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WO2015091777A1 - Procédé servant à produire un polyamide aliphatique ou en partie aromatique - Google Patents

Procédé servant à produire un polyamide aliphatique ou en partie aromatique Download PDF

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Publication number
WO2015091777A1
WO2015091777A1 PCT/EP2014/078436 EP2014078436W WO2015091777A1 WO 2015091777 A1 WO2015091777 A1 WO 2015091777A1 EP 2014078436 W EP2014078436 W EP 2014078436W WO 2015091777 A1 WO2015091777 A1 WO 2015091777A1
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Prior art keywords
polyamide
prepolymer
aliphatic
acid
ipda
Prior art date
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German (de)
English (en)
Inventor
Stefan Schwiegk
Joachim Clauss
Axel Wilms
Florian Richter
Christian Schmidt
Arnold Schneller
Gad Kory
Joachim DÖRR
Silke Biedasek
Ning Zhu
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BASF SE
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BASF SE
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    • 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
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • 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
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C08G69/30—Solid state polycondensation

Definitions

  • the present invention relates to a process for producing an aliphatic or partially aromatic polyamide, an aliphatic or partially aromatic polyamide obtainable by this process, and the use thereof.
  • Polyamides are among the world's most widely produced polymers and serve in addition to the main application areas of films, fibers and materials of a variety of other uses.
  • polyamide 6 polycaprolactam
  • polyamide 66 nylon, polyhexamethylene adipamide
  • the production of polyamide 66 is carried out predominantly by polycondensation of so-called AH salt solutions, d. H. aqueous solutions containing adipic acid and 1, 6-diaminohexane (hexamethylenediamine) in stoichiometric amounts.
  • polyamide 6 The classical process for the preparation of polyamide 6 is the hydrolytic ring-opening polymerization of ⁇ -caprolactam, which is still of great industrial importance.
  • Conventional production methods for polyamide 6 and polyamide 66 are z. B. in Kunststoffhandbuch,% engineering thermoplastics: polyamides, Carl Hanser Verlag, 1998, Kunststoff, p 42-71 described.
  • HTPA high-temperature polyamides
  • PPA polyphthalamide
  • HTPAs are used to produce connectors, microswitches and pushbuttons and semiconductor components, such as reflector housings of light-emitting diodes (LEDs).
  • LEDs light-emitting diodes
  • Amorphous HTPA or those with very low crystalline proportions are transparent and are particularly suitable for applications in which, in addition to the transparency, good chemical resistance is advantageous.
  • Semi-crystalline HTPA's are generally characterized by long-lasting resistance high ambient temperature and are suitable for. For applications in the engine compartment area.
  • the preparation of partly aromatic polyamides generally begins with the formation of an aqueous salt solution of at least one diamine and at least one dicarboxylic acid and optionally further monomer components, such as lactams, co-amino acids, monoamines, monocarboxylic acids and mixtures thereof, with the proviso in that at least one of the components has an aromatic group.
  • the formation of the salt solution is then followed by oligomerization in the liquid phase. This oligomerization can still be done without separation of water or already with water separation. At the end of this oligomerization, the oligomers have on average, for example, 4 to 10 repeat units at a conversion of about 70 to 80%. To further increase the molecular weight then two alternative routes are available.
  • the oligomer formed is transferred by dewatering in the solid phase and subjected to a so-called solid state polymerization (SSP).
  • SSP solid state polymerization
  • the second variant is carried out under controlled water separation and temperature increase, a transfer of the aqueous solution into the melt for further polycondensation.
  • a prepolymer is obtained which has, for example, a number-average molecular weight of about 2500 to 7500 g / mol.
  • the resulting copolymer can have an excess of carboxylic acid end groups or amino end groups, with excess amino end groups being preferred for many applications.
  • EP 0 693 515 A1 describes a process for the preparation of precondensates of semicrystalline or amorphous, thermoplastically processable partially aromatic polyamides in a multistage batch process which comprises the following steps a) to e): a) a salt formation phase for the preparation of salt (s) from diamine (s) and dicarboxylic acid (s) and optionally partial pre-reaction to low molecular weight oligogamides is carried out at temperatures between 120 ° C and 220 ° C and pressures of up to 23 bar, b) optionally, the conversion of the solution from step a) c) the reaction phase during which the conversion to the precondensates is advanced by heating the reactor contents to a predetermined temperature; temperature and controlled adjustment of the water vapor partial pressure to a predetermined value, which is maintained by controlled discharge of steam or optionally controlled supply of steam from a steam generator connected to the autoclave, d) a stationary phase to be maintained for at least 10 minutes at which the temperature of the reactor contents and the
  • the prepolymer is generally subjected to postcondensation.
  • EP 0 693 515 A1 contains no specific information. Only in the appreciation of the prior art is the possibility of postcondensation in a continuously operating extruder mentioned.
  • US 2003/0176624 A1 describes a process for solid-phase drying or solid-state polymerization of a polyamide based on xylylenediamine.
  • the solid state polymerization takes place in an inert gas stream or at reduced pressure.
  • WO 2003/048728 describes polyamides of m-xylylenediamine and adipic acid having an amino end group content of less than 15 mmol / kg. It is first prepared a prepolymer, optionally an extraction and a Festphasenkon- be subjected to condensation. The solid phase condensation can take place either in vacuo or under inert gas.
  • EP 0 667 367 A2 relates to partially aromatic semi-crystalline thermoplastic polyamide molding compositions containing
  • Examples 1 and 3 describe that the products of the polymerization can be subjected to tempering in the solid phase, wherein the tempering tube is traversed by superheated steam at a temperature of 200 ° C.
  • the present invention is based on the object to provide an improved process for the preparation of aliphatic or partially aromatic polyamides. These should be distinguished by advantageous product properties, in particular a not too broad molecular weight distribution and / or a low gel content.
