EP2758451A1 - Copolyimides thermoplastiques - Google Patents
Copolyimides thermoplastiquesInfo
- Publication number
- EP2758451A1 EP2758451A1 EP12759734.2A EP12759734A EP2758451A1 EP 2758451 A1 EP2758451 A1 EP 2758451A1 EP 12759734 A EP12759734 A EP 12759734A EP 2758451 A1 EP2758451 A1 EP 2758451A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- diamine
- acid
- copolyimide
- functions
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/04—Extrusion blow-moulding
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/09—Diamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/313—Monocyclic acids containing more than three carboxyl groups
-
- 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
- C08G73/1075—Partially aromatic polyimides
-
- 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
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
- B29K2079/08—PI, i.e. polyimides or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0085—Copolymers
Definitions
- the present invention relates to thermoplastic, semi-aromatic and semi-crystalline copolyimides obtained by polymerization of at least: (a) an aromatic compound comprising 2 anhydride functional groups and / or its carboxylic acid and / or ester derivatives; (b) a diamine of formula (I) NH 2 -R-NH 2 in which R is a divalent hydrocarbon and aliphatic radical and optionally comprising heteroatoms, the two amino functions are separated by a number of X-carbon atoms; X being between 4 and 12; and (c) a diamine of formula (II) NH 2 -R'-NH 2 in which R 'is a divalent hydrocarbon and aliphatic radical and optionally comprising heteroatoms, the two amino functions are separated by a number of carbon atoms Y; Y being between 10 and 20; it being understood that the diamine (b) is different from the diamine.
- the technical polyamides are used for the realization of many articles in different fields, such as the automotive field, where specific properties of rigidity, impact resistance, dimensional stability, especially at relatively high temperature, appearance of surface, density and weight are particularly sought after.
- the choice of a material for a given application is generally guided by the level of performance required vis-à-vis certain properties and by its cost. We are always looking for new materials that can meet specifications in terms of performance and / or costs.
- Some polyamides however, have a high water uptake which causes problems related to the dimensional stability of the articles used in many applications. Some polyamides also have insufficient temperature resistance, including a thermomechanical behavior that does not allow their use in applications where there are constraints of this type to meet. There was thus a need to overcome these disadvantages while using polymers having melting temperatures compatible with the transformation temperatures of conventional thermoplastic polyamides, a melting temperature generally below 330 ° C, and therefore be convertible by the processes of implementation known for thermoplastics, similar to polyamides, while enjoying excellent temperature resistance.
- copolyimides have melting temperatures that are entirely compatible with the transformation temperatures of conventional thermoplastic polyamides, the copolyimides according to the invention preferably having a melting temperature Tf of between 50 and 330 ° C. These copolyimides also have high crystallization temperatures to significantly reduce the production cycle time.
- the copolyimides according to the invention preferably have a glass transition temperature Tg of between -50 ° C. and + 170 ° C.
- copolyimides obtained are semi-crystalline and thermoplastic and have the property of not releasing or absorbing water during subsequent processing steps such as pultrusion, extrusion, or injection molding. These copolyimides are particularly hydrophobic and thus exhibit excellent dimensional stability.
- the present invention thus relates to a thermoplastic, semi-aromatic and semi-crystalline copolyimide obtained by polymerization of at least:
- R ' is a divalent hydrocarbon and aliphatic radical, saturated or unsaturated, and optionally comprising heteroatoms, the two amino functions are separated by a number of Y carbon atoms; Y being between 10 and 20 (limits included), the radical R 'has at most 20 carbon atoms; it being understood that the diamine (b) is different from the diamine (c).
- the invention relates to a thermoplastic, semi-aromatic and semi-crystalline copolyimide obtained by polymerization of at least two ammonium carboxylate salts obtained from the monomers (a) on the one hand and ( b) and (c) in the second part, wherein (a) is an aromatic compound comprising 4 carboxylic acid functions; (b) is a diamine of formula (I) NH 2 -R-NH 2 in which R is a divalent hydrocarbon and aliphatic radical, saturated or unsaturated, and optionally comprising heteroatoms, the two amino functions are separated by a number of X carbon atoms; X being between 4 and 12 (limits included); and (c) is a diamine of formula (II) NH 2 -R'-NH 2 in which R 'is a divalent hydrocarbon and aliphatic radical, saturated and / or unsaturated, and optionally comprising heteroatoms, the two amine functions are separated by a number of carbon atoms
- the polymerization involves two ammonium carboxylate salts, possibly unbalanced and / or with a chain limiter.
