in particular of type D, E, R, S2 or T
• boron fibers ceramic fibers, in particular silicon carbide fibers,
• these fibers can be chosen as follows:
• the mineral fibers can be chosen from: carbon fibers, fibers of carbon nanotubes, glass fibers, in particular of type D, E, R, S2, or T, boron fibers, ceramic fibers, in particular carbide fibers silicon, boron carbide fibers, boron carbonitride fibers, silicon nitride fibers, boron nitride fibers, basalt fibers or basalt based fibers; fibers or filaments based on metals and / or their alloys, fibers based on metal oxides such as AI203, metallized fibers such as metallized glass fibers and metallized carbon fibers or mixtures of the aforementioned fibers, and
• polymer or polymer fibers under the aforementioned condition, are chosen from:
• thermosetting polymers and more particularly chosen from: unsaturated polyesters, epoxy resins, vinyl esters, phenolic resins, polyurethanes, cyanoacrylates and polyimides, such as bis-maleimide resins, aminoplasts resulting from the reaction of an amine such as melamine with an aldehyde such as glyoxal or formaldehyde,
• thermoplastic polymers and more particularly chosen from: polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
• - aramid fibers such as Kevlar ®
• aromatic polyamides such as those corresponding to one of the formulas: PPD.T, MPD.I, PAA and PPA, with PPD and MPD being respectively p- and m- phenylene diamine, PAA being polyarylamides and PPA being polyphthalamides,
• PAEK polyarylether ketones
• PEEK polyetherether ketone
• PEKK polyetherketone ketone
• PEKEKK polyetherketoneetherketone ketone
• Preferred short reinforcing fibers are short fibers chosen among: carbon fibers, including metallic, glass fibers, including metallized type E, R, S2, T fibers or aramid (such as Kevlar ®) or aromatic polyamides, polyarylether ketone (PAEK) fibers, such as polyetherether ketone (PEEK), polyether ketone (PEKK) fibers, polyether ketoneetherketone ketone (PEKEKK) fibers, or mixtures thereof.
• carbon fibers including metallic, glass fibers, including metallized type E, R, S2, T fibers or aramid (such as Kevlar ®) or aromatic polyamides
• PAEK polyarylether ketone
• PEEK polyetherether ketone
• PEKK polyether ketone
• PEKEKK polyether ketoneetherketone ketone
• the natural fibers are chosen from fibers of flax, castor, wood, sisal, kenaf, coconut, hemp and jute.
• glass fiber within the meaning of the invention is meant any glass fiber, in particular as described by Frederick T. Wallenberger, James C. Watson and Hong Li, PPG industries Inc. (ASM Handbook, Vol 21: composites (# 06781G), 2001 ASM International).
• the reinforcing fiber can be:
• the reinforcing fibers are chosen from glass fibers, carbon fibers, and a mixture thereof.
• the reinforcing fiber is chosen from a glass fiber with a non-circular cross section, a glass fiber with a circular section, a carbon fiber and a mixture of these.
• the reinforcing fiber is chosen from a glass fiber with a non-circular cross section, a glass fiber with a circular section and a mixture of these.
• the reinforcing fiber is a glass fiber with a circular section.
• said composition further comprises semi-crystalline aliphatic polyamide, amorphous polyamide and reinforcing fibers:
• said composition consists of semi-crystalline aliphatic polyamide, amorphous polyamide, reinforcing fibers, and:
• additives preferably 0.5 to less than 2% by weight of additives, the sum of semi-crystalline aliphatic polyamide, amorphous polyamide, reinforcing fibers, an impact modifier, filler, fluidifying agent and additives being equal to 100%.
• said composition further comprises semi-crystalline aliphatic polyamide, amorphous polyamide and reinforcing fibers:
• said composition consists of semi-crystalline aliphatic polyamide, amorphous polyamide, reinforcing fibers, and:
• additives preferably 0.5 to less than 2% by weight of additives, the sum of semi-crystalline aliphatic polyamide, amorphous polyamide, reinforcing fibers, an impact modifier, filler, fluidifying agent and additives being equal to 100%.
• the proportion of filler in these compositions is from 5 to 30% by weight, in particular from 10 to 30% by weight, preferably from 15 to 30% by weight.
• the proportion of filler in these compositions is from 0 to 28% by weight, in particular from 1 to 28%, from 5 to 28% by weight, in particular from 10 to 28% by weight, preferably from 15 to 28% by weight.
• impact modifier should be understood to mean a polyolefin-based polymer having a flexural modulus of less than 100 MPa measured according to the ISO 178: 2010 standard (23 ° C RH50) and of Tg less than 0 ° C (measured according to standard 11357-2: 2013 at the inflection point of the DSC thermogram), in particular a polyolefin.
• the impact modifier can also be a block polymer of PEBA (polyether-block-amide) type having a flexural modulus ⁇ 200 MPa.
• PEBA polyether-block-amide