  • An object of the invention is therefore a process for producing an aliphatic or partially aromatic polyamide in which a prepolymer of the aliphatic or partially aromatic polyamide is provided and the prepolymer is subjected to solid phase postcondensation in which it is brought into contact with water vapor In a preferred embodiment, at least one fluidized bed is used to contact the prepolymer with the water vapor.
  • Another object of the invention are aliphatic or partially aromatic polyamides obtainable by a process as defined above and below.
  • Another object of the invention is a polyamide molding composition comprising at least one polyamide, obtainable by a method as defined above and in the following.
  • Another object of the invention is a molding, made from such a polyamide molding composition.
  • Another object of the invention is the use of a partially aromatic polyamide obtainable by a process as defined above and hereinafter for the production of electrical and electronic components and for automotive applications in the high temperature range. This also includes structural components which have a glass transition temperature of at least 70 ° C., preferably of at least 80 ° C., in the conditioned state.
  • Another object of the invention is the use of an aliphatic polyamide obtainable by a process as defined above and hereinafter for the production of films, monofilaments, fibers, yarns or textile fabrics.
  • a “solid phase postcondensation” is generally understood to mean a condensation reaction for increasing the molecular weight in a temperature range above the glass transition temperature and below the melting temperature of the polyamide. In this temperature range, unwanted thermal degradation of the polyamide can be largely avoided.
  • a prepolymer means a composition which comprises polymeric compounds having complementary functional groups which are capable of a condensation reaction with molecular weight increase.
  • the monomers of the acid component and the diamine component and of the optionally used lactam component form by the condensation repeat units or end groups in the form of amides, which are separated from the respective monomers. are leading. These usually make up 95 mol%, in particular 99 mol%, of all repeat units and end groups present in the copolyamide.
  • the copolyamide can also have small amounts of other repeat units which can result from degradation or side reactions of the monomers, for example the diamines.
  • polyamides For the designation of the polyamides, some customary abbreviations are used within the scope of the invention, which consist of the letters PA and subsequent numbers and letters. Some of these abbreviations are standardized in DIN EN ISO 1043-1. Polyamides derived from aminocarboxylic acids of the type H2N- (CH 2) x -COOH or the corresponding lactams are designated as PA Z, where Z denotes the number of carbon atoms in the monomer. So z. B. PA 6 for the polymer of ⁇ -caprolactam or ⁇ -aminocaproic acid.
  • Polyamides derived from diamines and dicarboxylic acids of the types H2N- (CH2) x-NH2 and HOOC- (CH2) y-COOH are identified as PA Z1 Z2, where Z1 is the number of carbon atoms in the diamine and Z2 is the number of carbon atoms Carbon atoms in the dicarboxylic acid.
  • copolyamides the components are listed in order of their proportions, separated by slashes. So z. B.
  • PA 66/610 the copolyamide of hexamethylenediamine, adipic acid and sebacic acid.
  • T terephthalic acid
  • I isophthalic acid
  • MXDA m-xylylenediamine
  • IPDA isophoronediamine
  • PACM 4,4'-methylenebis (cyclohexylamine) (commercial name Dicycan®)
  • MACM 2,2'-dimethyl-4,4'-methylenebis (cyclohexylamine).
  • C 1 -C 4 -alkyl includes unsubstituted straight-chain and branched C 1 -C 4 -alkyl groups.
  • Examples of C 1 -C 4 -alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl (1, 1-dimethyl-ethyl).
  • the carboxyl groups may each be present in a non-derivatized form or in the form of derivatives.
  • dicarboxylic acids none, one or both of the carboxyl groups may be present in the form of a derivative.
  • Suitable derivatives are anhydrides, esters, acid chlorides, nitriles and isocyanates.
  • Preferred derivatives are anhydrides or esters.
  • Anhydrides of dicarboxylic acids may be in monomeric or polymeric form.
  • esters are alkyl esters and vinyl esters, particularly preferably C 1 -C 4 -alkyl esters, in particular the methyl esters or ethyl esters.
  • Dicarboxylic acids are preferably as mono- or Dialkyl esters, particularly preferably mono- or di-C 1 -C 4 -alkyl esters, more preferably monomethyl esters, dimethyl esters, monoethyl esters or diethyl esters.
  • Dicarboxylic acids are furthermore preferably present as mono- or divinyl esters.
  • Dicarboxylic acids are furthermore preferably present as mixed esters, particularly preferably mixed esters with different C 1 -C 4 -alkyl components, in particular methyl ethyl esters.
  • the prepolymer is provided by polycondensation of an aqueous composition containing at least one component suitable for polyamide formation.
  • the prepolymer (and accordingly the aliphatic or partially aromatic polyamide) contains incorporated components which are selected from
  • a suitable embodiment is aliphatic polyamides.
  • aliphatic polyamides of the type PA Z1 Z2 such as PA 66
  • PA Z such as PA 6 or PA 12
  • a preferred embodiment are partially aromatic polyamides.
  • the aromatic dicarboxylic acids A) are preferably selected from unsubstituted or substituted phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acids or diphenyldicarboxylic acids and the derivatives and mixtures of the abovementioned aromatic dicarboxylic acids.
  • Substituted aromatic dicarboxylic acids A) preferably have at least one (eg 1, 2, 3 or 4) C 1 -C 4 -alkyl radical.
  • substituted aromatic dicarboxylic acids A) have 1 or 2 C 1 -C 4 -alkyl radicals.
  • Substituted aromatic dicarboxylic acids A) may also carry further functional groups which do not disturb the amidation, such as, for example, 5-sulfoisophthalic acid, its salts and derivatives.
  • a preferred example of this is the sodium salt of 5-Sulfoisophthal Acidimethylesters.
  • the aromatic dicarboxylic acid A) is selected from unsubstituted terephthalic acid, unsubstituted isophthalic acid, unsubstituted naphthalenedicarboxylic acids, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid and 5-sodium isophthalic acid.
  • the aromatic dicarboxylic acid A) is selected from unsubstituted terephthalic acid, unsubstituted isophthalic acid, unsubstituted naphthalenedicarboxylic acids, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid and 5-sodium isophthalic acid.
