Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/14—Polyamide-imides
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer
  • Y10T428/2969—Polyamide, polyimide or polyester

Definitions

• Copolyamides and compositions based on these copolyamides.
• the present invention relates to copolyamides obtained by using multifunctional monomers. It relates more particularly to copolyamides of high viscosity. It also relates to compositions based on these copolyamides.
• thermoplastic polyamides are used. Examples are given of threads, fibers and filaments, films, articles obtained by molding, injection or extrusion.
• polyamides of high melt viscosity This is the case for example for the polyamide fibers used for the manufacture of paper machine felts. This is also the case for example for the methods of shaping articles by extrusion blow molding.
• extrusion blow molding When implementing the latter process, it is generally important that the extruded part does not deform, or only deforms slightly under its own weight.
• the mechanical properties of the material, such as the elastic modulus and the impact resistance must also not be affected, or only be slightly affected.
• a first solution consists in carrying out a post-condensation in solid phase on linear polyamides. Post-condensation times are significant, which generates significant production costs.
• copolyamides obtained by using a multifunctional monomer comprising a reactive function forming amide bonds chosen from acids and amines, and at least two reactive functions forming amide bonds, of a different nature and complementary to the previous one. These copolyamides exhibit, for an identical duration of melt polycondensation, a viscosity in melt that is higher than that of linear polyamides. However, the copolyamides described in the document have a viscosity which is still sought to improve. Another objective is to achieve equivalent viscosities with shorter, and / or controlled, polymerization cycle times.
• the object of the invention is to propose new copolyamides having in particular a higher melt viscosity or which, at equal viscosity, can be obtained, by shorter polymerization cycles.
• the invention provides a copolyamide, comprising macromolecular units derived from the following monomers:
• multifunctional monomer is meant a monomer comprising at least two reactive functions.
• abbreviations (AB, A a B b , A c B d .) are used to designate organic molecules, or organometallic molecules, serving as monomers.
• the monomers are molecules having reactive functions of acid type A or of amino type B, capable of forming between them amide bonds.
• the acid type functions are advantageously chosen from the carboxylic acid, acid halide, ester functions.
• the amino type functions are advantageously chosen from amines, preferably primary amines, and amine salts.
• the number of functions of each type is represented for the different monomers by the letters a, b, c, d.
• the monomers (I) have a function of each type.
• the monomers (II) and (III) respectively comprise at least 3 and 2 functions, preferably at most 10.
• the number of functions for each is preferably chosen from 3, 4, 5 , 6.
• the monomers (II) have at least three reactive functions, at least one of each type.
• the monomers (III) comprise at least two reactive functions, either all of the same type, or of different types.
• the monomers (III) comprise functions of different types, the number of functions is then strictly greater than two.
• the number of moles of monomer (II) from which the copolyamide is obtained is designated by the letter x.
• the number of moles of monomer (III) from which the copolyamide is obtained is designated by the letter y.
• the number of moles of monomer (I) from which the copolyamide is obtained is designated by the letter z.
• the ratio ⁇ , ax + cy + bx + dy ⁇ is less than 0.05 (5%). It is preferably
• the ratio ⁇ , ⁇ ⁇ is preferably less than 0.25% x + y + 0.9 * z
• the monomers (II) and the monomers (III) can respectively consist of a mixture of several monomers A a ⁇ B l and A CJ Bd j where a réelleb ,, c, and d j meet, for at least one from them, under the conditions defined above for a, b, c, d, except possibly for the calculation of the ratios ⁇ , ⁇ and ⁇ , for which we mean:
• - represents the number of acid type functions of a monomer (III) referenced j
• d j represents the number of amino type functions of a monomer (III) referenced j
• monomers (III) mixture of monomer A C B 0 (acid multifunctional), and A 0 B d (amino multifunctional), with c> 0 and d> 0, and in quantities such that the ratios ⁇ and ⁇ are respected.
• the monomers (I) are advantageously chosen from:
• the monomers (I) can be the monomers used for the manufacture of linear thermoplastic polyamides.
• ⁇ -aminoalkanoic compounds comprising a hydrocarbon chain having from 4 to 12 carbon atoms, or lactams derived from these amino acids such as ⁇ -caprolactam.
• lactams derived from these amino acids such as ⁇ -caprolactam.
• mixtures of monomers corresponding to the abbreviation AB preferably chosen from the monomers proposed above.
• the monomers (II) are designated by the generic term of "tree monomers".
• - n is an integer greater than or equal to 2, preferably between 2 and 10 (limits included), and preferably equal to 2,
• R2 may be the same or different and represent a covalent bond, an aliphatic, arylaliphatic, aromatic or alkylaromatic hydrocarbon radical
• - R is a linear or branched aliphatic radical, a substituted or unsubstituted cycloaliphatic radical, a substituted or unsubstituted aromatic radical which may comprise several aromatic rings and / or heteroketones
• - X represents the amine function or amine salt, or the acid, ester, acid halide or amide function
• the suitable and preferred monomers (II) of the invention are, in particular, the thermally stable monomers at a temperature above 150 ° C.