- the invention also relates to a process for producing a thermoplastic, semi-aromatic and semi-crystalline copolyimide obtained by polymerization of at least the monomers mentioned above, in particular in the form of salts, and more particularly by polymerization in the state. solid.
- the invention also relates to copolyimides that can be obtained by the process as described above.
- Semi-crystalline means a copolyimide having an amorphous phase and a crystalline phase, for example having a degree of crystallinity of between 1% and 85%.
- Thermoplastic copolyimide is understood to mean a copolyimide having a temperature above which the material softens and melts and which beneath it becomes hard.
- the determination of the melting temperature of the copolyimide is preferably carried out by measuring the temperature at the peak of the melting endotherm measured by Differential Scanning Calorimetry (DSC) using a Perkin apparatus. Elmer Pyris 1, by heating the copolyimide from 20 ° C at a rate of 10 ° C / min.
- the copolyimides obtained from a single diamine and an aromatic compound comprising 2 anhydride functions or derivatives are polyimides, generally called homopolyimides.
- the reaction between at least 3 different monomers produces a copolyimide.
- the copolyimides can be defined by the molar composition in each constituent monomer.
- the compounds (a) preferably carry carboxylic acid functions in positions such that they generally make it possible to form two acid anhydride functions on the same molecule by a dehydration reaction.
- the compounds of the present invention generally have two pairs of carboxylic acid functions, each pair of functions being bonded to an adjacent carbon atom, at a and ⁇ .
- the tetracarboxylic acid functions can be obtained from dianhydrides by hydrolysis of the anhydride functions of acids. Examples of dianhydrides of acids and tetracarboxylic acid derived from dianhydrides are described in US Pat. No. 7,993,2012.
- the aromatic compounds comprising 2 anhydride functional groups are preferably chosen from the group consisting of: pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6 , 7-naphthalenetetracarboxylic dianhydride, and 2,2'-bis-3,4-dicarboxyphenyl) hexafluoropropane tetracarboxylic dianhydride.
- aromatic compounds comprising carboxylic acid functions derived from the 2 anhydride functions are preferably selected from the group consisting of: pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3-acid, 3 ', 4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 2,2', 3,3 'acid benzophenonetetracarboxylic acid, 1, 2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9-acid , 10-Perylenetetracarboxylic acid, 3,3 ', 4,4'-tetraphenylsilanetetracarboxylic acid,
- Compounds (a) of the invention may also be free of functional groups other than carboxylic acids.
- the compounds (a) are tetracarboxylic acids whose carboxylic functions are they they allow to give rise to two anhydride functions by a dehydration reaction.
- the compounds (a) may comprise a single aromatic ring.
- Diamines (b) and (c) are aliphatic diamines.
- the term "aliphatic diamine” means a compound in which the amine functions are each borne by an aliphatic carbon, in particular by an sp 3 carbon.
- the amino functions are primary amines.
- the aliphatic diamines comprise a saturated aliphatic R group.
- the diamines (b) and (c) of the present invention thus carry a main chain separating the two amine functions and optionally one or more pendant or so-called lateral chains.
- the main chain comprises between 4 and 12 carbon atoms.
- the main chain comprises between 10 and 20 carbon atoms.
- the radicals R and R ' independently of one another, may be saturated or unsaturated, linear or branched, and optionally comprising heteroatoms.
- the radicals R and R ', independently of one another, may optionally contain one or more heteroatoms, such as O, N, P or S, and / or one or more functional groups such as hydroxyl, sulphone or ketone functions. , ethers or others.
- the diamines (b) of the invention preferentially carry two primary amine functions.
- the diamines (c) of the invention preferentially carry two primary amine functions.
- the diamine (b) is preferably selected from the group consisting of: 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, hexamethylenediamine, 3-methylhexamethylene diamine, 2,5-dimethylhexamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 2,2 7,7-tetramethyloctamethylene diamine, 1,9-diaminonane, 5-methyl-1,9-diaminononane, 1,10-diaminodecane, 1,1,1-diaminoundecane, 1,12-diaminododecane, and 5-methyl-1,9-diaminononane.