  • the aromatic dicarboxylic acid A) used is particularly preferably terephthalic acid, isophthalic acid or a mixture of terephthalic acid and isophthalic acid.
  • the partly aromatic polyamide prepolymers provided according to the invention have a proportion of aromatic dicarboxylic acids on all dicarboxylic acids of at least 50 mol%, particularly preferably from 70 mol% to 100 mol%.
  • the partially aromatic polyamides prepared by the process according to the invention (and the prepolymers provided in step a), a proportion of terephthalic acid or isophthalic acid or a mixture of terephthalic acid and isophthalic acid relative to all dicarboxylic acids of at least 50 mol%, are preferred from 70 mol% to 100 mol%, on.
  • the aromatic diamines B) are preferably selected from bis (4-aminophenyl) methane, 3-methylbenzidine, 2,2-bis (4-aminophenyl) -propane, 1,1-bis- (4-aminophenyl) -cyclohexane , 1, 2-diaminobenzene, 1, 4-diaminobenzene, 1, 4-diaminonaphthalene,
  • the aliphatic or cycloaliphatic dicarboxylic acids C) are preferably selected from oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, undecane-a, co-dicarboxylic, dodecane-a, co-dicarboxylic, maleic, fumaric or itaconic acid , cis- and trans -cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans-cyclohexane-1,4-dicarboxylic acid, cis- and trans-cyclopentane-1,2 - dicarboxylic acid, cis- and trans-cyclopentane-1, 3-dicarboxylic acid and mixtures thereof.
  • the aliphatic or cycloaliphatic diamines D) are preferably selected from ethylenediamine, propylenediamine, tetramethylenediamine, heptamethylenediamine, hexamethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2-methylpentamethylenediamine,
  • the partially aromatic polyamides contain at least one diamine D) in copolymerized form, which is selected from hexamethylenediamine, bis (4-aminocyclohexyl) methane (PACM), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM), Isophorone diamine (IPDA) and mixtures thereof.
  • diamine D selected from hexamethylenediamine, bis (4-aminocyclohexyl) methane (PACM), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM), Isophorone diamine (IPDA) and mixtures thereof.
  • the partly aromatic polyamides contain, as diamine D), exclusively copolymerized hexamethylenediamine.
  • the partly aromatic polyamides contain, as diamine D), exclusively copolymerized bis (4-aminocyclohexyl) methane.
  • the partly aromatic polyamides contain, as diamine D), exclusively copolymerized 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM).
  • the partially aromatic polyamides contain
  • Diamine D exclusively 3,3 ', 5,5'-tetramethyl-4,4'-diaminodicyclohexylmethan polymerized.
  • the partially aromatic polyamides contain, as diamine D), exclusively copolymerized isophorone diamine (IPDA).
  • the prepolymers may contain at least one monocarboxylic acid E) in copolymerized form.
  • the monocarboxylic acids E) serve to end-cap the polyamides prepared according to the invention.
  • Suitable in principle are all monocarboxylic acids which are capable of reacting under the reaction conditions of the polyamide condensation with at least part of the available amino groups.
  • Suitable monocarboxylic acids E) are aliphatic monocarboxylic acids, alicyclic monocarboxylic acids and aromatic monocarboxylic acids. These include acetic acid, propionic acid, n-, iso- or tert.
  • the monocarboxylic acid E) is particularly preferably selected from acetic acid, propionic acid, benzoic acid and mixtures thereof.
  • the prepolymers (and correspondingly the aliphatic and the partly aromatic polyamides) comprise as the monocarboxylic acid E) copolymerized exclusively propionic acid.
  • the prepolymers (and correspondingly aliphatic and partly aromatic polyamides) comprise, as monocarboxylic acid E), copolymerized exclusively with benzoic acid.
  • the prepolymers (and correspondingly the aliphatic and the partially aromatic polyamides) comprise as the monocarboxylic acid E) copolymerized exclusively acetic acid.
  • the prepolymers (and correspondingly the aliphatic and partially aromatic polyamides) may contain at least one monoamine F) in copolymerized form.
  • the aliphatic polyamides contain only aliphatic monoamines or alicyclic monoamines in copolymerized form.
  • the monoamines F) serve to end-cap the polyamides prepared according to the invention.
  • Suitable in principle are all monoamines which are capable of reacting under the reaction conditions of the polyamide condensation with at least part of the available carboxylic acid groups.
  • Suitable monoamines F) are aliphatic monoamines, alicyclic monoamines and aromatic monoamines.
  • methylamine ethylamine, propylamine, butylamine, propylamine, hexylamine, heptylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine, aniline, toluidine, diphenylamine, naphthylamine and mixtures thereof.
  • At least one at least trivalent amine G include N '- (6-aminohexyl) hexane-1, 6-diamine, N' - (12-aminododecyl) dodecane-1,12-diamine, N '- (6-aminohexyl) dodecane-1,12-diamine, N '- [3- (aminomethyl) -3,5,5-trimethylcyclohexyl] hexane-1,6-diamine, N' - [3- (aminomethyl) -3,5,5-trimethylcyclohexyl] dodecane 1,12-diamine, N '- [(5-amino-1,3,3-trimethylcyclohexyl) methyl] hexane-1,6-diamine, N' - [(5-amino-1,3,3-trimethylcyclohexyl) methyl] hexane-1,6-diamine, N
  • Suitable lactams H are ⁇ -caprolactam, 2-piperidone ( ⁇ -valerolatam), 2-pyrrolidone ( ⁇ -butyrolactam), capryllactam, enanthlactam, laurolactam and mixtures thereof
  • Suitable ⁇ -amino acids I) are 6-aminocaproic acid, 7-aminoheptanoic acid,
  • co-condensable compounds K) are at least trivalent carboxylic acids, diaminocarboxylic acids, etc.