• the impact modifier can also be a polyolefin of SEBS type.
• the composition can also comprise one or more impact modifiers as defined above.
• the presence of an impact modifier makes it possible to confer greater ductility on the manufactured articles.
• the polyolefin of the impact modifier can be functionalized or non-functionalized or contain both as a mixture.
• the polyolefin When the polyolefin is functionalized, some or all of the polyolefins bear a function chosen from carboxylic acid, carboxylic anhydride and epoxide functions.
• the polyolefin can in particular be chosen from a copolymer of ethylene and propylene with an elastomeric character (EPR), an ethylene-propylene-diene copolymer with an elastomeric character (EPDM) and an ethylene / (meth) acrylate copolymer, a ethylene-higher alkene copolymer, in particular ethylene-octene copolymer, ethylene-alkyl acrylate-maleic anhydride terpolymer.
• EPR elastomeric character
• EPDM ethylene-propylene-diene copolymer with an elastomeric character
• EPDM ethylene / (meth) acrylate copolymer
• ethylene-higher alkene copolymer
• Peba polyether block amides
• Polyether block amides are copolymers comprising blocks with a polyamide pattern and blocks with a polyether pattern. They can also contain ester functions, in particular resulting from the condensation reaction of terminal carboxylic functions of the polyamide blocks with the hydroxyl functions of the polyether blocks.
• Peba are commercially available, in particular under the brand Pebax ® by the company Arkema.
• the impact modifier is selected from Fusabond ® F493, the Tafmer MFI5020, a Pebax ®, particularly Pebax ® 40R53 SP01, a Lotader ®, the Exxelor ® VA1803 or VA1801, the Orevac ® IM800 or a mixture thereof - here, in this case they are in a ratio ranging from 0.1 / 99.9 to 99.9 / 0.1.
• the impact modifier can also be a “core-shell” type modifier, also designated “core-shell copolymer”.
• the “core-shell” type modifier is in the form of fine particles having an elastomeric core and at least one thermoplastic shell, the size of the particles is generally less than 1 ⁇ m and advantageously between 150 and 500 nm.
• the “core-shell” type modifier has an acrylic or butadiene base.
• the content of impact modifier relative to the total weight of the composition can vary from 0 to 10% by weight, advantageously from 1 to 10% by weight.
• the composition comprises from 1 to 8%, and in particular from 2 to 5% by weight of impact modifier relative to the total weight of the composition.
• the content of the impact modifier in the composition can vary from 1 to 2% by weight; or from 2 to 3% by weight; or from 3 to 4% by weight; or from 4 to 5% by weight; or from 5 to 6% by weight; or from 6 to 7% by weight; or from 7 to 8% by weight; or from 8 to 9% by weight; or from 9 to 10% by weight.
• the composition can moreover also comprise fillers.
• the fillers envisaged include glass beads, in particular solid or hollow, conventional mineral fillers, such as kaolin, magnesia, slag, carbon black, expanded or non-expanded graphite, wollastonite, nucleating agents such as silica, alumina, clay or talc, in particular talc, pigments such as titanium oxide and zinc sulphide, antistatic fillers, flame retardant fillers, especially a halogen-free flame retardant, as described in US 2008/0274355 and in particular a phosphorus-based flame retardant, for example a metal salt chosen from a metal salt of phosphinic acid, in particular salts of dialkyl phosphinate, in particular diethylphosphinate aluminum salt or diethylphosphinate d aluminum, a metal salt of diphosphinic acid, a mixture of flame retardant based on aluminum phosphinate and a nitrogen synergist or a mixture of flame
• the glass beads are not reinforcing fibers.
• the composition can also include fluidifying agents.
• fluidifying agent in particular prepolymers.
• the prepolymer can be chosen from oligomers of aliphatic, linear or branched, cycloaliphatic, semi-aromatic or even aromatic polyamides.
• the prepolymer can also be a copolyamide oligomer or a mixture of polyamide and copolyamide oligomers.
• the prepolymer has a number-average molar mass Mn ranging from 1000 to 10000 g / mol, in particular from 1000 to 5000 g / mol. It can in particular be monofunctional NFhsi the chain limiter used is a monoamine for example.
• the content of thinning agent relative to the total weight of the composition can vary from 0 to 10% by weight, in particular from 1 to 10% by weight, in particular from 5 to 10%.
• the composition comprises from 1 to 5%, and in particular from 1 to 4%, by weight of thinning agent relative to the total weight of the composition.
• the content of thinning agent relative to the total weight of the composition is from 1 to 2% by weight; or from 2 to 3% by weight; or from 3 to 4% by weight; or from 4 to 5% by weight.