- the diamine (c) is preferably selected from the group consisting of: 1, 10-diaminodecane, 1, 1 1-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1, 14-diaminotetradecane, 1 , 15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctodecane, 1,19-diaminononadecane, and 1,20-diaminoeicosane.
- the diamine (c) is chosen from 1, 13-diaminotridecane, 1, 14-diaminotetradecane, 1, 15-diaminopentadecane, 1, 16-diaminohexadecane, 1, 17-diaminoheptadecane, 1, 18-diaminooctodecane, 1, 19- diaminononadecane, and 1, 20-diaminoeicosane, and even more particularly from 1, 14-diaminotetradecane, 1, 15-diaminopentadecane, 1, 16-diaminohexadecane, 1, 17-diaminoheptadecane, 1, 18-diaminooctodecane, 1, 19-diaminononadecane, and 1,20-diaminoeicosane.
- diamines containing heteroatoms examples include polyetherdiamines such as Jeffamine® and Elastamine® marketed by Hunstman. There is a variety of polyether, consisting of ethylene oxide units, propylene oxide, tetramethylene oxide.
- copolyimides using different types of monomers (a), (b) and / or (c); see also adding other types of monomers conducive to obtaining further imide function.
- the monomers (a), (b) and / or (c) may be in salt form or not.
- ammonium carboxylate salts formed by reaction between monomers (a), (b) and / or (c) mentioned above For example, there can be mentioned a mixture comprising the monomer (a), the monomer (c) and a salt formed by reaction between the monomers (a) and (b); or a mixture comprising the monomer (a), the monomer (b) and a salt formed by reaction between the monomers (a) and (c). There can also be mentioned a mixture between a salt formed by reaction between the monomers (a) and (b) and a salt formed by reaction between the monomers (a) and (c).
- ammonium carboxylate salt means a salt in which the diamine and tetraacid species are linked solely by polar interactions, in particular of the type -COO " H 3 + N-, and not by covalent bond (s), more particularly the salt comprises a tetraacid and a diamine, which are not linked by a covalent bond,
- the salt may have the following structure, with Ar representing an aromatic group:
- Such a salt can be synthesized in various ways, known to those skilled in the art.
- the diamines can be added either simultaneously or one after the other or sequentially in a solution comprising the compound (a).
- the compound (a) can also be dissolved in a solvent such as alcohol, such as ethanol or methanol for example, and the same for the diamines. These two solutions are then mixed with stirring.
- the ammonium carboxylate salt formed may be insoluble in the solvent used and thereby precipitate.
- the salt can then be recovered by filtration, washed and dried and optionally milled.
- concentration of the solution can be obtained by evaporation of the solvent such as water or alcohol or by another method by adding the compound (a) and / or diamines. It is also possible to saturate the solution, that is to say to carry out a process which makes it possible to modify the concentration of the salt in the solution to a value compatible with a crystallization of the latter. Generally this concentration is at least equal and more preferably greater than the saturation concentration of the salt at the temperature in question. More precisely, this concentration corresponds to a supersaturation of the salt solution.
- the compound (a) is dissolved in alcohol, such as ethanol for example, in a first medium.
- the diamine (b) and the diamine (c) are dissolved in alcohol in another medium and the two media are then mixed with stirring.
- the salt may be in the form of a dry powder, in the form of a powder dispersed in a solvent, or dissolved in solution.
- the salt can be recovered by filtration in the case of a precipitate and disintegrate the filter cake if necessary.
- the salt in the case where the salt is dissolved in solution, it can be recovered by a crystallization process by concentration, supersaturation or by precipitating it by addition of a non-solvent.
- the crystallized salt can then be recovered by filtration and the filter cake can be broken up if necessary.
- Another method for recovering the dispersed particles of dry salt is the atomization of the solution, that is to say in particular an operation of sudden evaporation of the solvent sprayed in the form of fine droplets in order to recover the dispersed particles of salt. .
- the mixture of the 3 different comonomers it is possible, for example, to carry out a mixture of preformed salts by preparing various diamine and compound (a) salts, and thus to mix the salts in the water and / or the alcohol.
- the mixture of salts can be homogeneous or heterogeneous.
- the salts are obtained by adding a mixture of diamines, that is, the diamines (b) and (c) are added concomitantly.
- the diamines are added sequentially, that is to say that the diamine (b) is added, then the diamine (c) is added, or vice versa.
- the salts obtained can lead to copolymers comprising or even consisting of block copolymers.