  • Suitable compounds K) are furthermore 4 - [(Z) -N- (6-aminohexyl) C-hydroxy-carbonimidoyl] benzoic acid, 3 - [(Z) -N- (6-aminohexyl) C-hydroxy] carbonimidoyl] benzoic acid, (6Z) -6- (6-aminohexylimino) -6-hydroxy-hexanecarboxylic acid, 4 - [(Z) -N - [(5-amino-1,3,3-trimethylcyclohexyl) methyl] - C-hydroxy-carbonimidoyl] benzoic acid, 3 - [(Z) -N - [(5-amino-1,3,3-trimethylcyclohexyl) methyl] C-hydroxy-carbonimidoyl] benzoic acid,
  • Suitable lactams H are ⁇ -caprolactam, 2-piperidone ( ⁇ -valerolatam), 2-pyrrolidone ( ⁇ -butyrolactam), capryllactam, enanthlactam, laurolactam and mixtures thereof
  • Suitable ⁇ -amino acids I) are 6-aminocaproic acid, 7-aminoheptanoic acid, 1-amino-undecanoic acid, 12-aminododecanoic acid and mixtures thereof.
  • the process according to the invention is used to prepare an aliphatic polyamide.
  • the polyamide is then preferably selected from PA 6, PA 11, PA 12, PA 46, PA 66, PA 666, PA 69, PA 610, PA 612, PA 96, PA 99, PA 910, PA 912, PA 1212 , and copolymers and mixtures thereof.
  • the aliphatic polyamide is PA 6, PA 66 or PA 666, very particularly preferably PA 6.
  • the process according to the invention is used to prepare a partially aromatic polyamide.
  • the polyamide is then preferably selected from PA 6.T, PA 9.T, PA8.T, PA 10.T, PA 12.T, PA 6.I, PA 8.I, PA 9.I, PA 10.1, PA 12.1, PA 6. T / 6, PA 6.T / 10, PA 6.T / 12,
  • PA 10.T / 6.T PA 10.T / 6.6, PA 10. T / 10.I, PA 10T / 10.I / 6.T, PA 10.T / 6.I, PA 4.T / 4.I / 46, PA 4.T / 4.I / 6.6, PA 5 .T / 5.I, PA 5.T / 5.I / 5.6, PA 5.T / 5.I / 6.6, PA 6.T / 6.I / 6.6, PA MXDA.6, PA IPDA.I, PA IPDA.T, PA MACM.I, PA MACM.T, PA PA PACM.I,
  • PA PACM.T PA MXDA.I
  • PA MXDA.T PA 6.T / IPDA.T
  • PA 6.T / MACM.T PA PACM.T, PA MXDA.I
  • PA MXDA.T PA MXDA.T
  • PA 6.T / IPDA.T PA 6.T / MACM.T
  • PA 6.T / 6.I / IPDA.T / IPDA.I PA 6.T / 6.I / MXDA.T / MXDA.I, PA 6.T / 6.I / MACM.T / MACM.I , PA 6.T / 6.I / PACM.T / PACM.I, PA 6.T / 10.T / IPDA.T, PA 6.T / 12.T / IPDA.T, PA 6.T / 10.T / PACM.T, PA 6.T / 12.T / PACM.T, PA 10.T / IPDA.T, PA 12.T / IPDA.T and copolymers and mixtures thereof.
  • the polyamide is then more preferably selected from PA 6.T, PA 9.T, PA 10.T, PA 12.T, PA 6.I, PA 9.I, PA 10.1, PA 12.1, PA 6.T / 6 .I, PA 6.T / 6, PA6.T / 8.T, PA 6.T / 10T, PA 10.T / 6.T, PA 6.T / 12.T, PA12.T / 6.T , PA IPDA.I, PA IPDAT,
  • PA 6.T / IPDA.T PA 6.T / 6.I / IPDA.T / IPDA.I
  • PA 6.T / 10.T / IPDA.T PA 6.T / IPDA.T
  • PA 6.T / 12.T / IPDA.T PA 6.T / 10.T / PACM.T, PA 6.T / 12.T / PACM.T, PA 10.T / IPDA.T, PA 12 .T / IPDA.T
  • the partly aromatic polyamide is PA 6.T / 6.I.
  • the partially aromatic polyamide is PA 6.T / 6.I / IPDA.T / IPDA.I.
  • the partially aromatic polyamide is PA 6.T / 6.I / MXDA.T / MXDA.I.
  • an aqueous composition which contains at least one component suitable for polyamide formation.
  • the preparation of the prepolymers can in principle be carried out by customary methods known to the person skilled in the art.
  • a suitable process for the preparation of partly aromatic polyamide oligomers is, for. As described in EP 0 693 515 A1.
  • the aqueous composition used to prepare the prepolymers preferably has a water content of from 15 to 55% by weight, more preferably from 20 to 35% by weight, based on the total weight of the composition.
  • an aqueous solution which contains a salt of at least one diamine and at least one carboxylic acid. This solution preferably has a water content of from 20 to 55% by weight, more preferably from 25 to 50% by weight, based on the total weight of the solution.
  • the aqueous composition used to prepare the prepolymers may contain further components. These are preferably selected from Catalysts, chain regulators, application-related additives and mixtures thereof. Suitable additives are flame retardants, inorganic and organic stabilizers, lubricants, dyes, nucleating agents, metallic pigments, metal flakes, metal-coated particles, antistatic agents, conductivity additives, mold release agents, optical brighteners, defoamers, fillers and / or reinforcing agents, etc.
  • At least one alkanol preferably ethanol, is used as defoamer to prepare the aliphatic or partly aromatic polyamides.
  • At least one catalyst can be used to prepare the prepolymers.
  • Suitable catalysts are preferably selected from inorganic and / or organic phosphorus, tin or lead compounds and mixtures thereof.
  • suitable tin compounds z. Tin (II) oxide, tin (II) hydroxide, tin (II) salts of mono- or polybasic carboxylic acids, e.g. Tin (II) dibenzoate, tin (II) di (2-ethylhexanoate), tin (II) oxalate, dibutyltin oxide, butylstannoic acid (C4Hg-SnOOH), dibutyltin dilaurate, etc.