• additives should be understood to mean colorants, stabilizers, surfactants, brighteners, antioxidants, lubricants, waxes as well as their mixtures.
• the stabilizers can be organic or inorganic stabilizers.
• the usual stabilizers used with polymers are, for example, phenols, phosphites, UV absorbers, stabilizers of the HALS (Hindered Amine Light Stabilizer) type, metal iodides. These include Irganox ® 1010, 245, 1098 of BASF, Irgafos ® 168, 126 from BASF, Tinuvin ®
• the lubricants can in particular be a stearate or a wax binder.
• the waxes can in particular be an amorphous wax such as a beeswax, a silicone wax, a polyethylene wax, an oxidized polyethylene wax, an ethylene copolymer wax, a montane wax and a wax of. polyether.
• amorphous wax such as a beeswax, a silicone wax, a polyethylene wax, an oxidized polyethylene wax, an ethylene copolymer wax, a montane wax and a wax of. polyether.
• additives of the same category or of different categories may be present in the composition.
• the additive content is from 0 to less than 2% by weight relative to the total weight of the composition.
• the composition comprises from 0.1 to less than 2%, and in particular from 0.5 to less than 2% by weight of additive relative to the total weight of the composition.
• the content of additive in the composition can vary from 0 to 0.5% by weight; or from 0.1 to 0.5% by weight, or from 0.5 to 1% by weight; or from 1 to 1.5% by weight; or from 1.5 to less than 2% by weight.
• the invention relates to a composition, in particular useful for injection molding, comprising:
• the reinforcing fibers, impact modifiers, fillers, thinning agents and additives are as defined above and all the concentration ranges relating to impact modifiers, thinning agents, fillers and additives, defined above, are also valid for said composition. as is.
• said composition in particular useful for injection molding, consists of:
• said composition in particular useful for injection molding, consists of:
• said composition in particular useful for injection molding, consists of:
• said composition in particular useful for injection molding, consists of:
• said composition in particular useful for injection molding, consists of:
• said composition in particular useful for injection molding, consists of:
• said composition in particular useful for injection molding, consists of:
• said composition in particular useful for injection molding, consists of:
• said composition in particular useful for injection molding, consists of:
• said composition in particular useful for injection molding, consists of:
• said composition in particular useful for injection molding, consists of:
• said composition in particular useful for injection molding, consists of:
• the proportion of filler in the latter composition is from 5 to 30% by weight, in particular from 10 to 30% by weight, preferably from 15 to 30% by weight and the maximum of the mixture of semi-crystalline polyamide and of polyamide amorphous present is then 58.9% respectively; 53.9% and 48.9%.
• said composition in particular useful for injection molding, consists of:
• the proportion of filler in the latter composition is from 5 to 30% by weight, in particular from 10 to 30% by weight, preferably from 15 to 30% by weight and the maximum of the mixture of semi-crystalline polyamide and of polyamide amorphous present is then 58.5% respectively; 53.5% and 48.5%.
• said composition in particular useful for injection molding, consists of:
• the proportion of filler in the latter composition is from 5 to 30% by weight, in particular from 10 to 30% by weight, preferably from 15 to 30% by weight and the maximum of the mixture of semi-crystalline polyamide and of polyamide amorphous present is then respectively 57.9%; 52.9% and 47.9%.
• said composition in particular useful for injection molding, consists of:
• the proportion of filler in the latter composition is from 5 to 30% by weight, in particular from 10 to 30% by weight, preferably from 15 to 30% by weight and the maximum of the mixture of semi-crystalline polyamide and of polyamide amorphous present is then respectively 57.5%; 52.5% and 47.5%.
• the proportion of filler in the compositions of the invention is from 0 to 28% by weight, in particular from 1 to 28%, from 5 to 28% by weight, in particular from 10 to 28% by weight, preferably from 15 to 28% by weight.
• the invention relates to a process for manufacturing the composition as defined above, in which the constituents of said composition are mixed by compounding, in particular in a twin-screw extruder, preferably co-rotating, a co-mixer, or an internal mixer.
• the invention relates to a molded article obtainable from the composition defined above, by injection molding.
• said molded article is for electrical and electronics, and in particular chosen from the group consisting of televisions, digital cameras, digital games, telephone parts, digital tablets, drones, printers. or computer parts.