- the absolute pressure during the polymerization is preferably between 0.005 MPa and 0.2 MPa.
- the temperature during the polymerization is preferably between 50 ° C and 250 ° C.
- a means for keeping the copolyimide salt particles in motion is used in order to prevent an aggregation of these particles.
- a mechanical stirrer such as an agitator, a rotation of the reactor or a stirring by vibrations, or a fluidification by a carrier gas.
- the polyimide is obtained by a polymerization involving one or more ammonium carboxylate salt (s) obtained from monomers (a), (b) and (c), and in particular a dry salt.
- dry salt means that the polymerization is not carried out in solution or suspension in a solvent, or in a melt.
- the polymerization does not involve the addition of solvent to the powder (s) placed in the reactor.
- the number-average molar mass Mn of the copolyimides can be between 500 g / mol and 50000 g / mol.
- chain limiters that is to say molecules chosen from monoamines, monoanhydrides, monoacids or diacids in the ⁇ , ⁇ positions such that they can form an anhydride function by dehydration reaction among the chain-limiting agents
- chain limiters that is to say molecules chosen from monoamines, monoanhydrides, monoacids or diacids in the ⁇ , ⁇ positions such that they can form an anhydride function by dehydration reaction among the chain-limiting agents
- chain limiters that is to say molecules chosen from monoamines, monoanhydrides, monoacids or diacids in the ⁇ , ⁇ positions such that they can form an anhydride function by dehydration reaction among the chain-limiting agents
- phthalic anhydride 1,2-benzenedicarboxylic acid, or ortho-phthalic acid
- the acid acetic acid, propionic acid benzoic acid, stearic acid, benzylamine, 1-aminopentane, 1-aminohexane, 1-aminoheptan
- branching agents that is to say molecules of functionality greater than 3
- the stoichiometric imbalance r may range from 1.01 to 1.2. That is, the imbalance is particularly related to an excess of monomer (a), and more particularly tetracarboxylic acid.
- the monomers are, and in particular the salt is:
- the chain limiter and / or stoichiometric excess is added to the salt of stage (a) already formed.
- the chain limiter and / or the stoichiometric excess of one of the monomers is also in salt form, in particular it forms a salt with the aliphatic diamine and / or with the tetracarboxylic acid. It can therefore be a salt having a stoichiometric imbalance and / or a co-salt or mixed salt of aliphatic diamines, tetracarboxylic acid and chain limiter.
- the chain limiter and / or the stoichiometric excess is present during the formation of the salt of step (a) and is added at the same time.
- the chain limiter allows the formation of salt, and in particular can be chosen from the above lists, with the exception of anhydrides.
- the chain limiter content may range from 0.1 to 10% by number of moles, especially from 1 to 5% by number of moles, relative to the total number of moles of monomers, ie monomers (a). ), (b) and (c) and chain limiter, or more particularly tetracarboxylic acid, diamine and chain limiter.
- chain limiter the amounts of amines and of acids can be balanced, that is to say that the sum of amino functions is substantially equal to half of the sum of acid functions with which they can react.
- substantially equal is meant a maximum difference of 1%.
- the amounts of amines and acids can be unbalanced, that is to say the sum of amino functions is substantially different to half the sum of acid functions with which they can react.
- substantially different is meant a difference of at least 1%.
- the invention thus also relates to a salt of tetracarboxylic acid and diamines:
- Catalysts can be used, added at any time of the process, such as, for example, in a mixture with compound (a), diamine (b) and / or diamine (c), as a mixture with the salt formed either in solution either by impregnation in the solid state.
- Solvent polymerization can also be carried out, in particular by following the traditional routes for the synthesis of polyimides in solvent, in 2 steps, for example via a polybasic amic acid.
- the copolyimide of the invention can be used to make compositions which are generally obtained by mixing the various compounds, fillers and / or additives. The procedure is carried out at a higher or lower temperature, at a higher or lower shearing force, depending on the nature of the different compounds. The compounds can be introduced simultaneously or successively.
- An extrusion device is generally used in which the material is heated, then melted and subjected to a shearing force, and conveyed. According to particular embodiments, it is possible to carry out melt pre-blends, or not, before preparation of the final composition. For example, premixing can be carried out in a resin, for example copolyimide, so as to produce a masterbatch.
- the invention thus also relates to a method of manufacturing a composition by melt blending, or not, the copolyimide with reinforcing or filling fillers, and / or impact modifiers and / or additives.