  • Suitable lead compounds are e.g. Lead (II) oxide, lead (II) hydroxide, lead (II) acetate, basic lead (II) acetate, lead (II) carbonate, etc.
  • Preferred catalysts are phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, phenylphosphonic acid, phenylphosphinic acid and / or their salts with monohydric to trivalent cations, such as. B. Na, K, Mg, Ca, Zn or Al, and / or their esters, such as. B. triphenyl phosphate, triphenyl phosphite or tris (nonylphenyl) phosphite.
  • Particularly preferred as a catalyst are the hypophosphorous acid and its salts, such as sodium hypophosphite.
  • the catalysts are used in an amount of 0.005 to 2.5 wt .-%, based on the total weight of the aqueous composition.
  • the ring-opening lactam polymerization can be carried out purely hydrolytically without the use of a catalyst.
  • Activated anionic lactam polymerization uses catalysts which allow the formation of lactama ions. Suitable catalysts and activators are known to the person skilled in the art.
  • the preparation of polyamide 6 from 6-aminocapronitrile (ACN) can be carried out in the presence of a heterogeneous catalyst such as ⁇ 2.
  • At least one chain regulator can be used to control the molar mass.
  • Suitable chain regulators are the monocarboxylic acids A) and monoamines F) mentioned above for the components suitable for polyamide formation.
  • the chain regulator is preferably selected from acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid, benzoic acid, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid, 3 , 5-di-tert-butyl-4-hydroxybenzoic acid, 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoic acid, 2- (3,5-di-tert-butyl-4-hydroxybenzylthio ) acetic acid, 3,3-bis (3-tert-butyl-4-hydroxyphenyl) butanoic acid, butylamine
  • Suitable monofunctional compounds which can react with an amino or acid group such as anhydrides, isocyanates, acid halides or esters, can also be used as regulators.
  • the usual amount of chain regulators used is in a range of 5 to 500 mmol per kg of polyamide oligomer, preferably 10 to 200 mmol per kg of prepolymer.
  • additives other than catalysts and chain regulators may be added to the aqueous composition.
  • the additives include z. As antioxidants, light stabilizers, common processing aids, nucleating agents and crystallization accelerators.
  • the prepolymers provided preferably have a number average molecular weight M n of from about 500 to about 8000 g / mol, preferably from about 800 to
  • the prepolymers preferably have a conversion in the range of 80 to 95%, based on the total amount of the monomer components used.
  • the prepolymer provided according to the invention is preferably in the form of a
  • the prepolymer provided in step a) preferably has a particle size in a range from 1 ⁇ m to 1 mm. This is preferably achieved by discharging the prepolymer into an inertized volume after its synthesis and before providing it in the process according to the invention.
  • the inertized volume refers to a possibly cooled cyclone or spray tower or a comparable unit.
  • the spray discharge into an inertized volume is preferably carried out in apparatuses which are also suitable for spray drying. Such apparatus are described, for example, in K. Masters, Spray Drying Handbook, 5th Edition, Longman, 1991, pages 23-66.
  • one or more spray nozzles can be used, with a pre-polymer fluid to be sprayed being supplied under pressure.
  • the division of the prepolymer fluid to be sprayed can take place in that it is relaxed after reaching a certain minimum speed in the nozzle bore.
  • single-substance nozzles such as, for example, slot nozzles or twist chambers or full cone nozzles (for example from the company Düsen-Schlick GmbH, Germany, or from the company Spraying Systems GmbH, Germany).
  • the prepolymer may also fall freely in an inert atmosphere in the form of drops. Suitable for this purpose are apparatuses as described, for example, in US Pat. No. 5,269,980.
  • the prepolymer is subjected to a solid-phase postcondensation in the presence of water vapor.
  • Suitable devices for contacting the prepolymer with the water vapor are, for. As stirred or stirred containers, dryers, fluidized beds, etc. and combinations of at least two of these devices. Suitable dryers are z. B. dry tubes, countercurrent, crossflow, plate, tumble, paddle, trickle, cone or shaft dryer.
  • a suitable embodiment is the discontinuous contact with steam in the tumble dryer or condenser dryer.
  • Another suitable embodiment is the continuous bringing into contact with water vapor in so-called dry tubes, which are traversed by a water vapor-containing gas.
  • the prepolymer is preferably subjected to a solid phase postcondensation in at least one fluidized bed (or a fluidized bed).
  • a bed of prepolymer particles which is caused by an upward flow of water vapor in a fluidized state.
  • the term "fluidized” in this context indicates that the bed now has fluid-like properties.
  • the prepolymer may be contacted with pure water vapor or with mixtures of water vapor and at least one other inert gas under the treatment conditions. Suitable inert gases are, for example, nitrogen, CO2, helium, neon and argon, and mixtures thereof. Preferably, nitrogen is used.
  • the gas mixture preferably contains from 30 to 100% by volume of water, based on the total gas mixture. If pure water vapor is used for the treatment, the pressure is preferably in the range from 0.1 MPa to 1.2 MPa.
  • the hydrogen partial pressure is preferably in the range from 0.03 MPa to 1.2 MPa.
  • the prepolymer is brought without pressure into contact with saturated or superheated steam.
  • the prepolymer is contacted in a fluidized bed with the water vapor or a mixture of water vapor and at least one inert gas.
  • the water vapor is preferably fed to the fluidized bed at a pressure in the range from 0.1 MPa to 1.2 MPa.
  • this is supplied to the fluidized bed with a partial pressure of water vapor in the range from 0.03 MPa to 1.2 MPa.
  • the solid phase postcondensation takes place at a temperature below the melting temperature of the polyamide.
  • the solid phase postcondensation is carried out at a temperature of at least 5 ° C, more preferably of at least 10 ° C, in particular of at least 20 ° C below the melting temperature of the polyamide.