• R represents an aromatic radical such as aminophthalic acid, or a linear aliphatic radical such as the 3-aminopimelic diacid, or the 6-amino undecandioic acid.
• ⁇ -amino acids such as aspartic acid and glutamic acid. Natural amino acids can also be used as monomer (II) if their thermal stability is sufficient. It is also possible to adapt the conditions of synthesis of the copolyamide as a function of the thermal stability of the monomer (II).
• the reactive functions of the monomer (III) are all identical, chosen from functions of acid or amino types. These monomers are designated under the generic term of "core monomers".
• a first category of core monomers consists of molecules or macromolecules (used as monomers) having a tree or dendritic structure. By way of example, mention may be made of polyamines comprising a high number of amino units. Mention is also made of the fully aromatic dendrimers described in patent applications WO 95/06081.
• a second category of core monomers consists of the compounds which can be chosen from the compounds mentioned below.
• - C is a covalent bond or an aliphatic hydrocarbon radical which can comprise heteroatoms, and comprising from 1 to 20 carbon atoms, preferably from 1 to 6 carbon atoms.
• X is a radical or [1 °
• H o - R4 is a hydrocarbon radical comprising at least 2 carbon atoms, linear or cyclic, aromatic or aliphatic and which can comprise heteroatoms.
• the radical R4 is either a cycloaliphatic radical such as the tetravalent cyclohexanonyl radical, or a 1, 1, 1- triyl-propane radical , 1,2,3-triyl-propane.
• radicals R4 suitable for the invention mention may be made, by way of example, of trivalent phenyl and cyclohexanyl radicals, substituted or not, tetravalent radicals of diaminopolymethylene with a number of methylene groups advantageously between 2 and 12 such as radical originating from EDTA (ethylene diamino tetracetic acid), the octovalent radicals of cyclohexanonyl or cyclohexadinonyl, and the radicals originating from compounds derived from the reaction of polyols such as glycol, pentaerythritol, sorbitol or mannitol.
• the radical A is preferably a methylene or polyethylenic radical such as the ethyl, propyl or butyl radicals, or a polyoxyalkylene radical such as the polyoxyethylene radical.
• the number m is greater than 3 and advantageously equal to 3 or 4.
• the reactive function of the multifunctional compound represented by the symbol X-H is a function capable of forming an amide function.
• -R4 represents a 1, 1, 1-triyl propane radical, or 1, 2,3-triyl propane
• - A represents a polyoxyethylene radical.
• multifunctional compounds which may be suitable are in particular cited in document US 5346984, in document US 5959069, in document WO 9635739, in document EP 672703. Mention is made more particularly of: Nitrilotrialkylamines, in particular nitrilotriethylamine, dialkylenetriamines, in particular diethylenetriamine, trialkylenetetramines and tetraikylenepentamines, the alkylene preferably being ethylene, 4-aminoethyl-1, 8, octanediamine.
• N is preferably an integer equal to 3 or 4, in particular 3, and x is preferably an integer between 2 and 6, preferably between 2 and 4 (limits included), in particular 2.
• Each radical R can be chosen independently of the others.
• the radical R is preferably a hydrogen atom or a group - (CH 2 ) n -NH2. Mention is also made of multifunctional compounds having 3 to 10 carboxylic acid groups, preferably 3 or 4.
• benzyl, naphthyl, anthracene, biphenyl and triphenyl radicals or heterocycles such as pyridine, bipyridine, pyrrole, indole, furan, thiophene, purine, quinoline, phenanthrene, porphyrin, phthalocyanine and naphthalocyanine.
• benzyl, naphthyl, anthracene, biphenyl and triphenyl radicals or heterocycles such as pyridine, bipyridine, pyrrole, indole, furan, thiophene, purine, quinoline, phenanthrene, porphyrin, phthalocyanine and naphthalocyanine.
• pyridine bipyridine
• pyrrole indole
• furan furan
• thiophene purine
• quinoline furan
• thiophene purine
• quinoline quinoline
• phenanthrene porphy
• Acids derived from phthalocyanine and naphthalocyanine 3,5,3', ⁇ '-biphenyltetracarboxylic acid, acid 1, 3,5,7- naphthalenetetracarboxylic acid, 2,4,6-pyridinetricarboxylic acid, 3,5,3 ', 5'-bipyridyltetracarboxylic acid, 3,5,3', 5'-benzophenonetetracarboxylic acid, l 'acid 1,3,6,8-acridinetetracarboxylic acid, more particularly still trimesic acid and 1,2,4,5-benzenetetracarboxylic acid.
• multifunctional compounds whose core is a heterocycle presenting a point of symmetry such as 1, 3,5-triazines, 1, 4-diazines, melamine, compounds derived from 2,3,5,6 -tetraethylpiperazine, 1, 4-piperazines, tetrathiafulvalenes. Mention is more particularly made of 2,4,6-triaminocaproic acid-1,3,5-triazine (TACT).
• TACT 2,4,6-triaminocaproic acid-1,3,5-triazine
• the monomers (III) are tree monomers, which can be chosen from those mentioned as monomers (II), it being understood: - that they are of different nature
• the copolyamide is obtained from systems of monomers (I), (II) and (III) whose monomers (II) and (III) are chosen from the following systems:
• no monofunctional monomer is used in addition to monomers (I), (II) or (III).