- the invention also relates to a composition comprising at least copolyimide, reinforcing or filling fillers and / or impact modifiers and / or additives.
- the composition according to the invention may comprise one or more other polymers.
- the composition according to the invention may comprise between 20 and 90% by weight, preferably between 20 and 70% by weight, and more preferably between 35 and 65% by weight of copolyimide according to the invention, relative to the total weight of the composition. .
- the composition may further comprise reinforcing or filling fillers.
- the reinforcing or filling fillers are fillers conventionally used for the production of thermoplastic compositions, especially based on polyamide.
- Fibrous reinforcing fillers such as glass fibers, carbon fibers, or organic fibers
- non-fibrous fillers such as particulate fillers, lamellar fillers and / or exfoliatable or non-exfoliatable nanofillers
- polymeric fillers such as, for example, dimethacrylate particles, glass beads or glass powder. It is particularly preferred to use reinforcing fibers, such as glass fibers.
- composition according to the invention may comprise between 5 and 60% by weight of reinforcing or filling fillers, preferably between 10 and 40% by weight, relative to the total weight of the composition.
- composition according to the invention comprising the copolyimide as defined above may comprise at least one impact modifier, that is to say a compound capable of modifying the impact resistance of a copolyimide composition.
- shock-modifying compounds preferably comprise functional groups that are reactive with the copolyimide.
- functional groups reactive with the copolyimide groups capable of reacting or chemically interacting with the residual anhydride, acid or amine functions of the copolyimide, in particular by covalence, ionic interaction or hydrogen or van der Walls bonding.
- reactive groups make it possible to ensure good dispersion of the impact modifiers in the copolyimide matrix.
- anhydride, epoxide, ester, amino, carboxylic acid or carboxylate or sulphonate derivatives may be mentioned.
- composition according to the invention may further comprise additives generally used for the manufacture of polyimide or polyamide compositions.
- additives generally used for the manufacture of polyimide or polyamide compositions.
- lubricants flame retardants, plasticizers, nucleating agents, anti-UV agents, catalysts, antioxidants, antistats, dyes, mattifying agents, molding aid additives or other additives. conventional.
- fillers, impact reinforcing agents and additives may be added to the copolyimide by customary means which are well known in the field of engineering plastics, such as, for example, during salification, after salification, during polymerization, or in admixture. fade.
- the copolyimide compositions are generally obtained by mixing the various compounds used in the cold or melt composition. The procedure is carried out at a higher or lower temperature, at a higher or lower shearing force, depending on the nature of the different compounds. The compounds can be introduced simultaneously or successively.
- An extrusion device is generally used in which the material is heated, then melted and subjected to a shearing force, and conveyed.
- All the compounds in the melt phase can be mixed in a single operation, for example during an extrusion operation.
- a mixture of granules of the polymeric materials can be introduced into the extrusion device in order to melt them and subject them to greater or lesser shear.
- We can, according to modes of realization in particular, pre-blending, melt or not, some of the compounds before preparation of the final composition.
- the copolyimide or the various compositions according to the invention can be used for any shaping process for the manufacture of plastic articles.
- the (co) polyimide may be unbalanced and / or comprise chain limiters.
- the invention thus also relates to a method of manufacturing a plastic article implementing the copolyimides of the invention.
- Various techniques can be mentioned for this purpose, such as the molding process, in particular injection molding, extrusion, extrusion blow molding, or even rotomolding, particularly in the automotive or electronic electricity for example.
- the extrusion process may in particular be a process for spinning or manufacturing films.
- the present invention relates for example to the manufacture of articles of the type of impregnated fabrics or composite articles with continuous fibers.
- These articles may in particular be manufactured by bringing together a fabric and the copolyimide according to the invention in the solid or molten state.
- the fabrics are textile surfaces obtained by assembling yarn or fibers joined together by any method, such as in particular gluing, felting, braiding, weaving, knitting.
- These fabrics are also referred to as fibrous or filamentary networks, for example based on glass fibers, carbon fibers or the like.
- Their structure can be random, unidirectional (1 D), or multidirectional (2D, 2,5D, 3D or other).
- the melting (Tf) and cooling crystallization (Te) temperatures of the copolyimides are determined by Differential Scanning Calorimetry (DSC), using a Perkin Elmer Pyris 1 device, at a rate of 10 ° C / min.