  • the solid phase postcondensation is carried out at a temperature in the range of 200 ° C to 300 ° C.
  • the solid phase postcondensation preferably takes place within a period of 2 minutes to 10 hours, more preferably of 5 minutes to 6 hours.
  • the polyamide obtainable by the process according to the invention preferably has a number average molecular weight M n in a range from 12,000 to
  • the polyamide preferably has a weight-average molecular weight M w in a range from 20,000 to 144,000 g / mol, preferably from 24,000 to 96,000 g / mol.
  • the aliphatic polyamides according to the invention and obtained by the process according to the invention preferably have a weight-average molecular weight Mw in a range from 20,000 to 140,000 g / mol.
  • the partially aromatic polyamides according to the invention and obtained by the process according to the invention preferably have a weight-average molecular weight Mw in a range from 25,000 to 125,000 g / mol.
  • the data of the number average molecular weight M n and the weight average molecular weight M w in the context of this invention relate to a determination by means of gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • PMMA is used as a polymer standard with low polydispersity.
  • the polyamide preferably has a polydispersity M w / M n of at most 6, preferably of at most 4.
  • the aliphatic polyamides obtainable by the process according to the invention are particularly suitable for the production of films, monofilaments, fibers, yarns or textile fabrics.
  • the aliphatic polyamides prepared according to the invention generally prove to be particularly stable to processing during melt extrusion through slot-type or annular nozzles into flat or blown films and through annular nozzles of smaller diameter into monofilaments.
  • the partially aromatic polyamides obtainable by the process according to the invention also have advantageous properties.
  • the partially aromatic polyamide according to the invention and obtained by the process according to the invention preferably has a gel content of at most 5% by weight, based on the total weight of the polyamide.
  • the partially aromatic polyamide according to the invention and obtained by the process according to the invention preferably has a viscosity number of 80 to 120 ml / g on.
  • the viscosity number is directly related to the average molar mass of the polyamide and provides information about the processability of a plastic.
  • the determination of the viscosity number can be carried out according to EN ISO 307 with an Ubbelohde viscometer.
  • the present invention relates to moldings (or moldings) at least partially made of a polyamide molding compound prepared by using a polyamide as stated above.
  • Another object of the invention is a polyamide molding composition containing at least one partially aromatic copolyamide according to the invention.
  • a polyamide molding composition comprising:
  • Nanoscale fillers such as carbon nanotubes, carbon black, nanoscale phyllosilicates, nanoscale aluminum oxide (Al 2 O 3), nanoscale titanium dioxide (TIO 2), graphene, permanently magnetic or magnetizable metal compounds and / or alloys , Phyllosilicates and nanoscale silica (S1O2).
  • the fillers may also be surface-treated.
  • Kaolins, serpentines, talc, mica, vermiculites, lllites, smectites, montmorillonite, hectorite, dopamine, pelhydroxide or mixtures thereof are used.
  • the layered silicates may be surface treated or untreated.
  • one or more fibers can be used. These are preferably selected from known inorganic reinforcing fibers such as boron fibers, glass fibers, carbon fibers, silica fibers, ceramic fibers and basalt fibers; organic reinforcing fibers such as aramid fibers, polyester fibers, nylon fibers, polyethylene fibers and natural fibers such as wood fibers, flax fibers, hemp fibers and sisal fibers.
  • inorganic reinforcing fibers such as boron fibers, glass fibers, carbon fibers, silica fibers, ceramic fibers and basalt fibers
  • organic reinforcing fibers such as aramid fibers, polyester fibers, nylon fibers, polyethylene fibers and natural fibers such as wood fibers, flax fibers, hemp fibers and sisal fibers.
  • glass fibers particularly preferred is the use of glass fibers, carbon fibers, aramid fibers, boron fibers, metal fibers or potassium titanate fibers.
  • component B comprises glass and / or carbon fibers, short fibers preferably being used. These preferably have a length in the range of 2 to 50 mm and a diameter of 5 to 40 ⁇ .
  • continuous fibers rovings
  • Fibers having a circular and / or non-circular cross-sectional area are suitable, wherein in the latter case the dimensional ratio of the main cross-sectional axis to the minor cross-sectional axis is in particular> 2, preferably in the range of 2 to 8 and particularly preferably in the range of 3 to 5.
  • component B) comprises so-called “flat glass fibers”. These have in particular an oval or elliptical or a constriction (s) provided elliptical (so-called “cocoon” or “cocoon” fiber) or rectangular or nearly rectangular cross-sectional area.
  • rovings of glass fibers these preferably have a diameter of 10 to 20 ⁇ , preferably from 12 to 18 ⁇ , on.
  • the cross section of the glass fibers can be round, oval, elliptical, almost rectangular or rectangular. Particularly preferred are so-called flat glass fibers with a ratio of the cross-sectional axes of 2 to 5.
  • E-glass fibers are used in particular. But it can also all other types of glass fiber, such.
  • A-, C-, D, M, S, R glass fibers or any mixtures thereof or mixtures with E glass fibers are used.
  • the novel polyamide molding compositions can be prepared by the known processes for producing long-fiber-reinforced rod granules, in particular by pultrusion processes, in which the endless fiber strand (roving) is completely saturated with the polymer melt and then cooled and cut.
  • the long fiber-reinforced rod granules obtained in this way which preferably has a granule length of 3 to 25 mm, in particular of 4 to 12 mm, can, with the usual processing methods, such as. As injection molding or pressing, to be processed into moldings.
  • the polyamide molding composition according to the invention preferably contains 25 to 75 wt .-%, particularly preferably 33 to 60 wt .-%, of at least one filler and reinforcing material B), based on the total weight of the polyamide molding composition.
  • Suitable additives C) are heat stabilizers, flame retardants, light stabilizers (UV stabilizers, UV absorbers or UV blockers), lubricants, dyes, nucleating agents, metallic pigments, metal flakes, metal-coated particles, antistatic agents, conductivity additives, mold release agents, optical brighteners, defoamers , Etc.