• said molded article is for sport, and in particular a ski boot or part of a ski boot or a rigid shoe with a stud, such as a soccer, rugby or American football boot.
• hockey or a game of hockey shoe, or a running shoe, a golf ball or a game of golf ball, or a lacrosse stick or a hockey article such as a helmet or sporting goods for the protection of the head, shoulders, elbows, hands, knees, back or shin, such as helmet, gloves, shoulder pads, elbow pads, knee pads or shin pads.
• Example 1 Synthesis of (co) polyamides of the invention.
• the various polyamides and copolyamides of the invention were prepared according to the usual technique for the synthesis of polyamides and copolyamides.
• PA 11 / B10 representative of the different copolyamides: the aminoundecanoic acid, bis- (3-methyl-4-aminocyclohexyl) -methane (B) and sebacic acid monomers are loaded together into the reactor according to the desired mass ratio.
• the medium is first inerted in order to remove the oxygen which can generate yellowing or side reactions. Water can also be charged to improve heat exchange and promote melting of the monomers. Two stages of temperature and pressure rise are carried out. The temperature (T °) and pressure conditions are chosen so as to allow the medium to be in the molten state. After reaching the maintenance conditions, degassing takes place to allow the polycondensation reaction.
• the medium gradually becomes viscous and the water of reaction formed is entrained by flushing with nitrogen or placed under vacuum.
• the stopping conditions in relation to the desired viscosity, the agitation is stopped and the extrusion and the granulation can start.
• the granules obtained will then be compounded with the glass fibers.
• compositions were prepared by melt blending the polymer granules with the short fibers. This mixture was carried out by compounding on a co-rotating twin-screw extruder with a screw diameter of 26 mm with a temperature profile (T °) flat at 290 ° C for the compositions CEI at CE3 and 11 at 18 and at 230 ° C. for compositions 19 and 110 and CE4.
• the screw speed is 250rpm and the flow rate is 20 kg / h.
• the introduction of the glass fibers is carried out by lateral force-feeding.
• the (co) polyamides, the fibers, the additives and optionally the fillers are added during the compounding process in the main hopper for the compositions CEI to CE3 and 11 to 18.
• compositions 18 and 19 and CE4 the resins and additives are introduced into the main hopper and the charges are added by a first side feeder and the glass fibers in a second side feeder.
• the values correspond to percentages by weight.
• BMNO Rilsan ® BMNO marketed by Arkema Flame retardant: OP1312 (Clariant) Circular section fibers CSX3J-451 marketed by the company Nittobo Injection
• Plates of 100 * 100 * 1 mm 3 were prepared by injection of the different compositions: - Injection temperature: 260 ° C - Mold temperature: 80 ° C The cycle time is adjusted according to the compositions to allow the injection of the compositions and is less than 50 seconds.
• compositions 11 to 110 all exhibit a Tg relative to the comparative IEC to CE3 compositions of greater than 5 ° C.
• compositions 11-18 of Table 1 and 19-110 of Table 2 all have crystallization enthalpies greater than 30 J / g.
• Example 2 Variation of the flexural modulus as a function of temperature and humidity
• the flexural modulus of test specimens of the compositions obtained on an Instron 5966 machine manufactured by the company Instron.
• the compositions are dried compositions and compositions saturated in water at 65 ° C beforehand. The tests were carried out at different temperatures, from -10 ° C to 60 ° C.
• Table 4 shows that the compositions of the invention exhibit higher flexural modulus stability than the comparative IEC to CE4 compositions.
• Example 3 Variation of the tensile modulus as a function of temperature and humidity
• the tensile modulus of test specimens was measured.
• the tests were carried out at different temperatures, from -10 ° C to 60 ° C.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Proteomics, Peptides & Aminoacids (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyamides (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=72717888

Family Applications (1)

Country Status (6)

Family Cites Families (15)

• 2020
  • 2020-09-16 EP EP20785812.7A patent/EP4031624A1/de active Pending
  • 2020-09-16 JP JP2022517960A patent/JP2022548387A/ja active Pending
  • 2020-09-16 WO PCT/FR2020/051597 patent/WO2021053292A1/fr not_active Ceased
  • 2020-09-16 KR KR1020227012502A patent/KR20220066112A/ko active Pending
  • 2020-09-16 CN CN202080078735.XA patent/CN114729184A/zh active Pending
  • 2020-09-16 US US17/642,311 patent/US12565585B2/en active Active
• 2025
  • 2025-08-08 JP JP2025133562A patent/JP2025179072A/ja active Pending

Also Published As

Similar Documents

Legal Events