- the Tf and Te of the copolyimides are determined at the peak of melting and crystallization peaks.
- the glass transition temperature (Tg) determined on the same apparatus at a rate of 40 ° C / min (when possible, it is determined at 10 ° C / min and specified in the examples).
- the measurements are made after melting of the copolyimide formed at T (Tm of the copolyimide + 20 ° C.).
- the endotherm temperature is measured by heating the salt to 10 ° C / min.
- Thermo-gravimetric analysis is performed on a Perkin-Elmer TGA7 device on a sample of about 10 mg.
- the precise conditions of use are defined in the examples.
- An ethanolic solution of pyromellitic acid is prepared by dissolving 0.00079 mol of pyromellitic acid in 4 ml of absolute ethanol. This solution is added dropwise to a solution heated to 50 ° C. containing 5 ml of absolute ethanol and 0.00079 mol of a mixture of 1,10-diaminodecane and 1,12-diaminododecane in molar proportions of 100% / 0. % (Example 1A), 75% / 25% (Example 1B), 50% / 50% (Example 1C), 25% / 75% (Example 1D) and 0% / 100% (Example 1E).
- the salt formed precipitates immediately and is recovered by evaporation of the solvent. The salt is allowed to dry overnight under vacuum at 50 ° C.
- the copolyimide formed is produced by heat treatment above 200 ° C. of the salt powder and then analyzed in DSC in the following Table 1:
- the copolyimides are semi-crystalline and have a single melting temperature, meaning that they are copolymers capable of co-crystallizing. This melting temperature may be between the Tf of the two homopolyimides or even lower. It also appears that the enthalpy of fusion is lower than the enthalpy of fusion of the homopolymers but remains high regardless of the molar composition of the diamines. From the copolymerization, it is possible to transform the PI 10PMA melting temperature of 334 ° C and difficult to transform by the processing techniques for thermoplastics into a semi-crystalline polymer having a melting temperature below 300 ° C much easier to process. It will be noted that the FTIR analysis of the copolyimide powder exhibits the characteristic absorption bands of the imide functions at 1700 and 1767 cm -1, and the absence of characteristic absorption bands of the amine functions is noted.
- an ethanolic solution of pyromellitic acid is added dropwise in a stoichiometric amount of a mixture of 1,10-diaminodecane and 1,13-diaminotridecane solubilized in pure ethanol.
- the molar ratio of the two diamines C10 / C13 chosen is 100% / 0% (Example 2A), 75% / 25% (Example 2B), 50% / 50% (Example 2C), 25% / 75% (Example 2D ) and 0% / 100% (example 2E).
- the formed salts precipitate immediately and are recovered by evaporation of the solvent, are dried overnight under vacuum at 50 ° C.
- the copolyimide formed is produced by heat treatment above 200 ° C. of the salt powder and then analyzed in DSC in the following Table 2:
- Tg is determined at 10 ° C / min
- Solution 1 2.807 g of 97.6% pyromellitic acid dissolved in 51.806 g of absolute ethanol. Solution 1 has a concentration of 1, 974 10 -4 mol / g of pyromellitic acid.
- Solution 0.831 g of a 32.25% by weight aqueous solution of hexamethylenediamine (diamine C6) dissolved in 16.754 g of ethanol.
- Solution 2 has a concentration of 1.31 ⁇ 10 -4 mol / g hexamethylenediamine.