  • the molding compositions according to the invention preferably contain 0.01 to 3 wt .-%, more preferably 0.02 to 2 wt .-%, in particular 0.1 to
  • the heat stabilizers are preferably selected from copper compounds, secondary aromatic amines, sterically hindered phenols, phosphites, phosphonites and mixtures thereof. If a copper compound is used, the amount of copper is preferably 0.003 to 0.5, in particular 0.005 to 0.3 and particularly preferably 0.01 to 0.2 wt .-%, based on the sum of components A) to C) ,
  • the amount of these stabilizers is preferably 0.2 to 2% by weight, particularly preferably 0.2 to 1.5% by weight, based on the sum of the components A). to C). If stabilizers based on sterically hindered phenols are used, the amount of these stabilizers is preferably from 0.1 to 1, 5 wt .-%, particularly preferably from 0.2 to 1 wt .-%, based on the sum of components A) to C).
  • the amount of these stabilizers is preferably from 0.1 to 1, 5 wt .-%, particularly preferably from 0.2 to 1 wt .-%, based on the sum of Components A) to C).
  • Suitable compounds C) of mono- or divalent copper are, for.
  • salts of mono- or divalent copper with inorganic or organic acids or monohydric or dihydric phenols the oxides of monovalent or divalent copper or the complex compounds of copper salts with ammonia, amines, amides, lactams, cyanides or phosphines, preferably Cu ( l) - or Cu (II) salts of hydrogen halides, hydrogen cyanide or the copper salts of aliphatic carboxylic acids.
  • Particularly preferred are the monovalent copper compounds CuCl, CuBr, Cul, CuCN and CU2O and the divalent copper compounds CuC, CuSO4, CuO, copper (II) acetate or copper (II) stearate.
  • the copper compounds are commercially available or their preparation is known in the art.
  • the copper compound can be used as such or in the form of concentrates.
  • Concentrate is to be understood as meaning a polymer, preferably of the same chemical nature as component A), which contains the copper salt in high concentration.
  • the use of concentrates is a common method and is particularly often used when very small amounts of a feedstock are to be dosed.
  • stabilizers based on secondary aromatic amines which can be used according to the invention are adducts of phenylenediamine with acetone (Naugard A), adducts of phenylenediamine with linolen, Naugard® 445,
  • Preferred examples of stabilizers based on sterically hindered phenols which can be used according to the invention are N, N'-hexamethylene-bis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionamide, bis (3,3-bis) (4'-hydroxy-3'-tert-butylphenyl) butanoic acid) - glycol ester, 2,1'-thioethyl bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4-4'-butylidene bis (3-methyl-6-tert-butylphenol ), Triethylene glycol 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate or mixtures of two or more of these stabilizers.
  • Preferred phosphites and phosphonites are triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl phthaloerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisopropylpentaerythritol diphosphite, bis (2,4-di tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxy-pentaerythritol diphosphite
  • a preferred embodiment of the heat stabilizer consists in the combination of organic heat stabilizers (in particular Hostanox PAR 24 and Irganox 1010), a bisphenol A based epoxide (especially Epikote 1001) and a copper stabilization based on Cul and Kl.
  • organic heat stabilizers in particular Hostanox PAR 24 and Irganox 1010
  • a bisphenol A based epoxide especially Epikote 1001
  • a copper stabilization based on Cul and Kl is, for example, Irgatec NC66 from BASF SE.
  • Particularly preferred is a heat stabilization based solely on Cul and Kl.
  • the molding composition according to the invention preferably no transition metals of group VB, VIB, VIIB or VIIIB of the Periodic Table, such. As iron or steel powder added.
  • the novel molding materials preferably comprise 0 to 30% by weight, more preferably 0 to 20% by weight, based on the total weight of components A) to C), of at least one flameproofing agent as additive C). If the molding compositions according to the invention contain at least one flame retardant, preferably in an amount of 0.01 to 30 wt .-%, particularly preferably from 0.1 to 20 wt .-%, based on the total weights of components A) to C).
  • Flame retardants C) come halogen-containing and halogen-free flame retardants and their synergists in question (see also Gumbleter / Müller, 3rd edition 1989 Hanser Verlag, Chapter 1 1).
  • Preferred halogen-free flame retardants are red phosphorus, phosphinic or diphosphinic salts and / or nitrogen-containing flame retardants such as melamine, melamine cyanurate, melamine sulfate, melamine borate, melamine oxalate, melamine phosphate (prim, sec.) Or sec.
  • Melamine pyrophosphate Melamine pyrophosphate, neopentylglycolboronic acid remelamin, guanidine and Expert known derivatives thereof and polymeric melamine phosphate (CAS No .: 56386-64-2 or 218768-84-4 and EP 1095030), ammonium polyphosphate, Trishydroxyethylisocyanurat (possibly also ammonium polyphosphate in admixture with Trishydroxyethylisocyanurat) (EP 584567).
  • N- or P-containing flame retardants or PN condensates suitable as flame retardants can be found in DE 10 2004 049 342, as well as the customary synergists such as oxides or borates.
  • Suitable halogen-containing flame retardants are, for. B. oligomeric brominated polycarbonates (BC 52 Great Lakes) or Polypen- tabrombenzylacrylate with N greater than 4 (FR 1025 Dead sea bromine), reaction products of tetrabromo-bis-phenol-A with epoxides, brominated oligomeric or polymeric styrenes, dechloran, which usually with Antimony oxides are used as synergists (for details and other flame retardants: see DE-A-10 2004 050 025).
  • antistatic agents in the molding compositions of the invention z.
  • carbon black and / or carbon nanotubes can be used. However, the use of carbon black can also serve to improve the black color of the molding composition.
  • the molding composition may also be free of metallic pigments.
  • the present invention relates to molded articles which are produced using the copolyamides or polyamide molding compositions according to the invention.
  • the partially aromatic polyamides according to the invention and prepared according to the invention are advantageously suitable for use in the production of electrical and electronic components and for automotive applications in the high-temperature range.