• monomers (I) (II) and (III) are monomers having sufficient thermal stability.
• the fluidity in the molten phase of the copolyamides, measured at 275 ° C. under 5 kg of pressure is less than 10 g / 10 minutes.
• the invention also relates to compositions comprising the copolyamide described above.
• the compositions can comprise at least one polyamide in accordance with the invention and optionally other additives such as aids for molding or demolding, heat stabilizers, light stabilizers, antioxidants, flame retardants, pigments, dyes, and lubricants.
• the composition may also include agents improving impact resistance and / or fillers or reinforcing fillers. Mention is made in particular of glass fibers.
• compositions of the invention can also comprise, as polymeric matrix, in addition to the polyamide as described above, other materials thermoplastics such as linear aliphatic polyamides, optionally compatibilized, or aromatic or semi-aromatic polyamides, for example.
• the compositions of the invention are obtained by generally mixing, in a single or twin-screw extruder, a polyamide according to the invention with the various additives, this mixture generally being carried out in the molten state.
• polyamide then extrusion of the mixture in the form of rods which are then cut into granules. Molded parts can then be produced by melting the granules produced above and feeding the composition in the molten state into the appropriate molding, injection or extrusion devices.
• the invention also relates to a process for manufacturing a copolyamide according to the invention.
• a mixture of monomers is produced with determined proportions of each component. Said mixture is polymerized under conditions and according to a procedure equivalent to those used for the manufacture of the linear polyamide corresponding to the bifunctional monomers used.
• water is added to the mixture of monomers to initiate the hydrolytic opening of the caprolactam.
• a linear polyamide prepolymer is produced by polycondensation of the monomers (I) to obtain a prepolymer of molecular weight in number Mn of the order of approximately 2000 to 3000.
• the monomers (II) and (III) are added to the linear prepolymer and the polymerization is continued either in a molten medium or in the solid phase.
• the solid phase embodiment makes it possible in particular to obtain copolyamides by using multifunctional monomers having thermal stability at relatively low temperatures, for example less than 200 ° C., since the postcondensation temperature in solid phase is carried out at higher temperatures. lower than those of melt polymerization.
• the addition of the monomers (II) and (III) can be carried out in an extruder or in a reactor, the solid phase postcondensation being carried out according to the conventional and usual conditions used for that of linear polyamides.
• the monomers (II) and (III) are added with a catalyst thus making it possible to carry out the reaction directly in the extruder.
• Suitable catalysts are the catalysts conventionally used for reactions amidification or polycondensation of amide functions such as phosphorous compounds for example.
• the invention also relates to a process for the manufacture by extrusion of new copolyamides or of new compositions, and the copolyamides or compositions obtained by the process.
• This process uses multifunctional compounds, under conditions close to those described above, and lead to macromolecular compounds or compositions whose characteristics are close if not similar to those of the copolyamides and compositions described above.
• a method of manufacturing a copolyamide or a composition comprising a copolyamide is therefore proposed, consisting in mixing in an extrusion device at least the following three compounds:
• z represents the number of moles of repeating units of compound (I) the radical being a hydrocarbon radical, optionally comprising heteroatoms.
• z m D / M D where m D is the mass of compound (I) used, and M D is the molar mass of a recurring unit. ax + cy
• the compound (I) is preferably chosen from polyamide 6, polyamide 11, polyamide 12, mixtures and copolymers based on these polyamides.
• the method may include the introduction of fillers or additives as mentioned above. Particular mention is made of glass fibers.
• copolyamides or compositions according to the invention can be used in numerous applications such as the manufacture of molded or injected parts.
• Articles can also be made with the copolyamides of the invention by injection methods. These articles have significantly higher mechanical properties than those of articles obtained by injection of a composition based on linear polyamide with the same fluidity in a molten medium.
• Copolyamides are synthesized according to one of the following two cycles:
• MFI Melt flow index
• RV Relative Viscosity
• the monomer (I) is caprolactam. x + y + 0.9 * z
• EXAMPLE 17 A solid phase post-condensation is carried out, at 175 ° C., under nitrogen, on a copolyamide according to example 1 and a linear polyamide 6, respectively, according to example 9. The relative viscosity is measured every two hours. polymers. The curves representing the evolution are presented in FIG. 1, with the time in hours on the ordinate, and the relative viscosity on the abscissa.
• copolyamides according to the invention particularly advantageous, in particular for the extrusion processes. They exhibit good processability in an extruder (high shear) as well as a high viscosity at low shear, after extrusion, for the blowing operation.
• Example 20 Bottles are manufactured by extrusion blow molding using a COMEC MS 1000 device, under the following conditions:
• Example 5 Polymer used: Example 5.
• the weight of the bottles obtained is 115 + 10 gr.
• the walls have a constant and regular thickness, with an excellent surface appearance.

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• 2000
  • 2000-08-09 FR FR0010483A patent/FR2812879B1/fr not_active Expired - Fee Related
• 2001
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