- Solution 3 2.202 g of 1,10-diaminodecane (diamine C10) at 99% dissolved in 41.992 g of ethanol. Solution 3 has a concentration of
- Example 4 In contrast to Example 3, in which a mixture of the C 6 and C 10 diamines is introduced into a solution of pyromellitic acid, we carry out here in Example 4 a sequential introduction of the diamines into the pyromellitic acid solution:
- solution 3 1,10-diaminodecane
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Abstract
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Application Number | Priority Date | Filing Date | Title |
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FR1158326A FR2980203B1 (fr) | 2011-09-20 | 2011-09-20 | Copolyimides thermoplastiques |
PCT/EP2012/068369 WO2013041532A1 (fr) | 2011-09-20 | 2012-09-18 | Copolyimides thermoplastiques |
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US (2) | US20150045501A1 (fr) |
EP (1) | EP2758451A1 (fr) |
JP (2) | JP2014526594A (fr) |
KR (1) | KR20140069168A (fr) |
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WO (1) | WO2013041532A1 (fr) |
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FR2980201B1 (fr) * | 2011-09-20 | 2014-10-24 | Rhodia Operations | Polyimides thermoplastiques |
FR2980203B1 (fr) * | 2011-09-20 | 2014-12-26 | Rhodia Operations | Copolyimides thermoplastiques |
WO2013041531A1 (fr) | 2011-09-20 | 2013-03-28 | Rhodia Operations | Polyimides thermoplastiques |
FR3019609B1 (fr) * | 2014-04-03 | 2016-05-13 | Hutchinson | Courroie de transmission de puissance. |
US10745520B2 (en) | 2014-12-18 | 2020-08-18 | Centre National De La Recherche Scientifique | Process for producing aromatic polyimides |
WO2019119337A1 (fr) * | 2017-12-21 | 2019-06-27 | Rhodia Operations | Procédé de préparation de diamines primaires au moyen d'une réaction de couplage par électrolyse de kolbe |
FR3092519B1 (fr) * | 2019-02-13 | 2021-09-24 | Arkema France | Poudre de monomere salifie et leur utilisation dans les procedes d’agglomeration de poudre |
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US2710853A (en) | 1953-10-19 | 1955-06-14 | Du Pont | Polyimides of pyromellitic acid |
US4251417A (en) * | 1979-04-25 | 1981-02-17 | Gulf Oil Corporation | Novel acetylene end-capped polyimide oligomers |
US4358562A (en) * | 1981-07-24 | 1982-11-09 | Standard Oil Company (Indiana) | Copolyimides from tetramethylcyclobutane-1,2,3,4-tetracarboxylic dianhydride and a mixture of diamines |
FR2592050B1 (fr) * | 1985-12-24 | 1988-01-08 | Centre Etd Mat Org Tech Avance | Copolyimides arylaliphatiques a enchainements ether, leur preparation, leurs melanges ou produits de reaction avec des resines epoxydes et leur utilisation pour la fabrication de materiaux composites flexibles |
WO2000068318A1 (fr) * | 1999-05-10 | 2000-11-16 | Teijin Limited | Composition de resine contenant un polyimide cristallin |
JP2001098070A (ja) * | 1999-09-30 | 2001-04-10 | Sumitomo Bakelite Co Ltd | テトラカルボン酸ジアミン塩の無溶剤製造方法 |
KR100354907B1 (ko) * | 2000-04-26 | 2002-09-30 | 페어차일드코리아반도체 주식회사 | 구동신호 입력단자 분리형 스위칭 소자와 그 구동회로 |
US6444783B1 (en) * | 2000-12-21 | 2002-09-03 | E. I. Du Pont De Nemours And Company | Melt-processible semicrystalline block copolyimides |
US7932012B2 (en) | 2004-03-31 | 2011-04-26 | Hitachi Chemical Dupont Microsystems Ltd. | Heat-resistant photosensitive resin composition, method for forming pattern using the composition, and electronic part |
JP4957583B2 (ja) * | 2007-02-22 | 2012-06-20 | 新日本理化株式会社 | 溶剤可溶性ポリイミド共重合体及びそれを含有するポリイミドワニス |
FR2980203B1 (fr) * | 2011-09-20 | 2014-12-26 | Rhodia Operations | Copolyimides thermoplastiques |
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- 2011-09-20 FR FR1158326A patent/FR2980203B1/fr active Active
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- 2012-09-18 EP EP12759734.2A patent/EP2758451A1/fr not_active Withdrawn
- 2012-09-18 WO PCT/EP2012/068369 patent/WO2013041532A1/fr active Application Filing
- 2012-09-18 US US14/345,070 patent/US20150045501A1/en not_active Abandoned
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- 2017-10-11 US US15/730,414 patent/US20180030206A1/en not_active Abandoned
- 2017-10-18 JP JP2017201707A patent/JP2018053251A/ja not_active Ceased
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FR2980203A1 (fr) | 2013-03-22 |
JP2018053251A (ja) | 2018-04-05 |
FR2980203B1 (fr) | 2014-12-26 |
JP2014526594A (ja) | 2014-10-06 |
US20180030206A1 (en) | 2018-02-01 |
WO2013041532A1 (fr) | 2013-03-28 |
KR20140069168A (ko) | 2014-06-09 |
US20150045501A1 (en) | 2015-02-12 |
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