  • a specific embodiment are moldings in the form of or as part of a component for the automotive sector, in particular selected from cylinder head covers, engine covers, intercooler housings, charge air cooler flaps, intake manifolds, intake manifolds, connectors, gears, fan wheels, cooling water boxes, housings. sen or housing parts for heat exchangers, coolant radiators, intercoolers, thermostats, water pumps, radiators, fasteners.
  • the partially aromatic polyamides according to the invention and produced according to the invention are particularly suitable for use in soldering processes under lead-free soldering, for the production of connectors, micro-switches, micro-probes and semiconductor components, in particular reflector housings of light-emitting diodes (LED).
  • LED light-emitting diodes
  • the partially aromatic polyamides according to the invention and prepared according to the invention are suitable, in particular, as or as part of an electrical or electronic passive or active component, a printed circuit board, a part of a printed circuit board, a housing component, a foil, a conduit, in particular in the form of or as part of a switch A connector, a socket, a distributor, a relay, a resistor, a capacitor, a coil or a bobbin, a lamp, a diode, an LED, a transistor, a connector, a controller, an integrated circuit (IC), a processor , a controller, a memory and / or a sensor.
  • Further molded parts are fastening elements of electrical or electronic components, printed circuit boards or component groups, such as spacers, bolts, strips, slide-in guides, screws and nuts.
  • a molded part in the form or as part of a base, a connector, a plug or a socket.
  • the molded part preferably contains functional elements which require mechanical toughness. Examples of such functional elements are film hinges, snap-in hooks and spring tongues.
  • dashboards In the car interiors, it is possible to use them for dashboards, steering column switches, seat parts, headrests, center consoles, transmission components and door modules, in the car exterior for door handles, exterior mirror components, windscreen wiper components, windscreen wiper housings, grilles, roof rails, sunroof frames, engine covers, cylinder head covers, intake pipes, windscreen wipers and bodywork exterior parts.
  • the gel content of the polymer was determined indirectly by GPC.
  • samples of the polyamide were dissolved in hexafluoroisopropanol + 0.05% trifluoroacetic acid potassium salt and filtered through a filter (Millipore Millex FG) with a pore size of 0.2 ⁇ .
  • concentration of the polymer which is eluted from the GPC was determined.
  • the gel fraction results from the difference of the theoretical polymer concentration, which is given by the amount of the polymer used before the filtration, with the measured concentration (based on the polymer used before the filtration).
  • the resulting prepolymer solution was discharged into a nitrogen-filled spray tower to obtain a 61 / 6T polyamide prepolymer granules.
  • the prepolymer granulate was then transferred to a fluidized bed where it undergoes solid phase condensation (SSP) to increase the molecular weight to a molecular weight M n 2. From the fluidized bed, it can then be transferred to an extruder or a dryer.
  • SSP solid phase condensation
  • the 61 / 6T polyamide prepolymer granules were exposed to steam in the fluidized bed for six hours at a temperature of 280 ° C.
  • the pressure of the water vapor was 0.1 MPa over the entire duration of treatment and 0.5 MPa in the example B2 over the entire treatment period.
  • Example B3 the pressure was lowered from 1.0 MPa at the beginning of the treatment to 0.2 MPa linear at the end of the treatment.
  • Table 1 Comparative Examples VB1 and VB2:
  • Comparative Example CB1 the 61 / 6T polyamide prepolymer granules were not placed in a fluidized bed but stored in vacuum for six hours at a temperature of 280 ° C.
  • Comparative Example CB2 the 61 / 6T polyamide prepolymer granules in the fluidized bed were exposed to an argon stream at a pressure of 0.5 MPa for six hours at a temperature of 280 ° C. The results are shown in Table 1.

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Abstract

L'invention concerne un procédé servant à produire un polyamide aliphatique ou en partie aromatique, dans lequel un prépolymère du polyamide aliphatique ou en partie aromatique est proposé et le prépolymère est soumis à une post-condensation en phase solide, dans laquelle il est mis en contact avec de la vapeur d'eau. L'invention concerne en outre un polyamide en partie aromatique, qui peut être obtenu par ce procédé, et son utilisation aux fins de la production de pièces de construction électriques et électroniques et pour des applications automobiles dans la plage des températures élevées.
PCT/EP2014/078436 2013-12-19 2014-12-18 Procédé servant à produire un polyamide aliphatique ou en partie aromatique Ceased WO2015091777A1 (fr)

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Cited By (1)

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CN114746462A (zh) * 2019-12-05 2022-07-12 巴斯夫欧洲公司 染成黑色的聚酰胺组合物、其制备和用途

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EP0584567A2 (fr) 1992-08-01 1994-03-02 Hoechst Aktiengesellschaft Compositions polymères iqnifuges à stabilité améliorée
EP0667367A2 (fr) 1994-02-10 1995-08-16 BASF Aktiengesellschaft Masses à mouler en polyamide semi-aromatique à cristallinité élevée
EP0693515A1 (fr) 1994-07-14 1996-01-24 Ems-Inventa Ag Procédé de préparation de précondensats de (co)polyamides semiaromatiques thermoplastiques semicristallins ou amorphes
EP1095030A1 (fr) 1998-07-08 2001-05-02 Dsm N.V. Sel polyphosphate d'un compose 1,3,5-triazine avec un degre eleve d'ions de condensation et son utilisation comme charge ignifugeante dans des compositions polymeres
WO2003048728A2 (fr) 2001-12-03 2003-06-12 Board Of Regents, The University Of Texas System Capteur d'impedance de particules
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EP0584567A2 (fr) 1992-08-01 1994-03-02 Hoechst Aktiengesellschaft Compositions polymères iqnifuges à stabilité améliorée
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Publication number Priority date Publication date Assignee Title
CN114746462A (zh) * 2019-12-05 2022-07-12 巴斯夫欧洲公司 染成黑色的聚酰胺组合物、其制备和用途

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